Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
PROCESSES AND SYSTEMS FOR THE
CONVERSION OF ACYCLIC HYDROCARBONS
FIELD OF THE INVENTION
This invention relates to processes and reactor systems for the conversion of
acyclic
hydrocarbons to alkenes, cyclic hydrocarbons and/or aromatics.
BACKGROUND OF THE INVENTION
Cyclic hydrocarbons, alkenes and aromatics, such as cyclopentadiene ("CPD")
and its
dimer dicyclopentadiene ("DCPD"), ethylene, propylene, and benzene, are highly
desired raw
materials used throughout the chemical industry in a wide range of products,
for example,
polymeric materials, polyester resins, synthetic rubbers, solvents, fuels,
fuel additives, etc. These
compounds are typically derived from various streams produced during refinery
processing of
petroleum. In particular, CPD is currently a minor byproduct of liquid feed
steam cracking (e.g.,
.. naphtha, and heavier feed). As existing and new steam cracking facilities
shift to lighter feeds,
less CPD is produced while demand for CPD is rising. High cost due to supply
limitations
impacts the potential end product use of CPD in polymers. More CPD-based
polymer product
could be produced if additional CPD could be produced at unconstrained rates
and preferably at
a cost lower than recovery from steam cracking. When producing CPD, co-
production of other
cyclic C5 compounds is also desirable. Cyclopentane and cyclopentene can have
high value as
solvents while cyclopentene may be used as a comonomer to produce polymers and
as a starting
material for other high value chemicals.
It would be advantageous to be able to produce these cyclic hydrocarbons,
alkenes and
aromatics, including CPD, propylene, ethylene, and benzene, as the primary
product from
plentiful hydrocarbon feedstock. Specifically, when producing CPD, it is also
desirable to
minimize production of light (G) byproducts. While a feedstock composed of
lower hydrogen
content (e.g., cyclics, alkenes, and dialkenes) could be preferred because the
reaction endotherm
is reduced and thermodynamic constraints on conversion are improved, non-
saturates are more
expensive than saturate feedstock. Linear hydrocarbon skeletal structure is
preferred over
branched hydrocarbon skeletal structures due to both reaction chemistry and
the lower value of
linear hydrocarbon relative to branched hydrocarbon (due to octane
differences). Further, an
abundance of hydrocarbons, such as CS hydrocarbons, are available from
unconventional gas and
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shale oil, as well as reduced use in motor fuels due to stringent
environmental regulations.
Various hydrocarbon feedstocks, such as C5 feedstock, may also be derived from
bio-feeds.
Various catalytic dehydrogenation technologies are currently used to produce
mono- and
di-olefins from C3 and C4 alkanes, but not cyclic mono-olefins or cyclic di-
olefins. A typical
process uses Pt/Sn supported on alumina as the active catalyst. Another useful
process uses
chromia on alumina. See, B. V. Vora, "Development of Dehydrogenation Catalysts
and
Processes," Topics in Catalysis, vol. 55, pp. 1297-1308, 2012; and J. C.
Bricker, "Advanced
Catalytic Dehydrogenation Technologies for Production of Olefins," Topics in
Catalysis, vol.
55, pp. 1309-1314, 2012.
Still another common process uses Pt/Sn supported on Zn and/or Ca aluminate to
dehydrogenate propane. While these processes are successful in dehydrogenating
alkanes, they
do not perform cyclization, which is critical to producing CPD. Pt-Sn/alumina
and Pt-
Sn/aluminate catalysts exhibit moderate conversion of n-pentane, but such
catalyst have poor
selectivity and yield to cyclic C5 products.
Pt supported on chlorided alumina catalysts are used to reform low octane
naphtha to
aromatics such as benzene and toluene. See, US 3,953,368 (Sinfelt),
"Polymetallic Cluster
Compositions Useful as Hydrocarbon Conversion Catalysts." While these
catalysts are effective
in dehydrogenating and cyclizing C6 and higher alkanes to form C6 aromatic
rings, they are less
effective in converting acyclic C5s to cyclic C5s. These Pt supported on
chlorided alumina
catalysts exhibit low yields of cyclic C5 and exhibit deactivation within the
first two hours of
time on stream. Cyclization of C6 and C7 alkanes is aided by the formation of
an aromatic ring,
which does not occur in Cs cyclization. This effect may he due in part to the
much higher heat
of formation for CPD, a cyclic C5, as compared to benzene, a cyclic C6, and
toluene, a cyclic C7.
This is also exhibited by Pt/Ir and Pt/Sn supported on chlorided alumina.
Although these
alumina catalysts perform both dehydrogenation and cyclization of C6+ species
to form C6
aromatic rings, a different catalyst will be needed to convert acyclic C5 to
cyclic C5.
Ga-containing ZSM-5 catalysts are used in a process to produce aromatics from
light
paraffins. A study by Kanazirev et al. showed n-pentane is readily converted
over Ga203/H-
ZSM-5. See Kanazirev Price et al., "Conversion of C8 aromatics and n-pentane
over Ga203/H-
ZSM-5 mechanically mixed catalysts," Catalysis Letters, vol. 9, pp. 35-42,
1991. No production
of cyclic C5 was reported while upwards of 6 wt% aromatics were produced at
440 C and 1.8
hr-1 YVHSV. Mo/ZSM-5 catalysts have also been shown to dehydrogenate and/or
cyclize
paraffins, especially methane. See, Y. Xu, S. Liu, X. Guo, L. Wang, and M.
Xie, "Methane
activation without using oxidants over Mo/HZSM-5 zeolite catalysts," Catalysis
Letters, vol. 30,
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pp. 135-149, 1994. High conversion of n-pentane using Mo/ZSM-5 was
demonstrated with no
production of cyclic Cs and high yield to cracking products. This shows that
ZSM-5-based
catalysts can convert paraffins to a C6 ring, but not necessarily to produce a
Cs ring.
U.S. Patent No. 5,254,787 (Dessau) introduced the NU-87 catalyst used in the
dehydrogenation of paraffins. This catalyst was shown to dehydrogenate C2-C6+
to produce their
unsaturated analogs. A distinction between C2_5 and C6+ alkanes was made
explicit in this patent:
dehydrogenation of C2-5 alkanes produced linear or branched mono-olefins or di-
olefins, whereas
dehydrogenation of C6+ alkanes yielded aromatics. U.S. Patent No. 5,192.728
(Dessau) involves
similar chemistry, but with a tin-containing crystalline microporous material.
As with the NU-
87 catalyst, Cs dehydrogenation was only shown to produce linear or branched,
mono-olefins or
di-olefins and not CPD.
U.S. Patent No. 5,284,986 (Dessau) introduced a dual-stage process for the
production
of cyclopentane and cyclopentene from n-pentane. An example was conducted
wherein the first
stage involved dehydrogenation and dehydrocyclization of n-pentane to a mix of
paraffins,
mono-olefins and di-olefins, and naphthenes over a Pt/Sn-ZSM-5 catalyst. This
mixture was
then introduced to a second-stage reactor consisting of Pd/Sn-ZSM-5 catalyst
where dienes,
especially CPD, were converted to olefins and saturates. Cyclopentene was the
desired product
in this process, whereas CPD was an unwanted byproduct.
U.S. Patent Nos. 2,438,398; 2,438,399; 2.438,400; 2,438,401; 2,438,402;
2,438,403; and 2,438,404 (Kennedy) disclosed production of CPD from 1,3-
pentadiene over
various catalysts. Low operating pressures, low per pass conversion, and low
selectivity make
this process undesirable. Additionally, 1,3-pentadiene is not a readily
available feedstock, unlike
n-pentane. See also, Kennedy et al., "Formation of Cyclopentadiene from 1,3-
Pentadiene,"
Industrial & Engineering Chemistry, vol. 42, pp. 547-552, 1950.
Fel'dblyum et al. in "Cyclization and dehydrocyclization of CS hydrocarbons
over
platinum nanocatalysts and in the presence of hydrogen sulfide," Doklady
Chemistry, vol. 424,
pp. 27-30, 2009, reported production of CPD from 1,3-pentadiene, n-pentene,
and an n-pentane.
Yields to CPD were as high as 53%, 35%, and 21% for the conversion of 1,3-
pentadiene, n-
pentene, and an n-pentane respectively at 600 C on 2%Pt/Si02. While initial
production of CPD
was observed, drastic catalyst deactivation within the first minutes of the
reaction was observed.
Experiments conducted on Pt-containing silica show moderate conversion of n-
pentane over Pt-
Sn/Si02, but with poor selectivity and yield to cyclic 0 products. The use of
H2S as a 1.3-
pentadiene cyclization promoter was presented by Fel'dblyum, infra, as well as
in
Marcinkowski, "Isomerization and Dehydrogenation of 1,3-Pentadiene," M.S.,
University of
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Central Florida, 1977. Marcinkowski showed 80% conversion of 1,3,-pentadiene
with 80%
selectivity to CPD with H2S at 700 C. High temperature, limited feedstock, and
potential of
products containing sulfur that would later need scrubbing make this process
undesirable.
Lopez et al. in "n-Pentane Hydroisomerization on Pt Containing HZSM-5, HBEA,
and
SAPO-11," Catalysis Letters, vol. 122. pp. 267-273, 2008, studied reactions of
n-pentane on Pt-
containing zeolites including H-ZSM-5. At intermediate temperatures (250 C-400
C), they
reported efficient hydroisomerization of n-pentane on the Pt-zeolites with no
discussion of
cyclopentene formation. It is desirable to avoid this deleterious chemistry as
branched C5 do not
produce cyclic C5 as efficiently as linear C5, as discussed above.
Li et al. in "Catalytic dehydroisomerization of n-alkanes to isoalkenes,"
Journal of
Catalysis, vol. 255, pp. 134-137, 2008, also studied n-pentane dehydrogenation
on Pt-containing
zeolites in which Al had been isomorphically substituted with Fe. These
Pt/IFelZSM-5 catalysts
were efficient dehydrogenating and isomerizing n-pentane, but under the
reaction conditions
used, no cyclic C5 were produced and undesirable skeletal isomerization
occurred.
U.S. Patent No. 5,633,421 discloses a process for dehydrogenating C2-05
paraffins to
obtain corresponding olefins. Similarly, U.S. Patent No. 2,982,798 discloses a
process for
dehydrogenating an aliphatic hydrocarbon containing 3 to 6, inclusive, carbon
atoms. However,
neither U.S. Patent No. 5,633,421 nor U.S. Patent No. 2,982,798 disclose
production of CPD
from acyclic Cs hydrocarbons, which are desirable as feedstock because they
are plentiful and
low cost.
Further, on-purpose production of CPD, propylene, ethylene, and benzene is
accomplished via endothermic reactions. Engineering process and reactor design
for catalyst
driven endothermic reactions present many challenges. For example, maintaining
high
temperatures required for the reactions, including transferring a large amount
of heat to a
catalyst, can be difficult. Production of CPD is especially difficult amongst
endothermic
processes because it is favored by low pressure and high temperature, but
competing reactions
such as cracking of n-pentane and other C5 hydrocarbons can occur at
relatively low temperature
(e.g., 450 C-500 C).
Additional challenges may include loss of catalyst activity due to coking
during the
process and further processing needed to remove coke from the catalyst, and
the inability to use
oxygen-containing gas to directly provide the heat input necessary to counter
the endothermic
nature of the reaction without damaging the catalyst. Moreover, non-uniform
catalyst aging can
also occur, which can impact resulting product selectivity and catalyst life.
Furthermore, challenges exist in reactor design, especially with respect to
material
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selection, since the reactions are carried out at higher temperatures and
highly carburizing
conditions. Metal alloys can potentially undergo carburization (resulting in
loss in mechanical
properties) as well as metal dusting (resulting in loss of metal via formation
of metastable
carbides) under the desired reaction conditions. Thus, given the need for
large heat input to drive
the reaction, metallic heat-transfer surfaces exposed to the reaction mixture
need to be capable
of resisting attack via carburization/metal dusting.
Hence, there remains a need for a process to convert acyclic hydrocarbons to
alkenes,
cyclic hydrocarbons and aromatics, particularly acyclic CS hydrocarbon to CPD,
preferably at
commercial rates and conditions. Further, there is a need for a catalytic
process targeted for the
production of CPD, which generates CPD in high yield from plentiful C5
feedstocks without
excessive production of C4- cracked products and with acceptable catalyst
aging properties.
Additionally, there is a need for processes and systems for on-purpose
production of CPD,
propylene, ethylene, and benzene from acyclic hydrocarbons, which addresses
the above-
described challenges.
SUMMARY OF THE INVENTION
In one aspect, this invention relates to a process for converting acyclic
hydrocarbons to
alkenes, cyclic hydrocarbons and/or aromatics in a reactor system, wherein the
process
comprises: contacting a feedstock comprising acyclic hydrocarbons and
optionally hydrogen
with a catalyst material in at least one reaction zone under reaction
conditions to convert at least
a portion of the acyclic hydrocarbons to a first effluent comprising alkenes,
cyclic hydrocarbons
and/or aromatics, wherein the feedstock enters the at least one reaction zone
at a temperature of
300 C to 700 C; and providing a co-feed comprising hydrogen, alkanes (e.g., Ci-
C) alkanes)
and/or alkenes (e.g., C1 -C4 alkenes) at a temperature of 600 C to 1100 C to
heat the at least one
reaction zone, wherein the feedstock and the co-feed are provided to the at
least one reaction
zone at different locations via different inlets. The feedstock and the co-
feed may be provided
to the at least one reaction zone simultaneously or not. Preferably, the
feedstock and the co-feed
are provided to the at least one reaction zone simultaneously.
In another aspect, this invention also relates to a reaction system for
converting acyclic
hydrocarbons to alkenes, cyclic hydrocarbons and/or aromatics, wherein the
reaction system
comprises a feedstock stream comprising acyclic hydrocarbons and optionally
hydrogen having
a temperature of 300 C to 700 C; a co-feed stream comprising hydrogen, alkanes
(e.g., Ci-C4
alkanes) and/or alkenes (e.g., C1-C4 alkenes) having a temperature of 600 C to
1100 C; an
effluent stream comprising alkenes, cyclic hydrocarbons and/or aromatics; a
separated catalyst
material stream; and a substantially catalyst-free effluent stream; at least
one reactor operated
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under reaction conditions to convert at least a portion of the acyclic
hydrocarbons to alkenes,
cyclic hydrocarbons and/or aromatics, wherein the at least one reactor
comprises: a feedstock
stream inlet; a co-feed stream inlet; a catalyst material stream inlet; and an
effluent stream outlet;
and a separator for separating catalyst material from the effluent stream to
produce the separated
.. catalyst material stream and the second effluent stream, wherein the
separator is in fluid
connection with the at least one reactor and comprises an effluent stream
inlet, a separated
catalyst material stream outlet and a substantially catalyst-free effluent
stream outlet.
BRIEF DESCRIPTION OF THE FIGURES
The Figure is a diagram of a reactor system according to an embodiment of the
invention.
DETAILED DESCRIPTION OF THE INVENTION
All numerical values within the detailed description and the claims herein are
modified
by "about" or "approximately" the indicated value, and take into account
experimental error and
variations that would be expected by a person having ordinary skill in the
art. Unless otherwise
indicated, room temperature is 23 C.
.. I. Definitions
To facilitate an understanding of the present invention, a number of terms and
phrases
are defined below.
As used in the present disclosure and claims, the singular forms "a," "an,"
and "the"
include plural forms unless the context clearly dictates otherwise.
The term "and/or" as used in a phrase such as "A and/or B" herein is intended
to include
"A and B," "A or B," "A", and "B."
As used herein, the term "about" refers to a range of values of plus or minus
10% of a
specified value. For example, the phrase "200" includes plus or minus 10% of
200, or from 180
to 220.
The term "hydrocarbon" means a class of compounds containing hydrogen bound 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. The
term "Cr,"
means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a
positive integer.
As used herein, the term "light hydrocarbon" means light paraffinic and/or
olefinic
hydrocarbons comprised substantially of hydrogen and carbon only and has one
to no more
than 4 carbon atoms.
The term "saturates" includes, hut is not limited to, alkanes and
cycloalkanes.
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The term "non-saturates" includes, but is not limited to, alkenes, dialkenes,
alkynes,
cyclo-alkenes, and cyclo-dialkenes.
The term "cyclic hydrocarbon" denotes groups such as the cyclopropane,
cyclopropene,
cyclobutane, cyclobutadiene etc., and substituted analogues of these
structures. These cyclic
hydrocarbons can be single- or multi-ring structures. Preferably, the term
"cyclic hydrocarbon"
refers to non-aromatics.
The term "cyclics 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
dicyclopentadiene via DieIs-
Alder condensation over a range of conditions, including ambient temperature
and pressure.
The term "acyclics" includes, but is not limited to, linear and branched
saturates and non-
saturates.
The term "alkane" refers to non-aromatic saturated hydrocarbons with the
general
formula C1f1(2,2), where n is 1 or greater. An alkane may be straight chained
or branched.
Examples of alkanes include, but are not limited to methane, ethane, propane,
butane, pentane,
hexane, heptane and octane. "Alkane" is intended to embrace all structural
isomeric forms of an
alkane. For example, butane encompasses n- butane and isobutane; pentane
encompasses n-
pentane, isopentane and neopentane.
The term "alkene," alternatively referred to as "olefin," refers to a branched
or
unbranched unsaturated hydrocarbon having one or more carbon-carbon double
bonds. A simple
alkene comprises the general formula C.H2, where n is 2 or greater. Examples
of alkenes
include, but are not limited to ethylene, propylene, butylene, pentene, hexene
and heptene.
"Alkene" is intended to embrace all structural isomeric forms of an alkene.
For example,
butylene encompasses but-I -ene, (Z)-but-2-ene, etc.
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 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 naphthalene, anthracene, chrysene,
and their
alkylated versions.
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The term "BTX" includes, but is not limited to, a mixture of benzene, toluene,
and xylene
(ortho and/or meta and/or para).
The term "coke" includes, but is not limited to, a low hydrogen content
hydrocarbon that
is adsorbed on the catalyst composition.
The term "Cn+" means hydrocarbon(s) having at least n carbon atom(s) per
molecule.
The term "Cn_" means hydrocarbon(s) having no more than n carbon atom(s) per
molecule.
The term "C5 feedstock" includes a feedstock containing n-pentane, such as a
feedstock
which is predominately normal pentane and isopentane (also referred to as
methylbutane), with
smaller fractions of cyclopentane and neopentane (also referred to as 2,2-
dimethylpropane).
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.
The term "Group 10 metal" means an element in Group 10 of the Periodic Table
and
includes, but is not limited to, Ni, Pd, and Pt, and a mixture of two or more
thereof.
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.
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.
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.
The term "rare earth metal" means an element in the Lanthanide series of the
Periodic
Table, as well as scandium and yttrium. The term rare earth metal includes,
but is not limited to,
lanthanum, praseodymium, neodymium, cerium, yttrium, and a mixture of two or
more thereof.
The term "oxygen" includes air, 02, H20, CO, and CO2.
The term "constraint index" is defined in US 3,972,832 and US 4,016,218.
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
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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 of 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.
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.
As used herein, the term "molecular sieve" is used synonymously with the term
"microporous crystalline material" or "zeolite."
As used herein, the term "selectivity" means the moles of carbon in the
respective cyclic
C5, CPD, Ci, and C2_4 formed divided by total moles of carbon in the pentane
converted. For
example, the term "carbon selectivity to cyclic C5 of at least 30%" means that
at least 30 moles of
carbon in the cyclic C5 is formed per 100 moles of carbon in the pentane
converted.
As used herein, the term "conversion" means the moles of carbon in the acyclic
C5
feedstock that is converted to a product. The phrase "a conversion of at least
70% of said acyclic
C5 feedstock to said product" means that at least 70% of the moles of said
acyclic C5 feedstock
was converted to a product.
As used herein, the term "Alpha Value" is used as a measure of the cracking
activity of a
catalyst and is described in U.S. Patent No. 3,354,078 and in the Journal of
Catalysis, Vol. 4, p.
527 (1965); Vol. 6, p. 278, (1966) and Vol. 61, p. 395, (1980). The
experimental conditions of
the test used herein included a constant temperature of 538 C and a variable
flow rate as described
in detail in the Journal of Catalysis, Vol. 61, p. 395, (1980).
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As used herein, the term "reactor system" refers to a system including one or
more reactors
and all necessary and optional equipment used in the production of
cyclopentadiene.
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, reactions 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 vessel having first and
second reaction zones.
Likewise, a first reactor 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.
A reactor/reaction zone may be an adiabatic reactor/reaction zone or a
diabatic
reactor/reaction zone. As used herein, the term "adiabatic" refers to a
reaction zone for which
there is essentially no heat input into the system other than by a flowing
process fluid. A reaction
zone that has unavoidable losses due to conduction and/or radiation may also
be considered
adiabatic for the purpose of this invention. As used herein, the term
"diabatic" refers to a
reactor/reaction zone to which heat is supplied by a means in addition to that
provided by the
flowing process fluid.
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<Umf), bubbling
regime
(Umf<U<Umb), slugging regime (Umb<U<Uc), transition to and turbulent
fluidization regime
(Uc<U<Utr), and fast-fluidization regime (U>Utr), where Umf is minimum
fluidizing velocity,
Umb is minimum bubbling velocity, Uc is the velocity at which fluctuation in
pressure peaks, and
tr 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.
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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,
2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6
of Chemical
Process Equipment, Revised 2nd 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.
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 velocity Umf)
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, 2nd
Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S. M., Chapter 6 of
Chemical
Process Equipment, Revised 2nd Edition, Butterworth-Heinemann, Boston, 2010. A
fluidized
bed reactor may be a moving fluidized bed reactor, 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. Additionally,
a fluidized bed reactor may be a "captive fluidized bed reactor" wherein
solids (e.g., catalyst
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material) may circulate between reaction zones but are not circulated, on a
continuous flow basis,
between the reactor and a separate vessel (e.g., to perform re-heating and/or
regeneration).
Solids (e.g., catalyst material) may be withdrawn from the reactor and
returned (along with any
fresh solids addition) to the reactor after batchwise regeneration performed
in a separate vessel.
Also, presence of an external cyclone (or any similar device to separate
solids from the reactor
effluent stream) and its return standpipe is considered part of the captive
fluidized bed reactor,
i.e., does not constitute a separate vessel for the purpose of defining a
captive fluidized bed
reactor.
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 (Utr). Fast fluidization
and pneumatic
conveying fluidization regimes are also described in 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 21'd Edition, Butterworth-
Heinemann,
Boston, 2010. A fluidized bed reactor, such as a circulating fluidized bed
reactor, may be
operated as a riser reactor. "Average diameter" for particles in the range of
1 to 3500 um is
determined using a Mastersizeri m 3000 available from Malvern Instruments,
Ltd.,
Worcestershire, England. Unless otherwise stated, particle size is determined
at D50. D50 is
the value of the particle diameter at 50% in the cumulative distribution. For
example, if D50=5.8
urn, then 50% of the particles in the sample are equal to or larger than 5.8
urn and 50% are
smaller than 5.8 um. (In contrast, if D90=5.8 um, then 10% of the particles in
the sample are
larger than 5.8 urn and 90% are smaller than 5.8 urn.) "Average diameter" for
particles in the
range of 3 mm to 50 mm is determined using a micrometer on a representative
sample of 100
particles.
For purposes of the invention, 1 psi is equivalent to 6.895 kPa. Particularly.
1 psia is
equivalent to 1 kPa absolute (kPa-a). Likewise, 1 psig is equivalent to 6.895
kPa gauge (kPa-g).
II. Acyclic Hydrocarbon Conversion Process
In a first aspect, this invention relates to a process for converting acyclic
hydrocarbons
to alkenes, cyclic hydrocarbons and/or aromatics in a reactor system. The
process may comprise
contacting a feedstock comprising acyclic hydrocarbons and optionally hydrogen
with a catalyst
material in at least one reaction zone under reaction conditions to convert at
least a portion of
the acyclic hydrocarbons to a first effluent comprising alkenes, cyclic
hydrocarbons and/or
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aromatics and providing a co-feed comprising hydrogen, alkanes (e.g., CI¨C4
alkanes) and/or
alkenes (e.g., Ci¨C4 alkenes) at a temperature of 600 C to 1100 C to heat the
at least one reaction
zone. In various aspects, the feedstock enters the at least one reaction zone
at a temperature of
300 C to 700 C. Additionally, the feedstock and the co-feed may be provided to
the at least one
reaction zone at different locations via different inlets.
In one or more embodiments, this invention relates to a process for conversion
of an
acyclic C5 feedstock to a product comprising cyclic CS compounds (e.g.,
cyclopentadiene). The
process comprises contacting said 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, and providing a co-feed
as described herein
to form said product.
In one or more embodiments, the product of the process for conversion of an
acyclic Cs
feedstock comprises cyclic C5 compounds. The cyclic Cs compounds comprise one
or more of
cyclopentane, cyclopentene, cyclopentadiene, and includes mixtures thereof. In
one or more
embodiments, the cyclic C5 compounds comprise at least 20 wt%, or 30 wt%, or
40 wt%, or 70
wt% cyclopentadiene, or in the range of from 10 wt% to 80 wt%, alternately 20
wt% to 70 wt%.
In one or more embodiments, the acyclic C5 conversion conditions include at
least a
temperature, an n-pentane partial pressure, and a weight hourly space velocity
(WHSV). The
temperature is in the range of 400 C to 700 C, or in the range from 450 C to
650 C, preferably,
in the range from 500 C to 600 C. The n-pentane partial pressure is in the
range of 3 to 100 psia
at the reactor inlet, or in the range from 3 to 50 psia, preferably, in the
range from 3 psia to 20
psia. The weight hourly space velocity is in the range from 1 to 50 hr1, or in
the range from I
to 20 hr-1. Such conditions include a molar ratio of the optional hydrogen co-
feed to the acyclic
C5 feedstock in the range of 0 to 3, or in the range from 1 to 2. Such
conditions may also include
co-feed Ci ¨ C4 hydrocarbons with the acyclic C5 feed.
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 ratio 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, and providing a co-feed as described herein to form cyclopentadiene
at a temperature of
400 C to 700 C, an n-pentane partial pressure of 3 to 100 psia at the reactor
inlet, and a weight
hourly space velocity of 1 to 50 hr-1.
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A. Feedstock and Co-Feed
In the process, a feedstock comprising acyclic hydrocarbons, preferably
acyclic C/¨Cio
hydrocarbons are provided to a reactor system comprising a catalyst material
and an inert
material. Acyclic C2¨Cio hydrocarbons include, but are not limited to alkanes
(e.g., ethane,
propane, butane, pentane, hexane, etc.), alkenes (e.g., ethylene, propylene,
butylene, etc.),
alkynes (e.g., ethyne, propyne, 1-butyne, 2-butyne, etc.). dialkenes (e.g.,
1,2-propadiene, 1,3-
butadiene, 1,3-pentadiene, etc.) and combinations thereof. An acyclic C2¨C10
hydrocarbon
feedstock, useful herein, is obtainable from crude oil or natural gas
condensate. Optionally,
hydrogen may be present in the feedstock as well. The molar ratio of optional
hydrogen to
.. acyclic hydrocarbon is preferably between 0 to 3, or in the range of 1 to
2. Hydrogen may be
included in the feedstock in order to minimize production of coke material on
the particulate
material and/or to fluidize the particulate material in the at least one
reaction zone.
Preferably, in one or more embodiments, the acyclic C5 feedstock comprises at
least 50
wt%, or 60 wt%, or 75 wt%, or 90 wt% acyclic hydrocarbons, or in the range
from 50 wt% to
100 wt% n-pentane. Preferably, an amount of the acyclic hydrocarbons in the
feedstock
converted to alkenes (e.g., propylene), cyclic hydrocarbons (e.g.,
cyclopentadiene) and/or
aromatics (e.g., benzene) is > 5.0 wt%, > 10.0 wt%, > 20.0 wt%, > 30.0 wt%, >
40.0 wt%, > 50.0
wt%, > 60.0 wt%, > 70.0 wt%, > 80.0 wt%, or > 90.0 wt%.
In various aspects, the feedstock may preferably be an acyclic C5 feedstock
and can
include cracked Cs (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.
In one or more embodiments, the acyclic C5 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 acyclic C5 feedstock comprises at
least 50 wt%, or
60 wt%, or 75 wt%, or 90 wt% n-pentane, or in the range from 50 wt% to 100 wt%
n-pentane.
The acyclic hydrocarbon feedstock optionally does not comprise C6 aromatic
compounds, such as benzene. Preferably, C6 aromatic compounds are present at
less than 5 wt%,
preferably less than 1 wt%, preferably less than 0.01 wt%, and preferably at
zero wt%.
Additionally, or alternatively, the acyclic hydrocarbon feedstock optionally
does not comprise
benzene, toluene, or xylene (ortho, meta, or para). Preferably, any benzene,
toluene, or xylene
(ortho, meta, or para) compounds are present at less than 5 wt%, preferably
less than 1 wt%,
preferably less than 0.01 wt%, and preferably at zero wt%.
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The acyclic hydrocarbon feedstock optionally does not comprise C6+ aromatic
compounds. Preferably. Co.. aromatic compounds are present at less than 5 wt%,
preferably less
than 1 wt%, preferably less than 0.01 wt%, and preferably at zero wt%.
Preferably, an amount of the Cs hydrocarbons (e.g., acyclic C5 hydrocarbons)
in the
feedstock converted to cyclopentadiene is > 5.0 wt%, > 10.0 wt%, > 20.0 wt%, >
30.0 wt%, >
40.0 wt%, > 50.0 wt%, > 60.0 wt%, > 70.0 wt%. > 80.0 wt%, or? 90.0 wt%.
Preferably, at least
30.0 wt% or at least 60.0 wt% of the C hydrocarbons (e.g., acyclic CS
hydrocarbons) is
converted to cyclopentadiene. Ranges expressly disclosed include combinations
of any of the
above-enumerated values; e.g., 5.0% to 90.0 wt%, 10.0 wt% to 80.0 wt%, 20.0
wt% to 70.0 wt%,
20.0 wt% to 60.0 wt%, etc. Preferably, 20.0 wt% to 90.0 wt% of the C5
hydrocarbons (e.g.,
acyclic C5 hydrocarbons) is converted to cyclopentadiene, more preferably 30.0
wt% to 85.0
wt%, more preferably 40.0 wt% to 80.0 wt%, more preferably 45.0 wt% to 75.0
wt%, and more
preferably 50.0 wt% to 70.0 wt%.
In various aspects, a co-feed comprising hydrogen and/or light hydrocarbons,
such as
Ci-C8 hydrocarbons, preferably Ci-C4 hydrocarbons, such as C1-C4 alkenes
and/or C1-C4
alkanes, are also fed into the at least one reaction zone (discussed herein).
In one or more
embodiments, the co-feed comprises at least 50 wt%, or 60 wt%, or 75 wt%, or
90 wt%
hydrogen, or in the range from 50 wt% to 100 wt% hydrogen. In one or more
embodiments, the
co-feed comprises at least 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% light
hydrocarbons, or in
the range from 50 wt% to 100 wt% light hydrocarbons. In a particular
embodiment, the co-feed
may comprise hydrogen, ethane, methane and/or a mixture of ethane and
ethylene. Preferably,
the feedstock and co-feed are substantially free of oxygen, e.g., less than
1.0 wt%, less than 0.1
wt%, less than 0.01 wt%, less than 0.001 wt%, less than 0.0001 wt%, less than
0.00001 wt%,
etc. Additionally, the feedstock and the co-feed may be provided to the at
least one reaction
zone at different locations via different inlets. Additionally, the feedstock
and the co-feed may
be provided to the at least one reaction zone simultaneously or not,
preferably simultaneously.
It is contemplated herein that co-feed and the feedstock are provided to the
at least one reaction
zone in different horizontal and/or vertical planes. For example, the co-feed
may be provided to
the at least one reaction zone at a lower position in the at least one
reaction zone with respect to
where the feedstock is provided, i.e., the feedstock may be provided to the at
least one reaction
zone at a position above (or higher than) where the co-feed is provided. In
such instances, the
co-feed and the feedstock may be provided to the at least one reaction zone at
different horizontal
planes, preferably where the co-feed is provided at a horizontal plane at a
lower position in the
at least one reaction zone with respect to horizontal plane where the
feedstock is provided, and
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optionally, the co-feed and the feedstock may be provided along the same or
different vertical
plane. Alternatively, the co-feed may be provided to the at least one reaction
zone at a position
above (or higher than) where the feedstock is provided in the at least one
reaction zone. In such
instances, the co-feed and the feedstock may be provided to the at least one
reaction zone at
different horizontal planes, preferably where the co-feed is provided at a
horizontal plane above
(or higher than) a horizontal plane where the feedstock is provided, and
optionally, the co-feed
and the feedstock may be provided along the same or different vertical plane.
Additionally, it is
contemplated herein that the feedstock and the co-feed may be provided to the
at least one
reaction zone at substantially the same locations via the same or different
inlet. Hydrogen may
.. be provided to the reactor via the feedstock, the co-feed, or a combination
of both. Preferably,
hydrogen is included in both the feedstock and the co-feed. The presence of
hydrogen in the feed
mixture at or near the inlet location, where the feed first comes into contact
with the catalyst,
can prevent or reduce the formation of coke on the catalyst particles.
Additionally, the presence
of hydrogen in the co-feed can prevent or reduce the formation of coke in co-
feed pre-heating
furnaces.
B. Reaction Zone
The feedstock is fed into a reactor system and contacted with a catalyst
material in at
least one reaction zone under reaction conditions to convert at least a
portion of the acyclic
hydrocarbons (e.g., acyclic C5 hydrocarbons) to a first effluent comprising
alkenes (e.g.,
propylene), cyclic hydrocarbons (e.g., cyclopentadiene) and/or aromatics
(e.g., benzene). For
example, The at least one reaction zone may be a circulating fluidized bed
reactor or a captive
fluidized bed reactor. The circulating fluidized bed reactor may be operated
in a bubbling or
turbulent fluidization regime; and a fast fluidization or transport regime,
both as described in
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. Additionally, or
alternatively, the at least
one reaction zone is not a radial-flow reactor or a cross-flow reactor.
Additionally, or alternatively, the at least one reaction zone may comprise at
least a first
reaction zone, a second reaction zone, a third reaction zone, a fourth
reaction zone, a fifth
reaction zone, a sixth reaction zone, a seventh reaction zone, and/or an
eighth reaction zone, etc.
As understood herein, each reaction zone may be an individual reactor or a
reactor may comprise
one or more of the reaction zones. Preferably, the reactor system includes 1
to 20 reaction zones,
more preferably 1 to 15 reaction zones, more preferably 2 to 10 reaction
zones, more preferably
2 to 8 reaction zones. Where the at least one reaction zone includes a first
and a second reaction
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zone, the reaction zones may be arranged in any suitable configuration,
preferably in series.
Each reaction zone independently may be a circulating fluidized bed or a
captive fluidized bed,
preferably each reaction zone is a captive fluidized bed. Additionally, or
alternatively, the
process described herein may further comprise moving a bulk of a partially
converted feedstock
from the first reaction zone to the second reaction zone and/or moving a bulk
of a particulate
material (e.g., catalyst material and/or inert material) from the second
reaction zone to the first
reaction zone. As used herein, "bulk" refers to at least a majority portion of
the partially
converted feedstock and the particulate material, e.g., portions of at least
50.0 wt%, at least 60.0
wt%, at least 70.0 wt%, at least 80.0 wt%, at least 90.0 wt%, at least 95.0
wt%, at least 99.0 wt%,
and 100.0 wt%.
Preferably, the at least one reaction zone may include at least one internal
structure,
preferably a plurality of internal structures (e.g., 2, 3, 4, 5, 6, 7, 8, 9,
10, 15, 20, 30, 40, 50, etc.)
to influence a velocity vector of the particulate material and/or gas flow.
Further, the internal
structure(s) can ensure movement of particulate material while minimizing the
degree of gas
back-mixing. Particularly, the at least one reaction zone may include a
plurality of internal
structures. Examples of suitable internal structures include a plurality of
baffles, sheds, trays,
tubes, tube bundles, tube coils, rods, and/or distributors.
The at least one reaction zone is operated under reaction conditions
sufficient to convert
at least a portion of the acyclic hydrocarbons feedstock, preferably acyclic
C5 hydrocarbons, to
a first effluent comprising alkene, cyclic hydrocarbons, and aromatics,
preferably
cyclopentadiene. Preferably, the feedstock (e.g., acyclic hydrocarbons) and/or
co-feed may be
fed to the reaction system at a weight hourly space velocity (WHSV, mass of
acyclic
hydrocarbons/mass of catalyst/hour) in the range of from 1.0 to 1000.0 hr-1.
The WHSV may be
1.0 to 900.0 hr, 1.0 to 800.0 hr-1, 1.0 to 700.0 hr-1, 1.0 to 600.0 hr', 1.0
to 500.0 hr-1, 1.0 to
.. 400.0 hr-1, 1.0 to 300.0 hr-', 1.0 to 200.0 hr', 1.0 to 100.0 hr', 1.0 to
90.0 hr', 1.0 to 80.0 hr-1,
1.0 to 70.0 hr-1, 1.0 to 60.0 hr-1, 1.0 to 50.0 1.0 to
40.0 hr-1, 1.0 to 30.0 hr', 1.0 to 20.0 hr',
1.0 to 10.0 hr, 1.0 to 5.0 , 2.0
to 1000.0 hr-1, 2.0 to 900.0 hr-1, 2.0 to 800.0 hr-1, 2.0 to 700.0
hr-1, 2.0 to 600.0 hr, 2.0 to 500.0 hr', 2.0 to 400.0 hr', 2.0 to 300.0 hr-1,
2.0 to 200.0 hr-1, 2.0
to 100.0 hr', 2.0 to 90.0 hr-1, 2.0 to 80.0 hr, 2.0 to 70.0 hr-1, 2.0 to 60.0
hr-1, 2.0 to 50.0 hr',
2.0 to 40.0 hr, 2.0 to 30.0 hrl, 2.0 to 20.0 hrl, 2.0 to 10.0 hr', and 2.0 to
5.0 hr-1. Preferably,
the WHSV is 1.0 to 100.0 hr-1, more preferably 1.0 to 60.0 hr-1, more
preferably 2.0 to 40.0 hr-1,
more preferably 2.0 to 20.0 hr-1.
As discussed above, on-purpose production of CPD, propylene, ethylene, and
benzene is
accomplished via endothermic reactions, which present various challenges, such
as maintaining
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high temperatures required for the reactions including transferring a large
amount of heat to a
catalyst). Advantageously, by pre-heating the co-feed via any suitable means,
for example a
furnace, such as a fired-tube furnace, the heated co-feed may provide the
endothermic heat of
reaction for the conversion process within the at least one reaction zone. In
various aspects, the
co-feed may contact the catalyst present in the at least one reaction zone and
heat the catalyst,
for example, where the co-feed is provided to the at least one reaction zone
at a position lower
than where the feedstock is provided. Thus, as the feedstock is provided to
the at least one
reaction zone, the feedstock may contact the heated catalyst and at least a
portion of the acyclic
hydrocarbons may be converted to alkenes, cyclic hydrocarbons and/or
aromatics. Direct mixing
or contacting of the heated co-feed and the acyclic feedstock, if both were to
be fed using the
same inlet of the reactor zone, would result in excessive thermal cracking of
acyclic
hydrocarbon(s) and formation of non-selective (C1-C4) light gases.
In particular, the co-feed provided to the at least one reaction may provide >
10%, > 20%,
>25%, >30%, > 35%, >40% > 45%, > 50%, >55%, >60%, >65%, >70%, >75%, > 80%,>
.. 85%, > 90%, > 95%, or 100% of the required heat for converting at least a
portion of the acyclic
hydrocarbons to the first effluent comprising alkenes, cyclic hydrocarbons
and/or aromatics,
particularly converting acyclic C5 hydrocarbons to cyclopentadiene. In
particular, the co-feed
may provide > 25% of the required heat for converting at least a portion of
the acyclic C5
hydrocarbons to the first effluent comprising cyclopentadiene. Ranges
expressly disclosed
include combinations of any of the above-enumerated values; e.g., 20% to 100%,
40% to 95%,
50% to 90%, etc. Preferably, the co-feed may provide 20% to 100% of the
required heat, more
preferably 40% to 100% of the required heat, or more preferably 50% to 100% of
the required
heat.
In various aspects, following heating, the co-feed may enter the at least one
reaction zone
at a temperature of > 450 C, > 500 C, > 550 C, > 600 C, > 650 C, > 700 C, >
750 C, > 800 C,
> 850 C, > 900 C, > 950 C,> 1000 C,> 1050 C,> 1100 C,> 1150 C,> 1200 C,> 1250
C,>
or 1300 C. Preferably, the co-feed may enter the at least one reaction zone at
a temperature of >
600 C, more preferably > 750 C, or more preferably > 900 C. Ranges of
temperatures expressly
disclosed include combinations of any of the above-enumerated values, e.g.,
450 C to 1500 C,
550 C to 1400 C, 600 C to 1250 C, 700 C to 1150 C, etc. Preferably, the
temperature of the
co-feed entering the reaction system is 550 C to 1150 C more preferably
600 C to 1100 C, more
preferably 650 C to 1050 C, and more preferably 700 C to 1000 C.
Thus, the feedstock may be heated to a lower temperature than the co-feed to
avoid
cracking in the feed and coking of the catalyst. Thus, the temperature of the
feedstock (e.g.,
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acyclic hydrocarbons) entering the reactor system at a feedstock inlet may be
<750 C, < 725 C,
<700 C, <675 C, <650 C, <625 C, <600 C, <575 C, <550 C, <525 C, <500 C, <475
C,
<450 C, < 425 C, <400 C, <375 C, <350 C, <325 C, < or 300 C. Preferably, the
temperature
of the feedstock (e.g., acyclic hydrocarbons) entering the reactor system is <
700 C, more
preferably < 650 C, or more preferably < 625 C. Ranges of temperatures
expressly disclosed
include combinations of any of the above-enumerated values, e.g., 300 C to 750
C, 350 C to
700 C, 450 C to 650 C, 475 C to 600 C, etc. Preferably, the temperature of the
feedstock (e.g.,
acyclic hydrocarbons) entering the reaction system is 300 C to 750 C, more
preferably 300 C
to 700 C, more preferably 400 C to 700 C, and more preferably 575 C to 675 C.
Providing the
feedstock (e.g., acyclic C5 hydrocarbons) at the above-described temperatures
may
advantageously minimize undesirable cracking of the C5 hydrocarbons (e.g.,
acyclic C5
hydrocarbons) before they can react in the presence of the catalyst material.
The feedstock may
be heated via any suitable means, for example a furnace, such as a fired-tube
furnace and/or heat
exchanger, prior to entering the at least one reaction zone.
Additionally, it may be preferable that an isothermal or substantially
isothermal
temperature profile be maintained in the at least one reaction zone. A
substantially isothermal
temperature profile has the advantages of maximizing the effective utilization
of the catalyst and
minimizing the production of undesirable C4- byproducts. As used herein,
"isothermal
temperature profile" means that the temperature at each point within the
reaction zone between
the reactor inlet and reactor outlet as measured along the tube centerline of
the reactor is kept
essentially constant, e.g., at the same temperature or within the same narrow
temperature range
wherein the difference between an upper temperature and a lower temperature is
no more than
40 C; more preferably no more than 20 C. Preferably, the isothermal
temperature profile is one
where the temperature along the length of the reaction zone(s) within the
reactor does not vary
.. by more than 40 C as compared to the average temperature within the
reactor, alternately not
more than 20 C, alternately not more than 10 C, alternately not more than 5 C.
Alternately, the
isothermal temperature profile is one where the temperature along the length
of the reaction
zone(s) within the reactor is within 20% of the average temperature within the
reactor, alternately
within 10%, alternately within 5%, alternately within 1% of the average
temperature within the
reactor.
Additionally, the temperature of a first effluent exiting the at least one
reaction zone at
an effluent outlet may be > 400 C, > 425 C, > 450 C, > 475 C, > 500 C, > 525
C, > 550 C. >
575 C, > 600 C, > 625 C, > 650 C, > 675 C, or > 700 C. Preferably, the
temperature of a first
effluent exiting the at least one reaction zone is > 550 C, more preferably >
575 C, more
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preferably > 600 C. Ranges of temperatures expressly disclosed include
combinations of any
of the above-enumerated values, e.g., 400 C to 700 C, 475 C to 675 C, 525 C to
650 C, 550 C
to 600 C, etc. Preferably, the temperature of a first effluent exiting the at
least one reaction zone
is 475 C to 700 C, more preferably 500 C to 650 C, more preferably 550 C to
625 C.
Additionally, or alternatively, reaction conditions in the at least one
reaction zone may
include a temperature of > 300 C, > 325 C, > 350 C, > 375 C, > 400 C, > 425 C,
> 450 C, >
475 C,> 500 C,> 525 C, >550 C. >575 C, > 600 C > 625 C, >650 C, >675 C, or >
700 C.
Ranges of temperatures expressly disclosed include combinations of any of the
above-
enumerated values, e.g., 300 C to 700 C, 350 C to 675 C, and 400 C to 700 C,
etc. Preferably,
the temperature may be 350 C to 700 C, more preferably 500 C to 700 C, or more
preferably
500 C to 650 C. Optionally, the at least one reaction zone may include one or
more means for
heating the at least one reaction zone in order to maintain a temperature
therein. Examples of
suitable heating means known in the art include, but are not limited to a
fired tube, heat transfer
tubes, a heated coil with a high temperature heat transfer fluid, an
electrical heater, and/or a
microwave emitter. As used herein, "coil" refers to a structure placed within
a vessel through
which a heat transfer fluid flows to transfer heat to the vessel contents. A
coil may have any
suitable cross-sectional shape and may be straight, include u-bends, include
loops, etc.
Additionally, or alternatively, reaction conditions at the effluent outlet of
the at least one
reaction zone may include a pressure of > 1.0 psia, > 2.0 psia, > 3.0 psia, >
4.0 psia, > 5.0 psia,
> 10.0 psia, > 15.0 psia, > 20.0 psia, > 25.0 psia, > 30.0 psia, > 35.0 psia,
> 40.0 psia, > 45.0
psia, > 50.0 psia, > 55.0 psia, > 60.0 psia, > 65.0 psia, > 70.0 psia, > 75.0
psia, > 80.0 psia, >
85.0 psia, > 90.0 psia, > 95.0 psia, > 100.0 psia, > 125.0 psia, > 150.0 psia,
> 175.0 psia or 200
psia. Ranges and combinations of temperatures and pressures expressly
disclosed include
combinations of any of the above-enumerated values, e.g., 1.0 psia to 200.0
psia, 2.0 psia to
175.0 psia, 5.0 psia to 95.0 psia, etc. Preferably, the pressure may be 3.0
psia to 100.0 psia, more
preferably 3.0 psia to 50.0 psia, more preferably 3.0 psia to 30.0 psia. In
particular, the reaction
conditions may comprise a temperature of 500 C to 700 C and a pressure of 3.0
psia to 100 psia.
Additionally, or alternatively, a delta pressure (or pressure drop) across the
at least one
reaction zone (pressure at feedstock inlet minus pressure at effluent outlet)
may be > 0.5 psia, >
1.0 psia, > 2.0 psia, > 3.0 psia, > 4.0 psia, > 5.0 psia, > 10.0 psia, > 14.0
psia, > 15.0, psia, > 20.0
psia, > 24.0 psia, > 25.0 psia, > 30.0 psia, > 35.0 psia, > 40.0 psia, > 45.0
psia, > 50.0 psia,?
55.0 psia, > 60.0 psia, > 65.0 psia, > 70.0 psia, > 75.0 psia, > 80.0 psia, >
85.0 psia, > 90.0 psia,
> 95.0 psia, > 100.0 psia, > 125.0 psia, or > 150.0 psia. As understood
herein, "at a feedstock
inlet," "at an inlet," "at an effluent outlet," and "at an outlet" includes
the space in and
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substantially around the inlet and/or outlet. Additionally, or alternatively,
a delta pressure (or
pressure drop) across the at least one reaction zone (pressure at feedstock
inlet minus pressure
at effluent outlet) may be < 2.0 psia. < 3.0 psia, < 4.0 psia, < 5.0 psia, <
10.0 psia, < 14.0 psia, <
15.0 psia, < 20.0 psia, < 24.0 psia, < 25.0 psia, < 30.0 psia, < 35.0 psia, <
40.0 psia, < 45.0 psia,
< 50.0 psia, < 55.0 psia, < 60.0 psia, < 65.0 psia, < 70.0 psia, < 75.0 psia,
< 80.0 psia, < 85.0
psia, < 90.0 psia, < 95.0 psia, < 100.0 psia, < 125.0 psia, < 150.0 psia, <
175.0 psia, or < 200.0
psia. Ranges of delta pressures expressly disclosed include combinations of
any of the above-
enumerated values, e.g.. 10 psia to 70.0 psia, 20.0 psia to 60.0 psia, 30.0
psia to 50.0 psia, etc.
In particular, the pressure substantially at an inlet of a feedstock (e.g.,
acyclic C5 hydrocarbons)
may be 10.0 psia to 70.0 psia, preferably 10.0 psia to 60.0 psia, more
preferably 10.0 psia to 40.0
psia. Additionally, the pressure substantially at an outlet of at least a
first effluent may be 1.0
psia to 60.0 psia, preferably 5 psia to 40.0 psia, more preferably 10.0 psia
to 30.0 psia.
C. Catalyst Material and Inert Material
The at least one reaction zone comprises particulate material including a
catalyst
material. The catalyst material, also referred to as a "catalyst composition,"
is present in the
reaction system for promoting conversion of at least a portion of the acyclic
hydrocarbons to
alkenes, cyclic hydrocarbons and/or aromatics, in particular conversion of
acyclic C5
hydrocarbons to cyclopentadiene.
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 he 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.
Particularly suitable microporous metallosilicates for use herein, include
those of
framework type MWW, MFI, LTL, MOR, BEA, TON, MTW, MIT, FER, MRE, MFS, MEL,
DDR, EUO, and FAU (such as zeolite beta, mordenite, faujasite, Zeolite L, ZSM-
5, ZSM-11,
ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, and MCM-22 family
materials) 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 of 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.
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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 crystalline aluminosilicate
has a constraint
index of 3 to 12 and is ZSM-5.
ZSM-5 is described in U.S. Patent No. 3,702,886. ZSM-11 is described in U.S.
Patent
No. 3,709,979. ZSM-22 is described in U.S. Patent No. 5,336,478. ZSM-23 is
described in U.S.
Patent No. 4,076,842. ZSM-35 is described in U.S. Patent No. 4,016,245. ZSM-48
is described
in U.S. Patent No. 4,375,573. ZSM-50 is described in U.S. Patent No.
4,640,829. ZSM-57 is
described in U.S. Patent No. 4,873,067. ZSM-58 is described in U.S. Patent No.
4,698,217.
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.
Materials of the MCM-22 family include MCM-22 (described in U.S. Patent No.
4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described
in U.S. Patent
No. 4,826,667), ERB- l (described in EP 0 293 032), ITQ-1 (described in U.S.
Patent No.
6,077,498), and ITQ-2 (described in WO 97/17290), MCM-36 (described in U.S.
Patent No.
5,250,277), MCM-49 (described in U.S. Patent No. 5,236,575), MCM-56 (described
in U.S.
Patent No. 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 U.S. Patent No. 6,756,030) and UZM-
8HS
(described in U.S. Patent No. 7,713,513), both of which are also suitable for
use as the molecular
sieve of the MCM-22 family.
In one or more embodiments, the crystalline metallosilicate has an Si/M molar
ratio
(where M is a group 8, 11, or 13 metal) greater than 3, or greater than 25, or
greater than 50, or
greater than 100, or greater than 400, or in the range from 100 to 2,000, or
from 100 to 1,500, or
from 50 to 2,000, or from 50 to 1,200.
In one or more embodiments, the crystalline aluminosilicate has an SiO2/A1203
molar
ratio greater than 3, or greater than 25, or greater than 50, or greater than
100, or greater than
400, or greater than 1,000, or in the range from 100 to 400, or from 100 to
500, or from 25 to
2,000, or from 50 to 1,500, or from 100 to 1,200, or from 50 to 1,000.
Typically, 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
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additional metals selected from Groups 8, 9, 11, and 13 of the Periodic Table
of the Elements
and the rare earth metals, such as Ga, In, Zn, Cu, Re, Mo, W, La, Fe, Ag, Rh,
Pr, La, and/or
oxides, sulfides, nitrides, and/or carbides of these metals. Alternatively, or
additionally, the
Group 10 metal is present in combination with a Group I alkali metal and/or a
Group 2 alkaline
earth metal.
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 0.005 wt% to 10
wt%, or from
0.005 wt% up to 1.5 wt%, based on the weight of the catalyst composition.
The Group 1 alkali metal is generally present as an oxide and the metal is
selected from
the group consisting of lithium, sodium, potassium, rubidium, cesium, and
mixtures of two or
more thereof. The Group 2 alkaline earth metal is generally present as an
oxide and the metal is
selected from the group consisting of beryllium, magnesium, calcium,
strontium, barium, and
mixtures of two or more thereof.
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 composition.
In one or more embodiments, the Group 11 content is in the range from 0.005
wt% to 10 wt%,
or from 0.005 wt% up to 1.5 wt%, based on the weight of the catalyst
composition. In one or
more embodiments, the molar ratio of said Group 11 metal to Group 10 metal is
at least 0.1, or
from at least 0.1 up to 10, preferably at least 0.5, more preferably at least
1. In one or more
embodiments, the Group 11 metal is present as an oxide.
A preferred Group 9 metal is Rh, which may form an alloy with the Group 10
metal.
Preferably, the molar ratio of Rh to Group 10 metal is in the range from 0.1
to 5.
Typically, the rare earth metal is selected from the group consisting of
yttrium,
lanthanum, cerium, praseodymium, and mixtures or combinations thereof.
Preferably, the molar
ratio of rare earth metal to Group 10 metal is in the range from 1 to 10. The
rare earth metal
may be added to the catalyst composition during or after synthesis of the
microporous crystalline
molecular sieve as any suitable rare earth metal compound.
In one or more embodiments of aluminosilicates, the molar ratio of said Group
1 alkali
metal to Al is at least 0.5, or from at least 0.5 up to 3, preferably at least
1, more preferably at
least 2.
In one or more embodiments of aluminosilicates, the molar ratio of said Group
2 alkaline
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earth metal to Al is at least 0.5, or from at least 0.5 up to 3, preferably at
least 1, more preferably
at least 2.
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 1.1 to 15. Alpha Value is
determined as
described in US 3,354,078; The Journal of Catalysis, v. 4, p. 527 (1965); v.
6, p. 278 (1966); and
v. 61, p. 395 (1980) using a constant temperature of 538 C and a variable flow
rate, as described
in detail in The Journal of Catalysis, v. 61 , p. 395, (1980).
In one or more embodiments, the use of any one of the catalyst compositions of
this
.. invention provides a conversion of at least 70%, or at least 75%, or at
least 80%, or in the range
from 60% to 80%, of said acyclic CS feedstock under acyclic CS conversion
conditions. This
includes an n-pentane containing feedstock with equimolar H2, a temperature in
the range of
550 C to 600 C, an n-pentane partial pressure between 3 and 10 psia, and an n-
pentane weight
hourly space velocity of 10 to 20 lit'.
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
30%, or at least 40%,
or at least 50%, or in the range from 30% to 80%, under acyclic C5 conversion
conditions. This
includes an n-pentane feedstock with equimolar II), a temperature in the range
of 550 C to
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-1.
In one or more embodiments, the use of any one of the catalyst compositions of
this
invention provides a carbon selectivity to cyclopentadiene of at least 30%, or
at least 40%, or at
least 50%, or in the range from 30% to 80%, under acyclic C5 conversion
conditions. This
includes an n-pentane feedstock with equimolar Hz, a temperature in the range
of 550 C to
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-1.
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 wi% 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 1
to 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 2 to 80 wt%
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of the composite. Preferred binder materials comprise one or more of silica,
titania, zirconia,
metal silicates of Group 1 or Group 13 of the Periodic Table, carbides,
nitrides, aluminum
phosphate, aluminum molybdate, aluminate, surface passivated alumina, and
mixtures thereof.
Preferably, suitable binder materials have a lower affinity for Group 10 metal
particles, e.g. Pt,
in comparison with the crystalline metallosilicate, e.g. aluminosilicate.
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) and a Group 1 alkali metal (such as sodium
or potassium);
4) a crystalline aluminosilicate (Zeolite L) combined with a Group 10 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 1 alkali metal (such as sodium), and a Group 11 metal (such as silver
or copper).
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 0.005 wt% to 10 wt%,
or from 0.005 wt%
up to 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
tradenames of DAVISIL
646 (Sigma Aldrich), DAVISON 952, DAVISON 948 or DAVISON 955 (Davison Chemical
Division of W.R. Grace and Company).
Catalyst composition shape and design are preferably configured to minimize
pressure
drop, increase heat transfer, and minimize mass transport phenomena. Suitable
catalyst shape
and design are described in WO 2014/053553. The catalyst composition may be an
extrudate
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Date Recue/Date Received 2021-06-25
with a diameter of 2 mm to 20 mm. Optionally, the catalyst composition cross
section may be
shaped with one or more lobes and/or concave sections. Additionally, the
catalyst composition
lobes and/or concave sections may be spiraled. The catalyst composition may be
an extrudate
with a diameter of 2 mm to 20 mm; and the catalyst composition cross section
may be shaped
with one or more lobes and/or concave sections; and the catalyst composition
lobes and/or
concave sections may be spiraled. Also, the formulated catalyst composition
may be made into
a particle, such as, for example, a spray dried particle, an oil drop
particle, a mulled particle, or a
spherical particle. The formulated catalyst composition may be made into a
slurry. Such slurry
materials typically contain the microporous crystalline metallosilicate, such
as zeolite, and a filler
to .. such as a silicate. For fluid bed reactors, spherical particle shapes
are particularly useful.
For more information on useful catalyst compositions, please see applications:
USSN
62/250,675, filed November 4, 2015; USSN 62/250,681, filed November 4, 2015;
USSN
62/250,688, filed November 4, 2015; USSN 62/250,695, filed November 4, 2015;
and USSN
62/250,689, filed November 4, 2015.
Preferably, the catalyst material comprises platinum on ZSM-5, platinum on
zeolite L,
and/or platinum on silica.
In addition to the catalyst material, inert material may also be present in
the at least one
reaction zone. As referred to herein, the inert material is understood to
include materials which
promote a negligible amount promote a negligible amount (e.g., < 3%, < 2%, <
1%, etc.) of
conversion of the feedstock, intermediate products, or final products under
the reaction conditions
described herein. In various aspects, the catalyst material and/or the inert
material may have an
average diameter of? 10 [tm > 25 [tm, > 50 [tm, > 100 [tm, > 200 [tm, > 300
[tm, > 400wn, > 500
[tm, > 600m, > 700 [tm, > 800wn, > 900wn, > 1000 [tm. Additionally, or
alternatively, the
catalyst material and/or the inert material may have an average diameter of <
50 [tm, < 100 [tm,
.. < 200 [tm, <300 [tm, < 400 [tm, < 500 [tm, < 600 [tm, < 700 [tm, <800 [tm,
< 900 [tm, < 1000 [tm.
Ranges expressly disclosed include combinations of any of the above enumerated
values, e.g.,
10 [tm to 1,000m, 50 [tm to 500wn, 100 [tm to 750m, 200 [tm to 500wn, etc.
Preferably, in a
circulating fluidized bed or a captive fluidized bed reactor, the catalyst
material and/or the inert
material may have an average diameter of 20 [tm to 300wn, more preferably 20
[tm to 100 [tm,
more preferably 40 [tm to 90m, more preferably 50 [tm to 80 [tm.
The catalyst material and the inert material may be combined as portions of
the same
particles and/or may be separate particles. Preferably the catalyst material
and the inert material
are separate particles. Additionally, the catalyst material and/or inert
material may be essentially
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spherical (i.e., < 20%, < 30%, <40%, or < 50% aberration in diameter).
Examples of suitable
inert materials include, but are not limited to metal carbides (e.g., silicon
carbide, tungsten
carbide, etc.), metal oxides (e.g., silica, zirconia, titania, alumina, etc.),
clays, metal phosphates
(e.g., aluminum phosphates, nickel phosphates, zirconium phosphates, etc.),
and combinations
thereof. In particular, the inert material may comprise silicon carbide,
silica, and a combination
thereof.
D. Effluent
An effluent (e.g., first effluent, second effluent) exiting the at least one
reaction zone may
comprise a variety of hydrocarbon compositions produced from the reaction of
the acyclic
hydrocarbons (e.g., acyclic C5 hydrocarbons) in the at least one reaction
zone. The hydrocarbon
compositions typically have mixtures of hydrocarbon compounds, such as
alkenes, cyclic
hydrocarbons, and aromatics, having from 1 to 30 carbon atoms (Ci-C30
hydrocarbons), from 1
to 24 carbon atoms (Ci-C14 hydrocarbons), from 1 to 18 carbon atoms (Ci-Cis
hydrocarbons),
from 1 to 10 carbon atoms (Ci-Clo hydrocarbons), from 1 to 8 carbon atoms (C1-
Cs
hydrocarbons), and from 1 to 6 carbon atoms (Ci-C6 hydrocarbons).
Particularly, the first
effluent comprises cyclopentadiene. The cyclopentadiene may be present in a
hydrocarbon
portion of an effluent (e.g., first effluent, second effluent) in an amount of
> 20.0 wt%, > 25.0
wt%, > 30.0 wt%, > 35.0 wt%, > 40.0 wt%, > 45.0 wt%, > 50.0 wt%, > 55.0 wt%, >
60.0 wt%,
> 65.0 wt%, > 70.0 wt%, > 75.0 wt%, or > 80.0 wt%. Additionally, or
alternatively, the
cyclopentadiene may be present in a hydrocarbon portion of an effluent (e.g.,
first effluent,
second effluent) in an amount of < 20.0 wt%, < 25.0 wt%, < 30.0 wt%, < 35.0
wt%, < 40.0 wt%,
< 45.0 wt%, < 50.0 wt%, < 55.0 wt%, < 60.0 wt%, < 65.0 wt%, < 70.0 wt%, < 75.0
wt%, <80.0
wt%, or < 85.0 wt%. Ranges expressly disclosed include combinations of any of
the above-
enumerated values, e.g., 20.0 wt% to 85.0 wt%, 30.0 wt% to 75.0 wt%, 40.0 wt%
to 85.0 wt%,
50.0 wt% to 85.0 wt%, etc. Preferably, the cyclopentadiene may be present in a
hydrocarbon
portion of an effluent (e.g., first effluent, second effluent) in an amount of
10.0 wt% to 85.0 wt%,
more preferably 25.0 wt% to 80.0 wt%, more preferably 40.0 wt% to 75.0 wt%.
In other aspects, an effluent (e.g., first effluent, second effluent) may
comprise one or
more other C5 hydrocarbons in addition to cyclopentadiene. Examples of other
C5 hydrocarbons
include, but are not limited to cyclopentane and cyclopentene. The one or more
other Cs
hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g.,
first effluent, second
effluent) in an amount > 10.0 wt%, > 15.0 wt%, > 20.0 wt%, > 25.0 wt%, > 30.0
wt%, > 35.0
wt%, > 40.0 wt%, > 45.0 wt%, > 50.0 wt%, > 55.0 wt%, > 60.0 wt%, > 65.0 wt%,
or > 70.0
wt%. Additionally, or alternatively, the one or more other C5 hydrocarbons may
be present in a
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hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in
an amount of < 15.0
wt%, < 20.0 wt%, < 25.0 wt%, < 30.0 wt%, < 35.0 wt%, < 40.0 wt%, < 45.0 wt%, <
50.0 wt%,
< 55.0 wt%, < 60.0 wt%, < 65.0 wt%, or < 70.0 wt%. Ranges expressly disclosed
include
combinations of any of the above-enumerated values, e.g., 10.0 wt% to 70.0
wt%, 10.0 wt% to
55.0 wt%, 15.0 wt% to 60.0 wt%, 25.0 wt% to 65.0 wt%, etc. Preferably, the one
or more other
C5 hydrocarbons may be present in a hydrocarbon portion of an effluent (e.g.,
first effluent, second
effluent) in an amount of 30.0 wt% to 65.0 wt%, more preferably 20.0 wt% to
40.0 wt%, more
preferably 10.0 wt% to 25.0 wt%.
In other aspects, an effluent (e.g., first effluent, second effluent) may also
comprise one or
more aromatics, e.g., having 6 to 30 carbon atoms, particularly 6 to 18 carbon
atoms. The one or
more aromatics may be present in a hydrocarbon portion of an effluent (e.g.,
first effluent, second
effluent) in an amount of > 1.0 wt%, > 5.0 wt%, > 10.0 wt%, > 15.0 wt%, > 20.0
wt%, > 25.0
wt%, > 30.0 wt%, > 35.0 wt%, > 40.0 wt%, > 45.0 wt%, > 50.0 wt%, > 55.0 wt%, >
60.0 wt%,
or > 65.0 wt%. Additionally, or alternatively, the one or more aromatics may
be present in a
hydrocarbon portion of an effluent (e.g., first effluent, second effluent) in
an amount of < 1.0 wt%,
< 5.0 wt%, < 10.0 wt%, < 15.0 wt%, < 20.0 wt%, < 25.0 wt%, < 30.0 wt%, < 35.0
wt%, < 40.0
wt%, < 45.0 wt%, < 50.0 wt%, < 55.0 wt%, < 60.0 wt%, or < 65.0 wt%. Ranges
expressly
disclosed include combinations of any of the above-enumerated values, e.g.,
1.0 wt% to 65.0 wt%,
10.0 wt% to 50.0 wt%, 15.0 wt% to 60.0 wt%, 25.0 wt% to 40.0 wt%, etc.
Preferably, the one or
more aromatics may be present in a hydrocarbon portion of an effluent (e.g.,
first effluent, second
effluent) in an amount of 1.0 wt% to 15.0 wt%, more preferably 1.0 wt% to 10
wt%, more
preferably 1.0 wt% to 5.0 wt%.
For information on possible dispositions of the effluents, please see
applications: USSN
62/250,678, filed November 4, 2015; USSN 62/250,692, filed November 4, 2015;
USSN
62/250,702, filed November 4, 2015; and USSN 62/250,708, filed November 4,
2015.
E. Stripping/Separation of the Effluent
In various aspects, catalyst material and/or inert material may become
entrained with
hydrocarbons (e.g., cyclopentadiene) in the effluent (e.g., first effluent,
second effluent) as the
effluent travels through and/or exits the at least one reaction zone. Thus,
the process may further
comprise separating catalyst material and/or inert material, which may be
entrained with
hydrocarbons (e.g., cyclopentadiene) in the effluent (e.g., first effluent,
second effluent). This
separating may comprise removal of the catalyst material and/or inert material
from the
hydrocarbons (e.g., cyclopentadiene) by any suitable means, such as, but not
limited to cyclones,
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filter, electrostatic precipitators, heavy liquid contacting, and/or other gas
solid separation
equipment, which may be inside and/or outside the at least one reaction zone.
The effluent
substantially free of particulate material may then travel to a product
recovery system.
Additionally, the separated catalyst material and/or inert material may then
be fed back into the
at least one reaction zone at any desirable location. In a particular
embodiment, a separated
catalyst material stream may be introduced into the at least one reaction zone
at a position above
where feedstock and co-feed are provided to the at least one reaction.
Additionally, or alternatively, co-feed may also be separated from the
effluent (e.g., first
effluent, second effluent) via any suitable means or combinations thereof such
as distillation,
adsorption (pressure-swing or temperature-swing), membrane separation,
liquid/solvent
absorption, condensation, etc. and the separated co-feed may be recycled back
to the at least one
reaction zone. Preferably, the separated co-feed is heated as described above
before being
reintroduced into the at least one reaction zone.
Additionally, or alternatively, the separated material with reduced level of
hydrocarbons
may then travel to a rejuvenation zone, and/or regeneration zone, and the
hydrocarbons stripped
from the particulate material may be directed to the product recovery system
or to the reactor
system.
F. Rejuvenation
As the reaction occurs in the at least one reaction zone, coke material may
form on the
particulate material, particularly on the catalyst material, which may reduce
the activity of the
catalyst material. Additionally, or alternatively, the particulate material
may cool as the reaction
occurs. The catalyst material exiting the at least one reaction zone is
referred to as "spent catalyst
material." Thus, the effluent and the separate catalyst material can comprise
spent catalyst
material. This spent catalyst material may not necessarily be a homogenous mix
of particles as
individual particles may have had a distribution of total aging in the system,
time since last
regeneration and/or rej uvenation, and/or ratio of times spent in reaction
zones relative to in the
regeneration and/or rejuvenation zones.
Thus, at least a portion of the particulate material (e.g., spent catalyst
material) may be
transferred from the at least one reaction zone to a rejuvenation zone to
produce rejuvenated
catalyst material. The transferring of the particulate material (e.g., spent
catalyst material) from
the at least one reaction zone to a reheating zone may occur after the
catalyst material has been
stripped and/or separated from the hydrocarbons after exiting the at least one
reaction zone.
Additionally, or alternatively, catalyst (e.g., spent catalyst material)
material may be transferred
directly from the at least one reaction zone to a reheating zone. The
reheating zone may include
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one more heating devices, such as but not limited to direct contacting, a
heating coil, and/or a
fired tube.
In various aspects, in the rejuvenation zone, the particulate material (e.g.,
spent catalyst
material) may be contacted with a gaseous stream comprising hydrogen and
substantially free of
reactive oxygen-containing compounds to remove at least a portion of
incrementally deposited
coke material on the catalyst material thereby forming a rejuvenated catalyst
material and a
volatile hydrocarbon, such as, but not limited to methane. As used herein, the
term
"incrementally deposited" coke material refers to an amount of coke material
that is deposited
on the catalyst material during each pass of the catalyst material through the
at least one reaction
zone as opposed to a cumulative amount of coke material deposited on the
catalyst material
during multiple passes through the at least one reaction zone. "Substantially
free" used in this
context means the rejuvenation gas comprises less than 1.0 wt%, based upon the
weight of the
gaseous stream, e.g., less than 0.1 wt%, less than 0.01 wt%, less than 0.001
wt%, less than 0.0001
wt%, less than 0.00001 wt% oxygen-containing compounds. The gaseous stream may
comprise
> 50 wt% H2, such as > 60 wt%, > 70 wt%, preferably? 90 wt% H2. The gaseous
stream may
further comprise an inert substance (e.g., and/or
methane. Contacting the spent catalyst
material with the gaseous stream may occur at a temperature of 500 C to 900 C.
preferably
575 C to 750 C and/or at a pressure between 5.0 psia to 250 psia, preferably
25 psia to 250 psia.
In alternative aspects, in the rejuvenation zone, the particulate material
(e.g., spent
catalyst material) may be rejuvenated via a mild oxidation procedure
comprising contacting the
particulate material with an oxygen-containing gaseous stream under conditions
effective to
remove at least a portion of incrementally deposited coke material on the
catalyst material
thereby forming a rejuvenated catalyst material. Typically, these conditions
include a
temperature range of 250 C to 500 C, and a total pressure of 0.1 bar to 100
bar, preferably at
atmospheric pressure. Further, the oxygen-containing gaseous stream is
typically supplied to
the rejuvenation zone at a total WHSV in the range of 1 to 10,000. Following
the mild oxidation,
purge gas is generally reintroduced to purge oxidants from the catalyst
composition using a purge
gas, for example, N2. This purging step may be omitted if CO2 is the oxidant
as it will not
produce a flammable mixture. Optionally, rejuvenation via mild oxidation
further comprises
one or more hydrogen treatment steps.
In any embodiment, the rejuvenated catalyst material may then be returned to
the at least
one reaction zone.
In any embodiment, rejuvenation is generally effective at removing at least 10
wt% (>
10 wt%) of incrementally deposited coke material. Between 10 wt% to 100 wt%,
preferably
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between 60 wt% to 100 wt%, more preferably between 90 wt% to 100 wt% of
incrementally
deposited coke material is removed.
Rejuvenation advantageously may have a time duration of < 90 mins, e.g., < 60
mins, <
30 mins, < 10 mins, such as < 1 min, or < 10 seconds. Rejuvenation may be
advantageously
performed > 10 minutes, e.g., > 30 minutes, > 2 hours, > 5 hours, > 24 hours,
> 2 days, > 5 days,
> 20 days, after beginning the specified conversion process.
Rejuvenation effluent exiting the rejuvenation zone and comprising, unreacted
hydrogen,
coke particulate, and optionally light hydrocarbon, may be further processed.
For example, in
aspects where rejuvenation is achieved via contact with a hydrogen-rich
gaseous stream, the
rejuvenation effluent may be sent to a compression device and then sent to a
separation apparatus
wherein a light hydrocarbon enriched gas and light hydrocarbon depleted gas is
produced. The
light hydrocarbon gas may be carried away, e.g., for use as fuel gas. The
light hydrocarbon
depleted stream may be combined with make-up hydrogen and make up at least a
portion of the
gaseous stream provided to the rejuvenation zone. The separation apparatus may
be a membrane
system, adsorption system (e.g., pressure swing or temperature swing), or
other known system
for separation of hydrogen from light hydrocarbons. A particulate separation
device, e.g., a
cyclonic separation drum, may be provided wherein coke particulate is
separated from the
rejuvenati on effluent.
G. Regeneration
The process may further comprise a regeneration step to recapture catalyst
activity lost
due to the accumulation of coke material and/or agglomeration of metal on the
catalyst material
during the reaction. This regeneration step may he carried out when there has
not been sufficient
removal of the coke material from the particulate material (e.g., spent
catalyst material) in the
rejuvenation zone.
Preferably, in the regeneration step, at least a portion of the spent catalyst
material from
the at least one reaction zone, from the separated catalyst material following
stripping from the
effluent, and/or from the rejuvenation zone may be transferred to a
regeneration zone and
regenerated by methods known in the art. For example, an oxidative
regeneration may be used
to remove at least a portion of coke material from the spent catalyst
material. In various aspects,
a regeneration gas comprising an oxidizing material such as oxygen, for
example, air, may
contact the spent catalyst material. The regeneration gas may oxidatively
remove at least 10
wt% (> 10 wt%) of the total amount of coke material deposited on the catalyst
composition at
the start of regeneration. Typically, an oxychlorination step is performed
following coke removal
comprising contacting the catalyst composition with a gaseous stream
comprising a chlorine
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source and an oxygen source under conditions effective for dispersing at least
a portion of metal,
e.g., Group 10 metal, particles on the surface of the catalyst and to produce
a metal
chlorohydrate, e.g., a Group 10 metal chlorohydrate. Additionally, a chlorine
stripping step is
typically performed following oxychlorination comprising contacting the
catalyst composition
with a gaseous stream comprising an oxygen source, and optionally a chlorine
source, under
conditions effective for increasing the 0/C1 ratio of the metal chlorohydrate.
Generally, a
reduction step, and optionally a sulfidation step may also be performed in the
regeneration step.
Typically, regeneration is effective at removing between 10 wt% to 100 wt%,
preferably between
90 wt% to 100 wt% of coke material is removed. Optionally, before or after
contacting the spent
catalyst material with the regeneration gas, the catalyst material may also be
contacted with a
purge gas, e.g., N2. Regeneration, including purging before and after coke
oxidation, requires
less than 10 days, preferably less than 3 days to complete.
Catalyst may be continuously withdrawn from and returned to the reaction zone
and/or
the rejuvenation zone or may be periodically withdrawn from and returned to
the reaction zone
and/or regeneration zone. For a periodic method, typically, the regeneration
times between when
withdrawals are made for coke burn, oxychlorination, chlorine stripping,
purge, reduction, and
optional sulfidation occurs are between 24 hours (1 day) to 240 hours (10
days), preferably
between 36 hours (1.5 days) to 120 hours (5 days). Alternatively for
continuous mode, the
removal/addition of particulate material rate may vary between 0.0 wt% to 100
wt% (e.g., 0.01
wt% to 100 wt%) per day of the particulate material inventory, and preferably
between 0.25 wt%
to 30.0 wt% per day of the particulate material inventory where there is
balanced
addition/removal of particulate material. Regeneration of the catalyst
material may occur as a
continuous process or may be done batch wise in both cases intermediate
vessels for inventory
accumulation and/or inventory discharge may be required.
The removal and addition of the particulate material (e.g., spent catalyst
material, fresh
catalyst material, fresh inert material, rejuvenated catalyst material,
regenerated catalyst
material) may occur at the same or different location in the reactor system.
The particulate
material (e.g., fresh catalyst material, fresh inert material, rejuvenated
catalyst material,
regenerated catalyst material) may be added after or before the rejuvenation
zone, while the
removal of the particulate material (e.g., spent catalyst material) may be
done before or after the
particulate material (e.g., spent catalyst material) is passed through the
rejuvenation zone. At
least a portion of the regenerated catalyst material may be recycled to the at
least one reaction
zone or at least one rejuvenation zone. Preferably, the regenerated catalyst
material and/or fresh
particulate material are provided to the rejuvenation zone to minimize any
loss in heat input and
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to remove any remaining species that may be carried by the regenerated
catalyst material from
the regeneration zone. Additionally, or alternatively, separators inside or
outside of the
regeneration zone may be used to separate the inert material from the catalyst
material prior to
regeneration so that j ust the catalyst material is regenerated. This
separation may be carried out
on the basis of size, magnetic, and/or density property differences between
the inert material and
the regenerated catalyst material using any suitable means.
For the above-described processes, standpipes, well known by those skilled in
the art
with the particle size and operating conditions described above, may be used
to provide the
means of transporting the particulate material between the at least one
reaction zone,
rejuvenation zone, and/or regeneration zone. Slide valves and lifting gas,
known by those skilled
in the art, may also be used to help circulate the particulate material and/or
build the necessary
pressure profile inside the regeneration zone. The lifting gas may be the same
as the fluidizing
gas used in the rejuvenation zone, e.g., a hydrogen stream that may contribute
in minimizing the
hydrogen usage in the reaction system, while also reducing the coke material
formation.
III. Reaction Systems for Conversion of Acyclic Hydrocarbons
In another embodiment, a reaction system 1 for converting acyclic hydrocarbons
(e.g.,
acyclic C5 hydrocarbons) to alkenes, cyclic hydrocarbons (e.g.,
cyclopentadiene) and/or
aromatics is provided, as shown in the Figure. The reaction system 1 may
comprise a feedstock
stream 2, a co-feed stream 3, at least one reactor 10, and an effluent stream
11. The feedstock
stream 2 may comprise an acyclic hydrocarbon (e.g., acyclic C5 hydrocarbons,
such as pentane)
stream 2a as described above, and optionally, a first hydrogen stream 2b. The
co-feed stream 3
may comprise a light hydrocarbon (e.g., Ci¨C4 alkanes and/or C1-C4 alkene)
stream 3a as
described above and a second hydrogen stream 3b. In particular, the co-feed
stream 3 may
comprise hydrogen, ethane, methane and/or a mixture of ethane and ethylene.
The reaction
system 1 may further comprise a first furnace 4 for heating the feedstock
stream 2 to produce a
heated feedstock stream 5, which may be provided to the least one reactor 10
at feedstock
temperatures as described herein (e.g., 300 C to 700 C). For example, a first
fuel gas stream 6
may be provided to the first furnace 4 for heating the feedstock stream 2.
Additionally, reaction
system 1 may further comprise a second furnace 7 for heating the co-feed
stream 3 to produce a
heated co-feed stream 8, which may be provided to at least one reactor 10 at
co-feed temperatures
as described herein (e.g., 600 C to 1100 C) and which may heat catalyst
material present in the
at least one reactor 10. For example, a second fuel gas stream 9 may be
provided to the second
furnace 7 for heating the co-feed stream 3. The at least one reactor 10 may
comprise a feedstock
stream inlet (not shown) for providing the heated feedstock stream 5 to the
reaction system, a
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co-feed stream inlet (not shown) for providing the heated co-feed stream 8,
and an effluent
stream outlet (not shown) for removal of the effluent stream 11. In a
particular embodiment, the
feedstock stream inlet (not shown) is a position in the at least one reactor
10 above the co-feed
stream inlet (not shown).
The at least one reactor 10 may be a circulating fluidized bed reactor or a
captive fluidized
bed reactor, preferably a captive fluidized bed reactor. Additionally, or
alternatively, the at least
one reactor is not a radial-flow reactor or a cross-flow reactor.
Additionally, or alternatively, the reaction system 1 may comprise at least a
first reactor,
a second reactor, a third reactor, a fourth reactor, a fifth reactor, a sixth
reactor, a seventh reactor,
etc. As used herein, each "reactor" may be individual vessels or individual
reaction zones within
a single vessel. Preferably, the reaction system includes 1 to 20 reactors,
more preferably 1 to
reactors, more preferably 2 to 10 reactors, more preferably 3 to 8 reactors. A
circulating
fluidized bed reactor may include multiple reaction zones (e.g., 3-8) within a
single vessel or
multiple vessels (e.g., 3-8). Where the reaction system includes more than one
reactor, the
15 reactors may be arranged in any suitable configuration, preferably in
series, wherein a bulk of
the feedstock moves from the first reactor to the second reactor and/or a bulk
of the particulate
material moves from the second reactor to the first reactor, and so on. Each
reactor,
independently, may be a circulating fluidized bed reactor or a captive
fluidized bed reactor.
Preferably, the at least one reactor 10 may include at least one or more
internal structures
8, as described above. Particularly, the at least one reactor 10 may include a
plurality of internal
structures (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 40, 50, etc.), such
as, baffles, sheds, trays,
tubes, tube bundles, tube coils, rods, and/or distributors.
The at least one reactor 10 is operated under reaction conditions as described
above to
convert at least a portion of the acyclic hydrocarbons (e.g., acyclic C5
hydrocarbons) to alkenes,
cyclic hydrocarbons (e.g., cyclopentadiene), and/or aromatics. For example,
the reaction
conditions may comprise a temperature of 500 C to 700 C and/or a pressure of
3.0 psia to 100
psia. Preferably, at least 30 wt% of the acyclic C5 hydrocarbons is converted
to cyclopentadiene.
Optionally, the at least one reactor 10 may include one or more heating means
(e.g., fired tube,
heated coil, heat transfer tubes) (not shown) as described herein in order to
maintain temperature
therein.
Additionally, the reaction system 1 may further comprise a separator 12, such
as a
cyclone, (one is shown, but two or more operating in series may be present
with one or more
operating in parallel) in fluid connection with the at least one reactor 10.
The separator 12 may
be located externally (as shown) or internally (not shown) within the reactor.
The separator 12,
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may separate the catalyst material, which may be entrained with hydrocarbons
(e.g.,
cyclopentadiene) in the effluent stream 11 to produce a separated catalyst
material stream 14 and
a substantially catalyst-free effluent stream 13. The substantially catalyst-
free effluent stream 13
may comprise a lower amount of catalyst material than the effluent stream 11,
preferably the
substantially catalyst-free effluent stream 13 comprises a negligible amount
(e.g., < 5.0 wt%,
2.0 wt%, < 1.0 wt%) of catalyst material or no catalyst material. The
substantially catalyst-free
effluent stream 13 may optionally travel to a product recovery system.
Additionally, the
separated catalyst material stream 14 may then be fed back into the at least
one reactor 10 (the
material may be returned at a position above where the heated feedstock stream
5 enters) via a
separated catalyst material inlet (not shown) in the at least one reactor 10.
The separator 12 may
comprise an effluent stream inlet (not shown), a separated catalyst material
stream outlet (not
shown), and a substantially catalyst-free effluent stream outlet (not shown).
Optionally, a third
hydrogen stream 15 may be present in the reaction system 1, which may be fed
to the first
separator 12 and/or combined with the separated catalyst material stream 14.
Additionally, or alternatively, the reaction system 1 may further comprise a
rejuvenating
and/or regenerating apparatus 16 for restoring activity of the spent catalyst
material, wherein the
rejuvenating and/or regenerating apparatus 16 is in fluid connection with the
at least one reactor
10. For example, a spent catalyst stream 17 comprising at least a portion of
the separated catalyst
material stream 14 may be provided to the rejuvenating and/or regenerating
apparatus 16 to
produce a rejuvenated and/or regenerated catalyst stream 18 which can be
combined with the
separated catalyst material stream 14 or alternatively, enter the reactor
through a separate outlet
(not shown).
Additionally, or alternatively, the reaction system 1 may further comprise a
fresh catalyst
material stream (not shown) in fluid connection with the at least one reactor
10.
IV. Industrial Applicability
A first hydrocarbon reactor effluent obtained during the acyclic CS 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.
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 wt% or greater,
or preferably 90
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wt% or greater of CPD is useful for producing DieIs-Alder reaction products
formed in
accordance with the following reaction Scheme (I):
Scheme I
a 4+2 cycloaddition
\ ____________ R ____________ .. R D iel s-Al de r reaction
product.
where R is a heteroatom or substituted heteroatom, substituted or
unsubstituted Ci-050
hydrocarbyl radical (often a hydrocarbyl radical containing double bonds), an
aromatic radical,
or any combination thereof. Preferably, substituted radicals or groups contain
one or more
elements from Groups 13-17, preferably from Groups 15 or 16, more preferably
nitrogen,
oxygen, or sulfur. In addition to the mono-olefin 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 Diels-Alder reaction products of CPD with
one or more of
the following: another CPD molecule, conjugated dienes, acetylenes, allenes,
disubstituted
olefins, trisubstituted olefins, cyclic olefins, and substituted versions of
the foregoing. Preferred
Diels-Alder reaction products include norbornene, ethylidene norbornene,
substituted
norbomenes (including oxygen-containing norbornenes), norbornadienes, and
tetracyclododecene, as illustrated in the following structures:
4 4 4. =
0
norbornene ethylidene norbornene
tetracyclododecene norbornadiene oxygen substituted
norbornenc.
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.
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.
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 (11).
- 36 -
Scheme ll
* ROMP
catalyst
Separated cyclopentane is useful as a blowing agent and as a solvent. Linear
and
branched C5 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.
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.
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.
PROPHETIC EXAMPLES
The following examples are derived from modeling techniques and although the
work was
actually achieved, the inventors do not present these examples in the past
tense to comply with
M.P.E.P. 608.01(p) if so required.
Example 1 ¨ Reactor Performance Modeling
Reactor modeling was performed using Invensys Systems Inc. PRO/II 9.3.4 for
the
purpose of estimating the performance at various commercially relevant
operating conditions.
Depending on specifics of the modeling, variation in results will occur but
the models will still
demonstrate the relative benefits of the present invention. Numerous
modifications and variations
are possible and it is to be understood that within the scope of the claims,
the invention may be
practiced otherwise than as specifically described herein.
Example lA ¨ Methane Diluent, 20 psia outlet pressure, 10 psia HC partial
pressure
A 20 psia outlet pressure, 575 C outlet temperature, fluidized bed reactor is
simulated
with a feed comprising of n-pentane, which is pre-heated to 621 C prior to
feeding into the
fluidized bed, and a co-feed comprising of methane and hydrogen, which is
separately pre-heated
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to a temperature required to supply 100% of the heat of reaction. Under these
conditions, the
catalyst is assumed to have a lights selectivity (C4- products) of - 18%. The
residence time
within the catalyst bed is assumed to provide for CPD concentration to reach
its thermodynamic
concentration at the reactor outlet conditions. The hydrogen molar rate in
reactor co-feed is set
to deliver a molar ratio of hydrogen:n-pentane in feed of 1:1. The methane
molar rate in reactor
co-feed is set to deliver a methane partial pressure at reactor outlet of 10
psia (i.e., combined
partial pressure of all other hydrocarbons including hydrogen of 10 psia).
Based on the reactor
yields, this corresponds to a molar ratio of methane:n-pentane in feed of 4:1.
To generate I lb-
mole of CPD in the fluidized bed reactor effluent, it is determined from the
simulation that 2.195
lb-moles of n-Pentane, 8.741 lb-moles of methane and a co-feed pre-heat
temperature of 1098 C
is required.
Example 1B - Methane Diluent, 950 C co-feed preheat, 10 psia outlet HC partial
pressure
As a comparative to Example IA, a 575 C outlet temperature, fluidized bed
reactor is
simulated with a feed comprising of n-pentane, which is pre-heated to 621 C
prior to feeding
into the fluidized bed, and a co-feed comprising of methane and hydrogen,
which is separately
pre-heated to 950 C. Under these conditions, the catalyst is assumed to have a
lights selectivity
(C4- products) of - 18%. The residence time within the catalyst bed is assumed
to provide for
CPD concentration to reach its thermodynamic concentration at the reactor
outlet conditions.
The hydrogen molar rate in reactor co-feed is set to deliver a molar ratio of
hydrogen:n-pentane
in feed of 1:1. The methane molar rate in reactor co-feed is set to deliver
100% of the heat of
reaction. The combined outlet pressure of all components including hydrogen,
with the
exception of methane, is set at 10 psia by adjusting the total outlet
pressure. To generate 1 lb-
mole of CPD in the fluidized bed reactor effluent, it is determined from the
simulation that 2.195
lb-moles of n-Pentane and 13.0 lb-moles of methane is required. Additionally,
the outlet reactor
pressure is determined to be 25 psia. As can be seen by comparing the
simulation results of
Example IA and Example 1B, reducing the methane pre-heat temperature from 1098
to 950 C
results in higher methane feed rate (increase from 8.7 to 13.0 lb-mol per lb-
mol of CPD
produced) in order to provide the same heat of reaction.
Example IC - Ethane Diluent, 20 psia outlet pressure, 10 psia HC partial
pressure
A 20 psia outlet pressure, 575 C outlet temperature, fluidized bed reactor is
simulated
with a feed comprising of n-pentane, which is pre-heated to 621 C prior to
feeding into the
fluidized bed, and a co-feed comprising of methane and hydrogen, which is
separately pre-heated
to a temperature required to supply 100% of the heat of reaction. Under these
conditions, the
catalyst is assumed to have a lights selectivity (C4- products) of - 18%. The
residence time
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within the catalyst bed is assumed to provide for CPD concentration to reach
its thermodynamic
concentration at the reactor outlet conditions. The hydrogen molar rate in
reactor co-feed is set
to deliver a molar ratio of hydrogen:n-pentane in feed of 1:1. The ethane
molar rate in reactor
co-feed is set to deliver an ethane partial pressure at reactor outlet of 10
psia (i.e., combined
partial pressure of all other hydrocarbons including hydrogen of 10 psia).
Based on the reactor
yields, this corresponds to a molar ratio of ethane:n-pentane in feed of about
4:1. To generate 1
lb-mole of CPD in the fluidized bed reactor effluent, it is determined that
2.195 lb-moles of
n-Pentane, 8.741 lb-moles of ethane and a co-feed pre-heat temperature of 911
C is required.
As can be seen by comparing the simulation results of Example lA and Example
1B, use of
ethane as co-feed allows for a lower pre-heat temperature owing to its higher
heat capacity
relative to methane.
Example 1D ¨ Ethane Diluent, 732 C co-feed preheat, 10 psia outlet HC partial
pressure
As a comparative to Example 1C, a 575 C outlet temperature, fluidized bed
reactor is
simulated with a feed comprising of n-pentane, which is pre-heated to 621 C
prior to feeding
into the fluidized bed, and a co-feed comprising of ethane and hydrogen, which
is separately
pre-heated to 732 C. Under these conditions, the catalyst is assumed to have a
lights selectivity
(C4- products) of ¨ 18%. The residence time within the catalyst bed is assumed
to provide for
CPD concentration to reach its thermodynamic concentration at the reactor
outlet conditions.
The hydrogen molar rate in reactor co-feed is set to deliver a molar ratio of
hydrogen:n-pentane
in feed of 1:1. The ethane molar rate in reactor co-feed is set to deliver
100% of the heat of
reaction. The combined outlet pressure of all components including hydrogen,
with the
exception of ethane, is set at 10 psia by adjusting the total outlet pressure.
To generate 1 lb-mole
of CPD in the fluidized bed reactor effluent, it is determined from the
simulation that 2.195
lb-moles of n-Pentane and 19.35 lb-moles of methane is required. Additionally,
the outlet reactor
pressure is determined to be 33 psia. As can be seen by comparing the
simulation results of
Example 1D and Example 1C, reducing the ethane pre-heat temperature from 911
to 732 C
results in higher ethane feed rate (increase from 8.7 to 19.4 lb-mol per lb-
mol of CPD produced)
in order to provide the same heat of reaction.
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
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Date Recue/Date Received 2021-06-25
made without departing from the spirit and scope of the invention.
Accordingly, it is not intended
that the invention be limited thereby. For example, the compositions described
herein may be
free of any component, or composition not expressly recited or disclosed
herein. Any method
may lack any step not recited or disclosed herein. Likewise, the term
"comprising" is considered
synonymous with the term "including." And whenever a method, composition,
element or 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.
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Date Recue/Date Received 2021-06-25
