CA 03004324 2018-05-03
TITLE: PROCESS AND SYSTEM FOR MAKING CYCLOPENTADIENE AND/OR
DICYCLOPENTADIENE
INVENTOR(s):
[0001] Larry L. Iaccino and Kevin C.P. Leung.
FIELD OF THE INVENTION
[0002] The present invention relates to processes and systems for making
cyclic C5s
including cyclopentadiene and/or dicyclopentadiene. In particular, the present
invention
relates to processes and systems for making cyclopentadiene and
dicyclopentadiene from
acyclic C5 hydrocarbons.
BACKGROUND OF THE INVENTION
[0003] Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are
highly
desired raw materials used throughout the chemical industry in a wide range of
products such
as polymeric materials, polyester resins, synthetic rubbers, solvents, fuels,
fuel additives, etc.
Typically, cyclopentadiene is produced as a minor byproduct in liquid fed
steam cracking
(e.g., naphtha and heavier feed) processes. As steam cracking processes shift
to using lighter
feed (e.g., ethane and propane feed), less CPD is produced while demand for
CPD continues
to rise. Cyclopentane and cyclopentene also have high value as solvents while
cyclopentene
may be used as a monomer to produce polymers and as a starting material for
other high value
chemicals.
[0004] Consequently, there is a need for on-purpose CPD production,
i.e., CPD
produced as a primary product from a feedstock as opposed to CPD produced as a
minor
byproduct. U.S. 5,633,421 generally discloses a process for dehydrogenating C2-
05
paraffins to obtain corresponding olefins. Similarly, U.S. 2,982,798 generally
discloses a
process for dehydrogenating aliphatic hydrocarbons containing 3 to 6,
inclusive, carbon
atoms. However, neither U.S. 5,633,421 nor U.S. 2,982,798 discloses production
of CPD
from acyclic C5 hydrocarbons, which are desirable as feedstock because they
are plentiful
and low cost. Further, many challenges exist in designing an on-purpose CPD
production
process. For example, the reaction converting C5 hydrocarbons to CPD is
extremely
endothermic and is favored by low pressure and high temperature but
significant cracking of
n-pentane and other C5 hydrocarbons can occur at relatively low temperature
(e.g.,
450 C-500 C). Other challenges include loss of catalyst activity due to coking
during the
- 1 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
production process and further processing is needed to remove coke from the
catalyst, and the
inability to use oxygen-containing gas to directly provide heat input to the
reactor without
damaging the catalyst.
[0005] From the perspective of storage and shipping, DCPD is easier to
handle than
CPD as a feed material for subsequent chemical syntheses. DCPD and CPD are
fungible in
many applications. In certain applications DCPD is preferably used directly in
lieu of CPD.
For other applications where CPD is needed, DCPD can be thermally
depolvmerized (aka
cracked) via retro-Diels-Alder reaction to CPD at the point of use.
[0006] Conventional processes for making CPD typically produce C5
hydrocarbon
to stream(s) comprising CPD at a modest concentration, acyclic diolefins at
significant
concentrations, and mono olefins. Because many of the C5 species have close
boiling points,
form azeotropes, and are reactive at distillation temperatures, CPD recovery
from the product
mixture via conventional distillation is not industrially feasible. In
conventional recovery
schemes, CPD is recovered from other C5 hydrocarbons utilizing dimerization
process(es)
which causes CPD to undergo Diels-Alder reaction to produce DCPD that can
easily be
separated from the C5 hydrocarbons by conventional distillation.
Unfortunately, CPD can
also react with other diolefins present in the stream to produce co-dimers,
which contaminate
the DCPD. Furthermore, reactions involving higher-order oligomers also occur
at moderate
to high temperatures. These side reactions produce undesirable co-dimers and
higher-order
2() oligomers, which necessitate more downstream processing steps, such as
repeated, multi-step
cracking and dimerization, to produce DCPD with sufficient purity required for
many
applications. Such processes are expensive, low in yield, and can be prone to
fouling.
[0007] Therefore, there is a need for processes and systems for the
production of CPD
and/or DCPD that address the above described challenges.
SUMMARY OF THE INVENTION
[0008] It has been found that by combining a catalytic acyclic C5
hydrocarbon
conversion process where production of CPD is favored over acyclic diolefins,
and an
effective separation process thereafter minimizing the Diels-Alder reactions
between CPD
and acyclic diolefins, CPD can be produced at a high yield, from which high-
purity DCPD
can be produced.
[0009] A first aspect of the present invention relates to a process for
making CPD and/or
DCPD comprising: (I) feeding a C5 feedstock comprising at least one acyclic C5
hydrocarbon into a first reactor; (II) contacting the at least one acyclic C5
hydrocarbon with a
catalyst under conversion conditions to obtain a first reactor hydrocarbon
effluent
- 2 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
comprising: C5 components including CPD and acyclic diolefins; light
components including
hydrogen and CI-C4 hydrocarbons; one-ring aromatics; and multiple-ring
aromatics; (III)
contacting the first reactor hydrocarbon effluent with a wash oil in a washing
vessel, thereby
obtaining: a heavy stream comprising at least a portion of the wash oil and at
least a portion
of the multiple-ring aromatics; and a washed first reactor hydrocarbon
effluent comprising at
least a portion of the light components, at least a portion of the C5
components, and,
optionally, a portion of the wash oil; (IV) separating the washed first
reactor hydrocarbon
effluent in a first separation sub-system to obtain: a first C5-rich fraction
comprising CPD
and depleted of the light components; a first light component-rich fraction
comprising
to hydrogen and C1-C4 hydrocarbons; and an optional first recovered wash oil
stream; (V)
supplying the heavy stream and, optionally. at least a portion of the optional
first recovered
wash oil stream to a wash oil recovery sub-system; (VI) obtaining, from the
wash oil
recovery sub-system: a heavy oil fraction comprising the multiple-ring
aromatics; a second
recovered wash oil stream; and an optional recovered C5-rich stream comprising
CPD; and
(VII) recycling at least a portion of the second recovered wash oil stream,
and, optionally, at
least a portion of the optional first recovered wash oil stream and/or the
optional recovered
C5-rich stream comprising CPD directly or indirectly to the washing vessel.
[0010] A second aspect of the present invention relates to a system for
making CPD
and/or DCPD, comprising: (A) a first reactor configured to receive a C5
feedstock
zo comprising at least one acyclic C5 hydrocarbon, an optional hydrogen co-
feedstock and an
optional C 1 -C4 hydrocarbon co-feedstock; (B) a catalyst loaded inside the
first reactor
capable of catalyzing the conversion of the C5 hydrocarbons under conversion
conditions to
produce a first reactor hydrocarbon effluent comprising: C5 hydrocarbons
including CPD and
acyclic diolefins: one-ring aromatics; multiple-ring aromatics; and light
components
including hydrogen and C1-C4 hydrocarbons; (C) a washing vessel configured to
receive (i)
at least a portion of the first reactor hydrocarbon effluent and (ii) a wash
oil, and to produce a
washed first reactor hydrocarbon effluent and a heavy stream comprising at
least a portion of
the wash oil and at least a portion of the multiple-ring aromatics; (D) a wash
oil recovery sub-
system configured to receive at least a portion of the heavy stream and to
produce a heavy oil
fraction comprising at least a portion of the multiple-ring aromatics and a
second recovered
wash oil stream; (E) a wash oil fluid communication channel configured to
recycle at least a
portion of the second recovered wash oil stream directly or indirectly to the
washing vessel;
(F) a fluid communication channel configured to supply at least a portion of
the washed first
reactor hydrocarbon effluent to the first separation sub-system; and (G) a
first separation sub-
- 3 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
system in fluid communication with the washing vessel configured to receive at
least a
portion of the washed first reactor hydrocarbon effluent and to produce (i) a
first C5-rich
fraction comprising CPD and depleted of hydrogen and C1-C4 hydrocarbons, (ii)
a first light
component-rich fraction comprising hydrogen and C1-C4 hydrocarbons, and (iii)
an optional
first recovered wash oil stream.
BRIEF DESCIPT1ON OF THE DRAWINGS
[0011] FIG. 1
is a schematic illustration of an exemplary process and system for making
CPD and/or DCPD of the present invention.
[0012] FIG. 2
is a schematic illustration of the details of the first separation sub-system
to in FIG. I.
DETAILED DESCRIPTION OF THE INVENTION
[0013] In the
present disclosure, a process is described as comprising at least one "step."
It should be understood that each step is an action or operation that may be
carried out once
or multiple times in the process, in a continuous or discontinuous fashion.
Unless specified
to the contrary or the context clearly indicates otherwise, each of the steps
in a process may
be conducted sequentially in the order as they are listed, with or without
overlapping with one
or more other steps, or in any other order, as the case may be. In addition,
one or more or
even all steps may be conducted simultaneously with regard to the same or
different batch of
material. For example, in a continuous process, while a first step in a
process is being
conducted with respect to a raw material just fed into the beginning of the
process, a second
step may be carried out simultaneously with respect to an intermediate
material resulting
from treating the raw materials fed into the process at an earlier time in the
first step.
Preferably, the steps are conducted in the order described.
100141 Unless
otherwise indicated, all numbers indicating quantities in the present
disclosure are to be understood as being modified by the term "about" in all
instances. It
should also be understood that the precise numerical values used in the
specification and
claims constitute specific embodiments. Efforts have been made to ensure the
accuracy of
the data in the examples. However, it should be understood that any measured
data
inherently contain a certain level of error due to the limitation of the
technique and/or
equipment used for making the measurement.
[0015] All
numbers and references to the Periodic Table of Elements are based on the
new notation as set out in Chemical and Engineering News. 63(5), 27 (1985),
unless
otherwise specified.
- 4 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Definitions
[0016] For the
purpose of this specification and appended claims, the following terms
are defined.
[0017] The term
"cyclic C5" or "cC5" includes, but is not limited to, cyclopentane,
cyclopentene, cyclopentadiene, and mixtures of two or more thereof The term
"cyclic C5" or
"cC5" also includes alkylated analogs of any of the foregoing, e.g., methyl
cyclopentane,
methyl cyclopentene, and methyl cyclopentadiene. It should be recognized for
purposes of
the invention that cyclopentadiene spontaneously dimerizes over time to form
di cy cl op entadi en e via Di el s- Al der condensation over a range of
conditions, including
to ambient temperature and pressure.
[0018] The term
"acyclic" includes, but is not limited to, linear and branched saturates
and non-saturates.
[0019] The term
"alkyl" includes saturated hydrocarbyl groups, which can be linear,
branched, cyclic, or a combination of cyclic, linear and/or branched linear.
[0020] The term -aromatic" means a planar cyclic hydrocarbyl with
conjugated double
bonds, such as benzene. As used herein, the term aromatic encompasses
compounds
containing one or more aromatic rings, including, but not limited to, benzene,
toluene and
xylene and polynuclear aromatics (PNAs) which include, but are not limited to,
naphthalene,
anthracene, chrysene, and their alkylated versions. The term -C6+ aromatics"
includes
compounds based upon an aromatic ring having six or more ring atoms,
including, but not
limited to, benzene, toluene and xylene and polynuclear aromatics (PNAs) which
include, but
are not limited to, naphthalene, anthracene, chrysene, and their alkylated
versions
[0021] The term
-BTX" includes, but is not limited to, a mixture of benzene, toluene, and
xylene (ortho and/or meta and/or para).
[0022] As used herein, the term "rich," when used to describe a component
in a given
mixture or stream produced from a predecessor mixture or stream, means that
the component
is present at a non-negligible concentration in the given mixture or stream
that is higher than
its concentration in the predecessor mixture or stream. Thus, a C5-rich
fraction produced
from a predecessor stream is a fraction comprising C5 hydrocarbons at a non-
negligible
concentration that is higher than the concentration of C5 hydrocarbons in the
predecessor
stream.
[0023] As used
herein, the term "depleted," when used to describe a component in a
given mixture or stream produced from a predecessor mixture or stream, means
that the
component is present at a concentration (which can be negligible) in the given
mixture or
- 5 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
stream that is lower than its concentration in the predecessor mixture or
stream. Thus, a
hydrogen-depleted fraction produced from a predecessor stream is a fraction
comprising
hydrogen at a concentration (which can be negligible) that is lower than the
concentration of
hydrogen in the predecessor stream.
[0024] As used herein, "wt%" means percentage by weight, "vol%" means
percentage by
volume, and "mol%" means percentage by mole. All ranges expressed herein
should include
both end points as two specific embodiments unless specified or indicated to
the contrary.
[0025] An "upper stream" as used herein may be at the very top or the
side of a vessel
such as a fractionation column or a reactor, with or without an additional
stream above it.
to Preferably, an upper stream is drawn at a location in the vicinity of
the top of the column.
Preferably, an upper stream is drawn at a location above at least one feed. A
"lower stream"
as used herein is at a location lower than the upper stream, which may be at
the very bottom
or the side of a vessel, and if at the side, with or without an additional
stream below it.
Preferably, a lower stream is drawn at a location in the vicinity of the
bottom of the column.
Preferably. a lower stream is drawn at a location below at least one feed. As
used herein, a
"middle stream" is a stream between an upper stream and a lower stream.
[0026] The term "divided-wall distillation column" means a distillation
column
producing an upper stream, a lower stream, and a middle stream from one or
more feed
stream, having a dividing wall within the shell partitioning the inner space
into two sections,
zo one comprising an inlet for receiving the feed stream, and the other
comprising an outlet for
ejecting the middle stream. The dividing wall limits mass transfer within the
shell to areas
above and below it only.
[0027] The term "light hydrocarbons" means hydrocarbons comprising 1 to 4
carbon
atoms in their molecule structures. The term "light components" means hydrogen
and
hydrocarbons comprising 1 to 4 carbon atoms in their molecule structures. The
term
"hydrogen" means molecular H2.
[0028] The term "normal boiling point" means boiling point under a
pressure of 101
kilopascal. The terms "vapor" and "gas" are both inclusive to mean a phase
that is entirely
vapor, entirely gas and mixtures of gas and vapor.
[0029] As used herein, the term "essentially free of" means comprising at a
concentration
not higher than 1 wt%, e.g., < 0.8 wt%, < 0.6 wt%, < 0.5 wt%, < 0.1 wt%, <
0.01 wt%, or
even < 0.001 wt%.
[0030] The term "mogas" means a mixture of organic compounds suitable as
fuel for use
in gasoline internal combustion engine.
- 6 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[0031] The term "coke" includes, but is not limited to, a low hydrogen
content
hydrocarbon that is adsorbed on the catalyst composition.
[0032] The term "Cn" means hydrocarbon(s) having n carbon atom(s) per
molecule,
wherein n is a positive integer. Thus, a C5 hydrocarbon feedstock, therefore,
comprises one
or more hydrocarbon, saturated or unsaturated, having 5 carbon atoms per
molecule, such as
n-pentane, 2-methyl-butane, 2,2-dimethylpentane, 1-pentene, 2-pentene, 2-
methyl-2-butene,
3-methy1-2-butene,1,3-pentadiene, 1,4-pentadiene, 2-methy1-1,3-butadiene,
cyclopentane,
cyclopentene, and the like.
[0033] The term "Cn+" means hydrocarbon(s) having at least n carbon
atom(s) per
to molecule.
[0034] The term "Cn-" means hydrocarbon(s) having no more than n carbon
atom(s) per
molecule.
[0035] The term "hydrocarbon" means a class of compounds containing
hydrogen
bonded to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii)
unsaturated
hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated
and/or
unsaturated), including mixtures of hydrocarbon compounds having different
values of n.
[0036] The term "CS feedstock" includes a feedstock containing n-pentane,
such as a
feedstock which is predominately normal pentane (n-pentane) and/or isopentane
(also
referred to as methylbutane), with smaller fractions of cyclopentane and/or
neopentane (also
referred to as 2,2-dimethylpropane).
[0037] The term "one-ring aromatics" means aromatic compounds having one
benzene
ring in the molecular stnictures thereof and includes alkylated versions
thereof such as
toluene, xylenes, and ethylbenzene.
[0038] The term "multiple-ring aromatics" means aromatic compounds having
two or
more aromatic rings in the molecular structures thereof and includes alkylated
versions
thereof.
[0039] The term "Group 10 metal" means an element in Group 10 of the
Periodic Table
and includes Ni, Pd and Pt.
[0040] The term "Group 1 alkali metal- means an element in Group 1 of the
Periodic
Table and includes, but is not limited to, Li, Na, K, Rb, Cs, and a mixture of
two or more
thereof, and excludes hydrogen.
[0041] The term "Group 2 alkaline earth metal" means an element in Group
2 of the
Periodic Table and includes, but is not limited to, Be, Mg, Ca, Sr, Ba, and a
mixture of two or
more thereof.
- 7 -
CA 03004324 2018-05-03
[0042] The term "Group 11 metal" means an element in Group 11 of the
Periodic Table
and includes, but is not limited to, Cu, Ag, Au, and a mixture of two or more
thereof.
[0043] The term "constraint index" is defined in US 3,972,832 and US
4,016,218.
[0044] As used herein, the term "molecular sieve of the MCM-22 family"
(or "material
.. of the MCM-22 family" or "MCM-22 family material" or "MCM-22 family
zeolite") includes
one or more of:
molecular sieves made from a common first degree crystalline building block
unit cell,
which unit cell has the MWW framework topology. (A unit cell is a spatial
arrangement of
atoms which if tiled in three-dimensional space describes the crystal
structure). Such crystal
structures are discussed in the "Atlas of Zeolite Framework Types", Fifth
edition, 2001);
molecular sieves made from a common second degree building block, being a
2-dimensional tiling of such MWW framework topology unit cells, forming a
monolayer of
one unit cell thickness, preferably one c-unit cell thickness;
molecular sieves made from common second degree building blocks, being layers
of
one or more than one unit cell thickness, wherein the layer of more than one
unit cell thickness
is made from stacking, packing, or binding at least two monolayers of one unit
cell thickness.
The stacking of such second degree building blocks may be in a regular
fashion, an irregular
fashion, a random fashion, or any combination thereof; and
molecular sieves made by any regular or random 2-dimensional or 3-dimensional
combination of unit cells having the MWW framework topology.
[0045[ The MCM-22 family includes those molecular sieves having an X-ray
diffraction
pattern including d-spacing maxima at 12.4+0.25, 6.9+0.15, 3.57+0.07 and
3.42+0.07
Angstrom. The X-ray diffraction data used to characterize the material are
obtained by
standard techniques using the K-alpha doublet of copper as incident radiation
and a
diffractometer equipped with a scintillation counter and associated computer
as the collection
system.
[0046] As used herein, the term "molecular sieve" is used synonymously
with the term
"microporous crystalline material".
[0047] As used herein, the term "carbon selectivity" means the moles of
carbon in the
respective cyclic C5, CPD, Cl, and C2-4 formed divided by total moles of
carbon in the C5
feedstock converted. The term "carbon selectivity to cyclic C5 of at least
30%" means that
- 8 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
30 moles of carbon in the cyclic C5 is formed per 100 moles of carbon in the
C5 feedstock
(such as n-pentane) converted.
[0048] As used herein, the term "conversion" means the moles of carbon in
the acyclic
C5 hydrocarbon(s) that is converted to a product. The term "conversion of at
least 70% of
said acyclic C5 hydrocarbon(s) to a product" means that at least 70% of the
moles of said
acyclic CS hydrocarbon(s) was converted to a product.
[0049] As used herein, the term "ferrosilicate" means an iron-containing
microporous
crystalline structure that contains iron in the framework structure and/or in
the channel
system.
to [0050] The term -alkylated naphthalene(s)" includes monoalkyl,
dialkyl, trialkyl, and
tetraalkyl naphthalenes.
The CS Feedstock
[0051] A C5 feedstock comprising acyclic C5 hydrocarbon(s) useful herein
is obtainable
from crude oil or natural gas condensate, can include virgin C5, and can
include cracked C5
(in various degrees of unsaturation: alkenes, dialkenes, alkynes) produced by
refining and
chemical processes, such as fluid catalytic cracking (FCC), reforming,
hydrocracking,
hydrotreating, coking, and steam cracking.
[0052] In one or more embodiments, the CS feedstock useful in the process
of this
invention comprises pentane, pentene, pentadiene and mixtures of two or more
thereof.
Preferably, in one or more embodiments, the C5 feedstock comprises at least
about 50 wt%,
or 60 wt%, or 75 wt%, or 90 wt% saturated acyclic C5 hydrocarbon(s), ideally n-
pentane, or
in the range from about 50 wt% to about 100 wt% saturated acyclic C5
hydrocarbon(s),
ideally n-pentane. Preferably, 2-methylbutane is present at less than 10 wt%.
[0053] The C5 feedstock optionally does not comprise C6 aromatic
compounds, such as
benzene. Preferably C6 aromatic compounds are present at less than 5 wt?/o, or
less than 1
wt%, or less than 0.01 wt%, or even 0 wt?/o.
[0054] The C5 feedstock optionally does not comprise toluene and/or one
or more of the
xylenes (ortho, meta and para). Preferably, toluene and xylenes (ortho, meta
and para) are
present in the C5 feedstock at less than 5 wt%, preferably less than 1 wt%,
preferably present
at less than 0.01 wt(?/o, preferably at 0 wt%.
[0055] The C5 feedstock optionally does not comprise C6+ aromatic
compounds,
preferably C6+ aromatic compounds are present at less than 5 wt%, preferably
less than 1
wt%, preferably present at less than 0.01 wt?/o, preferably at 0 wt%.
- 9 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[0056] The C5 feedstock optionally does not comprise C6+ compounds,
preferably C6+
compounds are present at less than 5 wt%, preferably less than 1 wt%,
preferably present at
less than 0.01 wt%, preferably at 0 wt%, preferably any C6+ aromatic compounds
are present
at less than 5 wt%, preferably less than 1 wt%, preferably present at less
than 0.01 wt%,
preferably at 0 wt%.
[0057] In the present invention, the acyclic C5 hydrocarbon(s) contained
in the C5
feedstock is fed into a first reactor loaded with a catalyst, where the
acyclic CS hydrocarbons
contact the catalyst under conversion conditions, whereupon at least a portion
of the acyclic
CS hydrocarbon(s) molecules are converted into CPD molecules, and a reaction
product
to containing CPD and, optionally, other cyclic hydrocarbons (e.g., CS
cyclic hydrocarbons
such as cvclopentane and cyclopentene) exits the first reactor as a first
reactor hydrocarbon
effluent. Preferably, a hydrogen co-feedstock comprising hydrogen and,
optionally, light
hydrocarbons, such as C1-C4 hydrocarbons, is also fed into the first reactor.
Preferably, at
least a portion of the hydrogen co-feedstock is admixed with at least a
portion, preferably the
entirety, of the C5 feedstock prior to being fed into the first reactor. The
presence of
hydrogen in the feed mixture at the inlet location, where the feed first comes
into contact with
the catalyst, prevents or reduces the formation of coke on the catalyst
particles. The catalyst
composition, which is described in greater detail below, may comprise a
microporous
crystalline metallosilicate, preferably having a constraint index in the range
of less than 12, a
Group 10 metal in combination with a Group 1 alkali metal and/or a Group 2
alkaline earth
metal; and, optionally, a Group 11 metal. The catalyst can be made by using a
method
described in greater detail below.
[0058] The first reactor can be a plug flow reactor or other reactor
configurations. The
catalyst can be loaded as a fixed bed, a catalyst particle fluid, and the
like. As used herein,
the term "reactor" refers to any vessel(s) in which a chemical reaction
occurs. Reactor
includes both distinct reactors as well as reaction zones within a single
reactor apparatus and
as applicable, reaction zones across multiple reactors. In other words and as
is common, a
single reactor may have multiple reaction zones. Where the description refers
to a first and
second reactor, the person of ordinary skill in the art will readily recognize
such reference
includes two reactors as well as a single reactor having first and second
reaction zones.
Likewise, a first reactor hydrocarbon effluent and a second reactor effluent
will be recognized
to include the effluent from the first reaction zone and the second reaction
zone of a single
reactor, respectively.
- io -
CA 03004324 2018-05-03
100591 As used herein, the term "moving bed" reactor refers to a zone or
vessel with
contacting of solids (e.g., catalyst particles) and gas flows such that the
superficial gas velocity
(U) is below the velocity required for dilute-phase pneumatic conveying of
solid particles in
order to maintain a solids bed with void fraction below 95%. In a moving bed
reactor, the
solids (e.g., catalyst material) may slowly travel through the reactor and may
be removed from
the bottom of the reactor and added to the top of the reactor. A moving bed
reactor may
operate under several flow regimes including settling or moving packed-bed
regime (U<Urnf),
bubbling regime (Umr<U<Umb), slugging regime (Umb<U<Uc), transition to and
turbulent
fluidization regime (Uc<U<Utr), and fast-fluidization regime (U>Utr), where
time is minimum
fluidizing velocity, Umb is minimum bubbling velocity, I.Jc is the velocity at
which fluctuation
in pressure peaks, and Ut, is transport velocity. These different fluidization
regimes have been
described in, for example, Kunii, D., Levenspiel, 0., Chapter 3 of
Fluidization Engineering,
2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6
of Chemical
Process Equipment, Revised 2nd Edition, Butterworth-Heinemann, Boston, 2010.
[0060] As used herein, the term "settling bed" reactor refers to a zone or
vessel wherein
particulates contact with gas flows such that the superficial gas velocity (U)
is below the
minimum velocity required to fluidize the solid particles (e.g., catalyst
particles), the minimum
fluidization velocity (Umf), U<Umf, in at least a portion of the reaction
zone, and/or operating
at a velocity higher than the minimum fluidization velocity while maintaining
a gradient in gas
.. and/or solid property (such as, temperature, gas or solid composition,
etc.) axially up the reactor
bed by using reactor internals to minimize gas-solid back-mixing. Description
of the minimum
fluidization velocity is given in, for example, Kunii, D., Levenspiel, 0.,
Chapter 3 of
Fluidization Engineering, 2" Edition, Butterworth-Heinemann, Boston, 1991 and
Walas, S.
M., Chapter 6 of Chemical Process Equipment, Revised rd Edition, Butterworth-
Heinemann,
Boston, 2010. A settling bed reactor may be a "circulating settling bed
reactor," which refers
to a settling bed with a movement of solids (e.g., catalyst material) through
the reactor and at
least a partial recirculation of the solids (e.g., catalyst material). For
example, the solids (e.g.,
catalyst material) may have been removed from the reactor, regenerated,
reheated and/or
separated from the product stream and then returned back to the reactor.
[00611 As used herein, the term "fluidized bed" reactor refers to a zone or
vessel
with contacting of solids (e.g., catalyst particles) and gas flows such that
the superficial
gas velocity (U) is sufficient to fluidize solid particles (i.e., above the
minimum fluidization
- 11 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
velocity Um) and is below the velocity required for dilute-phase pneumatic
conveying of
solid particles in order to maintain a solids bed with void fraction below
95%. As used herein
the term "cascaded fluid-beds- means a series arrangement of individual fluid-
beds such that
there can be a gradient in gas and/or solid property (such as, temperature,
gas or solid
composition, pressure, etc.) as the solid or gas cascades from one fluid-bed
to another. Locus
of minimum fluidization velocity is given in, for example, Kunii, D.,
Levenspiel, 0., Chapter
3 of Fluidization Engineering, 21Id Edition, Butterworth-Heinemann, Boston,
1991 and Walas,
S. M., Chapter 6 of Chemical Process Equipment, Revised 211d Edition,
Butterworth-
Heinemann, Boston, 2010. A fluidized bed reactor may be a moving fluidized bed
reactor,
to such as a -circulating fluidized bed reactor," which refers to a
fluidized bed with a movement
of solids (e.g., catalyst material) through the reactor and at least a partial
recirculation of the
solids (e.g., catalyst material). For example, the solids (e.g., catalyst
material) may have been
removed from the reactor, regenerated, reheated and/or separated from the
product stream
and then returned back to the reactor.
[0062] As used herein the term "riser" reactor (also known as a transport
reactor) refers to
a zone or vessel (such as, vertical cylindrical pipe) used for net upwards
transport of solids
(e.g., catalyst particles) in fast-fluidization or pneumatic conveying
fluidization regimes. Fast
fluidization and pneumatic conveying fluidization regimes are characterized by
superficial
gas velocities (U) greater than the transport velocity (Uir). Fast
fluidization and pneumatic
conveying fluidization regimes are also described in Kunii, D., Levenspiel,
0., Chapter 3 of
Fluidization Engineering, 2m1 Edition, Butterworth-Heinemann, Boston, 1991 and
Walas, S.
M., Chapter 6 of Chemical Process Equipment, Revised 2n1 Edition Butterworth-
Heinemann,
Boston, 2010. A fluidized bed reactor, such as a circulating fluidized bed
reactor, may be
operated as a riser reactor.
[0063] As used herein, the term "co-current" refers to a flow of two
streams (e.g., stream
(a), stream (b)) in substantially the same direction. For example, if stream
(a) flows from a
top portion to a bottom portion of at least one reaction zone and stream (b)
flows from a top
portion to a bottom portion of at least one reaction zone, the flow of stream
(a) would be
considered co-current to the flow of stream (b). On a smaller scale within the
reaction zone,
there may be regions where flow may not be co-current.
[0064] As used herein, the term "counter-current" refers to a flow of two
streams (e.g.,
stream (a), stream (b)) in substantially opposing directions. For example, if
stream (a) flows
from a top portion to a bottom portion of the at least one reaction zone and
stream (b) flows
from a bottom portion to a top portion of the at least one reaction zone, the
flow of stream (a)
- 12 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
would be considered counter-current to the flow of stream (b). On a smaller
scale within the
reaction zone, there may be regions where flow may not be counter-current.
Acyclic C5 Conversion Process
[0065] The process for the conversion of an acyclic C5 hydrocarbon to a
product
comprising cyclic C5 compounds comprises contacting the C5 feedstock and,
optionally,
hydrogen under acyclic C5 conversion conditions in the presence of one or more
catalyst
compositions, including but not limited to the catalyst compositions described
herein, to form
said product. The product of the process for conversion of an acyclic C5
feedstock comprises
cyclic C5 compounds. The cyclic C5 compounds can comprise one or more of
cyclopentane,
to cyclopentene, cyclopentadiene, and includes mixtures thereof
[0066] In one or more embodiments, the acyclic C5 conversion conditions
include at least
a temperature, a partial pressure, and a weight hourly space velocity (WHSV).
The
temperature is in the range of about 400 C to about 700 C, or in the range
from about 450 C
to about 650 C, preferably, in the range from about 500 C to about 600 C. The
partial
pressure is in the range of about 3 to about 100 psi (21 to 689 kilopascal),
or in the range
from about 3 to about 50 psi (21 to 345 kilopascal), preferably, in the range
from about 3 to
about 20 psi (21 to 138 kilopascal). The weight hourly space velocity is in
the range from
about 1 to about 50 hr-1, or in the range from about 1 to about 20 hr-1. Such
conditions
include a molar ratio of the optional hydrogen co-feed to the acyclic C5
hydrocarbon in the
range of about 0 to 3, or in the range from about 0.5 to about 2. Such
conditions may also
include co-feed C1¨C4 hydrocarbons with the acyclic C5 feed.
[0067] in one or more embodiments, this invention relates to a process
for conversion of
n-pentane to cyclopentadiene comprising the steps of contacting n-pentane and,
optionally,
hydrogen (if present, typically H2 is present at a molar ratio of hydrogen to
n-pentane of 0.01
to 3.0) with one or more catalyst compositions, including but not limited to
the catalyst
compositions described herein, to form cyclopentadiene at a temperature of 400
C to 700 C,
a partial pressure of 3 to about 100 psia, and a weight hourly space velocity
of 1 to about
50 hr'.
[0068] In the presence of the catalyst, a number of desired and
undesirable side reactions
may take place. The net effect of the reactions is the production of hydrogen
and the increase
of total volume (assuming constant total pressure). One particularly desired
overall reaction
(i.e., intermediate reaction steps are not shown) is:
n-pentane 4 CPD + 3H2.
[0069] Additional overall reactions include, but are not limited to:
- 13 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
n-pentane 1,3-pentadiene + 2H2,
n-pentane 4 1-pentene + H2,
n-pentane 4 2-pentene + Hz,
n-pentane 4 2-methy1-2-butene + H2,
n-pentane cycl pentane + Hz,
cyclopentane 4 cyclopentene + Hz, or
cyclopentene 4 CPD + Hz.
[0070] Fluids inside the first reactor are essentially in gas phase. At
the outlet of the first
reactor, a first reactor hydrocarbon effluent, preferably in gas phase, is
obtained. The first
to reactor hydrocarbon effluent may comprise a mixture of the following
hydrocarbons, among
others: heavy components comprising more than 8 carbon atoms such as multiple-
ring
aromatics; C8, C7, and C6 hydrocarbons such as one-ring aromatics; CPD (the
desired
product); unreacted CS feedstock material such as n-pentane; CS by-products
such as
pentenes (1-pentene, 2-pentene, e.g.), pentadienes (1,3-pentadiene, 1,4-
pentadiene, e.g.),
cyclopentane, cyclopentene, 2-methylbutane, 2-methyl-1-butene, 3-methyl-1-
butene, 2-
methyl-I,3-butadiene. 2,2-dimethylpropane, and the like; C4 by-products such
as butane, 1-
butene, 2-butene, 1,3-butadiene, 2-methylpropane, 2-methyl-1-propene, and the
like; C3 by-
products such as propane, propene, and the like; C2 by-products such as ethane
and ethene,
methane, and hydrogen.
[0071] The first reactor hydrocarbon effluent may comprise CPD at a
concentration of
C(CPD)1 wt%, based on the total weight of the CS hydrocarbons in the first
reactor
hydrocarbon effluent; and al < C(CPD)1 < a2, where al and a2 can be,
independently, 15,
16, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38, 40, 45, 50, 55, 60,
65, 70, 75, 80, or 85
as long as al <a2. The first reactor hydrocarbon effluent may comprise acyclic
diolefins at a
total concentration of C(ADO)1 wt%, based on the total weight of the C5
hydrocarbons in the
first reactor hydrocarbon effluent; and bl < C(ADO)1 < b2, where bl and b2 can
be,
independently, 20, 18, 16, 15, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, or 0.5, as
long as bl < b2.
Preferably, 0.5 < C(ADO) < 10. Preferably, the acyclic diolefins comprise 1,3-
pentadiene at
a concentration of C(PTD)1 wt%, based on the total weight of C5 components in
the first
reactor hydrocarbon effluent; and cl < C(PTD)1 < c2, where cl and c2 can be,
independently, 20, 18, 16, 15, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, 0.5, or 0.3,
as long as cl <c2.
[0072] As a result of the use of the catalyst and the choice of reaction
conditions in the
first reactor, a high CPD to acyclic diolefin molar ratio in the first reactor
hydrocarbon
effluent can be achieved such that C(CPD)1/C(ADO)1 > 1.5, preferably 1.6, 1.8,
2.0, 2.2, 2.4,
- 14 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
2.5, 2.6, 2.8, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, 5.0, 6.0, 8.0, 10, 12, 14,
15, 16, 18, or 20. The
high ratio of C(CPD)1/C(ADO)1 significantly reduces CPD loss as a result of
Diels-Alder
reactions between CPD and acyclic dienes in subsequent processing steps, and
therefore,
allows the processes of the present invention to achieve high DCPD yield and
high DCPD
purity for the subsequently produced DCPD fractions.
[0073] Desirably, the total absolute pressure and temperature of the
first reactor
hydrocarbon effluent should be maintained at levels such that the dimerization
of CPD to
form DCPD is substantially avoided, and the Diels-Alder reactions between CPD
and acyclic
dienes are substantially inhibited.
1() Catalyst Composition
[0074] Catalyst compositions useful herein include microporous crystalline
metallosilicates, such as crystalline aluminosilicates, crystalline
ferrosilicates, or other metal
containing crystalline silicates (such as those where the metal or metal
containing compound
is dispersed within the crystalline silicate structure and may or may not be a
part of the
crystalline framework). Microporous crystalline metallosilicate framework
types useful as
catalyst compositions herein include, but are not limited to, MWW, MFI, LTL,
MOR, BEA,
TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU.
[0075] Particularly suitable microporous metallosilicates for use herein
include those of
framework type MWW, MH, Lit, MOR, BEA, TON, M'I'W, Mil. FER, MRE, MFS,
MEL, DDR, EUO, and FAU where one or more metals from groups 8, 11, and 13 of
the
Periodic Table of the Elements (preferably one or more of Fe, Cu, Ag, Au, B,
Al, Ga, and or
In) are incorporated in the crystal structure during synthesis or impregnated
post
crystallization. It is recognized that a metallosilicate may have one or more
metals present
and, for example, a material may be referred to as a ferrosilicate but it will
most likely still
contain small amounts of aluminum.
[0076] The microporous crystalline metallosilicates preferably have a
constraint index of
less than 12, alternately from 1 to 12, alternately- from 3 to 12.
Aluminosilicates useful herein
have a constraint index of less than 12, such as 1 to 12, alternately 3 to 12,
and include, but
are not limited to Zeolite beta, mordenite, faujasite, Zeolite L, ZSM-5, ZSM-
11, ZSM-22,
ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-22 family materials and
mixtures of two or more thereof In a preferred embodiment, the microporous
crystalline
aluminosilicate has a constraint index of about 3 to about 12 and is ZSM-5.
[0077] ZSM-5 is described in US 3,702,886. ZSM-11 is described in US
3,709,979.
ZSM-22 is described in US 5,336,478. ZSM-23 is described in US 4,076,842. ZSM-
35 is
- 15 -
CA 03004324 2018-05-03
described in US 4,016,245. ZSM-48 is described in US 4,375,573, ZSM-50 is
described in US
4,640,829, and ZSM-57 is described in US 4,873,067. ZSM-58 is described in US
4,698,217.
Constraint index and a method for its determination are described in US
4,016,218.
[0078] The MCM-22 family material is selected from the group consisting
of MCM-22,
PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12,
EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, and mixtures of two or more
thereof.
[0079] Materials of the MCM-22 family include MCM-22 (described in US
4,954,325),
PSII-3 (described in US 4,439,409), SSZ-25 (described in US 4,826,667), ERB-1
(described
in EP 0 293 032), ITQ-1 (described in US 6,077,498), and ITQ-2 (described in
WO 97/17290),
MCM-36 (described in US 5,250,277), MCM-49 (described in US 5,236,575), MCM-56
(described in US 5,362,697), and mixtures of two or more thereof. Related
zeolites to be
included in the MCM-22 family are UZM-8 (described in US 6,756,030) and UZM-
8HS
(described in US 7,713,513), both of which are also suitable for use as the
molecular sieve of
the MCM-22 family.
[0080] In one or more embodiments, the microporous crystalline
metallosilicate has an
Si/M molar ratio greater than about 3, or greater than about 25, or greater
than about 50, or
greater than about 100, or greater than 400, or in the range from about 100 to
about 2,000, or
from about 100 to about 1,500, or from about 50 to 2,000, or from about 50 to
1,200.
[0081] In one or more embodiments, the microporous crystalline
aluminosilicate has an
SiO2/A1203 molar ratio greater than about 3, or greater than about 25, or
greater than about
50, or greater than about 100, or greater than 400, or in the range from about
100 to about 400,
for from about 100 to about 500, or from about 25 to about 2,000, or from
about 50 to about
1,500, or from about 100 to 1,200 from about 100 to 1000.
[0082] In another embodiment of the invention, the microporous
crystalline
metallosilicate (such as an aluminosilicate) is combined with a Group 10 metal
or metal
compound, and, optionally, one, two, three or more Group 1, 2, or 11 metals or
metal
compounds.
[0083] In one or more embodiments, the Group 10 metal includes, or is
selected from the
group consisting of, Ni, Pd, and Pt, preferably Pt. The Group 10 metal content
of said
catalyst composition is at least 0.005 wt%, based on the weight of the
catalyst composition.
In one or more embodiments, the Group 10 content is in the range from about
0.005 wt% to
- 16 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
about 10 wt%, or from about 0.005 wt% up to about 1.5 wt%, based on the weight
of the
catalyst composition.
[0084] In one or more embodiments, the Group 1 alkali metal includes, or
is selected
from the group consisting of, Li, Na, K, Rb, Cs, and mixtures of two or more
thereof,
preferably Na.
[0085] In one or more embodiments, the Group 2 alkaline earth metal is
selected from the
group consisting of Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof
[0086] In one or more embodiments, the Group 1 alkali metal is present as
an oxide and
the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and
mixtures of two or
to more thereof In one or more embodiments, the Group 2 alkaline earth
metal is present as an
oxide and the metal is selected from the group consisting of Be, magnesium,
calcium, Sr, Ba,
and mixtures of two or more thereof In one or more embodiments, the Group 1
alkali metal
is present as an oxide and the metal is selected from the group consisting of
Li, Na, K, Rb,
Cs, and mixtures of two or more thereof; and the Group 2 alkaline earth metal
is present as an
oxide and the metal is selected from the group consisting of Be, magnesium,
calcium. Sr, Ba,
and mixtures of two or more thereof
[0087] In one or more embodiments, the Group 11 metal includes, or is
selected from the
group consisting of, silver, gold, copper, preferably silver or copper. The
Group 11 metal
content of said catalyst composition is at least 0.005 wt%, based on the
weight of the catalyst
zo composition. In one or more embodiments, the Group 11 content is in the
range from about
0.005 wt% to about 10 wt%, or from about 0.005 wt% up to about 1.5 wt%, based
on the
weight of the catalyst composition.
[0088] In one or more embodiments, the catalyst composition has an Alpha
Value (as
measured prior to the addition of the Group 10 metal, preferably platinum) of
less than 25,
alternately less than 15, alternately- from 1 to 25, alternately from 1.110
15.
[0089] In one or more embodiments of aluminosilicates the molar ratio of
said Group 1
alkali metal to Al is at least about 0.5, or from at least about 0.5 up to
about 3, preferably at
least about 1, more preferably at least about 2.
[0090] In one or more embodiments of aluminosilicates, the molar ratio of
said Group 2
alkaline earth metal to Al is at least about 0.5, or from at least about 0.5
up to about 3,
preferably at least about 1, more preferably at least about 2.
[0091] In one or more embodiments, the molar ratio of said Group 11 metal
to Group 10
metal is at least about 0.1, or from at least about 0.1 up to about 10,
preferably at least about
0.5, more preferably at least about 1. In one or more embodiments, the Group
11 alkaline
- 17-
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
earth metal is present as an oxide and the metal is selected from the group
consisting of gold,
silver, and copper, and mixtures of two or more thereof
[0092] Preferably, catalyst compositions useful herein are employed at
conversion
conditions including a temperature in the range of from 400 to 800 C, a
pressure in the range
.. of from 10 to 1,000 kilopascal absolute, and a WHSV in the range of 1 to
100 hr'. In one or
more embodiments, the use of the catalyst compositions of this invention
provides a
conversion of at least about 60%, or at least about 75%, or at least about
80%, or in the range
from about 60% to about 80%, of said acyclic C5 feedstock under acyclic C5
conversion
conditions of an n-pentane containing feedstock with equimolar Hz, a
temperature in the
to range of about 550 C to about 600 C, an n-pentane partial pressure
between 3 and 10 psia,
and an n-pentane weight hourly space velocity of 10 to 20 hr'.
[0093] In one or more embodiments, the use of any one of the catalyst
compositions of
this invention provides a carbon selectivity to cyclic C5 compounds of at
least about 30%, or
at least about 40%, or at least about 50%, or in the range from about 30% to
about 80%,
under acyclic C5 conversion conditions including an n-pentane feedstock with
equimolar Hz,
a temperature in the range of about 550 C to about 600 C, an n-pentane partial
pressure
between 3 and 10 psia, and an n-pentane weight hourly space velocity between
10 and
hr-1.
[0094] In one or more embodiments, the use of any one of the catalyst
compositions of
20 this invention provides a carbon selectivity to cyclopentadiene of at
least about 30%, or at
least about 40%, or at least about 50%, or in the range from about 30% to
about 80%, under
acyclic CS conversion conditions including an n-pentane feedstock with
equimolar H2, a
temperature in the range of about 550 C to about 600 C, an n-pentane partial
pressure
between 3 and 10 psia, and an n-pentane weight hourly space velocity between
10 and
20 hr'.
[0095] The catalyst compositions of this invention can be combined with a
matrix or
binder material to render them attrition resistant and more resistant to the
severity of the
conditions to which they will be exposed during use in hydrocarbon conversion
applications.
The combined compositions can contain 1 to 99 wt% of the materials of the
invention based
on the combined weight of the matrix (binder) and material of the invention.
The relative
proportions of microcrystalline material and matrix may vary widely, with the
crystal content
ranging from about 1 to about 90 wt% and more usually, particularly when the
composite is
prepared in the form of beads, extrudates, pills, oil drop formed particles,
spray dried
particles, etc., in the range of about 2 to about 80 wt% of the composite.
- 18-
CA 03004324 2018-05-03
[0096] During the use of the catalyst compositions in the processes of
this invention, coke
may be deposited on the catalyst compositions, whereby such catalyst
compositions lose a
portion of its catalytic activity and become deactivated. The deactivated
catalyst compositions
may be regenerated by conventional techniques including high pressure hydrogen
treatment
and combustion of coke on the catalyst compositions with an oxygen-containing
gas.
[0097] Useful catalyst compositions comprise a crystalline
aluminosilicate or
ferrosilicate, which is optionally combined with one, two or more additional
metals or metal
compounds. Preferred combinations include:
1) a crystalline aluminosilicate (such as ZSM-5 or Zeolite L) combined with a
Group 10
metal (such as Pt), a Group 1 alkali metal (such as sodium or potassium)
and/or a Group 2
alkaline earth metal;
2) a crystalline aluminosilicate (such as ZSM-5 or Zeolite L) combined with a
Group 10
metal (such as Pt) and a Group 1 alkali metal (such as sodium or potassium);
3) a crystalline aluminosilicate (such as a ferrosilicate or an iron
treated ZSM-5) combined
with a Group 10 metal (such as Pt), a Group 1 alkali metal (such as sodium or
potassium);
4) a crystalline aluminosilicate (Zeolite L) combined with a Group I 0
metal (such as Pt) and
a Group 1 alkali metal (such as potassium); and
5) a crystalline aluminosilicate (such as ZSM-5) combined with a Group 10
metal (such as
Pt), a Group I alkali metal (such as sodium), and a Group 11 metal (such as
silver or copper).
[0098] Another useful catalyst composition is a group 10 metal (such as Ni,
Pd, and Pt,
preferably Pt) supported on silica (e.g., silicon dioxide) modified by a Group
1 alkali metal
silicate (such as Li, Na, K, Rb, and/or Cs silicates) and/or a Group 2
alkaline earth metal
silicate (such as Mg, Ca, Sr, and/or Ba silicates), preferably potassium
silicate, sodium silicate,
calcium silicate and/or magnesium silicate, preferably potassium silicate
and/or sodium
silicate. The Group 10 metal content of the catalyst composition is at least
0.005 wt%, based
on the weight of the catalyst composition, preferably, in the range from about
0.005 wt% to
about 10 wt%, or from about 0.005 wt% up to about 1.5 wt%, based on the weight
of the
catalyst composition. The silica (SiO2) may be any silica typically used as
catalyst support
such as those marketed under the trade names of DAVISIL 646 (Sigma Aldrich),
DAVISON
952, DAVISON 948 or DAVISON 955 (Davison Chemical Division of W.R. Grace and
Company).
- 19-
CA 03004324 2018-05-03
[0099] For more information on useful catalyst compositions, please see
please see: 1)
US 2017/0121253; 2) US 2017/0121245; 3) US 9,856,187; 4) US 9,849,440; and 5)
US
2017/0121246.
Cooling of the first reactor hydrocarbon effluent
[001001 To prevent undesirable side reactions such as thermal cracking,
condensation of
PNAs, and premature Diels-Alder reactions of reactive diolefinic species,
especially CPD, it
is highly desired that the first reactor hydrocarbon effluent is cooled down
once it exits the
first reactor. To that end, the first reactor hydrocarbon effluent may be
passed through at least
one heat exchanger located next to the outlet from the first reactor where its
temperature is
lowered to a range from Tc1 C to Tc2 C, where Tcl and Tc2 can be,
independently, 20, 50,
80, 150, 200, 250, 300, 350, 400, or 450 C, as long as Tel < Tc2. Alternately
or additionally,
the first reactor hydrocarbon effluent may be contacted with a quench liquid
so that the
temperature is lowered to a range from Tc1 C to Tc2 C, where Tel and Tc2 can
be,
independently, 20, 40, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200, 220,
240, 250, 260, 280,
.. 300, 320, 340, 350, 360, 380, 400, 420, 440, or 450, as long as Tel < Tc2.
Upon cooling, a
majority of the components from the first reactor hydrocarbon effluent are
still in gas or vapor
phase.
Washing/quenching of the first reactor hydrocarbon effluent
[00101] The first reactor hydrocarbon effluent comprises non-negligible
amounts of heavy
components, including but not limited to: polynuclear aromatic species
(naphthalene and
alkylated naphthalenes, anthracene and alkylated anthracenes, phenanthrene and
alkylated
phenanthrenes), DCPD, products formed as a result of undesired Diels-Alder
reactions
between CPD and acyclic diolefins. It is highly desired that these heavy
components,
especially C8+ hydrocarbons, are at least partly removed from the first
reactor hydrocarbon
effluent such that contamination of the C5-rich fraction and subsequent
contamination of
DCPD-rich fractions by them are avoided. For example, naphthalene is very
difficult to be
removed from DCPD by distillation; also naphthalene and heavier PNAs can
condense to form
solids which can foul equipment. Therefore, naphthalene and heavier PNAs are
desirably
removed from the first reactor hydrocarbon effluent before it is further
processed.
.. [00102] Advantageously, such heavy components can be effectively removed in
a vessel
by contacting the stream of the first reactor hydrocarbon effluent, preferably
after it is being
- 20 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
partially cooled down, with a wash oil. To that end, the wash oil, desirably
in liquid phase
during operation. can be sprayed into the washing vessel as liquid droplets
when contacting
the substantially vapor stream of the first reactor hydrocarbon effluent.
Additionally or
alternatively, the substantially vapor stream of the first reactor hydrocarbon
effluent can be
sent to a suitable gas-liquid contacting washing vessel capable of handling
fouling services
(e.g., a tower with grids and/or random packing). Sufficient contact between
the first reactor
hydrocarbon effluent and the liquid wash oil results in the extraction of the
heavy
components (i.e., C8+ hydrocarbons) from the substantially vapor stream of the
first reactor
hydrocarbon effluent into the wash oil liquid. A small amount of the wash oil
may be
to entrained in the first reactor hydrocarbon effluent vapor stream at a
low vapor pressure. The
entrained wash oil can be removed subsequently where necessary.
[00103] In the washing vessel, the first reactor hydrocarbon effluent vapor
stream can be
quenched down further to a temperature in a range from 10 to 300 C, preferably
from 20 to
100 C. Thus, from the washing vessel, a vapor stream of the first reactor
hydrocarbon
effluent, washed and cooled, is obtained. In addition, a wash oil liquid
stream (also called
"heavy stream-), comprising multiple-ring aromatics mentioned above, may also
be obtained.
[00104] Various wash oils can be used. Non-limiting examples of the wash oil
include:
cyclohexane; monoallsyl, dialkyl, and trialkyl cyclohexanes; benzene; monoalk-
yl, dialkyl,
and trialkyl benzenes; monoalkyl, dialkyl, trialkyl, and tetraalkyl
naphthalenes; other
alk-ylated multiple-ring aromatics; and mixtures and combinations thereof
Preferred wash
oils are: alkyl benzenes and mixtures thereof (herein referred to as light
wash oil); and alkyl
naphthalenes and mixtures thereof (herein referred to as heavy wash oil). More
preferably,
toluene, especially relatively pure toluene with a purity of at least 50 wt%,
or
alk-ylnaphthalene(s), especially those with purity of at least 50 wt%, is used
as the wash oil.
Wash oil recovery and/or recycle
[00105] The wash oil used in the present invention is recovered and
advantageously
recycled. To that end, the heavy stream exiting at the lower portion of the
washing vessel is
supplied to a wash oil recovery sub-system, from which (i) a heavy oil
fraction comprising
the multiple-ring component, typically as a lower stream, (ii) a second
recovered wash oil
stream depleted in multiple-ring components; and (iii) an optional recovered
C5-rich stream
comprising CPD (described below in greater detail) are obtained. Additionally,
a flux oil
may preferentially be supplied to the wash oil recovery sub-system and/or
blended with the
heavy stream upstream of the wash oil recovery sub-system (e.g., near the
tower bottom of
the washing vessel). This flux oil is chosen to be compatible with the heavy
stream and the
-21 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
heavy oil fraction; i.e., precipitation of insoluble species is not allowed to
occur at any of the
wash oil recovery sub-system process conditions or at any downstream
transportation or
storage conditions. The oil flux desirably has sufficient solvency and proper
solvent
volatility. Preferably the flux oil is added at a quantity such that the
resulted viscosity of the
mixture of the flux oil and the heavy oil fraction at 50 C is less than 600
centistokes (cSt,
mm 2/second), preferably less than 550 cSt, or less than 530 cSt, such as in
the range from 150
to 550 cSt, or from 180 to 530 cSt, or from 180 to 450 cSt, or from 200 to 400
cSt. Candidate
sources of flax oil are virgin distillate streams and/or cracked distillate
streams including
those produced in catalytic crackers or steam crackers.
to [00106] As described below, from the first separation sub-system used
for separating the
washed first reactor hydrocarbon effluent, and/or other downstream equipment
and processes,
one or more heavy streams comprising wash oil and/or heavy components depleted
in light
components may be produced. Such heavy streams, if any, may be fed into the
wash oil
recovery sub-system as well along with the heavy stream rich in wash oil from
the washing
vessel to recover the wash oil and other useful components therein.
[00107] In the fluid channel from the first reactor to the washing vessel,
including the heat
exchanger in between, if any, and inside the washing vessel, dimerization
between CPD
molecules may occur to form DCPD, and CPD may react with acyclic diolefins to
form other
C10+ hydrocarbons. A major portion of these heavy components, if formed, are
partitioned
in the wash oil liquid stream (the heavy stream) exiting the washing vessel.
If the wash oil
liquid stream is sent to a fuel disposition or other low value disposition
directly, a portion of
the CPD produced in the first reactor would be downgraded to low value. To
reduce such
undesirable yield loss, one can operate the wash oil recovery sub-system under
conditions
favoring retro-Diels-Alder reaction (also conveniently referred to as reverse
dimerization) to
convert DCPD and other C10+ components to CPD and other C5 species, thereby
obtaining
an upper recovered C5-rich stream and a lower wash oil-rich stream containing
residual C8+
and the wash oil. The upper C5-rich stream may be fed directly or indirectly
to a second
reactor as part of the first C5-rich fraction. The lower wash oil-rich stream
can be further
distilled to recover at least a portion of the wash oil, which can be recycled
to the wash vessel
directly or indirectly. Such conditions favoring reverse dimerization (retro-
Diels-Alder
reaction) include, e.g., a temperature in the range from 150 to 350 C,
preferably, from 170 to
260 C, a pressure in a range from 21 to 345 kilopascal absolute. preferably
from 21 to 138
kilopascal absolute, and a residence time from 0.01 to 10 hours, preferably
from 0.1 to 4
hours.
- 22 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[00108] In one example, the wash oil recovery sub-system comprises two
distillation
columns connected in series. The heavy stream from the washing vessel, the
optional heavy
stream(s) from the first separation sub-system and other down-stream
equipment, and,
optionally, a flux oil are fed into the first distillation column, from which
a lower stream
comprising the wash oil and rich in the multiple-ring aromatics is obtained
and fed into the
second distillation column. The first distillation column is advantageously
operated under
conditions favoring reverse dimerization described above. An upper recovered
C5-rich
stream is obtained from the first distillation column, which can be fed
directly to the second
reactor (the first dimerization reactor, described in greater detail below).
The first distillation
to column in the wash oil recovery sub-system can be optionally combined
with the washing
vessel. In a second distillation column which receives the lower stream from
the distillation
column, an upper, second recovered wash oil stream and a heavy oil fraction
stream including
multi-ring aromatics and the flux oil, if present, are obtained. The heavy oil
fraction stream
can be used as fuel or otherwise disposed of A portion of the second recovered
wash oil
stream can be directly or indirectly recycled to the washing vessel.
Additionally or
alternatively, the second recovered wash oil stream can be used to wash a
downstream vapor
stream rich in light components to recover low concentrations of C5
hydrocarbons contained
therein in another vessel (called "debutanizer" sometimes, described in
greater detail below),
and then recycled to the washing vessel. Often, to prevent buildup of
molecules with boiling
points close to that of the heavy wash oil, a side stream or purge is
withdrawn from the
second distillation column in the wash oil recovery sub-system.
[00109] In another example, the wash oil recovery sub-system comprises a
divided-wall
distillation column. The heavy stream(s) from the washing vessel; the optional
heavy
stream(s) from the first separation sub-system and other down-stream
equipment; and,
optionally, a flux oil are fed into the receiving side of the divided-wall
distillation column as
feed streams. From this single distillation column, a lower effluent rich in
the heavy fraction
(including multiple-ring aromatics and the flux oil, if present), an upper
recovered C5-rich
stream, and a middle effluent rich in the wash oil as the second recovered
wash oil stream on
side of the dividing wall opposite to the feed stream(s), can be produced
simultaneously from
a single column. The hem)/ fraction lower stream can be used as fuel or
otherwise disposed
of A portion of the second recovered wash oil stream can be directly or
indirectly recycled
to the washing vessel as described above in connection with the two-column
example.
Because the majority of the feed stream(s) can be the wash oil, use of a
divided-wall
distillation column can be particularly advantageous in cost and energy
efficiency.
- 23 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Separation of the first reactor hydrocarbon effluent
[00110] The first reactor hydrocarbon effluent, which is preferably cooled at
the outlet of
the first reactor as described above, and washed in a washing vessel as
described above is
then processed in a first separation sub-system to obtain a C5-rich fraction
that is depleted of
Cl -C4 hydrocarbons and hydrogen, and desirably, depleted of heavy components
such as
C8+ hydrocarbons. Due to the nature of the reactions taking place in the first
reactor,
substantial volume of hydrogen is present in the first reactor hydrocarbon
effluent. Effective
separation of hydrogen and C1-C4 light hydrocarbons from the C5 hydrocarbons
(including
CPD) needs to take into consideration that much of the C5 hydrocarbons can be
held as vapor
to in the hydrogen/light hydrocarbon stream. Thus, desirably, a compression
train with inter-
stage cooling and liquid/vapor separation can be advantageously used as the
first separation
sub-system to minimize the loss of C5 hydrocarbons to the hydrogen and light
hydrocarbon
stream.
[00111] Exemplary compression trains with inter-stage cooling and liquid/vapor
separation
are those comprising at least 3-stages of compression/inter-stage cooling with
an exiting
pressure from the last stage of at least 100 psia (689 kilopascal absolute).
[00112] From the first separation sub-system (a compression train, e.g.), one
or more
streams of C5-rich hydrocarbon (the first C5-rich fraction) may be obtained
from the multiple
stages. Where multiple streams of the first C5-rich fractions are obtained,
two or more of
them may be optionally combined into a single first C5-rich rich fraction
stream and then
processed together subsequently. The first C5-rich fraction generally
comprises: (i) CPD; (ii)
unreacted C5 hydrocarbon(s) from the C5 feedstock such as n-pentane; and (iii)
cyclopentane
and cyclopentene.
[00113] The first C5-rich fraction may further comprise a portion of the wash
oil,
especially if the wash oil contains C6 and C7 hydrocarbons, such as
cyclohexane and
alkylcyclohexanes, benzene and alkylbenzenes (e.g., toluene). Such wash oil
may be
removed subsequently where necessary. Even if high boiling point wash oils
such as alkyl
naphthalenes are used, the first C5-rich fraction may comprise C6 hydrocarbons
(as by-
products from the first reactor) such as benzene at a low concentration.
[00114] From the first separation sub-system (the first liquid/vapor separator
in a multi-
stage compression train, e.g.), an optional heavy-containing stream may be
produced,
especially at one of the early stages, comprising wash oil and C8+
hydrocarbons (DCPD, and
other products as a result of the Diels-Alder reactions between CPD and other
dienes, e.g.),
and the like. Such heavy stream can be in non-negligible quantity if high
boiling point wash
- 24 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
oil such as methylnaphthalene(s) is used. If such heavy stream is produced
from the
compression train, it may be advantageously combined with the wash oil liquid
stream
produced from the washing vessel described above, and then processed together
subsequently
as described above.
[00115] From the first separation sub-system (a compression train, e.g.), a
light
components-rich fraction comprising hydrogen and CI-C4 hydrocarbons is also
obtained.
This light components-rich fraction is desirably depleted of C5 components,
especially CPD,
or at least minimized, such that C5 molecules are used to the highest degree
in the process of
the present invention. If the light components-rich fraction exiting the first
separation sub-
to system contains C5 components at a non-negligible amount, one may wash
it in a washing
vessel (an absorber) where it is contacted with a solvent (e.g., the wash oil
used in the
washing vessel described above), such as a fresh solvent stream or and/or at
least a portion of
the second recovered wash oil stream from the wash-oil recovery sub-system
described
above, such that the C5 components are substantially extracted by the solvent
(e.g., the wash
oil). The bottom stream from said absorber can then be delivered to the
washing vessel for
washing the first reactor hydrocarbon effluent as described above. The thus
washed light
components-rich fraction is then substantially depleted in C5 hydrocarbons.
Separation of the light components-rich fraction and recycling of hydrogen
and/or light
hydrocarbons
[00116] A significant component of the light components-rich fraction coming
from the
first separation sub-system separating the first reactor hydrocarbon effluent
is hydrogen gas.
C1 -C4 hydrocarbons are produced at small quantities in the first reactor from
the C5
feedstock. Alternatively, in certain exemplary processes of the present
invention, a CI-C4
light hydrocarbon, such as CH4, may be supplied to the first reactor as a co-
feedstock,
resulting in higher concentrations of the C1-C4 light hydrocarbons in the
light components-
rich fraction obtained from the first separation sub-system.
[00117] Given the large quantity of hydrogen produced in the process, it is
desirable to
separate the light components-rich fraction to obtain a higher purity hydrogen
stream, which
can be used or sold as a highly valuable industrial gas. To that end, various
processes and
equipment may be used to recover and concentrate hydrogen, such as pressure-
swing
adsorption (PSA), rapid cycle pressure-swing adsorption (RCPSA), thermal-swing
adsorption
(TSA), cryogenic processes, membrane separation, and the like, with PSA or
RCPSA being
preferred. By using any of these processes or any combinations thereof, it is
possible to
obtain three gas streams from the light components-rich fraction: a hydrogen-
rich stream
- 25 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
comprising hydrogen at a purity of at least 95 mol%, based on the total moles
of the
hydrogen-rich stream, a middle stream comprising hydrogen and C1-C4
hydrocarbons that is
preferably low in C2+ hydrocarbons; and a C1-C4-rich hydrocarbon stream which
may also
contain C5+ hydrocarbons which can be subsequently recovered by washing or low
temperature fractionation (absorber, e.g.). A portion of the hydrogen-rich
stream and/or a
portion of the middle stream (if CI-C4 hydrocarbon is co-fed into the first
reactor) can be
recycled to the first reactor. Additionally or alternatively, at least a
portion of the middle
stream and/or the C1-C4 hydrocarbon stream can be used as fuel gas to produce
the thermal
energy needed for certain steps (such as the conversion process in the first
reactor) in the
to process of the present invention. Alternatively-, the CI-C4-rich
hydrocarbon stream can be
utilized as a feedstock for other process such as light olefins production
and/or further
processed to obtain an LPG fraction.
[00118] As discussed above, the recycle hydrogen may be advantageously admixed
with at
least a portion of the C5 feedstock before being fed into the first reactor to
reduce coke
formation on the catalyst particles, thereby increasing the life of the
catalyst used in the first
reactor. Additionally or alternatively, the recycle hydrogen may be fed
separately into the
first reactor. Additionally or alternatively, the recycle hydrogen may be
utilized for
rejuvenation or reduction of the catalyst.
Dimenzation of the first CS-rich fraction
[00119] The first C5-rich fraction advantageously comprises CPD at a high
concentration
in a range from cal wt% to ca2 wt%, based on the total weight of C5
hydrocarbons in the
first C5-rich fraction, where cal and ca2 can be, independently, 20, 25, 30,
35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, or 90, as long as cal < ca2. Such CPD may be used
directly as a CPD
feed for the production of, e.g., norbornene, vinyl norbornene, ethylidene
norbornene,
hydrocarbon resin adhesives or tackifiers, unsaturated polyester resins,
cyclopentane, and/or
cy clopentene.
[00120] Additionally or alternatively, at least a portion of the first C5-rich
fraction can be
supplied to a first dimerization reactor (the second reactor in the system)
operating under a
first set of dimerization conditions, where a portion of the CPD is
advantageously converted
into DCPD. This can be highly desirable because DCPD is much more stable than
CPD, and
therefore can be stored and/or transported to a different location where it is
used as DCPD or
converted into CPD and used for the production of value-added products.
[00121] The first dimerization reactor (the second reactor in the system) can
be
advantageously a plug flow reactor, a back mixed reactor, a continuous stirred-
tank reactor, a
- 26 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
boiling point reactor, and/or a baffled reactor; additionally the reactor may
contain heat
transfer devices such as coils. The first dimerization reactor may consist of
one or more
reaction zones within a single vessel or in multiple vessels and may include
one or more heat
exchanging devices within the reaction zones or between the reaction zones.
[00122] The first set of dimerization conditions in the first dimerization
reactor can
advantageously include: a temperature in the range from Tb1 C to Tb2 C, where
Tbl and
Tb2 can be, independently, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200,
220, 240, or
250, as long as Tbl < Tb2; an absolute pressure in the range from Nil
kilopascal to Pb2
kilopascal, where Ph] and Pb2 can be, independently, 345, 350, 400, 450, 500,
550, 600, 700,
800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 6500,
6894, or 7000,
as long as Pbl < Pb2: and a residence time in the range from Trl minutes to
Tr2 minutes,
where Trl and Tr2 can be, independently, 1, 10, 20, 30, 40, 50, 60, 70, 80,
90, 100, 110, 120,
130, 140, 150, 160, 170, 180, 190, 200, 210, or 220, as long as Trl < Tr2.
Preferably, if two
dimerization reactors in series are utilized in the system, the first set of
dimerization
.. conditions include a temperature in the range from 70 to 130 C, a total
pressure in the range
from 689 to 3447 kilopascal absolute, and a residence time in the range from
20 to 200
minutes, such as from 100 to 200 minutes; preferably, if three dimerization
reactors in series
are utilized in the system, the first set of dimerization conditions include a
temperature in the
range from 90 to 140 C, a total pressure in the range from 689 to 3447
kilopascal absolute,
zu and a residence time in the range from 1 to 30 minutes.
[00123] A portion of the CPD contained in the first C5-rich fraction supplied
into the first
dimerization reactor is converted into DCPD. At the outlet of the second
reactor (the first
dimerization reactor), a second reactor effluent is obtained comprising CPD
and DCPD.
Preferably, the degree of conversion in the second reactor is limited so that
high purity DCPD
may be produced; i.e., the extent of conversion is limited so that the
quantity of CPD co-
dimers with acyclic dienes and mono olefins is maintained below a level so as
to be able to
obtain the desired purity of DCPD.
Separation of the first DCPD-rich fraction
[00124] At least a portion of the second reactor effluent is then supplied to
a second
separation device, such as a distillation column, where a first DCPD-rich
fraction (as a lower
stream such as a bottom effluent from the column, e.g.) and a second C5-rich
fraction (as an
upper stream such as an overhead effluent from the column, e.g.) are obtained.
Advantageously, the first DCPD-rich fraction can have a DCPD concentration of
C(DCPD)1
wt%; and xl < C(DCPD)1 < x2, wherein xl and x2 can be, independently, 80, 82,
84, 85, 86,
- 27 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/1JS2016/056038
88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.2, 99.4, 99.5, 99.6, 99.8, or
100, as long as xl <
x2. Ultra high purity DCPD (i.e., UHP DCPD) with a concentration of at least
98 wt%,
99 wt%, or even 99.5 wt%, can be obtained as the first DCPD-rich fraction. At
least a
portion of the first DCPD-rich fraction can be optionally supplied to at least
another
separation device, such as a distillation column, where the purity of the
first DCPD-rich
fraction can be further increased. CPD concentration in the second CS-rich
fraction tends to
be lower than in the first CS-rich fraction.
Dimerization of the second C5-rich fraction
[00125] At least a portion of the second CS-rich fraction obtained from the
second
to .. separation device may advantageously comprise CPD at a high
concentration in the range
from ca3 wt% to ca4 wt%, based on the total weight of C5 hydrocarbons in the
second C5-
rich fraction, where ca3 and ca4 can be, independently, 1, 5, 10, 20, 25, 30,
35, 40, 45, 50, 55,
or 60, as long as ca3 < ca4. Such CPD in the second C5-rich fraction may be
directly used as
a CPD feed for the production of, e.g., norbomene, vinyl norbomene, ethylidene
norbomene,
.. hydrocarbon resin adhesives or tackifiers, unsaturated polyester resins,
cyclopentane, and/or
cy clopentene.
[00126] Additionally or alternatively, the second C5-rich fraction can be
supplied to a
second dimerization reactor (the third reactor in the system) operating under
a second set of
dimerization conditions, where a portion of the CPD is advantageously
converted into DCPD,
similar to the operation in the first dimerization reactor (the second reactor
in the system) but
preferably operating at a higher temperature and/or longer residence time to
enable
satisfactory conversion of the lower concentration CPD.
[00127] Thus, the second set of dimerization conditions in the second
dimerization reactor
can advantageously include: a temperature in the range from Tb3 C to Tb4 C,
where Tb3 and
Tb4 can be, independently, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200,
220, 240, or
250, as long as Tb3 < Tb4; an absolute pressure in the range from Pb3
kilopascal to Pb4
kilopascal, where Pb3 and Pb4 can be, independently, 345, 350, 400, 450, 500,
550, 600, 700,
800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 6500,
6894, or 7000,
as long as Pb3 < Pb4: and a residence time in the range from Tr3 minutes to
Tr4 minutes,
.. where Tr3 and Tr4 can be, independently, 1, 10, 20, 30, 40, 50, 60, 70, 80,
90, 100, 110, 120,
130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270,
280, 290, or 300
as long as Tr3 < Tr4. Preferably. if two dimerization reactors in series are
utilized in the
system, the second set of dimerization conditions include a temperature in the
range from
75to 140 C, such as from 100 to 140 C, a total pressure in the range from 689
to 3447
- 28 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
kilopascal absolute, and a residence time in the range from 100 to 300
minutes, such as from
150 to 300 minutes; preferably, if three dimerization reactors in series are
utilized in the
system, the second set of dimerization conditions include a temperature in the
range from 100
to 140 C, a total pressure in the range from 689 to 3447 kilopascal absolute,
and a residence
time in the range from 1 to 30 minutes.
[00128] The second dimerization reactor (the third reactor in the system) can
be a reactor
similar to the first dimerization reactor (the second reactor in the system).
[00129] A portion of the CPD contained in the second C5-rich fraction supplied
into the
second dimerization reactor is converted into DCPD. At the outlet of the
second dimerization
to reactor), a third reactor effluent is obtained comprising CPD and DCPD.
Preferably, the
degree of conversion in the third reactor is limited so that high purity DCPD
may be
produced; i.e., the extent of conversion is limited so that the quantity of
CPD co-dimers with
acyclic dienes and mono olefins is maintained below a level so as to be able
to obtain the
desired purity of DCPD.
Separation of a second DCPD-rich fraction
[00130] At least a portion of the third reactor effluent can be then supplied
to a third
separation device, such as a distillation column, where a second DCPD-rich
fraction (as a
lower stream such as a bottom effluent from the column, e.g.) and a third C5-
rich fraction (as
an upper stream such as an overhead effluent from the column, e.g.) are
obtained.
Advantageously, the second DCPD-rich fraction can have a DCPD concentration of
C(DCPD)2 wt%; and x3 < C(DCPD)2 < x4, wherein x3 and x4 can be, independently,
40, 50,
60, 65, 70, 75, 80, 82, 84, 85, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, or
99 as long as x3 <
x4. Usually, the purity of the second DCPD-rich fraction is lower than the
first DCPD-rich
fraction because of the lower ratio of CPD to acyclic diolefins in the second
C5-rich fraction
than the first C5-rich fraction. Nonetheless, very high purity DCPD (HP DCPD)
with a
concentration of at least 90 wt%, or 92 wt%, or 93 wt%, or even 95 wt% can be
obtained as
the second DCPD-rich fraction. At least a portion of the second DCPD-rich
fraction can be
optionally supplied to at least another separation device, such as a
distillation column, where
the purity of the second DCPD-rich fraction can be further increased.
Likewise, CPD
concentration in the third C5-rich fraction tends to be lower than in the
second C5-rich
fraction.
Dimerization of the third C5-rich fraction
[00131] At least a portion of the third C5-rich fraction obtained from the
third separation
device may advantageously comprise CPD at a concentration in the range from
ca5 wt% to
- 29 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
ca6 wt%, based on the total weight of the C5 hydrocarbons in the third C5-rich
fraction,
where ca5 and ca6 can be, independently, 1, 5, 10, 15, 20. 25, 30, 35, 40, 45,
50. 55, or 60, as
long as ca5 < ca6. Such CPD in the third CS-rich fraction may be directly used
as a CPD
feed for the production of, e.g., norbomene, vinyl norbomene, ethylidene
norbomene,
hydrocarbon resin adhesives or tackifiers, unsaturated polyester resins,
cyclopentane, and/or
cy clopentene.
[00132] Additionally or alternatively, at least a portion of the third C5-rich
fraction can be
supplied to a third dimerization reactor (the fourth reactor in the system)
operating under a
third set of dimerization conditions, where a portion of the CPD is
advantageously converted
to into DCPD, similar to the operation in the first dimerization reactor
(the second reactor in the
system).
[00133] The third dimerization reactor (the fourth reactor in the system) can
be a reactor
similar to the first dimerization reactor (the second reactor in the system),
but preferably
operating at a higher temperature and/or longer residence time to enable
satisfactory
conversion of the lower concentration CPD.
[00134] Desirably, a majority of the CPD contained in the third CS-rich
fraction supplied
into the third dimerization reactor is converted into DCPD. Additionally or
alternatively, it is
desirable to react acyclic C5 diolefins (e.g., 1,3-pentadiene; 1,4-pentadiene,
1,2-pentadiene,
and/or 2-methyl-1,3-butadiene) with CPD to produce co-dimers in the third
dimerization
reactor. Additionally or alternatively, additional streams containing acyclic
C5 diolefins
(e.g., steam cracked naphtha, light cat naphtha, heavy cat naphtha) and/or C6
diolefins (e.g.,
methyl cy cl openta di en e and h ex a di en es) may be added to the feed to
the third dimerization
reactor. Additionally, trimers and tetramers of the C5 and C6 species may also
be
advantageously produced. At the outlet of the third dimerization reactor, a
fourth reactor
.. effluent is obtained comprising CPD and DCPD, preferably in combination
with other C5 co-
dimers, -trimers, and/or -tetramers.
[00135] Thus, the third set of dimerization conditions in the third
dimerization reactor can
advantageously include: a temperature in the range from Tb5 C to Tb6 C, where
Tb5 and
Tb6 can be, independently, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200,
220, 240, or
250, as long as Tb5 < Tb6; an absolute pressure in the range from Pb5
kilopascal to Pb6
kilopascal, where Pb5 and Pb6 can be, independently, 345, 350, 400, 450, 500,
550, 600, 700,
800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 6500,
6894, or 7000,
as long as Pb5 < Pb6: and a residence time in the range from Tr5 minutes to
Tr6 minutes,
where Tr5 and Tr6 can be, independently, 100, 200, 300, 400, 500, 600, 700,
800, 900, or
-30 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
1000, as long as Tr5 < Tr6. Preferably, the third set of dimerization
conditions include a
temperature in the range from 80 to 150 C, such as from 100 to 150 C, a total
pressure in the
range from 689 to 3447 kilopascal absolute, and a residence time in the range
from 150 to
300 minutes.
Separation of a third DCPD-rich fraction
[00136] At least a portion of the fourth reactor effluent can then be supplied
to a fourth
separation device, such as a distillation column, where a third DCPD-rich
fraction (as a
bottom effluent from the column, e.g.) and fourth CS-rich fraction (as an
overhead effluent
from the column, e.g.) are obtained. Advantageously, the third DCPD-rich
fraction can have
to a DCPD concentration of C(DCPD)3 wt%; and x5 < C(DCPD)3 < x6, wherein x5
and x6 can
be, independently, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 85, 86,
88, 90, 91, 92, 93,
94, or 95, as long as x5 <x6. Usually, the purity of the third DCPD-rich
fraction is lower
than the second DCPD-rich fraction because of the lower ratio of CPD to
acyclic dienes in
the third CS-rich fraction than the second CS-rich fraction. Nonetheless,
moderate purity
DCPD with a concentration of at least 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90
wt% can be
obtained as the third DCPD-rich fraction. At least a portion of the third DCPD-
rich fraction
can be optionally supplied to at least another separation device, such as a
distillation column,
where the purity of the third DCPD-rich fraction can be further increased.
Likewise, CPD
concentration in the fourth CS-rich fraction tends to be lower than in the
third CS-rich
fraction.
Recycling of CS-rich fractions to the first reactor
[00137] At least a portion of the first, second, third, and fourth CS-rich
fractions described
above, if produced at all in the process of the present invention, can be
recycled to the first
reactor described above, where the unreacted C5 hydrocarbon(s) and partially
converted C5
hydrocarbons from the C5 feedstock can be further converted into CPD.
[00138] The first, second, third, and fourth CS-rich fractions, if produced,
may contain
C6+ hydrocarbons, such as cyclohexane, benzene, toluene, and the like. To
prevent the
accumulation of such C6+ components in the reaction product in the first
reactor, it is highly
desirable that, prior to being recycled to the first reactor, at least a
portion of the C6+
components is separated and removed from the CS-rich stream in a separation
device, such as
a distillation column, to produce a fifth CS-rich stream and a C6+-rich
stream. Thus, a
purified fifth CS-rich fraction is then recycled to the first reactor.
Forming mogas blending components from the C5+ components
-31-
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[00139] Mogas is a blended mixture comprising C4 through C12 hydrocarbons
having an
initial normal boiling point of about 35 C and a final boiling point of about
200 C. Mogas is
used primarily as fuel for internal combustion engines in automotive vehicles.
There are
many different mogas specifications that have been mandated by various local,
state or
national governmental agencies. One example is Reid Vapor Pressure (RVP) of
final mogas
product. The vapor pressure of mogas is a measure of its volatility and high
vapor pressures
resulting in high evaporative emissions of smog-forming hydrocarbons.
[00140] From a performance standpoint, an important attribute of mogas is its
octane
rating. Linear paraffinic hydrocarbons (i.e., straight-chain saturated
molecules) tend to have
to lower octane ratings than other hydrocarbons such as aromatics, olefins,
and branched
paraffins. To that end, many of the refining processes used in petroleum
refineries are
designed to produce hydrocarbons with these latter molecular configurations.
For example,
catalytic reforming is a widely practiced industrial process used to convert
naphtha feed
typically having low-octane ratings into high-octane liquid products to make
premium
blending stocks for mogas. The process converts paraffins and naphthenes into
high-octane
aromatic hydrocarbons. However, naphtha catalytic reforming is limited to C6+
feedstocks.
[00141] Converting n-pentane to isopentane (a/k/a i-pentane) can result in a
favorable
increase in octane but also an unfavorable increase in the RVP. Conversion of
n-pentane to
cyclopentyl and internal olefinic species ¨ which occurs in the first reactor
in the present
zo invention ¨ favorably increases the octane and favorably decreases the RVP.
DCPD-rich
streams may also be partially or fully hydrogenated to produce a low RVP /
higher octane
blend component.
[00142] Thus, additionally or alternatively, at least a portion of the
first, second, third,
fourth, and fifth CS-rich fractions and the C6+-rich stream described above,
if produced at all
in the process of the present invention, can be optionally combined with
additional streams
containing diolefins (e.g., steam cracked naphtha, light cat naphtha, heavy
cat naphtha) and
can be selectively hydrogenated to produce a mogas component. Because the
first, second,
third, fourth, and fifth CS-rich fractions contain high concentrations of
unsaturated C5
hydrocarbons, including CPD and cyclopentene, once partially hydrogenated they
tend to
have higher octane-value and lower Reid Vapor Pressure (RVP) than the acyclic
saturated C5
feedstock supplied to the first reactor. As used herein, a "selective
hydrogenation" process is
a treatment of a mixture comprising both diolefins and mono olefins with
hydrogen in the
presence of a selective hydrogenation catalyst under selective hydrogenation
conditions
favoring the conversion of diolefms into mono olefins over the conversion of
mono olefins
- 32 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
into saturates. It is highly desired that the selectively hydrogenated mogas
component
comprises diolefins at a total concentration not higher than 1.0 wt%, based on
the total weight
of the mogas component. Thus, mogas component can then be blended with
additional
mogas components to obtain mogas with the desired composition and properties.
[00143] Additionally or alternatively, prior to or after hydrogenation
thereof, at least a
portion of the first, second, third, fourth, and fifth C5-rich fractions
described above, if
produced at all in the process of the present invention, and/or a portion of
their hydrogenated
products, may be separated to obtain high-purity cyclopentene, cyclopentane, 2-
methyl-1,3-
butadiene, and/or 1,3-pentadiene, each of which can be used or sold as
valuable industrial
materials.
[00144] Non-limiting examples of hydrogenation catalyst include: palladium-
based or
nickel-based catalysts. Exemplary hydrogenation conditions include: a
temperature in the
range from 30¨ 250 C and a pressure in the range from 1,700¨ 5,500 kilopascal
absolute.
[00145] The present invention can be used to convert low value C5 feedstock
into higher
value CPD, DCPD, mogas components with high octane and/or lower RVP,
cyclopentene,
cyclopentane, 1,3-pentadiene, and the like, and hydrogen.
Description according to the drawings
[00146] The drawings schematically illustrate the block flow diagrams of
exemplary
system(s) and sub-system(s) thereof of the present invention operating to
implement
exemplary process(es) or aspects thereof of the present invention. It should
be understood
that only major components are shown in the drawings. Auxiliary equipment such
as control
valves, pumps, heat exchangers, reboilers, recycle loop, and the like,
although not all shown
in all drawings, are used liberally throughout the whole process to manipulate
stream and
equipment thermodynamic conditions.
[00147] In the system 101 shown in FIG. 1, a C5 feedstock stream 103
comprising n-
pentane at, e.g., at least 50 wt% is combined with a hydrogen co-feedstock
stream 105 to
form a combined stream 107, which is then combined with a recycle third C5-
rich stream 109
to form a combined feed stream 111, which is fed to a first reactor 113 (also
labeled RI).
The molar ratio of hydrogen to the C5 feedstock in stream 111 can range from
0.1 to 3.0,
preferably from 0.3 to 2.0, more preferably from 0.5 to 1.5. A major purpose
of co-feeding
hydrogen is to prevent coke formation on the catalyst, especially at locations
where the in-
situ produced hydrogen is at a relatively low concentration. The reactor 113
may be a fixed
bed reactor with a bed of catalyst 115 loaded therein. The catalyst 115 is
chosen from the
compositions described above. Reactions of the C5 hydrocarbons in the presence
of the
- 33 -
catalyst particles are highly endothermic. Thus, reactor 113 is heated by
external heating to
maintain an internal temperature in the range from 450 C to 800 C. The weight
hourly space
velocity is in the range from Ito 100 hour* A substantial portion of the C5
hydrocarbons in
the feed 111 is converted into CPD and byproducts such as acyclic diolefins,
acyclic mono
olefins, cyclopentane, cyclopentene; light components including hydrogen and C
1 -C4
hydrocarbons; one-ring aromatics; and multiple-ring aromatics at a total
conversion of n-
pentane in the range from 50% to 99%. At the outlet of the first reactor 113,
a first reactor
hydrocarbon effluent 117 is drawn at a temperature in the range from 500 to
800 C and at a
total absolute pressure in the range from 20 to 700 kilopascal absolute.
[00148] The first reactor hydrocarbon effluent 117 can comprise CPD at a
total
concentration in the range from 15 wt% to 80 wt%, on the basis of the total
weight of C5
hydrocarbons in the first reactor hydrocarbon effluent 117. Once it exits the
first reactor 113,
the first reactor hydrocarbon effluent stream 117 is promptly cooled down by
one or more heat
exchanger 119 to obtain a stream 121 to avoid undesired side reactions such as
thermal
cracking, condensation of PNAs, and premature Diels-Alder reactions of
reactive diolefinic
species, especially CPD. A quantity of wash oil (not shown) may be added prior
to and/or
within exchanger 119 to help prevent fouling.
[00149] The cooled stream 121 and a wash oil steam 125 are then fed into a
washing vessel
123, where the first reactor hydrocarbon effluent is further quenched down to
obtain a washed
first reactor hydrocarbon effluent stream 129. The wash oil used in the
example shown in
FIGs. 1 and 2 comprises alkylnaphthalene(s) and/or alkylbenzene at a total
concentration of at
least 50 wt%, although other wash oil as described above may be used. Stream
129 comprises
C5 components and light components from the first reactor hydrocarbon
effluent. Stream 129
may also contain C6, C7, C8, and the wash oil at non-negligible amounts. A
wash oil bottom
stream 127, comprising the wash oil, one-ring aromatics and multiple-ring
aromatics, is also
obtained from the washing vessel 123.
[00150] The upper stream 129, as clean first reactor hydrocarbon effluent,
is then supplied
to a first separation sub-system 131 (also labeled SDI), where a first C5-rich
stream 133, one
or more additional CS-rich streams 134 (one shown in FIG. 1), and a light
component stream
161 comprising hydrogen and C1-C4 hydrocarbons are obtained. The CS-rich
streams 133 and
134 are advantageously depleted of Cl-C4 hydrocarbons. Stream 133 can comprise
one or more
of C6, C7, C8+, and the heavy wash oil at non-negligible amounts. Stream 134
desirably
comprises C6, C7, C8+, and the heavy wash oil at significantly lower
concentrations than stream
- 34 -
CA 3004324 2019-07-12
133. Preferably, stream 134 is essentially free of Cl 0+ and the heavy wash
oil. Stream 161 is
fairly large in total volume, given the amount of hydrogen produced in the
first reactor 113. To
recover the non-negligible amount of C5 components present in stream 161,
stream 161 is
further contacted with a fresh solvent (sometimes such as the wash oil) stream
165 and/or a
recovered wash oil stream 168 in vessel 163 (also called "debutanizer" or
"debutanizer section")
to obtain a stream 167 comprising H2 and Cl-C4 hydrocarbons and depleted of C5
components.
The debutanizer bottom stream 125 exiting debutanizer vessel 163 is then
recycled to the
washing vessel 123 as described above. Stream 167 can be further separated by
using various
equipment and processes (now shown), such as PSA, RCPSA, TSA, cryogenic
method, and
membrane separation, to obtain one or more of the following: (i) a high-purity
H2 stream; (ii) a
H2/C1-C4 hydrocarbon mixture stream; and (iii) a C1-C4-rich hydrocarbon
stream.
1001511 Stream 133, to the extent it may comprise one or more of C6,
toluene, C8+, and the
wash oil at non-negligible concentration(s), is fed into a heavy wash oil
(e.g., alkylnapthalene)-
removal column 135 together with stream 127 described above, where an upper
stream 137
rich in C5 and depleted of C10+, and a lower stream 138 comprising C7 and C8+
are obtained.
Stream 138 is then fed into distillation column 301, from which an upper, wash
oil-rich stream
305 and a lower stream 307 rich in heavy oil are obtained. Stream 305 (also
labelled as stream
168) is recycled to debutanizer vessel 163 (shown) (and/or partly or entirely
recycled to
washing vessel 123, not shown) described above for extracting residual C5
hydrocarbons from
the light components-rich stream 161. Lightly used wash oil stream 125 exiting
debutanizer
163 is then recycled to washing vessel 123. Efforts should be taken to reduce
reactions between
CPD and acyclic diolefins in heat exchanger 119, vessels 123, 135, and the
front end of the
first separation sub-system 131. Nonetheless, because such side reactions may
take place at
various degrees, it is highly desirable that column 135 is operated under a
condition such that
reverse dimerization reaction is favored over dimerization, such that heavy
components such
as DCPD, reaction products between DCPD and acyclic diolefins are converted
into CPD and
other C5 components, and therefore CPD and other C5 components that otherwise
would be
lost to side reactions are at least partially recovered. To that end, the
conditions in the column
135 comprise advantageously a column bottom temperature in the range from 150
to 350 C,
preferably from 170 to 260 C, and a total absolute pressure in the range from
3 psia to 50 psia
(21 to 345 kilopascal absolute), preferably from 20 psia to 40 psia (138 to
276 kilopascal
absolute), and a residence time in the range from 0.01 to 10 hours, preferably
from 0.1 to 4
hours.
- 35 -
CA 3004324 2019-07-12
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[00152] Stream 137 and stream 134, both CS-rich and depleted of C10+, together
as the
first C5-rich fraction obtained from the first separation sub-system, is then
delivered to the
second reactor (also labeled R2, and called first dimerization reactor) 139
operating under a
first set of dimerization conditions to convert a portion of the CPD contained
therein into
DCPD. The first set of dimerization conditions advantageously comprise: a
temperature in
the range from 30 to 250 C, preferably from 70 to 140 C, such as from 90 to
130 C, and a
total absolute pressure in the range from 50 psia to 1000 psia (345 to 6895
kilopascal
absolute), preferably from 100 psia to 500 psia (689 to 3447 kilopascal
absolute), and a
residence time in the range from 1 to 220 minutes, preferably from 20 to 200
minutes, such as
to from 100 to 200 minutes. Such conditions are optimized to favor the
dimerization reaction
between CPD molecules and to minimize the reactions between CPD and other
diolefins.
[00153] From the reactor 139, a second reactor effluent 141 comprising CPD,
other C5
hydrocarbons, and DCPD is then fed into a second separation device 143 (SD2),
which can
be a distillation column. From column 143, an ultra high-purity DCPD lower
stream 147 and
an upper stream comprising CPD and other CS hydrocarbons are obtained. Stream
147 can
comprise DCPD at a concentration of at least 95 wt%, such as 96 wt%, 98 wt%,
99 wt%, or
even higher, based on the total weight of the C10 hydrocarbons of the stream
147. Stream
147 may be purified in a subsequent distillation column (not shown) to obtain
(1) an ultra
high-purity DCPD, which comprises DCPD at a concentration of at least 95 wt%,
such as 96
wt%, 98 wt%, 99 wt%, or even higher, based on the total weight of the stream;
(2) a light
wash oil-rich stream, which can be recycled to vessel 163 and/or washing
vessel 123
described above (not shown) to further reduce the net import of fresh wash
oil.
[00154] Upper stream 145, which is the second CS-rich fraction in the process
of the
present invention, is then fed into a second dimerization reactor (the third
reactor of the
present invention, R3) 149 operated under a second set of dimerization
conditions, where the
remaining CPD in stream 147 is partly converted into DCPD. The second set of
dimerization
conditions advantageously comprise: a temperature in the range from 30 to 250
C, preferably
from 100 to 140 C, and a total absolute pressure in the range from 50 psia to
1000 psia (345
to 6895 kilopascal absolute), preferably from 100 psia to 500 psia (689 to
3447 kilopascal
absolute), and a residence time in the range from 1 to 300 minutes, preferably
from 150 to
300 minutes. Such conditions are optimized to maximize recovery of the
remaining CPD
while achieving on-spec production of a subsequent DCPD fraction.
[00155] From the reactor 149, a third reactor effluent 151 comprising CPD,
other CS
hydrocarbons, and DCPD is then fed into a third separation device 153 (SD3),
which can be a
-36 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
distillation column. From column 153, a high-purity DCPD lower stream 155 and
an upper
stream comprising CPD and other C5 hydrocarbons 157 are obtained. Stream 155
can
comprise DCPD at a concentration of at least 90 wt%, such as 92 wt%, 94 wt%,
95 wt%, or
even higher, based on the total weight of the C10 hydrocarbons of the stream
155. Stream
155 may be purified in a subsequent distillation column (not shown) to obtain
(1) a high-
purity DCPD, which comprises DCPD at a concentration of at least 90 wt%, such
as 92 wt%,
94 wt%, 95 wt%, or even higher, based on the total weight of the stream; (2) a
light wash oil-
rich stream, which can be recycled to vessel 163 and/or washing vessel 123
described above
(not shown) to further reduce the net import of fresh wash oil.
to [00156] DCPD streams 147 and 155 may be sold or delivered as products.
The user may
convert these streams back into CPD or other compounds, depending on the
intended
applications.
[00157] Upper stream 157, which is the third CS-rich fraction in the process
of the present
invention, can be fed into a third dimerization reactor (not shown), where the
remaining CPD
therein can be converted into an additional amount of DCPD, which can be
separated and
recovered as a third DCPD-rich fraction in a fourth separation device (not
shown), if so
desired. If a third dimerization reactor is utilized, the preferred modes of
operation for the
first dimerization reactor and second dimerization reactor can be
advantageously adjusted for
the purpose of producing DCPD products at optimal quality levels, each with
optimal
quantities. Typically, the third DCPD-rich fraction would have a lower purity
than the first
and second DCPD-rich fractions produced upstream in the process as described
above.
[00158] As shown in FIG. 1, the third C5-rich fraction stream 157 from the
third
separation device 153 is divided into two streams 159 and 161. To the extent
streams 157,
159 and 161 may comprise C6+ in addition to C5 hydrocarbons, stream 161 is
then separated
in distillation column 163 to obtain a fifth C5-rich stream 165 that is
depleted with C6+ and a
C6-rich stream 167. Stream 165 can then be recycled to the first reactor 113
(R1) as stream
109, as described above. Stream 167 may be purged or used in other
applications, such as an
untreated mogas component as described below. It has been found that in this
particular
embodiment, without the distillation column 163, if the weight ratio of stream
161 to stream
159 is higher than 0.4:0.6, accumulation of C6+ species may occur in the
system. It is highly
desired that stream 161 is subjected to purification in column 163 before
being recycled to
the first reactor to eliminate such restriction on the recycle ratio.
[00159] Stream 159 (and, optionally, a portion of the first CS-rich fraction
stream 137, and
a portion of the second CS-rich fraction stream 145, not shown in FIG. 1) can
be used for
-37-
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
many purposes, due to the many useful components contained therein: CPD,
cyclopentane,
cyclopentene. pentene. pentadiene, 2-methylbutadiene, and the like.
[00160] For example, stream 159 (and other C5-rich fraction streams, and C6-
rich stream
167) can be partly or entirely converted into a mogas component by selective
hydrogenation
to convert at least a portion of the dienes therein to mono olefins and/or
saturates. The high
concentrations of cyclopentane and cyclopentene in stream 159 after
hydrogenation makes it
particularly suitable for mogas blending due to the high octane and lower Reid
Vapor
Pressure values of cyclopentane and cyclopentene relative to the starting
feedstock of acyclic
C5 hydrocarbon such as n-pentane. The C6-rich stream 167 may be used directly
as a mogas
to component after selective hydrogenation as well.
[00161] For another example, before or after selective hydrogenation, stream
159 (and
other C5-rich fraction streams) may be separated to obtain at least one pure
stream of the
following: cyclopentane, cyclopentene, pentene, 1,3-pentadiene, 1,4-
pentadiene, and 2-
methylbutadiene.
[00162] FIG. 2 schematically illustrates an exemplary first separation sub-
system 201
useful in the process and system of the present invention, particularly in the
exemplary
process illustrated in FIG. 1. The first separation sub-system 201 in FIG. 2
comprises a
compression train including multiple-stage compression, cooling and
liquid/vapor separation.
In the process of this figure, the upper stream 129 comprising a majority of
washed first
reactor effluent obtained from column 123 is first fed into a first-stage
compressor 203, from
which a stream 205 at a higher pressure is obtained. Stream 205 is then cooled
by a first-
stage heat exchanger 207 to obtain a liquid/vapor mixture stream 209, which is
fed into a
first-stage liquid/vapor separation device (such as a drum) 211 to obtain a
first-stage lower
liquid stream 215 comprising C5 hydrocarbons but depleted of hydrogen and C1-
C4
hydrocarbons and a first-stage upper vapor stream 213 comprising C5
hydrocarbons and rich
in hydrogen and C1-C4 hydrocarbons. Stream 213 is then compressed by a second-
stage
compressor 217 to obtain a stream 219 with an even higher pressure, which is
then cooled by
a second-stage heat exchanger 221 to obtain a second-stage lower temperature
liquid/vapor
mixture stream 223, which is separated in a second-stage liquid/vapor
separation device (such
as a drum) 225 to obtain a second-stage lower liquid stream 229 comprising C5
hydrocarbons
but depleted of hydrogen and C1-C4 hydrocarbons and a second-stage vapor
stream 227
comprising C5 hydrocarbons and rich in hydrogen and C1-C4 hydrocarbons. Stream
227 is
then compressed by a third-stage compressor 231 to obtain a stream 233 with an
even higher
pressure, which is then cooled by a third-stage heat exchanger 235 to obtain a
lower
-38 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
temperature third-stage liquid/vapor mixture stream 237, which is separated in
a third-stage
liquid/vapor separation device (such as a drum) 239 to obtain a third-stage
lower liquid
stream 241 comprising C5 hydrocarbons but depleted of hydrogen and Cl-C4
hydrocarbons
and a third-stage upper vapor stream 161 comprising rich in hydrogen and C1-C4
hydrocarbons and, optionally, comprising C5 hydrocarbons at a lower
concentration. Stream
161 is then fed to a vessel 163 as illustrated in FIG. 1 and described above.
[00163] As shown in FIG. 2, stream 215, to the extent it may comprise non-
negligible
concentrations of at least one of the wash oil, C7, and C8+ (such as DCPD),
can be fed into
the heavy wash oil-removal column 135 together with stream 127, where it is
processed to
to obtain a C5-rich stream 137 depleted with heavy wash oil as described
above in connection
with FIG. 1. Downstream streams 229 and 241, to the extent they tend to
comprise lower
concentrations of the heavy wash oil, C7, and C8+, may be combined to form a
single stream
134, which is then combined with stream 137 as the first C5-rich fraction
directly fed into the
first dimerization reactor 139 (R2) as illustrated in FIG. 1.
[00164] It is contemplated, though not shown, that streams 215, 229, and 241,
to the extent
they may all contain non-negligible concentrations of at least one of the
heavy wash oil, C7,
and C8+ (such as DCPD), may be all delivered to the heavy wash oil-removal
column 135
along with stream 127, where the C5-rich stream 137 is obtained and delivered
to the first
dimerization reactor 139.
[00165] It is also contemplated, though not shown, that streams 215, 229, and
241, to the
extent they may all contain the heavywash oil. C7, and C8+ at sufficiently low
concentrations, if any at all, may be combined with stream 137 and then
delivered directly to
the first dimerization reactor 139.
Industrial Applicability
[00166] The first hydrocarbon reactor effluent obtained during the acyclic C5
conversion
process containing cyclic, branched and linear C5 hydrocarbons and,
optionally, containing
any combination of hydrogen, C4 and lighter byproducts, or C6 and heavier
byproducts is a
valuable product in and of itself Preferably, CPD and/or DCPD may be separated
from the
reactor effluent to obtain purified product streams which are useful in the
production of a
variety of high value products.
[00167] For example, a purified product stream containing 50 wt% or greater,
or
preferably 60 wt% or greater of DCPD is useful for producing hydrocarbon
resins,
unsaturated polyester resins, and epoxy materials. A purified product stream
containing 80
- 39 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
wt% or greater, or preferably 90 wt% or greater of CPD is useful for producing
Diels-Alder
reaction products formed in accordance with the following reaction Scheme (I):
Scheme I
+ \\ 4+2 cycloaddition
\
5 R Diels-Alder reaction product. ¨R
where R is a heteroatom or substituted heteroatom, substituted or
unsubstituted C1-05o
hydrocarbyl radical (often a hydrocarbyl radical containing double bonds), an
aromatic
radical, or any combination thereof Preferably, substituted radicals or groups
contain one or
to more elements from Groups 13-17, preferably from Groups 15 or 16, more
preferably
nitrogen, oxygen, or sulfur. In addition to the monoolefin Diels-Alder
reaction product
depicted in Scheme (I), a purified product stream containing 80 wt% or
greater, or preferably
90 wt% or greater of CPD can be used to form DieIs-Alder reaction products of
CPD with
one or more of the following: another CPD molecule, conjugated dienes,
acetylenes, allenes,
15 disubstituted olefins, trisubstituted olefins, cyclic olefins and
substituted versions of the
foregoing. Preferred Diels-Alder reaction products include norbomene,
ethylidene
norbomene, substituted norbomenes (including oxygen containing norbomenes),
norbomadienes, and tetracyclododecene, as illustrated in the following
structures:
norbornene ethylidene norbomene tetracyclododecene
norbomadiene oxygen substituted
norbomene.
[00168] The foregoing Diels-Alder reaction products are useful for producing
polymers
and copolymers of cyclic olefins copolymerized with olefins such as ethylene.
The resulting
cyclic olefin copolymer and cyclic olefin polymer products are useful in a
variety of
applications, e.g., packaging film.
[00169] A purified product stream containing 99 wt% or greater of DCPD is
useful for
producing DCPD polymers using, for example, ring opening metathesis
polymerization
(ROMP) catalysts. The DCPD polymer products are useful in forming articles,
particularly
molded parts, e.g., wind turbine blades and automobile parts.
[00170] Additional components may also be separated from the reactor effluent
and used
in the formation of high value products. For example, separated cyclopentene
is useful for
producing polycyclopentene, also known as polypentenamer, as depicted in
Scheme (II).
- 40 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Scheme II
ROMP
catalyst
[00171] Separated cyclopentane is useful as a blowing agent and as a solvent.
Linear and
branched Cs products are useful for conversion to higher olefins and alcohols.
Cyclic and
non cyclic C5 products, optionally after hydrogenation, are useful as octane
enhancers and
transportation fuel blend components.
Examples
[00172] The following non-limiting examples 1-7 illustrate the invention.
Examples 1-5
are obtained by using simulation. In these examples, the respective first
reactor effluents are
fed forward to the quench/wash section (123), a compression train section
(SDI, 131), and a
to debutanization section (163) in similar manners as discussed above. All
the recovered C5-
rich fractions produced from the quench/wash section (135), the compression
train section
(SD1 , 131), and debutanization section (163) are routed to the heavy wash oil-
removal
column (135), and subsequently to a first dimerization reactor (R2, 139), an
ultra high-purity
DCPD recovery column (SD2. 143), a second dimerization reactor (R3, 149), and
then a
high-purity DCPD recovery column (SD3, 153).
Example 1
[00173] In this example, a first reactor effluent produced from pure n-pentane
feedstock, a
pure hydrogen co-feedstock with 1:2 hydrogen/n-pentane molar ratio, without co-
feeding a
light hydrocarbon or recycling of any down-stream C5-rich fractions to the
first reactor. The
process temperature, pressure, weight hourly space velocity, and molecular
weight at the
reactor inlet are 475 C, 62 psia (401.9 kilopascal absolute), 15 hr-1, and
49.01 g/mol,
respectively. Temperature and pressure at the reactor outlet are 575 C and 10
psia (68.9
kilopascal absolute), respectively. The reactions generate an additional 1.87
moles of
molecules in the first reactor effluent exiting the outlet per mole of
molecules in the total feed
material at the inlet. This 1.87-fold molar expansion has the effects of
lowering the
molecular weight and density of the stream mixture from 49.01 g/mol at the
inlet to 27.05
g/mol at the outlet and from 3.08 kg/m3 at the inlet to 0.26 kg/m3 at the
outlet, respectively.
The pressure drop from the inlet to the outlet of the first reactor is
calculated to be about 52
psi (359 kilopascal). Composition of the first reactor effluent at the outlet
is given in Table I
below.
-41 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
[00174] The entire third C5-rich fraction is used as a mogas blend for making
mogas, the
composition of the mogas blend is provided in Table I below as well.
[00175] In this example, to produce 100 tons of CPD in stream 117, a total
weight of 403
tons of n-pentane feed is fed to the system (representing a total CPD yield of
24.8 wt%, based
on all weight of the n-pentane feed), a total weight of 13.1 tons of hydrogen
is produced, a
total weight of 82 tons of UHF' DCPD with purity level exceeding 99.0 wt%
(stream 147) is
produced, a total weight of 11 tons of DCPD with purity level exceeding 90.0
wt% (stream
155) is produced, and a total weight of 238 tons of mogas blend is produced.
Example 2
.. [00176] The reactor inlet and outlet temperature and pressure remain the
same as in
Example 1 above. However, in this example, a CS-rich stream, produced as 35%
of the third
CS-rich fraction obtained by separating the third reactor effluent produced
from a second
dimerization reactor described above, is recycled to the first reactor, where
it is admixed with
n-pentane before being fed into the first reactor. Hydrogen is co-fed at
H2/(all C5
hydrocarbons except (iso-05 hydrocarbons and CPD)) molar ratio of 1:2. It has
been
experimentally found that the reaction pathway from iso-05 hydrocarbons to CPD
is
kinetically inhibited under the reaction conditions. The composition of the
total feed to the
first reactor is given in Table I below.
[00177] The remaining 65% of the third C5-rich fraction is used as a mogas
blend for
making mogas. The composition of the mogas blend is provided in Table I below
as well.
[00178] In this example, to produce 100 tons of CPD in stream 117, a total
weight of 308
tons of n-pentane feed is fed into the system (representing a CPD yield of
32.5 wt%, based on
the total weight of the n-pentane feed), a total weight of 11.7 tons of
hydrogen is produced, a
total weight of 85 tons of UHP DCPD (stream 147) with purity level exceeding
99.0 wt% is
produced, a total weight of 8 tons of DCPD (stream 155) with purity level
exceeding 90.0
wt% is produced, and a total weight of 146 tons of mogas blend is produced.
[00179] To produce the same amount of CPD, Example 2 (with 35% recycle of the
third
C5-rich fraction to the first reactor) requires 23.4% less of fresh n-pentane
feed than Example
1 (without recycle of any of the C5-rich fraction to the first reactor).
[00180] To produce the same amount of CPD, Example 2 produces 10.8% less of
hydrogen than Example 1, due to using partially unsaturated feed versus a
fully saturated
feed. This has the benefit of reduced volumetric flow rates in the reactor(s)
and downstream
equipment. For example, the first reactor in Example 2 shows a 7.8% reduction
in volumetric
- 42 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
flow than in Example 1. This may have significant impacts on the equipment
sizing of the
downstream quench tower(s), gas compressor(s), and debutanizer(s).
[00181] The enthalpy changes of the stream across the first reactor also shows
significant
reduction in Example 2 compared to Example 1. This translates into a 10.9 %
reduction in
furnace firing in Example 2, which can have a significant impact of the
equipment sizing of
the reactor(s) and fuel costs. The amount of heat required for sustaining the
endothermic
reactions in the first reactor is comparatively lower when using a partially
converted C5
feedstock.
[00182] To produce 100 tons of CPD, Example 2 shows a 38.6 wt% of reduction of
to materials diverted to mogas production. Furthermore, it can be seen from
Table 1 that the
mogas stream in Example 2 has a slightly higher octane value of C5+ byproduct
than in
Example 1 since more kinetically limited isomerization and aromatization
products will be
concentrated into a smaller byproduct stream.
[00183] Thus, clearly, it may be advantageous to recycle at least part of the
C5-containing
streams to the CPD reactor(s). This is especially beneficial if demand for the
partially
converted C5 hydrocarbons are reduced, e.g., during certain seasons when the
RVP spec on
mogas limits the amount of C5 hydrocarbons that can be blended. This allows
the plant to
continue to operate at desired DCPD product rates with lower quantities of co-
products.
Table I
Composition of First Composition of
Total Feed Composition Reactor Hydrocarbon Mogas Blend
(wt%) Effluent at Exit (wt%) (wt%)
Example Example Example
Component 1 2 1 2 1 2
Hydrogen 1.30 1.30 4.51 4.28 -
Methane 0.00 0.00 1.50 1.34 - -
Ethylene 0.00 0.00 0.11 0.10 - -
Ethane 0.00 , 0.01 , 0.97 , 0.87 -
Propylene 0.00 0.04 0.73 0.70 0.04 0.07
Propane 0.00 0.06 0.75 0.72 0.05 0.08
Isobutane 0.00 0.00 0.00 0.00 0.00 0.00
Isobutylene 0.00 0.03 0.14 0.16 0.03 0.05
1-butene 0.00 0.18 0.73 0.82 0.14 0.27
1,3-butadiene 0.00 0.05 0.19 0.22 0.04 0.07
n-butane 0.00 0.22 0.79 0.93 0.17 0.33
t-2-butene 0.00 0.23 0.80 0.94 0.18 0.35
- 43 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Composition of First Composition of
Total Feed Composition Reactor Hydrocarbon Mogas Blend
(wt%) Effluent at Exit (wt%) (wt%)
Example Example Example
Component 1 2 1 2 1 2
c-2-butene 0.00 0.18 0.58 0.70 0.13 0.27
3-methyl-I -butene 0.00 0.02 0.05 0.06 0.01 0.03
1,4-pentadiene 0.00 0.02 0.05 0.05 0.01 0.02
Isopentane 0.00 0.10 0.22 0.30 0.06 0.14
1-pentene 0.00 1.28 3.99 3.98 1.19 1.95
2-methyl-1-butene 0.00 0.09 0.19 0.26 0.06 0.13
Isoprene 0.00 0.02 0.06 0.08 0.01 0.03
n-pentane 98.70 88.73 32.64 30.87 9.81 15.27
t-2-pentene 0.00 2.51 7.72 7.67 2.34 3.81
c-2-pentene 0.00 1.41 4.35 4.31 1.32 2.14
2-methyl-2-butene 0.00 0.15 0.33 0.46 0.10 0.23
CPD 0.00 0.17 24.51 25.57 0.08 0.25
t-1,3-pentadiene 0.00 0.91 2.78 2.81 0.82 1.38
c-1,3-pentadiene , 0.00 0.74 2.28 2.32 0.67 1.12
Cyclopentene 0.00 1.14 3.43 3.51 1.03 1.73
Cyclopentane 0.00 0.18 0.56 0.56 0.17 0.27
Benzene 0,00 0.25 0.72 0,89 0,19 0.37
Toluene 0.00 0.00 0.00 0.00 - -
Meta-xylene 0.00 0.00 0.00 0.00 - -
DCPD 0.00 0.00 0.00 0.00 - -
Di-isoprene 0.00 0.00 0.00 0.00 - -
Naphthalene 0.00 0.00 2.45 2.55 - -
Methylnaphthalene 0.00 0.00 0.00 0.00 - -
Anthracene 0.00 0.00 1.70 1.77 - -
Pyretic 0.00 0.00 0.19 0.20 - -
TOTAL 100.00 100.00 100.00 100.00 100.00 100.00
Example 3
[00184] In this prophetic example, obtained by simulation, a model third C5-
rich fraction
used as the mogas blend and a corresponding partially hydrogenated mogas
component
having the following compositions in Table II can be obtained:
- 44 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Table II
Concentration in (wt%)
Components Third C5-rich Fraction Post-Selective Hydrogenation
Propylene 0.22 0.22
Propane 0.27 0.27
Isobutane 0.00 0.00
Isobutylene 0.14 0.14
1 -butene 0.75 0.81
1,3-butadiene 0.21 0.00
n-butane 0.91 0.91
t-2-butene 0.95 1.01
c-2-butene 0.72 0.79
3-methyl-1-butene 0.07 0.07
1,4-pentadiene 0.07 0.00
Isopentane 0.34 0.34
1 -p entene 6.36 9.11
2-methyl-1-butene 0.30 0.32
Isoprene 0.05 0.00
n-pentane 52.59 52.59
t-2-pentene 12.54 15.21
c-2-pentene 7.08 9.75
2-methyl-2-butene 0.54 0.56
Cy cl opentadi ene 0.44 0.00
t-1,3-pentadiene 4.41 0.00
c-1,3-pentadiene 3.61 0.00
Cy cl opentene 5.54 5.98
Cy cl opentane 0.90 0.90
Benzene 1.01 1.01
C10 (dimers) 0.00 0.00
Total 100.00 100.00
Example 4
[00185] In this example, a first reactor effluent produced from pure n-pentane
feedstock, a
pure hydrogen co-feedstock with 1:1 hydrogen/n-pentane molar ratio, without co-
feeding a
light hydrocarbon or recycling of any down-stream C5-rich fractions to the
first reactor. The
process temperature, pressure, weight hourly space velocity, and molecular
weight at the
- 45 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
reactor inlet are 475 C, 62 psia (401.9 kilopascal absolute), a lower weight
hourly space
velocity than Example 1 to attain a closer approach to thermodynamic
equilibrium, and 49.01
g/mol, respectively. Temperature and pressure at the reactor outlet are 575 C
and 10 psia
(68.9 kilopascal absolute), respectively. In this example, the reaction system
also employs a
different catalyst system from Example 1. The reactions generate an additional
2.02 moles of
molecules in the first reactor effluent exiting the outlet per mole of
molecules in the total feed
material at the inlet. This 2.02-fold molar expansion has the effects of
lowering the
molecular weight and density of the stream mixture from 36.72 g/mol at the
inlet to 18.16
g/mol at the outlet and from 2.44 kg/m3 at the inlet to 0.18 kg/m3 at the
outlet, respectively.
to The pressure drop from the inlet to the outlet of the first reactor is
calculated to be about 52
psi (359 kilopascal). Composition of the first reactor effluent at the outlet
is given in Table
III below.
[00186] The entire third CS-rich fraction is used as a mogas blend for making
mogas, the
composition of the mogas blend is provided in Table III below as well.
[00187] In this example, to produce 100 tons of CPD in stream 117, a total
weight of 222
tons of n-pentane feed is fed to the system (representing a total CPD yield of
45.0 wt%, based
on all weight of the n-pentane feed), a total weight of 18.3 tons of hydrogen
is produced, a
total weight of 54 tons of UHP DCPD with purity level exceeding 99.0 wt%
(stream 147) is
produced, a total weight of 44 tons of DCPD with purity level exceeding 90.0
wt% (stream
155) is produced, and a total weight of 77 tons of mogas blend is produced.
[00188] In this example, toluene is used as wash oil. Net import of toluene is
estimated to
be no more than 7 tons due to effective wash oil recycle built into the
process. Without
recycling, net import of toluene would increase to 251 tons on a once-through
basis. This
may have significant impacts on the overall process economic viability.
Table III
Composition of First Composition of
Total Feed Composition Reactor Hydrocarbon Mogas Blend
Component (wt%) Effluent at Exit (wt%) (wt%)
Hydrogen 2.78 8.01
Methane 0.00 2.02 0.01
Ethylene 0.00 0.11
Ethane 0.00 2.42 0.05
Propylene 0.00 0.98 0.13
Propane 0.00 2.29 0.38
Isobutane 0.00 0.04 0.03
- 46 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Composition of First Composition of
Total Feed Composition Reactor Hydrocarbon Mogas Blend
Component (wt%) Effluent at Exit (wt%) (wt%)
Isobutylene 0.00 0.23 0.17
1-butene 0.00 0.71 0.53
1,3-butadiene 0.00 0.04 0.03
n-butane 0.00 1.63 1.72
t-2-butene 0.00 0.81 0.90
c-2-butene 0.00 0.62 0.79
3-methyl-1-butene 0.00 0.24 0.60
1,4-pentadiene 0.00 0.14 0.38
Isopentane 0.00 0.54 1.46
1-pentene 0.00 1.69 4.62
2-methyl-1-butene 0.00 0.93 2.55
Isoprene 0.00 0.43 1.10
n-pentane 97.23 5.35 14.33
t-2-pentene 0.00 4.14 11.37
c-2-pentene 0.00 2.10 5.78
2-methyl-2-butene , 0.00 1.49 4.09
CPD 0.00 43.76 1.97
t-1,3-pentadiene 0.00 1.13 2.96
c-1,3-pentadiene 0.00 0.93 2.43
Cyclopentene 0.00 12.21 32.99
Cy clopentane 0.00 3.13 7.97
Benzene 0.00 0.48 0.01
Toluene 0.00 0.38 -
Meta-xylene 0.00 0.04 -
DCPD 0.00 0.00 -
Di-isoprene 0.00 0.00 -
Naphthalene 0.00 0.87 -
Methylnaphthalene 0.00 0.07 -
Anthracene 0.00 0.01 -
Pyrene 0.00 0.00 -
TOTAL 100.00 100.00 100.00
Example 5
[00189] In this prophetic example, obtained by simulation, a model third CS-
rich fraction
used as the mogas blend and a corresponding partially hydrogenated mogas
component
haying the following compositions in Table IV can be obtained:
- 47 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
TABLE IV
Concentration in (wt%)
Components Third C5-rich Fraction Post-Selective Hydrogenation
Propylene 0.13 0.08
Propane 0.38 0.26
Isobutane 0.03 0.02
Isobutylene 0.17 0.15
1-butene 0.53 0.49
1,3-butadiene 0.03 0.00
n-butane 1.72 1.53
t-2-butene 0.90 0.81
c-2-butene 0.79 0.71
3-methyl-1-butene 0.60 0.57
1,4-pentadiene 0.38 0.00
Isopentane 1.46 1.43
1 -p entene 4.62 4.93
2-methyl-1-butene 2.55 3.07
Isoprene 1.10 0.00
n-pentane 14.33 14.30
t-2-pentene 11.37 14.41
c-2-pentene 5.78 8.29
2-methyl-2-butene 4.09 4.64
Cy cl opentadi ene 1.97 0.08
t-1,3-pentadiene 2.96 0.00
c-1,3-pentadiene 2.43 0.00
Cy cl opentene 32.99 35.52
Cy cl opentane 7.97 8.14
Benzene 0.01 0.01
C10 (dimers) 0.00 0.00
Total 100.00 100.00
Example 6 - ZSM-5 Catalyst Composition Synthesis
[00190] A synthesis mixture with - 20.3% solids was prepared from 10,000 g of
deionized
(DI) water, 600 g of 50% NaOH solution, 25g of 45% Sodium Aluminate solution,
730 g of
n-propyl amine 100% solution, 80 g of ZSM-5 seed crystals, and 3,190 g of
Ultrasil PMTm.
- 48 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
Modified silica were mixed in a 5-gal pail container and then charged into a 5-
gal autoclave
after mixing. The synthesis mixture had the following molar composition:
SiO2/A1203 ¨ 470
H20/SiO2 - 12.1
OH/SiO2 ¨ 0.16
Na/SiO2 ¨ 0.16
¨ 0.25.
to -- [00191] The synthesis mixture was mixed and reacted at 230 F (110 C) at
250 rpm for 72
hurs. The resulting product was filtered and washed with DI water and then
dried in the oven
at ¨ 250 F (121 C) overnight. A portion of the as-synthesized crystals were
converted (for
characterization) into the hydrogen form by three ion exchanges with ammonium
nitrate
solution at room temperature, followed by drying at 250 F (121 C) and
calcination at 1000 F
-- (540 C) for 6 hours. The resulting ZSM-5 crystals had a SiO2/A1203 molar
ratio of ¨ 414,
total surface area (SA)/(micropore SA + mesopore SA) of 490 (440 + 51) m2/g,
Hexane
sorption of 117 mg/g and an Alpha value (as measured on the proton form) of
31. A second
portion of the material was used as synthesized for Pt impregnation.
[00192] ZSM-5 having a SiO2/A1203 molar ratio of 414 and a sodium content of
0.38 wt%
was calcined for 6 hours in nitrogen at 900 F (482 C). After cooling, the
sample was re-
heated to 900 F (482 C) in nitrogen and held for three hours. The atmosphere
was then
gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in four stepwise
increments. Each step
was held for 30 minutes. The temperature was increased to 1000 F (540 C), the
oxygen
content was increased to 16.8%, and the material was held at 1000 F (540 C)
for 6 hours.
-- After cooling, 0.5 wt% Pt was added via incipient wetness impregnation
using an aqueous
solution of tetraamine platinum hydroxide. The catalyst composition was dried
in air at room
temperature for 2 hours, then at 250 F (121 C) for 4 hours, and lastly
calcined in air at 660 F
(349 C) for 3 hours. The catalyst composition powder was pressed (15 ton),
crushed, and
sieved to obtain 20-40 mesh particle size.
-- Example 7 - Catalyst Composition Performance Evaluation
[00193] The above material of Example 6 was evaluated for performance. The
catalyst
composition (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and
loaded into a
reactor. The catalyst composition was dried for 1 hour under He (100 mL/min,
30 psig (207
kPa), 250 C) then reduced for 1 hour under H2 (200 mL/min, 30 psig (207 kPa),
500 C). The
-- catalyst composition was then tested for performance with feed of n-
pentane, H2, and balance
He, typically at 550 C - 600 C, 5.0 psia (35 kPa-a) C51412, 1.0 molar H2:C51-
112, 14.7
WHSV, and 30 psig (207 kPa) total. Catalyst composition stability and
regenerability was
- 49 -
CA 03004324 2018-05-03
WO 2017/078902 PCT/US2016/056038
tested post initial tests at 550 C to 600 C by treatment with H2 (200 mLimin,
30 psig (207
kPa), 650 C) for 5 hours, then retesting performance at 600 C.
[00194] Cyclopentadiene and three equivalents of hydrogen are produced by
dehydrogenation and cyclization of n-pentane (Equation 1). This is achieved by
flowing n-
pentane over a solid-state, Pt containing catalyst composition at elevated
temperature. The
performance of ZSM-5(414:1)/0.5% Pt of Example 6 was evaluated based on n-
pentane
conversion, cyclic C5 production (cC5), cracking yields, and stability. These
results are
summarized in Table V, Table VI, Table VII, and Table VIII.
A
C5H12-)C5H6+ 3H2 Equation (1)
Table V
Conversion Selectivity (mol %) Yield (mol %)
(%)
Temperature C5H12 cC5 CPD Cl C2-4 iC5 cC5 CPD Cl C2-4 iC5 cC5:C1-4
( C)
545 71 33 20 11 21 4.4 24
14 8.1 15 3.1 1.0
570 80 37 26 13 22 3.7 30 21 10 17 3.0 1.1
595 84 40 32 13 22 3.1 34 26 11 18 2.6 1.1
595, Post H2 76 38 30 16 22 2.4 29 23 12 17 1.8 1.0
Table VI
Conversion Selectivity (mol %) Yield (mol (Yo)
(%)
Temperature C5H12 iC5 iC5o iC5= iC5 == iC5 iC5o iC5 = iC5==
( C)
545 71 4.4 1.1 3.2
0.04 3.1 0.8 2.3 0.03
570 80 3.7 0.8 2.8
0.05 3.0 0.7 2.3 0.04
595 84 3.1 0.7 2.4
0.05 2.6 0.6 2.0 0.05
595, Post H2 76 2.4 0.6 1.8 0.04 1.8 0.5 1.4
0.03
Table VII
Conversion Selectivity (C %) Yield (C %)
Temperature C5H12 cC5 CPD Cl C2-4 iC5 cC5 CPD Cl C2-4 iC5 cC5:C1-4
( C)
545 71 40 24 2.8 15 5.3 28 17 2.0 11 3.7 2.2
570 80 45 32 3.1 16 4.5 36 26 2.5 13 3.6 2.3
595 84 50 39 3.3 16 3.8
42 33 2.8 14 3.2 2.5
595, Post H2 76 48 38 4.1 17 3.0 37 29 3.1 13 2.3
2.3
- 50 -
CA 03004324 2018-05-03
Table VIII
Conversion Selectivity (C %) Yield (C %)
(%)
Temperature C5H12 iC5 iC5o iC5= iC5 == iC5 iC5o iC5= iC5=
( C)
545 71 5.3 1.4 3.8 0.05 3.7 1.0 2.7 0.04
570 80 4.5 1.0 3.5 0.06 3.6 0.8 2.8 0.04
595 84 3.8 0.8 2.9 0.07 3.2 0.7 2.5 0.06
595, Post H2 76 3.0 0.8 2.2 0.05 2.3 0.6 1.7 0.03
[00195] Table V and Table VII show the conversion of n-pentane and selectivity
and yield
of cyclic C5, CPD, iso-Cs, CI, and C2-4 cracking products at varying
temperatures (average
values over 8 hours at each temperature) for a catalyst composition of 0.5 g
ZSM-5(Si:Al2
molar ratio 414:1)/0.5wt%Pt at conditions of 5.0 psia (35 kPa-a) C5H12, 1:1
molar H2:C5, 14.7
WHSV, 45 psia (310 kPa-a) total. In Table V, the selectivities and yields are
expressed on a
molar percentage basis for the respective cyclic C5, CPD, iso-05, Cl, and C2-4
of
hydrocarbons formed; i.e., the molar selectivity is the moles of the
respective cyclic C5, CPD,
CI, and C24 formed divided by total moles of pentane converted. In Table VII,
the selectivities
and yields are expressed on a carbon percentage basis for the respective
cyclic C5, CPD, iso-
05, Cl, and C2-4 of hydrocarbons formed; i.e., the carbon selectivity is the
moles carbon in
the respective cyclic C5, CPD, iso-05, Cl, and C2-4 formed divided by total
moles of carbon
in the pentane converted. As can be seen, Table V and Table VII show greater
than 80%
conversion of pentane, at high WHSV, and 40% selectivity to cyclic C5 species
at 595 C.
While not the specific end product, cyclopentane and cyclopentene can be
recycled to produce
CPD.
[00196] Tables VI and VIII further specify the individual iC5 components which
are shown
as totals in Tables V and VII. iC5o is iso pentane; including 2-methyl butane
and 3-methyl
butane. iC5= is isopentenes including 2-methyl butene and 3-methyl butene. iC5
== is iso-
pentadienes; including 2-methyl butadiene and 3-methyl butadiene. These
results show the
low levels of iso-pentadienes that are possible with the example catalyst.
[00197] As is apparent from the foregoing general description and the
specific
embodiments, while forms of the invention have been illustrated and described,
various
modifications can be made without departing from the spirit and scope of the
invention.
-51 -
CA 03004324 2018-05-03
Accordingly, it is not intended that the invention be limited thereby.
Likewise, the term
"comprising" is considered synonymous with the term "including." Likewise,
whenever a
composition, an element or a group of elements is preceded with the
transitional phrase
"comprising," it is understood that we also contemplate the same composition
or group of
elements with transitional phrases "consisting essentially of," "consisting
of," "selected from
the group of consisting of," or "is" preceding the recitation of the
composition element, or
elements and vice versa.
- 52 -
