Note: Descriptions are shown in the official language in which they were submitted.
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NOZZLE REACTOR AND METHOD OF I UUSE
This patent application claims priority to US, Provisional Patent Application
No.
61 `l.69,569, filed April 15, 2009, and UÃ.S. Patent Application No.
12/466,9213., fled May 15,
200. each of which is hereby incorporated by reference. In the event of a
conflict, the subject
matter explicitly recited or sho'~wn herein controls over any suject matter
incorporated by
reference. All definitions of a term (express or implied) contained in any of
the subject matter
incorporated by reference herein are hereby disclaimed.
B.ACKGRO U ND
Some nozzle reactors operate to cause interactions between materials and
achieve
alteration of the physical or chemical composition of one or more of the
materials. Such
interaction and alteration typically occurs by injecting the materials into a
reactor chamber in the
nozzle reactor. The manner in which the .a aaaterials are injected into the
reactor chamber and the
configuration of the various components of the nozzle reactor may both
contribute to how the
materials interact and what types of alterations are achieved.
U.S. Patent No. 7,618,597 describes various configurations fora nozzle reactor
wherein
the cracking material and the material to be cracked are injected into the
reactor chamber of the
nozzle reactor at approximately transverse directions. Additionally, the
nozzle reactors
described in the `597 patent describe a cracking material injection pathway
capable of
accelerating the cracking material to a supersonic speed as it enters the
reactor chamber. These
features of the disclosed nozzle reactors, along with additional Ifeatures,
can help to achieve
increased conversion rates of material to be cracked injected into the nozzle.
reactor.
Additionally, these features can help to ensure that the material to be
cracked is sufficiently
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altered (eg., broken down into smaller compounds having a sufficiently low
molecular weight
for the desired product).
While the nozzle reactors disclose(] M. the '597 patent can provide an
increase in
conversion rates of the material to be cracked passing therethrough, it is
still possible that
material to be cracked will pass through the disclosed nozzle reactors
unaltered. Such unaltered
material may therefore. not be suitable for use as a desired end product of
the nozzle reactor
process. In some instances, the unaltered material may have to be discarded as
a waste product
of the process, which clearly makes the process less economical.
One option for dealing with material that passes through the '597 nozzle
reactors
unaltered is to recycle the unaltered material back through the nozzle
reactor. Ho'~w~ever, such a
recycle stream does not always lead alteration of the recycled n>aatc rial.
The nozzle reactors
disclosed in the `597 reference can be operating under conditions that do not
provide the best
environment for the recycled material to be altered. Accordingly, the recycled
material may
remain unaltered no matter how many times it is re-inj ected into the same
nozzle reactor.
SUMMARY
Disclosed below are representative embodiments that are not intended to be
limiting in
any way. Instead, the present disclosure is directed toward features, aspects,
and equivalents of
the embodiments of the nozzle reactor and method of use described below. The
disclosed
features and aspects of the embodiments can be used alone or in various
combinations and sub-
combinations with one another.
In some embodiments, a method of cracking residual oil. is disclosed. The r
rethod
includes the steps of providin g a nozzle reactor, inject n a stream of
cracking material through
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the first material injector into the reactor body, and injecting residual oil
through the second
material feed port into the reactor body and transverse to the stream of
cracking material entering
the reactor body from the first material. injector to produce cracked residual
oil and uncrack.ed
residual oil. The residual oil can include distillation bottoms, asphaitenes,
or stripped
hydrocarbon material.
In some embodiments, a method of modifying a refinery plant including at least
one of a
Coker, a hydrocracker, and a deasphalting unit is disclosed. The method
includes the stop of
replacing at least one of the c_ol er, hydrocracker, and deasphalting unit
with a nozzle reactor.
In some embodiments, a refinery plant is disclosed, The refinery plant
includes a refinery
residue-producing processing unit that includes a refinery residue outlet and
a nozzle. reactor
located downstream of the refinery. residue-producing processing unit. The
nozzle reactor is in
fluid communication with the refinery residue outlet cfthe refinery residue-
producing processi1n4g
unit, such that refinery residue from the refinery residue-producing
processing unit may be
injected into the nozzle reactor.
In some embodiments, a feed material cracking :method is disclosed, The
.method
includes the steps of injecting a stream of cracking material through a
cracking material injector
into a reaction chamber, and a step of injecting residual oil into the
reaction chamber adjacent to
the cracking material injector and t",sverse to the stream. of cracking
material entering the
reaction chamber from the cracking material injector.
In some embodiments, a nozzle reactor system of the type useable to inject a
first
material and a second material to cause interaction between the first material
and the second
material is disclosed. The nozzle reactor wstem includes a first nozzle
reactor, a second nozzle
reactor, and a first separation unit in fluid communication with the first
nozzle reactor. The first
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separation unit includes a light stream outlet and a heavy stream outlet in
fluid communication
with the second nozzle reactor.
In some errmbodirrments, a material cracking method is disclosed. The material
cracking
method includes injecting a first stream of cracking rriaterial through a
injection passage of a first
nozzle reactor into an interior reactor chamber of a first nozzle reactor,
injecting a .material feed
into the interior reactor chamber of the first nozzle reactor adjacent to the
injection passage of the,
first nozzle reactor and transverse to the first stream of cracking material
entering the interior
reactor chamber- of the first nozzle .reactor .from the :injection passage of
the first nozzle reactor to
produce first light material and first heavy .rrmaterial, injecting a second
stream of cracking
material through an injection passage of a second nozzle reactor into an
interior reactor chamber
of a second nozzle reactor, and injecting the first heavy material into the
interior reactor chamber
of the second nozzle reactor adjacent to the is jection passage of the second
nozzle reactor and
transverse to the second stream of cracking material entering the interior
reactor chamber of the
second nozzle reactor from the injection passage of the second nozzle reactor
to thereby produce
second light mrmte:rial and second heavy material.
The foregoing and other features and advantages of the present application
will become
apparent from the. follo,~w~ing detailed description, which proceeds with
reference to the
accompanying figures. It is thus to be understood that the scope of the
invention is to be
determined by the claims as issued and not. by whether a claim includes any or
all features or
advantages recited in this Brief Summary or addresses any issue identified in
the :Background
$
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BRE F :DESCRIPTION OF THE :DR AWI NGS
The preferred and other embodiments are disclosed in association with the
accompanying
drawings in which.-
Figure f is a flow diagram illustrating a feed material cracking method
according to an
embodiment disclosed he..rein.
Figure. 2 is a. cross sectional, schematic view of one embodiment of a nozzle
reactor.
Figure 3 is a cross-sectional view of the nozzle reactor of Figure ", showing
further
construction details for the nozzle reactor.
Figure 4 is a cross-sectional view of an alternative embodiment of a nozzle
reactor.
Figure 5 is a cross-sectional, schematic view of one embodiment of an
injection nozzle
for use with a nozzle reactor.
Figure 6 is an end view of the injection nozzle of Figure ? taken from the
inlet end of the
nozzle.
Figure 7 is a cross-sectional, schematic view of one embodiment of an
injection nozzle
for use with a nozzle reactor, with the nozzle having a z raterial feed
injection passage formed in
t:he nozzle body.
Figure. 8 is a cross-sectional, schematic view of one embodiment of an
injection nozzle
for use with a nozzle reactor, with the nozzle having a material feed
injection passage formed in
the flow directing insert.
Figure 9 is a flow diagram illustrating a feed material cracking method
according to an
embodiment disclosed herein.
Figure 1.0 is a flow diagram illustrating a feed rmaterial cracking r aethod
according to all
en-lbodiment disclosed herein,
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DETAILED DESC'RIPTlO:
Before describing the details of the various embodiments herein, it should be
appreciated
that the tern-r "hydrocarbon" and "hydrocarbons" as used herein may include
organic n aaterial
besides hydrogen and carbon, such as vanadyl, sulfur, nitrogen, and any other
organic compound
that may be in oil.
In some embodiments disclosed herein, methods of cracking residual oil are
disclosed,
With reference to Figure 1, the met=hods generally include a step 1000 of
providing a nozzle
reactor, a step 1100 of injecting a stream of cracking material into the,
reactor body of the nozzle
reactor, and a step 1200 of injecting residual oil into the reactor body of
the nozzle reactor.
The nozzle reactor provided in step 1000 can generally include any suitable
nozzle
reactor for altering the physical or chemical structure of the feed material
injected into the nozzle
reactor. The nozzle reactor can generally include a reactor body where, the
cracking material and
feed material interact to alter the feed material., a cracking material
injector for injecting cracking
material into the reactor body, and a feed r material injector for injecting
feed material into the
reactor body. The cracking material injector and the feed material injector
can be the same
injection passageway or can be separate injection passages ays, or a
combination of both.
In some embodiments, the nozzle reactor provided in step J000 is similar or
identical to
the nozzle reactors disclosed in U.S. Patent No. 7,618,597. With reference to
Figure 2, a nozzle
reactor 1.0 as disclosed in the ' 597 patent includes a reactor body injection
end 12, a reactor body
14 extending from the reactor body injection end 12, and an ejection pork 13
in the reactor body
1.4 opposite its injection end 12. The reactor body injection end 12 includes
an injection passage
15 extending into the interior reactor chamber 16 of the reactor body 14. The
central axis A of
the injection passage 1.5 is coaxial. with the central axis B of the interior
reactor chamber 16.
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With continuing reference to Figure 2, the injection passage 15 has a circular
diametric
cross-section and, as shown in the axially-extending cross-sectional view of
Figure 2, opposing
inwardly curved side wall portions 17, 19 (i.e., curved inwardly toward the
central axis A of the
injection passage 15) extending along the axial length of the injection
passage ge 15. In certain
embodiments, the axially inwardly curved side wall portions 17, 19 of the
injection passage 15
allow for a higher speed of cracking material when passing throe ;h the
injection passage 15 into
the interior reactor chamber 16.
In certain ernbodiments, the side wall of the injection passage 15 provides
one or more
among: (i) uniform axial acceleration of cracking material passing through the
injection passage;
(ii) minimal radial acceleration of such material, (iii) a smooth finish; (iv)
absence of sharp
edges; and (v) absence of sudden or sharp changes in direction, The side wall
configuration can
render the injection passage 15 substantially isentropic. These latter types
of Sick: wall and
injection passage 1.5 features can be, among other things, particularly useful
for pilot plant nozzle
reactors of minimal size.
A material feed passage 1S extends from the exterior of the reactor body 14
toward the
interior reactor chamber 16 transversely to the axis B of the interior reactor
chamber 16. The
material feed passage 1S penetrates an annular material feed port 20 adjacent
the interior reactor
chamber wall 22 at the interior reactor chamber injection end 24 abutting the
reactor body
injection end 12. The material feed port 20 includes an annular, radially
extending reactor
chamber feed slot 26 in material-injecting communication with the interior
reactor chamber 1.6.
The material feed port 26 is thus configured to inject feed material; (i) at
about a 90' angle to the
axis of travel of cracking material injected from the ire jection passage IS,-
(ii) around the entire
circumference of a cracking material injected through the injection passage
15; and (iii) tc
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impact the entire circumference of the free cracking material stream virtually
immediately upon
its emission from the injection passage 15 into the interior reactor chamber
16.
The annular material feed port. 20 can have a U-shaped or C-shaped cross-
section among
others. In certain embodiments, the annular material feed port 20 is open to
the interior reactor
chamber 1.6, with no arms or barrier in the path of fluid flow from the
material feed passage l
toward the interior reactor chamber 16. The junction of the annular material
feed port 20 and
material feed passage 18 can have a radiused cross-section.
In alternative embodiments, the material feed passage 18, annular material
feed port 20,
and/or injection passage 15 have differing orientations and configurations. ,
and there earl be more
than one material feed port and associated structure. Similarly, in certain
embodiments the
injection passage 15 is located on or in the interior reactor chamber side 23
(and if desired can
include an annular cracking material port rather than at the reactor body
injection end 1.2 of the
reactor body 1.4 and the annular material feed port 20 may be non-annular and
located at the
reactor body injection end 12 of the reactor body 14.
With continuing :reference to Figure .2, the interior reactor chamber 16 is
bounded by
stepped, telescoping side walls 28, 30, 32 extending along the axial length of
the reactor body 14.
In certain embodiments, the stepped side walls 28, 30, 32 are configured to:
(i) allow a free jet
of injected cracking material, such as superheated steams, natural gas,
carbon. dioxide, or other
gas, to travel generally along and withill the conical jet. path C generated
by the injection passage
1.5 along the axis B of the interior reactor chamber 16, while (ii) reducing
the size or involvement
of back flow areas, e.g., 34, 36, outside the conical or expanding jet path C,
thereby forcing
increased contact between the high speed cracking material jet stream within
the conical. path
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C and feed material, such as heavy hydrocarbons, injected through the annular
material feed port
20,
As indicated bye the drawing gaps 38, 40 in Figure 2, the reactor body 14 has
an axial
length (along- axis 13) that is much greater than its width. Exemplary length-
to-width ratios are
typically in the range of 2. to 4 or more.
The dimensions of the various components of the nozzle reactor illustrated in
Figure 2 are
not limited, and may generally be adjusted based on the amount of material
feed to be cracked
inside the nozzle reactor. 'Fable 1 provides exe.mplaryr dimensions for the
various components Of
the nozzle reactor based on the hydrocarbon input in barrels per day (BP.D).
Material Feed Input (BPD)
Nozzle Reactor Component mm) 5,000 10,000 20,000
Injection Passage, Enlarged Volume
Injection Section Diameter 148 207 295
injection Passage, Reduced Volume
1 iid Section -Diameter 50 7 101
Injection Passage, Enlarged Volume
Ejection Section Diameter 105 147 210
injection Passage Length-- -------- ---- 00-- ------ 840 1,200
Interior Reactor Chamber Injection End
Diameter 157 262 375
Interior Reactor Chamber Ejection End
Diameter 1,231 1,435 1,821
Interior- Reactor Chamber Length 6,400 7,160 8,800
-------------------------------------------------------------------------------
----------------- --------------------- -------------------------- ------------
-------------
Overall Nozzle Reactor Length tl 7,000 8,000 10,000
Overall Nozzle Reactor Outside
diameter 1,300 1.600 2,000
Table 1
With reference now to Fi~ur'e 3, the reactor body 44 includes a generally.
tubular central
section 46 and a frustoconical ejection end 48 extending from the central
section 46 opposite an
insert end 50 of the central section 46, with the insert end 50 in turn
abutting the injection nozzle
52. The insert end 50 of the central section 46 includes a generally tubular
central body 51. The
central body 51 has a tubular material feed passage 54 extending from the
exte.rrial periphery 56
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of the insert end 50 radially inwardly to injectingly communicate with the
annular
circumferential feed port depression or channel 58 in the otheR-irise planar,
radially inwardly
extending portion 59 of the axially stepped face 61 of the insert end 50 The
inwardly extending
portion 59 abuts the planar radially internally extending portion 53 of a
matingly stepped face 55
of the in jection nozzle 52. The feed port channel 58 and axially opposed
radially internally
extending portion -5-3) of the injection nozzle -452 cooperatively provide. an
annular feed port 57
disposed transversely laterally, or radially outwardly, from the axis A of a
preferably non-linear
i.rr_jeetion passage 60 in the injection nozzle 52.
The tubular body 51 of the insert end 50 is secured within and adjacent the
interior
periphery 6$ of the reactor body 44. The mechanism for seeming the insert end
50 in this
position can incl.aude an axially-extending nut-and-bolt arrangement (not
shown) penetrating co-
linearly nmatin4s passa4ges (not shown) in: (1) an capper radially extending
lip 66 on the reactor
body $4; (ii) an abutting, radially outs.ardly extending thickened neck
section 68 on the insert
end SCI; and (iii) in turn., the abutting injector nozzle 52. Other mechanisms
for securing the
insert end 50 within the reactor body 44 include a press .tit (not shown) or
mating threats (not
shown) on the outer periphery 62 of the tubular body 51 and on the inner
periphery: 64 of the
reactor body 44, Seals, e.g., 70, can be mounted as desired between, for
example, the radially
extending lip oo and the abutting the neck section 68 and the neck section 68
and the abutting
i nhj ector nozzle 52,
The non-linear injection passage 60 has, from an axially-extending cross-
sectional
perspective, mating?, radially inwardly curved opposing side Avail sections
72; 74 extending along
the axial length of the non-linear injection passage 60, The entry end 76 of
injection passage 60
provides a rounded circumferential face aabuttin4g an injection feed tube 78,
which can be bolted
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(not showvn) to the Mating planar, radially outwardly extending distal face 80
on the injection
nozzle 52.
With continuing reference to Figure 3e the injection passage 60 is a DeLaval
type of
nozzle and has an axially convergent section 82 abutting an intermediate
relatively narrower
throat section 84, which in turn abuts an axially divergent section 86. The
injection I passage 60
also has a circular diametric cross-section (i,e., in cross-sectional view
perpendicular to the axis
of the nozzle passage) all along its axial length, In certain embodiments, the
injection passage 60
presents a somewhat roundly curved thick $2, less curved thicker $4, and
relatively even less
curved and more gently sloped relatively thin 86 axially extending cross-
sectional configuration
from the entry end 76 to the it jection end 88 of the injection passage 60 in
the injection nozzle
5`'.
The injection passage 60 can thus be configured to present a substantially
isentropic or
frictionless configuration for the injection nozzle 52. This configuration can
vary,; however,
depending on the application involved in order to yield a substantially
isentropic configuration
for the application
.1'he injection passage 60 is formed in a replaceable injection nozzle insert
90 press-fit or
threaded into a mating injection nozzle mounting passage 92 extending axially
through an
injection nozzle body 94 of the injection nozzle 52. The injection nozzle
insert 90 is preferably
niade of hardened steel alloy, a and the balance of the nozzle reactor 100
components other than
seals, if any., are preferably made of steel or stainless steel.
An exemplary diameter I) within the injection passage 60 is 1 0 mm. An
exemplary
diameter E of the ejection passage opening 96 in the ejection end 48 of the
reactor body 44 is 2.2
11.
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meters. An exemplary axial length of the reactor body $4, from the injection
end 88 of the
injector passage 60 to the ejection passage opening 96. is 10 meters.
The interior peripheries 49, 91 of the insert on(] 50 and the tubular central
section 46,
respectively-, cooperatively provide a stepped or telescoped structure
expanding radially
outwardly from the injection end 88 of the injection passage 60 toward the
frustoconical end 48
of the reactor body 44. The particular dimensions of the various components,
however, will vary
based on the particular application for the nozzle reactor, generally 100.
Factors taken into
account in determining the particular dimensions include he physical
properties of the cracking
gas (density, enthalpy, entropy, heat capacity, etc.) and the pressure ratio
from the entry, end 76
to the injection end SS' of the injection passage 0.
The nozzle reactors disclosed herein can be used to, for example, crack heavy
hydrocarbon a material, including residual oil, into tigla.ter hydrocarbons
and other components. In
order to do so in certain embodiments, superheated steam (not shown) is
injected into the
injection passage 0. The pressure differential from the entry end 76, where
the pressure is
relatively high, to the ejection end 88. where the pressure is relatively
lower, aids in accelerating
the supe...dieated steam through the i.rxjection passage 60.
In certain embodiments having one or more non-linear cracking material
injection
passages, e.g., 60, such as the coi ergert/divergent configuration illustrated
in Figure 3, the
pressure differential can yield a steady increase in the kinetic energy of the
cracking material as
it moves along the axial length of the cracking material injection passage(s)
60. The cracking
material thereby ejects from the ejection end 88 of the injection passage 60
into the interior of
the reactor body 44 at supersonic speed with a commensurately relatively high
level. of kinetic
energy, In these embodiments, the level of kinetic energy of the supersonic
discharge cracking
1?
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material is therefore greater than can be achieved by certain prior art
straight-through injectors or
other injectors.
Other embodiments of a cracking material injection passage n ray not be as
isentropic but
may provide a substantial increase in the speed and kinetic energy of the
cracking material as it
moves through the injection passage 60. For example., an injection passage ?
caar cc naprise a
series of conical or toroidal sections (not shown) to provide varying cracking
material
acceleration through the passage 60 and, in certain embodiments, supersonic
discharge of the
cracking material from the passage 60.
In certain methods of use of the nozzle reactor embodiment .illustrated in
Figure 3, the
material to be cracked (not shown) is pre-heated, for example at 2-15 bar,
which is generally the
same pressure as that in the reactor body 44. In some embodiments, the preheat
should provide a
feed stock temperature of '100'C to 500'C, and most advantageously 400"C; to
450"C:.
Contemporaneously, the preheated feed stock is injected into the material feed
pass ge 54 and
then through the mating annular feed port 57. The feed stock thereby travels
radially inwardly to
impact a transversely (i.e, axially) traveling high speed cracking material
jet (for example,
steam. natural gas, carbon dioxide or other gas not shown) virtually
immediately upon its
ejection from the ejection end 88 of the injection passage 61. The collision
of the radially
injected fired stock with the axially traveling high speed steam jet delivers
kinetic energy to the
feed stock. The applicants believe that this process may continue, but with
diminished intensity
and productivity, through the length of the reactor body 44 as injected feed
stock is forced along
the axis of the reactor body 44 and yet constrained from avoiding contact with
the jet stream by
the telescoping interior walls, e.g., 89, 91 1 31, of the reactor body 44.
Depending on the nature
of the feed stock and its pre-feed treatnment, differing results can be
procured, such as cracking
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heavy hydrocarbons into lighter hydrocarbons and, if present in the heavy
hydrocarbons or
injected material, other materials.
With reference now to Figure 4, an embodiment of the nozzle reactor, generally
110, has
a nozzle 111 and a reactor body 128 with an insert end 112 intermediate the
reactor body 128
injector insert 130, The insert end 112. has a. conical interior periphery
section 11_a that; (i)
extends, and expands otm.w ardly, from the injection end 114 of the injection
passage 116 of the
nozzle 11 1, and (Ii) terminates with a maximum diameter at the abutting
tubular interior
periphery section 115 of the insert end 1 I.2 opposite the ejection end 114 of
the :innjection passage
116. This alternative embodiment also has a feed material i.njectio.n passage
118 :f=ormed of a
material fed line or tube 1220 in communication with an annular material feed
distribution
channel 122, which in turn is in communication with. an axially narrower
annular n aatcrial feed
injection ring or port 124, The a aa:terial feed injection ring 1.24 is
laterally adjacent the ejection
end 114 of the injection passage 116 to radially inwardly inject material feed
stock, into contact
with axially injected cracking material. (not shown) virtually immediately
upon the ejection of
the cracking i a aterial from the ejection end 114 into the interior 126 of
the reactor- body 128.
The injection passage 116 can be configured to eject a free stream of cracking
material,
such as super-heated steam (not shown) for example, generally conically with
an included angle
of about I 8". The conical interior section 113 can be configured to surround
or interfere with
such a free stream of cracking material ejection stream. In certain such
embodiments, after
engaging tl e injected material feed stock adjacent t(he ejection end 114, the
resulting jet mixture -
a mixture of cracking material and material feed stock - preferably makes at
least intermittent
interrupting contact with the tubular interior section 113 and, if desired-,
the downstream tubular
ira'terior section 115. This intermittent, interrupting contact increases
turbulence and concentrates
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shear stresses into an axially shortened reaction zone within the reactor body
1" Preferably,
however, the jet mixture travels through the interior 1.26 of the reactor body
1218 -,pith minimal
backflow of any components of the: jet mixture, resulting in more rapid plug
flow of all jet.
mixture components through the reactor body 128.
Once the material feed stock is cracked by the cracking material ejection
stream adjacent
the injection end 114, the configuration of the. reactor body facilitates
substantially Ãr mediate
cooling of the jet mixture. This cooling of the jet mixture acts to arrest the
chemical reaction
between the mate.riaal .feed stock and the cracking material ejection stream.
The applicants believe that, in certain embodiments, sufficient steam cracking
of at least
certain heavy hydrocarbons may be. achieved at jet velocities above. about 300
meters per second
while the retention time in the reactor body zone providing such. extreme
.hear can be very short,
on the order of only about 0.01 seconds. In such enibodinments, cracking of
material feed stock
can be caused by extreme shear of the cracking material. In certain of these
types of
embodiments, the retention time of the material feed or cracking material in
the reactor body '128
therefore can have little or no impact on such cracking or, if desired., any
other substantial
cracking. in other embodiments, an increased retention time of the .material
feed or cracking
material in the reactor body 128 can result in increased cracking rates,
In some embodiments, a catalyst can be introduced into the nozzle reactor to
enhance
cracking of the material feed stock by the cracking material ejection
streaa)m.
In the applicant's view, the methodology of nozzles of the type shown in the
illustrated
embodiments, to inject a cracking material such as steam, can be based can the
following equation
lT<r =l"Ir - iiij+ Kivc3 (1)
,here KE is the kinetic energy of the cracking material. (referred to as the
free Jet)
immediately upon emission from an injection nozzle, IIf, is the enthalpy of
cracking material
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upon entry into the injection nozzle, Hr is the enthalpy of cracking material
upon emission from
the injection nozzle, and KE is the kinetic energy of the cracking material at
the inlet of the
nozzle.
T his equation derives from the first law of thermodyna-nlics - that regarding
the
conservation of energy - in which the types of energy to be considered include-
potential energy.
kinetic ener ', chemical energy, thermal energy, and work energy. In the case
of the use of the
nozzles of the illustrated embodiments to inject steam, the only significantly
pertinent types of
energy are kinetic energy and thermal energy. The others ,- potential,
chemical, and work energy
., can be zero or low enough to be disregarded. Also. the inlet kinetic energy
can below enough
to be disregarded. Thus, the resulting kinetic energy of the cracking material
as set forth in the
above equation is simplified to the change M. enthalpy AIM
The second law, of thermodynamics W an expression of the universal law of
increasing
entropy, stating that the entropy of an isolated system that is not in
equilibrium will tend to
increase over time, approaching a maximum value at equilibrium - means that no
real process is
perfectly :isentropic. _l-However, a practically isentropic nozzle (re., a
nozzle commonly referred
to as "isentropic" in the art) is one in which the increase in entropy through
the nozzle results in
a relatively complete. or very high conversion of thermal energy into kinetic
energy. On the
other hand, a .on-isentropic nozzles such. as a straight-bore nozzle not only
result in much less
efficiency in conversion of thermal energy into kinetic energy but also can
impose upper limits
on the amount of kinetic energy available from therm.
For example, since the velocity of an ideal gas through a nozzle is
represented by the
equation
V ..: (_2./\}{)1 2 (2)
16
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and the velocity in a straight-bore nozzle is limited to the speed of sound,
the kinetic
energy of a gas jet delivered by a straight-bore nozzle is limited. However, a
practically
iseratr'opic" c;Erraverorart di ergirrg nozzle, such as those disclose(]
herein, can yield, r. t:. ejsct, a
gas jet that is supersonic. Consequently, the kinetic energy of the gas jet
delivered by such an
isentropic converging/diverging nozzle can be substantially greater than that
of the straight-bore
nozzle.
It can thus be seen that nozzle reactors as described herein can provide
enhanced transfer
of kinetic energy to the a aaterial feed stock through many aspects such as,,
for example, by
providing a supersonic cracking gas jet, improved orientation of the direction
of flow of a
cracking material (or cracking material mixture) with respect to that of the
material feed stock,
a,nd/'or more complete cracking material stream impact with the material feed
stock as a result of,
for example, an annular material fc.eci port and the telescoped reactor body
interior. Certain
embodiments also can result in reduced retention of by-products, such as
coking, on the side
walls of the reactor chamber. Embodiments of the nozzle reactor can also be
relatively rapid in
operation, efficient, reliable, easy to maintain and repair, and relatively
economical to make and
Use.
It should be noted that, in certain embodiments including in conjunction with
the
embodiments shown in Figures 2-4 above, the injection material may comprise a
cracking fluid
or other motive material rather than, or in addition to, a cracking material.
Accordingly, it. is to
be understood that certain embodiments may utilize components that comprise
motive material
compatible components rather than, as described in particular embodiments
above, cracking
material compatible components such as, for exarxaple, the injection passage,
e.g., 60, referenced
17
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WO 2010/121041 PCT/US2010/031260
above. When utilized in conjunction with an inwardly narrowed motive material
injection
passage, however, the motive material preferably is compressible.
In some embodiments, a nozzle reactor of the present application can include
an injection
passage that has a flow directing insert around which a first material can
flow to increase the
velocity of the first material in preparation for an interaction with aa.
second material to alter the
mechanical or chemical composition of the first and/or second materials. For
example, as shown
in Figures 5 and 6, an injection nozzle 150 includes an injection nozzle body
152 having an
injection passage 1.54 extending axially through the body. In certain
:implementations. the
passage 154 has a. constant diameter along the axial length of the passage. In
other
implementations, the diameter of the passage. 154 varies, such as decreasing
along the. axial
length of the passage, i.e., narrowing of the passage., or increasing along
the axial length of the
passage, i. e,, widenin of the passage, or various combinations of both. A
flow directing insert
166 is positioned within the injection passage 1.54, but remains out of direct
contact with the
inner surface of the injection passage through. use of a supporting insert
156. The flow directing
insert 166 can be coupled to the supporting insert 1.56, which is inserted and
secured within a
mating supporting insert recess 170 formed in the injection nozzle body 152..
The supporting insert 156 can include one or more. support rods 168 connected
to a
cylindrical. portion 165 of the flow directing insert. 166. The cylindrical
portion 165 includes
outer peripheral surfaces that run parallel to the axis of the insert 156, The
supportin<g insert 156
includes a generally annular shaped fluid flow passage 172 corresponding to
the injection
passage 1.54 of the injection nozzle body 152 such that when inserted in the
recess 170, the
interior periphery of the passage 172 is t enerall flush with. the interior
periphery of passage
1.51. Cross-sectional areas of the fluid flow passage 1.72 on places
perpendicular- to the axis of
1s
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the fluid flow passage 172 remain substantially the same extending the axial
length of the
passage. 1 72. In other words, an outer diameter and inner diameter of the
fluid flow passage 1.72
remain generally unchanged throughout the passage.
In some implementations, the inserts 156, 158 are replaceable, In specific
implementations, the insert 156, w pith insert 158 secured thereto, can
include external threads and
can be removably secured within the mating supporting insert recess 170 by
threadably engaging
internal threads formed in the recess. In other specific implementations, the
insert 158 is press-
fit into the recess 170. Yet in other i.nrplementa:tions,, the insert 156 is
bonded to the recess 1 70
pressure-activated adhesive,
1') applying bonding material, such as a. beat-activated adhesive,
pressure-activated adhesive, or other similar adhesive, between the outer
periphery of the. insert
and the recess, and activating the bonding material.
Fluid, such as cracking material, is allowed to flog through the nozzle 150 by
first
passing through a. flow inlet opening 174 in the supporting insert 156, the
fluid tlo {~ passage 172
and a flow outlet opening '176 in the supporting insert. As shown in Figure 5,
the fluid flows
around the cylindrical portion 1.65 and the support rods 168 as it flows
through the fluid flow
passage 172 at a generally constant velocity. Preferably, the number and cross-
sectional area of
the support rods 168 are minimized so as not to substantially disrupt the flow
of fluid through the
fluid flow passage 172.
When the flow directing insert. is positioned within the injection passage
154, a generally
annular fluid passage 180, defined between the surface of the injection
passage and the
exterior surface of the flow directing insert 158, is four ed.
The flow directing insert 158 includes a diver in,~. , or expanding, portion
164, a
converging, or contractin4g, portion 166 and a transit.iorrirr
g portion 1.67 coupling the diverging
19
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and converging portions. In the illustrated embodiments, the divers. in and
converging portions
164, 166 are generally frust:oconically shaped and conically shaped,
respectively, with abutting
base surfaces proximate the transitioning portion 167. Tile diameter of the
diverging portion
increases and the diameter of the converging portion decreases along the axial
length of the flow
directing insert 158 in the fluid flow direction as indicated in Figure 5.
Accordingly, the annular
fluid flow passage 180 between the diverging portion 164 of the flow directing
insert 158 and the
outer periphery of the injection passage 154, i:e., converging region. 200,
narrows in the fluid
flow direction and the annular fluid flow passage between the converging
portion 166 of the flow
direction insert and the outer perip:he.Ã r: of the injection passage, i.e.,
diverging region 204,
widens in the fluid flow direction. As can be recognized, the annular fluid
flow passage ISO is
most narrow between the transition portion 167 of the insert 158 and the outer
periphery of the
injection passage 154, i.e., transition, or throat, region 202.
Fluid flowing through the fluid f ov w passage 172 in the supporting insect
156 exits
through the outlet opening 176 of the passage '172 and into the annular fluid
flow passage 180.
The nozzle can be configured such that fluid flowing through the fluid flow
passage 172 and into
t:l-ae annular fluid flow passage 180 flows at a. velocity less than the speed
of sound, i.e., subsonic
flow. As the florid flows through the fluid flow passage 180, the narrowing of
the converging
region and the widening of the diverging region. help to induce a back
pressure, i.e., pressure is
higher at the entry of the passage 1.80 than at the exit of the passage, which
increases the velocity
of the fluid. The fluid velocity can be increased such that as the fluid exits
the transition region
its velocity is at or above the speed of sound, i.e., supersonic flow. The
fluid remains at
supersonic flow through the diverging region and as it exits the nozzle 1.50
at the end of the
diverging region.
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Like the reactor body injection end 12. of Figure 2 the injection nozzle 52 of
Figure 3,
and the reactor body injection insert 130 of Figure 4, the nozzle 150 can be
coupled to a reactor
chamber.. Further, the fluid flowing through the nozzle can be a cracking
material that, upon
exiling from the nozzle, immediately contacts radially inwardly injeeted
material feed stock
proximate the nozzle exit to induce interaction between the cracking material
and the material
feed,
Alternatively, with reference to Figure 7, a feed material injection passage
190 extends
from an exterior of injection nozzle body 191 toward the injection passage
193. The material
feed injection passage 190 penetrates an annular material feed port 192
adjacent the outer
periphery of the injection passage 191 proximate transition region 195. The
annular material
feed port 192 includes are annular, radially extending chamber feed slot 194
in material-injecting
communication with an exit of the transition region 195. Similar to Figure I.
the feed port 192 is
configured to inject feed material: (i) at about a 90' angle to the axis of
travel of cracking
material flowing through. the transition. region 195; (ii) around the entire
circumference of
cracking :material flowing out of the transition :region, and (Iii) to impact
the entire circumference
of the free cracking material virtually immediately upon its emission from the
transition region
into diverging region 197,
With reference to Figure 8, nozzle 210 is similar to the nozzle 150 of Figures
5 and 6 and
nozzle 1.89 of Figures 7_. except that feed material injection passage 210 is
fc rnned in the flow
directing insert 212 and axially. extends from an end of the flow directing
insert toward a.
transitioning portion 214 of the insert. The injection passage 210 penetrates
a disk-shaped feed
slot 21 6 in material-injecting communication with. an exit of a. transition
region 2.1 S. Feed
material can be injected through the passage 21.0 through the -feed slot 216
and around the entire
2.1.
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circumference of cracking matrr-tial flowing out of the transition region'18
at a 90" angle to the
axis of travel of fluid: e,g, cracking material, flowing through the
transition region. 'File feed
material then impacts the entire circumference of the fluid as described
above.
Certain embodiments of the present reactor nozzle and method of use can
therefore
accomplish cracking of hydrocarbon material, such as residual oil, primarily,
or at least more
substantially, by mechanical shear at a molecular level rather than by
temperature, retention time,
or involvement of catalysts. Although such cracking of the hydrocarbon
molecules yields
smaller, charge-irlrbalariced hydrocarbon chains which subsequently satisfy
their charge
imbalance by chemical interaction with other materials in the mixed jet stream
or otherwise, the
driving force of the hydrocarbon cracking process can be. mechanical rather
than chemical. In
addition, certain embodiments can utilize the greater susceptibility- of at
least certain heavy
hydrocarbons to mechanical cracking in order to selectively crack particular
hydrocarbons as
opposed to other lighter hydrocarbons or other materials that may be in the
material feed stock. as
it passes through. the nozzle reactor.
Also, in certain embodiments, the configuration of the :nozzle reactor can
reduce and even
virtually eliminate back mixing while enhancing, for example, plug flow of the
cracking material
and material feed mixture thrc.}nigh the reactor body and cooling of the
mixture through to
reactor body. This can aid in not only enhancing mechanical cracking of the
material feed but
also in reducing coke formation and wall scaling within the reactor body, In
combination with
injection of a high velocity cracking material or other motive material from
the trajection nozzle
into the reactor body, coke formation and wall scaling can be even more
significantly reduced if
not virtually or practically eliminated. In these embodiments, the nozzle
reactor can thus provide
more efficient and complete cracking, and if desired selective cracking, of
heavy hydrocarbons,
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while reducing and in certain embodiments virtually eliminating wall scaling
within the reactor
body.
The dimensions of the various components of the nozzle reactor provided in
step 1000
are not limited, and can generally be aadjustted based on the amount of
hydrocarbon (e.g., residual
oil) to be cracked inside the nozzle reactor. Tablet provides c empla.ryF
dimensions for the
various components of a nozzle reactor based on the. hydrocarbon input in
barrels per day (BPD}.
Hydro arbon In ut (BPD)
Nozzle Reactor Com onent mml 6,000 10,000 20,000
First Material Injector, Enlarged Volume
..Injection Section Diameter 148 .............._207.................295
. ..................................................
First Material Injector, Reduced Volume
Mid-Section Diameter 50 70 101
----------------------------------------------------------------------------- -
-------------------- ------------------------- --------------------------
First Material Injector, Enlarged Volume
Ejection Section--Diameter - ---------
- ----------- ----------105--- ---------------147-- ------------ 2-11-0--
-
-
First--Mat erial Injector Length 600 840 1.200
-------------------------------------------------------------------------------
----- --------------------- ------------------------- -------------------------
-
------------------------------------------------------------------------------
--------------------- ------------------------- --------------------------
Reactor Body Passage injection End
Diameter 187 262 375
Reactor Body Passage Ejection End
Diameter 1,231 1,435 1,821
Reactor Body Length 6,4003 .7160 ------------------------------- ----- --------
------------------ -------------------------
000 8060 .8800
0,000
Overall Nozzle Reactor Outside
Diameter 1,300 1,600 2,000
Table 2
As can be seen from Table 2, the first material injector may be small relative
to the
reactor bodyThe size of the first r xaterial injector is beneficial in that
the :first. material injector
may be a replaceable insert that is easily removed from the reactor body. As
such, other first
material injectors having different internal dimensions and providing
different tyrpes of injection
flow properties for the cracking material can be used to increase the
versatility of the nozzle
reactor as a whole. To the contrary., conventional units used for processing
residual. oil are large
and cumbersome apparatus that do not provide versatility.
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In step 1100, a stream of cracking material is injected into the nozzle
reactor. in some
embodiments, the stream of cracking material is injected into the reactor body
of the nozzle
reactor via the injection passage. The cracking material may be any suitable
material for
cracking, the feed material, including those materials described in greater
detail above, In some
embodiments, the cracking material is steam.
In a step 1200, residual oil is injected into the reactor body via the
material feed passage.
The residual oil can be any refinery residue produced during any part of a
refinement process. In
some embodiments, :refinery residue can be defined as the remainder of any
stream of material
fed to a unit of a refinement process after removal of a part or parts of the
stream of material or
as a part of any stream of material removed from the stream of material after
having been fed to
a unit of refinement process. The residual oil can be a mixture of various
refinery residues. The
residual (Al ican also be a refinery residue mixed with other waste materials,
such as slop oil, In
some embodiment, the residual oil includes hydrocarbon material remaining
after separation is
performed on a hydrocarbon source or hydrocarbon material removed from a
hydrocarbon
source. The hydrocarbon residual oil can have an average molecular weight
greater than about
300 Daltons. The hydrocarbon source from which residual oil is separated is
not limited and can
be any hydrocarbon source that requires refinery processing to produce useful
lighter
hydrocarbon material, Examples of hydrocarbon sources include, but are not
limited to, heavy
oil, bituarmen, crude oil, and kerogen from oil shale processing.
In some embodiments, the residual oil includes distillation bottoms.
Distillation bottoms
can include the remainino portion or portions of a material fed to a
distillation unit that has not
separated from the feedstock via evaporation. In a typical distillation unit,
the distillates are the
components that are evaporated and then condensed as a means of separating
each component
24
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WO 2010/121041 PCT/US2010/031260
from the feed. The varying boiling points of each of the components allow for
their separation
from the feed and from each other. The heaviest component ((Yr components) of
the material
being distilled does not undergo evaporation, but rather is separated from the
:feed by virtue of
being the only remaining component (or components) after all other lighter
components have
been evaporated out of the feed. As such, the heav est component (or
components) of the
distilled material can be considered distillation bottoms. The distillation
bottoms can be bottoms
from any type of distillation unit, including an atmospheric distillation unit
or a vacuum
distillation unit. The residual oil can also be a. combination of different
bottoms, such as a
combination of atmospheric bottoms and vacuum bottoms.
In some embodiments, the residual oil includes the as halter es and asphalt
residue that
are obtained from a deasphalting process. ing processes include processes for
precipitating asphaltenes and solvent dea.splrlatng processes, such as a
residual oil supercritical
extraction ((Yr ROSE"""') process. Where the residual oil is asphaltenes and
asphalt residue, the
material may require some form of pretreatment and/or conditioning prior to
being injected into
the nozzle reactor.
In some embodiments, the pretreatment or conditioning of asphaltenes includes
mixing
the atsphalteracs with a solvent in order to form a liquid composition that
may be injected into the
nozzle reactor. The asphaltene can be mixed with any solvent capable of
dissolving the
aslrlrarltcares and keeping them in solution until the mixture is .fed into
the nozzle reactor. In son le
embodiments, the solvent can be an aromatic solvent, such as toluene, Aromatic
100, Aromatic
150, or vacuum gas oil (YGO)_ Mixing the asphaltene and solvent can be
accomplished by any
.suitable method, including through the use of a powered mixing unit. The
amount of solvent
CA 02762093 2011-11-15
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added to the asphaltene is also not limited. In some embodiments, the
asphaltene:solvent ratio is
from about 1:2 to about 2.1..
In some embodiments, the asphaltenea and solvent mixture is preheated prior to
injection
into the nozzle reactor. In some embodiments, the mixture of solvent and
asphaltene is
preheated to an incipient cracking temperature of from about 350 T to about
450T prior to
entering the nozzle reactor.
Where the asphaltene is pretreated with a solvent as described above, the
cracked product
can undergo a separation process to separate the various components of the
cracked product,
illChlding removing any remaining solvent from the cracked product:,
Additionally, distillates
from the cracked products can be separated and recycled back into the system
and used as
solvent. The separation process can be any suitable process, such as a heating
step that causes
the solvent to evaporate .f-om the cracked products.
The residual oil can also include bottoms from a hydrocracking operation or a.
coking
operation, Residue from. a cokes is typically referred to as coke, and the
coke is typically
difficult to dispose of. One possible use of the inert coke has been to
utilize the coke in high cost
gasifiers for the production of CO and f-12 as feed to an expensive Fischer-
Tropsch plant.
However, when utilizing a nozzle reactor as disclosed herein, the coke from a
calker can be fed
into the nozzle reactor for upgrading of the high nmolecular weight coke. The
coke may require
some form of pretreatment and/or- conditioning prior to injection.
In some embodiments, the pretreatment or conditioning of coke includes tine
grinding the
coke and mixin{g it with in an organic solvent, The coke may be ground into
pieces having a size
less than 250 microns. Such grinding can be accomplished by any grinding
method known to
those or ordinary skill in the art In one example, the grinding nay be
pertbrnmed by hand. In
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another example, the coke may be ground in an industrial grinding mill. The
ground coke can
then be mixed with an organic solvent. In some embodiments, the organic
solvent can be
selected from Aromatic 100, Aromatic 150, and \'GO. The ground coke may be
mixed with the
organic solvent while being ground into smaller particles or after the coke
has been ground into
smaller particles. Where solvent is added to the coke after grinding, the
pretreatment process
may also include a mixing or agitation step to form a solvent/coke sltiurry,
Any method for
mixing the materials may be used, including manual mixing and powered mixing.
The organic
solvent a aayr be added to the ground up coke in any suitable amount .for
creating a mixture of the
two materials. In some embodiments, solvent is added to ground coke at a
weight ratio of from
2:1 to 1;1.
In some embodiments, the finely ground coke can be mixed with a gaseous
carrier
material prior to being injected into the nozzle reactor. Any carrier gas
suitable for transporting
the coke into the nozzle reactor can be used. In some embodiments, the carrier
gas is natural gas,
nitrogen, or ref nem, fuel. gas, The mechanism of transporting the mixture of
ground coke and
carrier was towards and into the nozzle reactor can generally be via dense
phase pneumatic
conveying. Any suitable ratio of coke to carrier gas can be used. In some
embodiments, the
ratio of coke to carrier gas ranges from ;30:1 to 50: 1 on a weight basis.
In some embodiments, the mixture of ground coke and solvent. can be preheated
prior to
injection into the nozzle reactor. The mixture of ground coke and solvent can
be heated to a
temperature below the solvent boiling point in order to avoid coking of pipes
and furnaces.
Where the coke is pretreated with solvent as described above, the cracked
product can
undergo a separation process to separate the various components of the cracked
product,
including removing any remaining organic solvent from the cracked product. The
separation
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process can include any suitable process, including any process for removing
the product
distillates from coke conversion. The unreacted coke material and the VGO can
be recycled
back to the initial stages of the process and blended with additional flesh
mixtures of solvent and
ground coke.
In some embodiments, the residual oil includes the stripped remainder of a
vacuum
stripping unit, Vacuum stripping units are stripper units operated at reduced
pressure to facilitaate
the transfer of less volatile components into the stripping gas. Vacuum
stripping units generally
include a feed inlet at the top of the unit where feed material is dispersed
over a packed column.
The vacuum stripping unit also includes a stripping gas inlet at the bottom of
the unit. In
operation, the stripping gas rises through the packed column as the feed
material trickles down
through the packed column. The packed column increases the surface area of the
feed a aaateriaal..
In Operation, Volatile components of the feed material transfer into the
stripping gas as it rises up
and past the feed material. The reduction of pressure inside the packed column
facilitates the
transfer of less volatile components (i.e., components that would not transfer
into the stripping
gas at atmospheric conditions). Thus, stripping gas leaving the top of the
unit includes Volatile
components stripped from the f=eed material. Conversely, the feed material
leaving the bottom of
the unit is stripped of the volatile components and includes only the least
volatile components of
the feed material. Where the feed material is a hydrocarbon source, the
lighter hydrocarbon
fractions of the feed aaaterial will be stripped away from the feed material
in the stripping gas,
while the heavy hydrocarbons will remain in the stripped material that
trickles to the bottom of
the packed column. This material can be collected at the bottom of the packed
column as
residual oil and injected into the nozzle reactor.
0
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As can be understood from the above description, residual oil can include
hydrocarbon
material where the lighter fractions of a hydrocarbon source are not part of
the residual oil,
Removing the light hydrocarbon fractions of a hydrocarbon material prior to
injection of the
hydrocarbon material into the nozzle reactor (such as in the case of vacuum
stripping as
described above) can provide several benefits Firstly, steam utilization in
the nozzle reactor can
be reduced. The lighter fractions of the hydrocarbon material will typically
be in a gaseous state
When entering the nozzle reactor, which tends to dilute the steam after it is
injected into the
nozzle reactor. .Additional superheated steam is typically required to make up
for this dilution.
By reducing or eliminating the gaseous light hydrocarbon :fractions, less
steam consumption can
occur, in some embodiments, because the steam is more. concentrated inside.
the nozzle. reactor-,
The conversion rate of the hydrocarbon material. injected into the nozzle
reactor can also be
improved by the absence of the lighter hydrocarbon material, which tends to
only interfere With
the cracking of the heavier hydrocarbon material. Finally, a more compact
system can be used.
The nozzle reactor provided in stop 1000 generally operates on the principle
that the
fractions of the residual ail having the largest molecular mass will be
cracked (most likely by
shockwaves) first inside the nozzle reactor. Introducing at least a fraction
of the residual oil into
the nozzle reactor in a liquid phase can thereby ensure that the liquid
fraction will be cracked
before any gaseous fraction of the residual oil introduced into the nozzle
reactor. Accordingly,
the temperature of residual oil can be adjusted such that at least a .fraction
of the residual oil is
injected into the nozzle reactor in a liquid phase. The temperature to which
the residual oil is
adjusted is not limited, and can van y, based on the properties of the
residual oil, including the
various boiling points of the di-ferent fractions of the residual oil,
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In some embodiments, the method can further include a. recycle step. More
specifiically,
any residual oil that exits the nozzle reactor uncracked can be recycled back
to the second
material feed port. In this rnanner, the uncracked residual oil. undergoes an
additional pass
through the nozzle reactor, thereby possibly increasing the overall efficiency
of the nozzle
reactor a it:lr respect to cracking of the re ideal OiI The untracked
residual oil can be passed
back to the second material feed port in any suitable manner, such as by
piping, and can include
a pump to help transport the uncracked residual oil back to the second
material feed port.
The small amount of pitch that may be produced by the nozzle reactor can also
be
transported to other processing equipment located upstream of the nozzle
reactor in the refilling
process. For example., where the. nozzle reactor is located downstream of a
hydrocracker or a
cok.er and generally receives the residues from these processing units, the
small amount of pitch
material produced by the nozzle reactor can be recycled back to the
hydrocrack.er or the coker.
The coke precursor carbon, also known as Conradson Carbon, disappears when
hydrocarbon
material is fed through a nozzle reactor, thus resulting in an absence of coke
precursor carbon in
the small amount, of pitch produced by the nozzle reactor. As such, this
rnaterial can be recycled
back to a. hydrocracker or coker, and processing of this material in the
hydrocracker or Coker is
less likely to produce waste coke products. The recycle stream from a nozzle
reactor can also
blend back with the initial material fed into the re.fineiA, process. That is
to say, the recycle
stream m can blend with material that has not yet. undergone. anti refinery
processing,
The blend of
the recycle stream and the initial material then undergoes refinery processing
steps.
The recycle stream can be pre-heated prior to injecting the recycle stream
into the nozzle
reactor or upstream processing units as discussed in greater detail above.
More specifically, if
the recycle stream is blended with material that has not been at least
partially preheated, then the
CA 02762093 2011-11-15
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combined stream can be preheated prior to being introduced into the nozzle
reactor or upstream
processing units. The temperature to which the blended material is pre-heated
can generally be
any suitable temperature for facilitating cracking of the blended material
inside the nozzle
reactor or processing the blended material in upstream processing units, In
some embodiments,
t:lre blended material is pre-heated to a range of from 300'(' to 440 C, If
the recycle stream is
injected directly into the nozzle reactor or upstream processing unit without
blending, then the
recycle stream may not need to be pre-heated. This is because the recycle
stream will already be
at the temperature to Which material fed into the nozzle reactor or upstream
processing unit is
pre-heated,
In some embodiments, a method of modifying a refinery plant including at least
one of a
coker. a hydrocrackc r, and a deaasphalting unit is disclosed, The method
generally includes
replacing a coker, a hydrocracker, and/or a deaasphaiting unit with a nozzle
reactor as disclosed
herein. Substituting a coker, a hydrocracker, aand or a deasphalting unit with
a nozzle reactor can
beneficially improve the conversion of the residual oil into light
hydrocarbons. For example,
cokers generally convert up to 60 wt $; of residual oil and hydrocrackers
generally convert 75
wt-% of residual oil, while a nozzle reactor .may convert as much as 95 wt-%
of the residual oil.
SOstituting the nozzle reactor for at least one of a Coker, a hydrocracker,
and a
deaasphalting unit can be carried out by any suitable procedure for
disconnecting at least. one the
coker, hydrocracker, and deasphalting unit .from the refinery process and
connecting the nozzle
reactor to the refinery process. Generally speaking,, substitution may only
require diverting the
stream normally fed to at least one of the Coker, hydrocracker, and/or
deasphalting unit to, for
exaaxmple, the Hats rial. feed passage of a nozzle reactor, In this manner,
the food stream for at
least one of a Coker, hydrocrack.er, ands or deasphalting unit can be fed into
the reactor body of
_}1.
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the nozzle reactor where a cracking material will work to crack the heavy
hydrocarbons in the
feed stream.
The nozzle reactor generally includes a nozzle reactor according to any
embodiment of
the nozzle reactors described in greater detail above.
The nozzle reactor can replace any type of cokes, hydrocracker, or
deasplralti.ng unit. For
example, the nozzle reactor can replace a delayed coker, a fluid, coker or a
flexicoker. The
nozzle reactor can also replace a ROSETRM deasphalting unit (or be used in
conjunction with it to
treat asphal tunes).
The nozzle reactor used in place of at least one of the coker, hydrocracker
and/or
deasphalting unit may produce a small quantity of pitch by-product. The. pitch
bye-product can be
recycled back into the nozzle reactor via, for example, the material feed
passage. Such a recycle
stream is not possible in, for example, a corker, since it is difficult. .for
a coker to process the very
stable coke.
In. some embodiments, the small amount of pitch bye-product that may be
produced by the
nozzle reactor can be recycled back to any of the at least one coker,
hydrocracker or solvent
deasphalting unit that -aas not been replaced in the system by a nozzle
reactor. For example, in a
refining process having a coker and a hydrocra.cker and where only the
hydrocracker is replaced
with a nozzle reactor, the pitch by-product that may be produced by the nozzle
reactor can be
recycled back to the coker.
If such a pitch by-product is not recycled back into the nozzle reactor or a
remaining
cuker, hydrocracker or deaspha.ltin;y unit, the pitch by-product can still be
used for steam
generation, such as the steam can be used as a cracking material in the nozzle
reactor.
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t.Unrecycled pitch by-product can also be further processed to generate
asphalt product that can be
used for road surfacin{g, roof shingle production, and other products
utilizing asphalt,
With respect to replacing corkers, the use of a nozzle reactor can include the
added benefit
of producing a stable product. Generally speaking, cokers produce highly
oleuinic and hence
very unstable products. 'T'hese materials generally need an immediate
hydrotreating step to
produce a more stable product. To the contrary,, the nozzle reactor produces
products that are
stable and do not require any fur'th.er processing before transport to a feral
product production
facility. Furthermore, the as produced in the nozzle can be less than 10 of
what a cok.e:r
produces, which results in environmental advantages. Also, as noted above,
cokers generally do
not allow for the recycle of stable coke produced. by the Coker, which thereby
drastically reduces
the total liquid product yield possible in a Coker-
With respect to replacing hydrocrackers, the use of a nozzle reactor can
include the added
benefit of being less expensive and less complex than a traditional
hydrocracker. Moreover,
unlike the h>cirocrrc:lcers, no hydra glen is necessary in operation of the
nozzle reactor while still
producing a stable product.
With respect to replacing deasphaltin4g units, the use of a nozzle reactor can
include the
added benefit of limiting or eliminating the need to dispose of asphaltene
waste. Refineries
using deasphalting units typically have to pay to dispose of these hydrocarbon
wastes, but this
material can readily be further processed through the nozzle reactor.
Replacing a deasphalting
unit with a nozzle reactor can also increase the versatility of a ref nery
plant normally employing
a deasphalting unit. Typically, deasphalting units are used in light oil
refineries. "These light oil
refineries are not capable of processing heavy oil due to the heavy waste
components found
therein. However, when a nozzle reactor is used to replace a deaslrhaitin<g
font, the light oil
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refinery obtains the ability to process the heavy oil it previously could not.
Deasphalting units
such as those performing the ROSE process may be eliminated from the refinery
by
substituting a nozzle reactor and a vacuum distillation tower while also
expanding the ability of
the refinery to handle different types of material.
In a. refinery plant including any combination of a coker, a hydrocracker, and
a
deasphalting unit, the.. method of modifying the refinery plant can include
replacing any
combination of the units with one or more nozzle reactors. The units (.e., the
Coker,
hydrocracker, and deasphalting unit) can be replaced with a nozzle reactor at
a l :1 ratio (Ã.er., one
nozzle reactor for each unit replaced). Furthermore, one Coker, one
hydrocracker, and or one
deasphalting unit can be replaced with multiple nozzle reactors.
In some embodiments, one or more nozzle reactors are used in conjunction with
existing
cokers, hydrocrackers, or deasphaltirg units. For example, where the
capacities of the existing
cokers, hydrocrackers, or deasphalting units are limited nozzle reactors can
be added to increase
the overall capacity of the refinery.
In some embodiments, a refinery plant utilizing the nozzle reactors described
herein is
disclosed. The refinery plant generally utilizes a .refinery: residue-
producing processing, unit
having a refiner residue. outlet and a nozzle. reactor. The re-finery residue
outlet of the refinery
residue-producing processing unit is fluidly connected to the nozzle reactor
such that refinery.
residue leaving the refinery residue--producing processing unit can be fed
into the reactor body of
the nozzle reactor for- cracking with cracking material.
The refinery plant can generailly be any type of refinery plant used for
processing of
heavy hydrocarbon material, such as heavy oil, bitumen and crude oil, into
useful, lighter
hydrocarbon materials. The refinery plant can therefore also include any
additional units needed
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for- the processing of heavy hydrocarbon material. The refiner plant can
include at least one of
a Coker, a hydrocracker, and a deasphalting unit, although in some
embodiments, the refinery
plant excludes these units. In their place, the refinery plant utilizes one or
more nozzle reactors
to crack feeds typically sent to a Coker, hydrocracker, or deasphaitià .g
unit.
The refinery residue-producing processing unit of the .ref nery plant can be
any type of
refinery residue-producing processing unit used in heavy hydrocarbon
processing. Examples of
refinery residue-producing processing unit that can be included in the
refinery plant include, but
are not limited to, distillation units, vacuum stripping units,
hydrocracke.rs, cok.er-s, and
deasphalting units. The refinery plant can include more than one refinery
residue-prod ucin4g
processing unit and can include more than one type of refinery residue-
producing processing
unit. As noted above, the refinery residue-producing processing unit can
include a refinery
residue outlet. The refinery residue outlet can he the outlet for the residue
portion of the feed
stream fed to the refinery residue-producing processing unit The refinery.
residue can be as
described above in the previous embodiment, and therefore generally includes
the remainder of
any stream of material fed to a unit of a refinement process after removal of
a part or parts of the
stream of material.
The nozzle reactor used in the refinery plant can generally be a nozzle
reactor according
to any embodiments described in greater detail above.
As noted above, the refinery residue-producing processing unit can include a
refinery
residue outlet and the refinery residue outlet can be in fluid communication
with nozzle reactor
such that refinery residue leaving the refinery residue-producing processing
unit via the refinery
residue outlet is injected into the reactor body of the nozzle reactor for
cracking with cracking
material. In some embodiments, the refinery residue outlet is in fluid
communication with the
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material feed passage of the nozzle reactor. In some embodiments, the refinery
residue outlet is
in fluid communication with the injection passage. Fluid communication between
the refiner >
residue-producing processing omit and the nozzle reactor can be achieved by
any suitable rneanns.
For example, the fluid communication can be achieved via a pipe running
between the two units.
As with other embodiments described above, the .nozzle reactor can also
include a recycle
stream so that any material leaving the nozzle reactor can be fed back to the
nozzle. reactor. The
material that can be recvcled back. into the nozzle reactor can include
cracked material,
uncracked :naate.rial, or pitch by-product. The recycle stream can connect
with the refinery
residue stream being fed to the nozzle reactor or can recycle back to a
different inlet near the
injection end of the reactor body of the nozzle. reactor. A recycle stream of
material leaving the
nozzle reactor can. also be recycled back to an upstream processing unit M.
the refinery plant. In
some embodiments, a light product stream of the nozzle reactor is recycled all
the way back to
the feed stream initially entering the refinery system such as prior to being
introduced into a
distillation unit. In some embodiments, pitch by-product produced by the
nozzle reactor is
recycled back to a. Coker, hydrocracker or other processing unit.
The refinery residue need not be pro-heated prior to being injected into the
nozzle reactor.
The refinery residue leaving the refinery residue-producing processing unit
can already be at a
temperature suitable of injection into the nozzle reactor. For example.,
refinery residue such. as
distillation to tier bottoms leave the distillation towers at a high
temperature, and therefore can be
injected into the nozzle reactor without a pre-heating step. In some cases,
the refinery residue is
cooled before introduction into the nozzle reactor. For example, LC Finer
bottoms can be cooled
when valuable syncrude or virgin oil is blended into the bottoms to make
transportation feasible.
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The discharge temperature of the hydrocracker furnace (---525 `C) is higher
than the feed for the
nozzle reactor (4215 C).
In some embodiments, a method of assembling a refinery plant is disclosed.
with
reference to Figure 9, the method generally includes a step 2000 of providing
a refinery residue-
producing processing unit, a step 2100 of providing a nozzle reactor, and a.
step 2200 of
providing refinery residue, fluid communication between the refinery residue
outlet of the
refinery residue-producing processing unit and the second material feed port
of the nozzle
reactor. More specifically, the refinery :residue-producing processing unit
has a refinery residue
outlet and the nozzle reactor has a material feed passage. The fluid corm
Unication between the
refinery, residue-producing processing unit and the nozzle reactor is provided
by connecting the
refinery residue outlet of the refinery residue-producing processing unit with
the material feed
passage of the nozzle reactor.
4
The refinery plant to be assembled can generally be any type of refinery plant
used for
processing of heavy hydrocarbon material., such. as heavy oil., bitumen. and
crude oil, into useful.,
lighter lad<drocarbon .materials The :refinery plant being assembled can
therefore also include any
additional units needed for the processing of heavy hydrocarbon material.
The refinery residue-producing processing unit provided in step 2000 can be
any type of
refinery residue-producing processing unit used in hydrocarbon processing.
Examples of
refinery residue-producing processing unit include distillation units and
deasphalting units. The
distillation units that can be included in the refinery plant include, but are
not limited to,
atmospheric distillation units and vacuum distillation units. The refinery
plant can include more
than one refinery residue-producing processing unit and can include more than
one type of
refinery residue-producing processing unit. As noted above, the refinery
residue-producing
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processing unit can include a. refinery residue outlet. The refinery residue
outlet can be the outlet
for the residue portion of the feed stream fed to the refinery residue-
producino processing unit
that is not separated from the feed strean-a.
T ie step 2000 of providing a refinery residue-producing processing unit can
include, but
is not limited to, partially or wholly constructing the refiner: residue-
producing processing unit
or obtaining the refinery residue-producing processing unit from a third
party, such as via a sale,
donation or lease of the equipment.
The nozzle reactor provided in step 2..1.00 can generally be a. nozzle reactor
according to
any embodiment described in greater detai I above.
The step 2100 of providing a nozzle reactor can include partially of wholly
constructing
the nozzle reactor or obtaining the nozzle reactor from a third party, such as
via a sale, donation
or lease of the equipment.
The step 2200 of providing refinery residue fluid communication between the
refinery
residue outlet of the refinery residue-producing processing unit and the
material feed passage of
the nozzle reactor can be accomplished by any suitable :means for allowing
refinery residue from
the .refiner residue-producing processing unit to travel into the reactor body
of the nozzle, An
example of providing such a fluid communication includes providing piping
between the refinery
residue outlet of the refinery residue-producing processing unit and the
material feed passage of
the nozzle reactor. Such fluid communication can include allowing the refiner
Y residue to travel
through the pipe via gravity or through the use of a punmp.
Providing refiner y residue fluid communication betAveen the refinery residue
outlet and
the material feed passage can also allow for the addition of other streams to
the fluid
communication provided between the refinery residue-producing processing unit
and the nozzle
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reactor. For example, where piping is used to provide the fluid communication,
the piping
between the refiner = residue-producing processing unit and the nozzle reactor
can receive other
piping that delivers additional components to the refinery residue stream
traveling to the nozzle
reactor. Such components can include, but are not limited to, a solvent to
decrease the viscosity
of the refinery residue or a recycle stream returning untracked refiner:
residue that has passed
through the nozzle reactor back to the sr;cond material fee port. Other
chemicals, reagents and
or hydrocarbons can also be added to enhance the uptake of hydrogen. from the
first material into
the second ma.terial.
In some embodiments, fluid communication is provided between two or more
refinery
residue-producing processing units and a. nozzle reactor or between a refinery
residue-producing
processing unit and two or more nozzle reactors. For example, providing the
fluid
communication can include piping that branches in order to either split the
ref ner y residue
stream so that it can be injected into multiple nozzle reactors or by joining
together several
refinery residue streams from diferent refinery residue-producing processing
unit to travel to
one nozzle reactor. As such, the nozzle reactor can receive a refinery residue
stream comprising
refinery residue from both a different types of .ref=inery residue-producing
processing Unit, such
as from a vacuum distillation column and an atmospheric distillation column.
In several of the embodiments described above, a recycle stream is
contemplated,
whereby material leaving the nozzle reactor is recycled back through the
nozzle reactor in an
attempt to further crack the material or, in the case of material that passes
through the nozzle
reactor untracked, crack the material for the first time. In addition to the
recycle stream or
alternative to the recycle stream, further nozzle reactors may be used to
crack this material..
Method utilizing multiple nozzle reactors can be used to increase the overall
conversion of
}
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material feed into lighter components via. cracking. The nozzle reactor system
described herein
can achieve this increase in overall conversion by utilizing; a first nozzle
reactor to conduct a first
cracking step, and then passing any material not cracked or not su f- ciently
cracked by the :first.
nozzle reactor into a second nozzle reactor that operates under conditions
selected for cracking
the untracked or not sufficiently cracked material.
With reference to Figure 10, the nozzle reactor system 300 generally includes
a first
nozzle reactor 310 and a second nozzle reactor _ 2(?. Nozzle reactor system
300 also includes a
first separation unit 330. First separation unit 3:30 generally separate the
material leaving first,
nozzle reactor 310 into a light stream and a heavy stream. .Accordingly, first
separation unit 330
include a light stream outlet 332 and a heavy stream outlet 334. Heavy stream
outlet 334 is in
fluid communication with the material feed passage of second nozzle reactor
32.0 so that the
heavy components of heavy stream outlet 334 are transported to second nozzle
reactor 320 for
cracking.
First and second nozzle reactors 310, 3220 can generally be a nozzle reactor
according to
any embodiments described herein.
First and second nozzle reactors 310, 320 can. be identical or first and
second nozzle
reactors 310, 320 can be different, In some embodiments, second nozzle reactor
320 has a
smaller interior body chamber volume than the interior reactor chamber volume
of first nozzle
reactor- :310. For example, the interior reactor- chamber volume of second
nozzle reactor 320 can
be V3 3 or less the interior reactor chamber volume of first nozzle reactor
310. Additionally
nozzle reactor system 300 en include more than two nozzle reactors. Other
features of the nozzle
reactor are described in greater detail above.
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First separation unit 330 can generally include any type of separation unit
capable of
separating the lighter r aaterÃal that is the product of cracking the material
feed fed into first
nozzle reactor 3.10 from the heavy material that is generally made tip of
material feed that was
not cracked or not sufficiently cracked in first nozzle reactor 310. Examples
of suitable
separation units include, but are not limited to, distillation units, gravity
separation units,
filtration units, and cyclonic separation units.
First separation unit 3310 can be in fluid communication with the ejection end
of first
nozzle reactor 310 such that the material leaving, first nozzle reactor 310 is
fed into first
separation unit 330. Any manner of fluid communication can be used between
first nozzle
reactor 310 and first separation unit :330. In one example, the fluid
communication can be piping
extending between the ejection end of first nozzle reactor ;310 and first
separation unit 330.
AS noted above, first separation unit. 3303 can generally include light stream
outlet 33'
and heavy stream outlet 334. Light stream outlet 332 generally includes any
materials having a
predetermined property or properties, such as a molecular eight, boiling
point, API gravity, or
viscosity. As such, light stream outlet 332 can include, for example, a)
material feed that is not
cracked inside first nozzle reactor 310 but that possessed a predetermined
property prior to being
introduced into first nozzle reactor 310, and b) material feed that has been
cracked inside first
nozzle reactor 310 such that the cracked material obtains the predetermined
property. Thus,
where the material feed injected into first nozzle reactor 310 via the
material feed passage is
bitumen, light stream outlet 332' can include uncracked hydrocarbons that had
the predetermined
property when injected into first nozzle reactor 310 and cracked hydrocarbon
molecules that
obtained the predetermined property upon being cracked inside of first nozzle
reactor 310.
Correspondirr ;ly, heavy stream outlet. 3334 generally includes any materials
not having the
41,
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predetermined property or properties. As such, heavy stream outlet 334 can
include, for
example, a) material feed that is not cracked inside first nozzle reactor 310
and that did not
possess the predetermined property upon being introduced into first nozzle
reactor 310, and b)
material feed that has been cracked inside first nozzle reactor 31.0 but that
did not result in the
cracked material possessing the predetermined property. Thus, where the
material feed is, e=g=,
bitumen, heavy stream outlet 334 may include untracked hydrocarbon molecules
that did not
have the predetermined property when. infected into first nozzle reactor 310
and cracked
hydrocarbon molecules that did not obtain the predetermined property upon
being cracked inside
of first nozzle reactor 3 10.
Any property, propertyy, value or property range can be selected to determine
whether a
Material is part of light stream outlet -3.32 or heavy stream outlet 334.
Examples of properties and
property values that can be used to classify the material leaving first nozzle
reactor 3 1.0 include a
molecular weight above a selected value, a molecular weight below a. selected
value, a molecular
weight within a selected range, a boiling point above a selected value, a
boiling point below a
selected value, a boiling point within a selected range, an API gravity above
a. selected value, are
API gravity below a. selected value, an API within a. selected range, a
viscosity above a selected
value, a viscosity below a selected value, or a viscosity within a selected
range. Fu thernmore,
multiple properties can be used to determine whether a material leaving first
nozzle reactor ;31 3
is part of light stream outlet 332 or heavy stream outlet. 331. For example,
the material may have
to have both a molecular weight below a selected value and a boiling point
below a selected
value to be part of light stream outlet 332. The value or range selected for
the property is also
not limited. The value or range of values selected can be based on known
property values for
useful factions of a material feed.
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In order to transport the components of heavy stream outlet 334 to second
nozzle reactor
320: a fluid communication is established between heavy stream outlet 334 and
second nozzle
reactor 320, More specifically; a fluid communication is established between
heavy strearn
outlet 334 and the material feed passage of second nozzle reactor 320.
However, fluid
communication can also be established between heavy stream outlet 334 and any
portion of
second nozzle reactor 3"0. Any, manner of fluid communication can be used
between second
nozzle reactor 320 and heavy stream outlet 334.. In one example, the fluid
communication is
piping extending between the heavy stream outlet. 134 and second nozzle
reactor 320 A pump
can also be used in connection with the fluid communication to assist the flow
of material
through the fluid communication.
Second nozzle reactor 320 can be operated at different operating conditions
than first
nozzle reactor 31 0 so as to increase the likelihood of cracking the
components of heavy stream,,
outlet : 34. As discussed in greater detail abo e, it is theorized that nozzle
reactors as
described herein crack the molecules having the largest molecular mass first.
In first nozzle
reactor 3 10, a relatively high operat:in temperature can be selected such
that only a high boiling
point fraction of the feed material is present in the reaction chamber as a.
liquid (or possibly a
solid), while the remaining fractions are present in the reaction chamber as a
gas. As such, the
fraction that is present in the reaction chamber as a liquid or solid has the
largest molecular mass
and will be the first material cracked by the shock waves produced inside the
nozzle reactor.
Gaseous fractions can pass through the reaction chamber without being cracked.
These gaseous
fractions can then become part of the heavy stream fed to second nozzle
reactor 320. If second
nozzle reactor 320 is operated at the same operating conditions as first
nozzle reactor 310, the
heavy stream will remain in the gas phase and likely pass through second
nozzle reactor 320 with
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no further cracking being accomplished. Accordingly, the operating conditions
that can be
altered bete een the first and second nozzle reactors 310, 320 are those which
will increase the
rnass of the components of heavy stream outlet 334 as they enter second nozzle
reactor 320. In
other words, operating second nozzle reactor 320 under conditions that will
transform the
gaseous hea.. f stream into a liquid or solid ma y increase the rate at which
second nozzle reactor
320 cracks the components of heavy stream outlet 334. Exemplary operating
conditions that can
be altered between first nozzle reactor 31.0 and second nozzle reactor 320 and
that will increase
the mass of the components of heavy stream outlet 334 include decreasing the
temperature of the
components of heavy stream outlet 334. Reduction in temperature can be
achieved by reducing
the ratio of cracking material mass to material feed mass or by reducing the
superheat in the
cracking material while maintaining the ratio of cracking material mass to
material feed mass.
In some embodiments, nozzle reactor system '100 ..further includes a second
separation
unit 340. Second separation unit 340 can be in fluid communication with the
ejection end of
second nozzle reactor 320 such that material leaving second nozzle reactor 320
is fed into second
separation unit 340. Second separation unit 340 can generally include a light
stream outlet 342
and a. heavy stream outlet 34.
Like first separation unit 330, second separation unit 340 generally includes
any type of
separation unit capable of separating lighter material that possesses a
predetermined property
when leaving Second nozzle reactor 320 from the heavy mmatenal that does net
possesses the
predetermined property when leaving second nozzle reactor 320. Examples of
suitable
separation units include, but are not limited to, distillation units, gravity
separation units,
filtration units, and cyclonic separation units.
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Second separation unit 340 can be in fluid communication with the ejection end
of
second nozzle reactor 320 such that the rna.terial leavin{g second nozzle
reactor 320 is fed into
second separation unit 340. Any manner of fluid communication can be used
between second
nozzle reactor 320 and second separation unit 340. In one example, the fluid
communication is
piping extending between the ejection end of second nozzle reactor 320 and
second separation
unit 340.
As noted above, second separation. unit _i40 generally includes light stream
outlet 342 and
heavy stream outlet f Li
.> ght stream outlet 342 generally includes material that has a.
predetermined property or properties when leaving second nozzle reactor 320.
Correspondingly,
heavy stream outlet 344 generally includes material that does not have the
predetermined
property or properties when. lowing second nozzle reactor 320. The
predetermined property or
properties used to separate streams in second separation unit 340 need not be
the same
predetermined property or properties used to separate streams in first
separation unit 330.
Alternatively, the same predetermined property or properties can be used in
both first separation
unit 330 and second separation unit 340. As with first separation unit 330,
any property,
property value or property value ranged can be selected as the parameter for
separating light and
heavy streams.
In some embodiments, light stream outlet 342 is in fluid communication with
first nozzle
reactor 31.0 or second nozzle reactor 320 via a recycle stream, Despite
possessing a
predetermined property, or properties, the material that makes up light stream
outlet 342 may still
be too large and heavy to be used as useful product, and taus requires further
cracking. Such
cracking can take place in either first nozzle reactor 33.10 or second nozzle
reactor 320 or both
depending on the characteristics (such as molecular weight or boiling p(int)
of the material that
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makes up light stream outlet 342. Accordingly, providing a fluid communication
betNw,een light
stream outlet 342 and first nozzle reactor 310 a.nd/or second nozzle reactor
320 allows for this
second attempt at cracking the armaterial, although this time in an improved
condition for
cracking. Any manner of fluid communication can be used between light stream
output 342 and
first nozzle reactor 310 and/'or second nozzle reactor 320. In One e: ample,
the fluid
communication is piping extending between the light stream output 342 and the
material feed
passage of first nozzle reactor 31 0 and/or second nozzle reactor 320..
.A similar recycle stream can be used to divert the material of heavy stream
outlet 344
back to eit-her first nozzle reactor 31C) or second nozzle reactor 320 The
manner of providing,
such a recycle stream can be similar to the. recycle stream as described
above, such as by
providing piping between heavy stream outlet 344 and either first nozzle
reactor 310 or second
nozzle reactor 320.
Similar recycle streams can also be provided between light stream outlet 332
and first
nozzle reactor 310. Additionally, a portion of heavy stream outlet 334 can be
recycled back to
first nozzle reactor, while the remainder of heavy stream outlet 334 is
injected into second nozzle
reactor 320 as described in greater detail above. Furthermore, a portion of
light stream 332 can
be recycled back to first nozzle reactor 310,
In the above description, two nozzle reactors are discussed. However, the
nozzle reactor
system is not limited to two nozzle reactors. Any number of nozzle reactors
arranged in series
can be used. Each nozzle reactor can operate at different conditions with each
nozzle reactor
operating under conditions specifically selected to increase the likelihood of
cracking a material
that has passed through a previous nozzle reactor uncracked or not
sufficiently cracked.
Furtherniore, the nozzle reactors can be arranged in parallel in addition to a
series arrangement.
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For example, a first nozzle reactor can produce a heavy stream and a light
streams, with the heavy
stream being transported to a second nozzle reactor and a light stream being?
transported to at hi rd
nozzle reactor.
In some embodiments, a material feed crtacking, method is disclosed. The
material feed
cracking method generally allows for an increase in conversion of material
feed into lighter
components by utilizing two or more. reactor nozzles. The first reactor nozzle
is utilized in a
similar fashion to the detailed discussion above re garding the nozzle
reactor, However, an
additional nozzle reactor is used to deal with the material that passes
through the first nozzle
reactor but that is not cracked or not sufficiently cracked, More
specifically, the operating
conditions of the second nozzle reactor are selected so that the second nozzle
reactor is more
likely to break down material that passes through the first nozzle reactor
uncracked or not
sut.t.icc.ratly cracked.
The material feed cracking method generally includes a first step of injecting
a first
stream of cracking material through an injection passage of a first nozzle
reactor into an interior
reactor chamber of a first nozzle reactor. Material .teed is then injected
into the :interior reactor
chamber of the first nozzle reactor adjacent to the injection passage of the
first nozzle reactor and
transverse to the first stream of cracking material entering the interior
reaction chamber of the
first nozzle reactor from the injection passage of the first nozzle reactor,
in this manner, a first
light material and a first heavy material are produced. The method then
includes a step of
injecting a. second stream of cracking material through an injection passage
of a second nozzle
reactor into an interior reactor chamber of a second nozzle reactor.
Additionally, the first heavy
r aaterial is injected into the interior reactor chamber of the second nozzle
reactor adjacent to the
irljecti()n pas cage Of the second nozzle reactor and transverse to the second
stream of cracki110
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Material entering the interior reactor chamber of the second nozzle reactor
from the injection
passage of the second nozzle reactor. In this manner, a second light material
and a second heavy
rnaterial are produced..
`Be first and second nozzle reactors referred to above can generally include a
nozzle
reactor according to any embodiment described herein.
The first and second streams of cracking material can be any suitable cracking
material
for cracking the material feed. In some embodiments, the cracking material is
a cracking gas,
such as steam. The first and second streams of cracking material can be
introduced into the
injection passages at any suitable temperature and pressure. In some
e.mabodi.ments, the first and
second streams of cracking material are, injected into the injection passage
at a temperature of
from. about 600 C to about 850 "tr.': and at a pressure of from about 1.5 bar
to about 2100 bar.
The material teed can be any type of material that may be broken down into
smaller and
lighter components. In some embodiments, the material feed is a hydrocarbon
source, such as
heavy oil, bitumen, crude oil, or any residue with. a high asphaaltene
content. The residue can. be
any residual portion of a. separated hydrocarbon stream, such as the bottoms
fzac:tiorl from a
distillation unit. The high aasphaltene content can be an asphaltene content
greater than 4 wt% of
the residue. Hydrocarbon sources such as these require cracking to break down
the heavy and
large molecules of the hydrocarbon into light components that may be
beneficially used.
The material feed and first heavy stream can be introduced into the material
feed
passages at any suitable temperature and pressure. In some embodiments; the
material feed and
first heavy stream are injected into the material feed passages at a
temperature of from about 300
C to 500 C an(] at a pressure of from about 2 about to about 15 bar.
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The pressure inside the interior reactor chamber of the first and second
nozzle reactor can
range from about 2. bar to about 15 bar. The ratio of cracking material to
material feed can range
from. about 0-5- 1.0 to about 4-1 1. The ratio of cracking material to first
heavy, material can range
from about 0,1:10} to about 0.8;1Ø
As noted above, the in ection of the material feed and the first stream of
cracking material
can result in the production of first light material and first heavy material.
This is because the
nozzle reactor does not achieve total cracking of all. material feed injected
into the first nozzle
reactor. The short retention time of the .material feed in the interior
reactor chamber combined
with the preference of the nozzle reactor to crack the largest molecules first
does not allow for
shockwaves generated by the injection passage to crack all of the material
feed, and some
material feed will therefore pass all the x%-ay through the first nozzle
reactor without being
cracked. Specifically, fractions of the material feed in a gaseous phase when
passing through the
interior reactor chamber can pass through the nozzle reactor without being
cracked. These
gaseous fractions can be considered nonparticipating in that they will not be
cracked by the
shock waves. Where such material feed passing through the nozzle untracked
includes large
molecules, further work may need to be done to accomplish cracking of the
material into useful
mater ial.
In some embodiments, the operating conditions of the first nozzle reactor can
be selected
such that only a fraction of the material feed in the nozzle reactor is ire a
liquid or solid phase,
while the remaining fractions of the material feed are in a gaseous phase.
This can be achieved
by, for example, pre-heating the material feed prior to injection into the
nozzle reactor. In an
example where the material feed includes bitumen, the bitumen can comprise a
fraction having a
boiling point higher than 200'C, The pre--heating temperature can be selected
such that only this
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fraction of the bitumen is in liquid or solid form, and therefore is the
fraction most likely to be
cracked by the first nozzle reactor. The remaining fractions of the bitumen in
the gaseous phase
can pass through. the first nozzle reactor uncracked, at which point they can
be fed to a second
nozzle reactor. The temperature of the gaseous material leaving the first
nozzle reactor can be
altered such that the gas transforms into liquid or solid and thereby
increases the chances of the
material being cracked in the second nozzle reactor.
Accordingly, the first heavy material can be injected into the second nozzle
reactor to
undergo another attempt at cracking the material in the nozzle reactor. The
second nozzle
reactor cab be identical in size and dimension to the first nozzle reactor, or
may be different than
the first nozzle reactor. In some embodiments, the operating conditions of the
second nozzle
reactor are different from the operating conditions of the first nozzle
reactor as described in
greater detail above. For example, the temperature of the material injected
into the second
nozzle reactor can be reduced to add mass to the gaseous components being fed
into the second
nozzle reactor to better accomplish the cracking of the hydrocarbons that make
up the first heavy
material injected into the second nozzle reactor.
In some embodiments, the first light material and the first heavy material
leaving the :first
nozzle reactor are separated prior to the introduction of the first heavy
material into the second
nozzle reactor. In this manner, the lighter and smaller components that make
Lip the first light
r material can be separated for consumption or recycle while the heavy and
large components that
make up the first heavy material can be sent to the second nozzle reactor.
Sending only the first
heavy material to the second nozzle reactor can be beneficial because the
second nozzle reactor
will function to specifically crack these components while not being impeded
by the presence. of
the first light material.
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Separation of the first light material and the first heavy material can be
accomplished by
any suitable means for separation of the components. Properties such as
density and boiling
point can be used to effect separation. Separation can include, but is not
limited to, separation by
distillation units, gravity separation saints, filtration units, and cyclonic
separation units.
As with the first light material and the first lleav material, the second
light material and
the second heavy material can also be sepaara:ted. Any suitable means for
separation, such as
those mentioned above, can be used to effect the separation.
The met and can .further comprise a step of injecting the first light
material, first heavy
material, second light material. or second heavy material into the reaction
chamber of the first
nozzle reactor or second nozzle reactor. In addition or in place of such a
recycle stream, the
method can further comprise a step of injecting the first light material or
second light material
into the reaction chamber of the .first nozzle reactor.
EXAMPLES
Background Example
A conventional refinery includes four separate hydrocarbon processing units:
1, : , Distillation Unit (1;)
.2. A lalaaicl (':ata7:l tic f':racker i:;l ('. `)
?. A Hydrotreater
4. Coker
Cold lake bitumen is fed to the Distillation Unit where the bitumen feed is
fractionated
as follows:
20.8% light fraction (boiling point 700 deg F)
24.2` o ra id-tlistillaate fraction (boiling pout between 7[l l and 10.50 tle
p}
54.9% bottoms fraction (boiling point W50 deg F).
100% Total
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The bottoms fraction (549%)') is fed to a Coker, which converts the bottoms as
follows:
18.4% petroleum cokes for disposal
11.7% heavy Coker oil (1-1C0)
19.9% 1.1 gilt gas oil
4 9%~% gas
54,9% `rota)
The HCO (11.7%) from the Coker is joined with the mid-distillate fraction
(24.2%) :frog
the distillation unit, and the mixture (35 9% total) is fied to the Fluid
Catalytic Cracker. In the
FCC, the mixture is cracked into the following products
5.0% marketable .fuel oil
7.8% combined gas (5,6%) and FCC cokes (2.22%)
"3._10 liq d product
5,9% Total
The FCC liquid product (2.3.1joins the Coker light gas oil (19 9%) and
Distillation
Unit light fraction (20.8%) as feed (total 63.8%) to the hyrdrotreater, where
all feed is converted
into light products. The following overall balance is the result:
l3ituur men? Feed 100.0 r
Hydrotreater Light : roduct 63.8%
FCC Marketable Fuel Oil 5,0%i)
Cokes- 20.6%
Gases: 10.5%
100%
Exarple: A
A modified refinery can have four separate hydrocarbon processing units, where
a Nozzle
Reactor System replaces the traditional Coker:
1. A Distillation Unit (DU)
?. A Fluid Catalytic Cracker (.FCC.')
3.
A llyclrotreater, a d
4. A Nozzle Reactor System (NRS)
Cold lake bitumen is fed to the Distillation Unit where the bitumen feed is
fractionated
as .f ollow's:
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20.8% light fraction (boiling point 700 deg F)
24..21 raid-distillate fraction (boiling point between 700 and 1.050 deg f,)
54.9% bottoms fraction (boiling point > 1050 deg :F),
100% Total
The DU bottoms fraction (5,4.9%) is fed to a Nozzle Reactor System and is
converted into
the following products:
T4% a N_t;S liquid pitch for t'uriher processing or disposal
?2.8 NRS mid-distillate.
24.7% liquid pitch stream (recycled back to DU)
54.9% Total
The NRS.mid -distillate (30.9%)joins the DtJ raid-distillate (24.2%) as feed
stock (55.l
total) for the Fluid Catalytic Cracker. In the FCt', the feedstock is cracked
into the following
products:
6.01/1% fuel oil (recycled back to the N RS for further c racking)
9.8% combined gas (7.S%) and FCC cokes (2.0%)
.0,2% liquid product
5. 1% Total
The FCC liquid product (39.2%)') joins the NRS mid-distillate product
(212,8%)') and
Distillation Units light fraction (20.8%) as feed (total S21S%) to the
hydrotreater where all is
converted into light products. The following overall balance is the result:
Bitumen Feed 100.0 r
Hydrotreater Light .Product 82.8%
FCC Cokes: 2.%
Gases: 7.81%
NRS Liquid Pitch 7.4%
Comparing Background Example (coking) with Example A (nozzle reactor), a
nozzle
reactor system will produce 229,6% more valuable product than a canker unit
operation will
generate. Further.mc re the nozzle reactor systern also produces less gas and
a liquid pitch product
that can be farther processed if needed. The reduction in the amount of cokes
can be an
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advantage to the system described in Example A, as it is well known that the
disposal of solid
petroleum coke can present an environmental problem.
F\:ampie B
(Distillation bottoms comprising hydrocarbons having, predominantly molecular
weights
in the range of 300 to 4,000 are adjusted to a. temperature of 425 deg C. The
distillation
bottoms are injected into a nozzle reactor via the second material feed port
of the. nozzle reactor.
Simultaneously, superheated steam at a temperature of about 1250 deg F is
injected into the
conver Ain- section of the nozzle of the nozzle reactor at a flow rate of
about 1.5 times the flow
rate of the distillation bottoms into the nozzle reactor. The distillation-r
bottorras and steam are
retained inside the nozzle reactor for a period of time around ft6 seconds.
tile.}ck~.w~aves produced
inside the nozzle convert approximately 45% of the distillation bottoms having
a boiling point
above 1050 deg F into lighter hydrocarbons having a boiling point less than
1050 deg, 1". The
nozzle reactor emits a mixture of steam, cracked, and uncracked hydrocarbons
at a temperature
of about 400 deg C.
Example
Cold Lake bitumen is injected into the lower section of a Vacuum Distillation
Unit (VDU-"). The bottoms of the VDU J are withdrawn from the YDU and comprise
a heavy
hydrocarbon source having a molecular weight range of from about 300 Daltons
to 5,000
Daltons or more. The heavy hydrocarbon source is pre-heated to a temperature
of about 7522 F
(400 CC). At this ter aperalure, only the hydrocarbon fraction with a
molecular weight lar er then
about 350 Dalton will be in the liquid and/or solid phase, while the remainder
of the hydrocarbon
source is in a gaseous state. The hydrocarbon source is injected into an
interior reactor chamber
of a first nozzle reactor via the material feed passage of the first nozzle
reactor,
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Simultaneously, superheated steam at a temperature of about 1256"1~ (680"C) is
injected
into the converging section of the injection passage of the first nozzle
reactor at a flow rate of
about 1 5 times the flow rate of the hydrocarbon source..
The first nozzle reactor has an overall length of 8,000 min and an outside
diameter of
1,600 mm. The .interior reactor chamber is 7, l.60 mm long with an injection
end diarmaeter of 262
mm and an ejection end diameter of 1,435 mm. The injection passage, has a
length of 840 mm,
with an enlarged volume injection section diameter of 2107 am., a reduced
volume mid-section
diameter of 70 min and an enlarged volume e=jection section diameter of 147
mm. T ie pressure
in the interior reactor chamber is about 2.
The hydrocarbon source and steam are retained in the first nozzle reactor for
a time
period of around 1.2 seconds. Shockwaves produced inside the nozzle convert
approximately
45 %~ per Pass of the hydrocarbon source that has a boiling point of greater
than 1.050 ":F (566 "C)
into lighter hydrocarbons with a boiling point of less than 1050 F (566 C).
The nozzle reactor
emits a mixture of steam, cracked hydrocarbons, and untracked hydrocarbons at
a temperature of
about 788 1 (420 C).
The mixture leaving the nozzle reactor is recycled to the same 'S'DI as noted
before.
Steam in the VDU is condensed. The VDL separates the hydrocarbon into a
gaseous
hydrocarbon phase: (C6 and smaller), gas tail, vacuum. distillate and VDU
bottoms having a
molecular weight range of .from 300 Daitons to 5,000 Dal tons or more. The
gaseous hydrocarbon
phase, gas oil and vacuum distillate are collected for consumption. The VDU
bottoms are split
into two individual streams. A first stream including about 75% of the total
VDU bottoms stream
is recycled back to the first nozzle reactor, while a second stream including
the remaining 25% is
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diverted to a second nozzle reactor. This split purges a fraction of the
bottoms that has an
increased amount of inorganic material, such as vanadium, nickel, and sulfur.
Prior to being introduced into the second nozzle reactor, the second stream is
cooled to a
temperature of about 700'1 (371 CC). At this temperature, all of the
hydrocarbon material of the
second stream is in the liquid phase. The second stream is infected into an
interior reactor
chamber of a second nozzle reactor via the material feed passage of the second
nozzle reactor.
Simultaneousl >, steam at a temperature of 1256 'F (680 T) is injected into
the interior reactor
chamber of the second nozzle reactor via. the injection passage at a flow rate
of about _2.0 times
the flow rate of the hydrocarbon injected into the second nozzle reactor.
The. second nozzle reactor has an overall length of 7,000 am and an outside
diameter of
1,300 mm. The interior reactor chamber is 6,400 mm. long with an injection end
diameter of 187
mm and an ejection end diameter of 1,231 mna. The injection passage has a
length of 600 nmm,
with an enlarged volume injection section diameter of 148 mm, a reduced volume
mid-section
diameter of 50 mm and an enlarged volume ejection section diameter of 105 mm..
The pressure
in the interior reactor chamber is about 2.
The second stream and steam are injected into the second nozzle reactor for a.
time period
of no more than ft6 seconds. Shockwaves produced inside the nozzle reactor
convert
approximately 65% of the second stream into lighter hydrocarbons. The nozzle
reactor emits a
mixture of steam, cracked hydrocarbons and uncracked hydrocarbons at a
temperature of about
788 "Tf
The mixture leaving the second nozzle reactor is fed to a small Vacuum
Separation Unit
(VSU The small VSU? separates the mixture into a lighter hydrocarbon having a
molecular
weight in the range of from about 25 to about 200 Daltons and a heavier
hydrocarbon stream
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having a molecular weight in the range of from about 200 to about 1,000
Dalton.. The light
hydrocarbon stream is recycled back to the first and large VSU while the
heavier hydrocarbon
stream is cooled down to about 700 of (371 ") and collected as the :final
pitch stream for
disposal.
In view of the many possible embodiments to which the principles of the
disclosed
invention may be applied, it should be recognized that the. illustrated
embodiments are. only
preferred examples of the invention and should not be taken as limiting the
scope of the
invention. Rather, the scope of the invention is defined by the following
claims. We there.ibre
claim as our invention all that comes within the scope and spirit of these
claims.
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