CA2388605A1 - Process for selectively producing c3 olefins in a fluid catalytic cracking process - Google Patents
Process for selectively producing c3 olefins in a fluid catalytic cracking process Download PDFInfo
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- CA2388605A1 CA2388605A1 CA002388605A CA2388605A CA2388605A1 CA 2388605 A1 CA2388605 A1 CA 2388605A1 CA 002388605 A CA002388605 A CA 002388605A CA 2388605 A CA2388605 A CA 2388605A CA 2388605 A1 CA2388605 A1 CA 2388605A1
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- propylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A process for producing polymers from olefins selectively produced from a catalytically cracked or thermally cracked naphtha stream is disclosed herein. The naphtha stream is introduced into a process unit comprised of a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feedstream is contacted in the reaction zone with a catalyst containing from about 10 to 50 wt.% of a crystalline zeolite having an avera ge pore diameter less than about 0.7 nanometers at reaction conditions which include temperatures ranging from about 500.degree . to 650 .degree.C and a hydrocarbon partial pressure from about 10 to 40 psia. Vapor products are collected overhead and the catalyst particles are passed through the stripping zone on the way to the catalyst regeneration zone. Volatiles are stripped with steam in the strippi ng zone and the catalyst particles are sent to the catalyst regeneration zone where coke is burned from the catalyst, which is then recycled to the reaction zone. Overhead products from the reaction zone are passed to a fractionation zone where a stream of C3 produc ts is recovered and a stream rich in C4 and/or C5 olefins is recycled to the stripping zone. The olefins can be further processed and polymerized to form a variety of polymer materials.
Description
WO 02/26628 PCT/~S(?1!16036 PROCESS FOR SELECTIVELY PRODUCING C; OLEFINS IN A
FLUID CATALYTIC CRACKING PROCESS
Cross-Reference To Related Apt~lication This is a continuation-in-part of U. S. Patent Application Serial No.
09/073,083, filed May 5, 1998.
Back rg odd The present invention relates to a process for producing propylene from a naphtha stream.
The need for low emissions fuels has created an increased demand for light olefins used in alkylation, oligomerization, MTBE and ETBE synthesis processes.
In addition, a low-cost supply of light olefins, particularly propylene, continues to be in demand to serve as feedstock for polyolefin, particularly polypropylene.
Fixed bed processes for light parafFn dehydrogenation have recently attracted renewed interest for increasing olefin production. However, these types of processes typically require relatively large capital investments and high operating costs. It is therefore advantageous to increase olefin yield using processes, which require relatively small capital investment. It would be particularly advantageous to increase olefin yield in catalytic cracking processes so that the olefins could be further processed into polymers such as polypropylene.
A problem inherent in producing olefins products using FCC units is that the process depends on a specific catalyst balance to maximize production of light olefins while also achieving high conversion of the 650°F +
0340°C) feed components. In addition, even if a specific catalyst balance can be maintained to maximize overall olefin production, olefin selectivity is generally low because of undesirable side reactions, such as extensive cracking, isomerization, aromatization and hydrogen transfer reactions. Light saturated gases produced from undesirable side reactions result in increased costs to recover the desirable light olefins. Therefore, it is desirable to maximize olefin production in a process that allows a high degree of control over the selectivity of C3 and C4 olefins.
WO 02/26628 PCT/IISOIl16036 Summary Of The Invention One embodiment of the present invention is a process for producing polypropylene comprising the steps of (a) feeding a naphtha stream comprising from about 10 to 30 wt.% paraffns and between about 15 to 70 wt.% olefins and co-feeding a stream comprising CQ olefins to a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone; (b) contacting the naphtha stream with a fluidized bed of catalyst in the reaction zone to form a cracked product, the catalyst comprising a zeolite having an average pore diameter of less.than about 0.7 nm and wherein the reaction zone is operated at a temperature from about 500° to 650°C, a hydrocarbon partial pressure of 10 to 40 psia (about 70- about 280 kPa), a hydrocarbon residence time of 1 to 10 seconds, and a catalyst to feed weight ratio between about 4 and about 10, thereby producing a reaction product wherein no more than about 20 wt. % of paraffms are converted to olefins and wherein propylene comprises at least about 90 mol.%
of the total C3 products; (c) passing the catalyst through said stripping zone; (d) passing the stripped catalyst from the stripping zone to the catalyst regeneration zone where the catalyst is regenerated in the presence of an oxygen-containing gas; (e) recycling the regenerated catalyst to the reaction zone; (f) fractionating the cracked product to produce a C3 fraction, a C4 fraction rich in olefins, and optionally a CS fraction rich in olefins.
In another embodiment of the present invention the catalyst is a GSM-5 type catalyst.
In an embodiment of the present invention a C5 fraction rich in olefins is also recycled.
In another embodiment of the present invention the feedstock contains about 10 to 30 wt. % paraffins, and from about 20 to 70 wt. % olefins.
In another embodiment of the present invention the reaction gone is operated at a temperature from about 525°C to about 600°C.
Detailed Description Of 'The Invention Feedstreams that are suitable for producing the relatively high C2, C3, and C~ olefin yields are those streams boiling in the naphtha range containing from WO 02/26628 PCT/US(11116036 about 5 wt. % to about 35 wt. %, preferably from about 10 wt. % to about 30 wt.
%, and more preferably from about 10 to 25 wt. % paraffins, and from about 15 wt. %, preferably from about 20 wt. % to about 70 wt. % olefins. The feed may also contain naphthenes and aromatics. Naphtha boiling range streams are typically those having a boiling range from about 6.5°F to about 430°F (about 18°C
to about 225°C), preferably from about 65°F to about 300°F (about 18°C to about 150°C).
The naphtha can be a thermally cracked or a catalytically-cracked naphtha.
The naphtha streams can be derived from the fluid catalytic cracking (FCC) of gas oils and resids, or they can be derived from delayed or fluid coking of resids.
Preferably, the naphtha streams used in the practice of the present invention derive from the fluid catalytic cracking of gas oils and resids. FCC naphthas are typically rich in olefins and/or diolefins and relatively lean in parafrns. It is within the scope of the instant invention to feed or co-feed other olefinic streams that are not catalytieally- or thermally-cracked naphthas into said reaction zone with the primary feed. It is believed that this will increase the yield of propylene.
1n another embodiment of the present invention, a C4 olefin stream containing n-butenes is co-fed with the naphtha feed. The C4 olefin stream may come from suitable sources such as conventional FCC units, coker units, steam crackers and other process units that produce C4 olefins streams that can be recycled to the cracking unit. In one embodiment, the C4 olefin stream may be a raffmate from a methyl-tert-butyl-ether (MTBE) process. MTBE units typically feed a mixture of methanol and C4 olefins. Only the iso-butylene reacts with the methanol to yield MTBE, leaving a significant amount of Ca olefins, including n-butenes, in the MTBE raffinate.
The C4 olefin stream preferably comprises at least about 75 wt.% n-butenes, moxe preferably greater than about 90 wt.°ia n-butenes.
Streams containing lower amounts of n-butenes are also acceptable, such as where a stream containing a significant amount of diolefins, such as butadiene, is employed. When the Ca olefin stream is injected into the reaction zone along with the naphtha feed, the C4 olefins undergo rapid disproportionation reactions with other olefins in the naphtha feed, followed by cracking reactions. These reactions increase propylene yields.
The process of the present invention is performed in a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feed is fed into the reaction zone where it contacts a source of hot, regenerated catalyst. The hot catalyst vaporizes and cracks the feed at a temperature from about 500°C to about 650°C, preferably from about 525°C to about 600°C. The cracking reaction deposits coke on the catalyst, thereby deactivating the catalyst. The cracked products are separated from the coked catalyst and sent to a fractionator. The coked catalyst passes through the stripping zone where a stripping medium, such as steam, strips volatiles from the catalyst particles. The stripping can be preformed under low-severity conditions to retain a greater fraction of adsorbed hydrocarbons for heat balance. The stripped catalyst is then passed to the regeneration zone where it is regenerated by burning coke on the catalyst in the presence of an oxygen containing gas, preferably air. Decoking restores catalyst activity and simultaneously heats the catalyst to a temperature from about 650°C to about 750°C. The hot regenerated catalyst is then recycled to the reaction zone to react with fresh naphtha feed. Flue gas formed by burning coke in the regenerator may be treated for removal of particulates and for conversion of carbon monoxide. The cracked products from the reaction zone are sent to a fractionation zone where various products are recovered, particularly a C3 fraction, a C4 fraction, and optionally a CS
fraction.
The Ca fraction and the Cs fraction will typically be rich in olefins. One or both of these fractions can be recycled to the reactor. They can be recycled to either the main section of the reactor, or a riser section, or a stripping section. It is preferred that they be recycled to the upper part of the stripping section, or stripping zone.
Recycling one or both of these fractions will convert at least a portion of these olefins to propylene.
It may also be desirable to inject a C4 olefin stream into the stripper section. Such a Ca olefin stream (not to be confused with a C4 fraction recycled from the cracked products of the cracking process) would be derived from one or more suitable sources such as conventional FCC units, coker units, steam crackers and other process units that produce Ca olefins, streams that can be recycled to the cracking unit. In one embodinnent, the C4 olefin stream may be a raffmate from a methyl-tert-butyl-ether (MTBE) process as previously described. In another embodiment, the C4 olefin stream injected into the stripper section also preferably comprises at least about 75 wt.% n-butenes, more preferably greater than about wt.% n-butenes. Streams containing lower amounts ofn-butcnes are also acceptable, such as where a stream containing a significant amount of diolefins, such as butadiene, is employed.
While attempts have been made to increase light olefins yields in the FCC
I 0 process unit itself, the present invention uses its own distinct process unit, as previously described, which receives naphtha from a suitable source in the refinery. The reaction zone is operated at process conditions that will maximize CZ to Ca olefins (particularly propylene) selectivity with relatively high conversion of CS+ olefins. Suitable catalysts used with the present invention contain a 15 crystalline zeolite having an a~rerage pore diameter less than about 0.7 nanometers (nm), said crystalline zeolite comprising from. about 10 wt. % to about 50 wt.
% of the total fluidized catalyst composition. It is preferred that the crystalline zeolite be selected from the family of medium-pore size (< 0.7 nm) crystalline aluminosilicates, otherwise referred to as zeolites. Of particular interest are the 20 medium-pore zeolites with a silica to alumina molar ratio of less than about 75:1, preferably less than about 50::1, and more preferably less than about 40:1, although some embodiments rnay incorporate a silica to alumina ratio greater than 40:1. The pore diameter, also referred to as el:fective pore diameter, is measured using standard adsorption tecrmiques and hyd~rocarbonaceous compounds of 25 known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 and Anderson et al., J. Catalysis 58, 114 ( 1979), both of which axe incorporated herein by reference.
Medium-pore size zeolites that can be used in the practice of the present invention are described in "Atlas of Zeolite Structure Types", eds. W. H.
Meier 30 and D. H. Olson, Butterworth-Heineman, Third Edition, 1992, which is hereby incorporated by reference. The medium-pore size zeolites generally have a pore size from about SA, to about 7~ and include for example, :MFI, MFS, MEL, WO 02/26628 PCT/iJSO1116036 MTW, EUO, MTT, HEU, FER, and TON structure type zeolites (IIJPAC
Commission of Zeolite Nomenclature). Non-limiting examples of such medium-pore size zeolites, include ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite, and silicalite 2. The most preferred is S ZSM-5, which is described in U.S. Patent Nos. 3,702,886 and 3,770,614. ZSM-is described in U.S. Patent No. 3,709,979; ZSM-12 in U.S. Patent No.
3,832,449;
ZSM-21 and ZSM-38 in U.S. Patent No. 3,948,758; ZSM-23 in U.S. Patent No.
4,076,842; and ZSM-35 in U.S. Patent No. 4,016,245. All of the above patents are incorporated herein by reference. Other suitable medium-pore size zeolites include the silicoaluminophosphates (SAPO), such as SAPO-4 and SAPO-11 which is described in U.S. Patent No. 4,440,871; chromosilicates; gallium silicates; iron silicates; aluminum phosphates (ALPO), such as ALPO-11 described in U.S. Patmt No. 4,310,440; titanium aluminosilicates (TASO), such as TASO-45 described in EP-A No. 229,295; boron silicates, described in U.S.
Patent No. 4,254,297; titanium aluminophosphates (TAPO), such as 'TAPO-11 described in U.S. Patent No. 4,500,651; and iron aluxninosilicates.
The medium-pore-size zeolites can include "crystalline admixtures" which are thought to be the result of faults occurring within the crystal or crystalline area during the synthesis of the zeolites. Examples of crystalline admixtures of and ZSM-11 are disclosed in U.S. Patent No. 4,229,424, which is incorporated herein by reference. The crystalline admixtures are themselves medium-pore-size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals of crystallites of different zeolites are physically present in the same catalyst composite or hydrotherrnal reaction mixtures.
'The catalysts of the present invention may be held together with an inorganic oxide matrix material component. The inorganic oxide matrix component binds the catalyst components together so that the catalyst product is hard enough to survive intcrparticle and reactor wall collisions. The inorganic oxide matrix can be made from an inorganic oxide sol or gel which is dried to "bind" the catalyst components together. Preferably, the inorganic oxide matrix is not catalytically active and will be comprised of oxides of silicon and aluminum. It is also preferred that separate alumina phases be incorporated into the inorganic oxide matrix. Species of WO 02/26628 PCT/i1S01116036 aluminum oxyhydroxides-g-alumina, boehnnite, diaspore, and transitional aluminas such as a-alumina, b-alumina, g-alumina, d-alumina, e-alumina, k-alumina, and r-alumina can be employed. Preferably, the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite. The matrix material may also contain phosphorous or aluminum phosphate.
Process conditions include temperatures from about 500°C to about 650°C, preferably from about 500°C to 600°C; hydrocarbon partial pressures from about to 40 psia (about 70-about 280 kPa) to about, preferably from about 20 to 35 psia (about 140- about 245 kPa); and a catalyst to naphtha (wt/wt) ratio from 10 about 3 to 12, preferably from about 4 to 10, where catalyst weight is total weight of the catalyst composite. Steam may be concurrently introduced with the naphtha stream into the reaction zone, with the steam comprising up to about wt. % of the naphtha feed. Preferably, the naphtha residence time in the reaction zone is less than about 10 seconds, for example from about 1 to 10 seconds.
The reaction conditions will be such that at least about 60 wt. % of the Cs+
olefins in the naphtha stream are converted to C4- products and less than about 25 wt. %, preferably less than about 20 wt. % of the paraffins are converted to Ca-products, and that propylene comprises at least about 90 mol.%, preferably greater than about 95 mol % of the total C3 reaction products with the weight ratio of propylene/total CZ- products greater than about 3.5.
Preferably, ethylene comprises at least about 90 mol.% of the CZ products, with the weight ratio of propylene:ethylenc being greater than about 4, and that the "full range" Cs+ naphtha product is enhanced in both motor and research octanes relative to the naphtha feed. It is within the scope of this invention to pre-coke the catalysts before introducing the feed to further improve the selectivity to propylene. It is also within the scope of this invention to feed an effective amount of single-ring aromatics to the reaction zone to also improve the selectivity of propylene versus ethylene. The aromatics may be from an external source such as a reforming process unit or they may consist of heavy naphtha recycle product from the instant process.
The following examples are presented for illustrative purposes only and arc not to be taken as limiting the present invention in any way.
Examples 1-12 The following examples illustrate the criticality of process operating conditions for maintaining chemical grade propylene purity with samples of cat naphtha cracked over ZCAT-40 (a catalyst that contains ZSM-5) which had been steamed at 1500°F 0815°C) for 16 hrs to simulate commercial equilibrium.
Comparison of Examples 1 and 2 show that increasing Cat/Oil ratio improves propylene yield, but sacrifices propylene purity. Comparison of Examples 3 and and S and 6 shows reducing oil partial pressure greatly improves propylene purity without compromising propylene yield. Comparison of Examples 7 and 8 and 9 and 10 shows increasing temperature improves both propylene yield and purity.
Comparison of Examples 11 and 12 shows decreasing cat residence time improves propylene yield and purity. Example 13 shows an example where both high propylene yield and purity are obtained at a reactor temperature and cat/oil ratio that can be achieved using a conventional FCC reactor/regenerator design for the second stage.
WO 02/26628 PCT/tISOl/16036 ° ° . ° ° ° ° ° °
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.r N M V V1 ~D h 00 O~ ~ .~.. ..Nr ,.M-a' x WO 02/26628 PCT/~ISOII16036 Table 1 Continued Ratio of C3 Ratio of C3°
Example Wt.% C,' Wt % Ci to~' ° toto C; Wt.% C~
1 2.35 2.73 4.9 4.2 11.4 2 3.02 3.58 4.2 3.6 12.8 3 2.32 2.53 3.5 3.2 8.2 4 2.16 2.46 2.9 2.6 6.3 5 6.97 9.95 2.4 1.7 16.7 6 6.21 8.71 2.7 1.9 16.8 7 1.03 1.64 S.R 3.7 6.0 8 1.48 2.02 4.9 3.6 7.3 9 2.16 2.46 2.9 2.6 6.3 10 5.21 6.74 2.0 1.5 10.4 11 4.99 6.67 1.9 1.4 9.6 12 4.43 6.27 2.3 1.6 10.1 13 4.45 5.76 3.3 2.6 15.0 C2 - CH4 + C2H4 + C2H6 5 The above examples (1,2,7 and 8) show that C3-/CZ > 4 and C3~/CZ > 3.5 can be achieved by selection of suitable reactor conditions.
Examples 14 - 17 The cracking of olefins and paraffins contained in naphtha streams (e.g.
10 FCC naphtha, coker naphtha) over small or medium-pore zeolites such as ZSM-can produce significant amounts of ethylene and propylene. The selectivity to ethylene or propylene and selectivity of propylene to propane varies as a function of catalyst and process operating conditions. It has been found that propylene yield can be increased by co-feeding steam along with cat naphtha to the reactor.
The catalyst may be ZSM-5 or other small or medium-pore zeolites. Table 2 below illustrates the increase in propylene yield when 5 wt. % steam is co-fed with an FCC naphtha containing 38.8 wt. % olefins. Although propylene yield increased, the propylene purity is diminished. Thus, other operating conditions may need to be adjusted to maintain the targeted propylene selectivity.
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w Egam~les I8 - 21 ZCAT-40 was used to crack cat cracker naphtha as described for the above examples. The coked catalyst was then used to crack a Ca stream composed of 6 wt.% n-butane, 9 wt % i-butane, 47 wt.% 1-butene, and 38 wt.% i-butene in a reactor at the temperatures and space velocities indicated in the table below.
As can be seen from the results in the table below, a significant fraction of the feed stream was converted to propylene.
WHSV, Hr-1 35 18 12 6 Temperature C 575 575 575 575 Butylene Conversion wt.
Product Yields. wt.%
Ethylene 2.4 4.7 5.9 8.8 Propylene 20.5 27.1 28.8 27.4 Butylenes 39.7 29.0 25.5 19.2 C,-C4 Light Saturates 18.2 19.2 19.8 22.0 CS+ Products 19.3 20.0 20.0 22.6 Light olefins resulting from the preferred process may be used as feeds for processes such as oligimcrization, polymerization, co-polymerization, ter-polymerization, and related processes (hereinafter "polymerization") to form macromolecules. Such light olefins may be polymerized both alone and in combination with other species, in accordance with polymerization methods known in the art. In some cases it may be desirable to separate, concentrate, purify, upgrade, or otherwise process the light olefins prior to polymerization.
Propylene and ethylene are preferred polymerization feeds. Polypropylene and polyethylene are preferred polymerization products made therefrom.
FLUID CATALYTIC CRACKING PROCESS
Cross-Reference To Related Apt~lication This is a continuation-in-part of U. S. Patent Application Serial No.
09/073,083, filed May 5, 1998.
Back rg odd The present invention relates to a process for producing propylene from a naphtha stream.
The need for low emissions fuels has created an increased demand for light olefins used in alkylation, oligomerization, MTBE and ETBE synthesis processes.
In addition, a low-cost supply of light olefins, particularly propylene, continues to be in demand to serve as feedstock for polyolefin, particularly polypropylene.
Fixed bed processes for light parafFn dehydrogenation have recently attracted renewed interest for increasing olefin production. However, these types of processes typically require relatively large capital investments and high operating costs. It is therefore advantageous to increase olefin yield using processes, which require relatively small capital investment. It would be particularly advantageous to increase olefin yield in catalytic cracking processes so that the olefins could be further processed into polymers such as polypropylene.
A problem inherent in producing olefins products using FCC units is that the process depends on a specific catalyst balance to maximize production of light olefins while also achieving high conversion of the 650°F +
0340°C) feed components. In addition, even if a specific catalyst balance can be maintained to maximize overall olefin production, olefin selectivity is generally low because of undesirable side reactions, such as extensive cracking, isomerization, aromatization and hydrogen transfer reactions. Light saturated gases produced from undesirable side reactions result in increased costs to recover the desirable light olefins. Therefore, it is desirable to maximize olefin production in a process that allows a high degree of control over the selectivity of C3 and C4 olefins.
WO 02/26628 PCT/IISOIl16036 Summary Of The Invention One embodiment of the present invention is a process for producing polypropylene comprising the steps of (a) feeding a naphtha stream comprising from about 10 to 30 wt.% paraffns and between about 15 to 70 wt.% olefins and co-feeding a stream comprising CQ olefins to a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone; (b) contacting the naphtha stream with a fluidized bed of catalyst in the reaction zone to form a cracked product, the catalyst comprising a zeolite having an average pore diameter of less.than about 0.7 nm and wherein the reaction zone is operated at a temperature from about 500° to 650°C, a hydrocarbon partial pressure of 10 to 40 psia (about 70- about 280 kPa), a hydrocarbon residence time of 1 to 10 seconds, and a catalyst to feed weight ratio between about 4 and about 10, thereby producing a reaction product wherein no more than about 20 wt. % of paraffms are converted to olefins and wherein propylene comprises at least about 90 mol.%
of the total C3 products; (c) passing the catalyst through said stripping zone; (d) passing the stripped catalyst from the stripping zone to the catalyst regeneration zone where the catalyst is regenerated in the presence of an oxygen-containing gas; (e) recycling the regenerated catalyst to the reaction zone; (f) fractionating the cracked product to produce a C3 fraction, a C4 fraction rich in olefins, and optionally a CS fraction rich in olefins.
In another embodiment of the present invention the catalyst is a GSM-5 type catalyst.
In an embodiment of the present invention a C5 fraction rich in olefins is also recycled.
In another embodiment of the present invention the feedstock contains about 10 to 30 wt. % paraffins, and from about 20 to 70 wt. % olefins.
In another embodiment of the present invention the reaction gone is operated at a temperature from about 525°C to about 600°C.
Detailed Description Of 'The Invention Feedstreams that are suitable for producing the relatively high C2, C3, and C~ olefin yields are those streams boiling in the naphtha range containing from WO 02/26628 PCT/US(11116036 about 5 wt. % to about 35 wt. %, preferably from about 10 wt. % to about 30 wt.
%, and more preferably from about 10 to 25 wt. % paraffins, and from about 15 wt. %, preferably from about 20 wt. % to about 70 wt. % olefins. The feed may also contain naphthenes and aromatics. Naphtha boiling range streams are typically those having a boiling range from about 6.5°F to about 430°F (about 18°C
to about 225°C), preferably from about 65°F to about 300°F (about 18°C to about 150°C).
The naphtha can be a thermally cracked or a catalytically-cracked naphtha.
The naphtha streams can be derived from the fluid catalytic cracking (FCC) of gas oils and resids, or they can be derived from delayed or fluid coking of resids.
Preferably, the naphtha streams used in the practice of the present invention derive from the fluid catalytic cracking of gas oils and resids. FCC naphthas are typically rich in olefins and/or diolefins and relatively lean in parafrns. It is within the scope of the instant invention to feed or co-feed other olefinic streams that are not catalytieally- or thermally-cracked naphthas into said reaction zone with the primary feed. It is believed that this will increase the yield of propylene.
1n another embodiment of the present invention, a C4 olefin stream containing n-butenes is co-fed with the naphtha feed. The C4 olefin stream may come from suitable sources such as conventional FCC units, coker units, steam crackers and other process units that produce C4 olefins streams that can be recycled to the cracking unit. In one embodiment, the C4 olefin stream may be a raffmate from a methyl-tert-butyl-ether (MTBE) process. MTBE units typically feed a mixture of methanol and C4 olefins. Only the iso-butylene reacts with the methanol to yield MTBE, leaving a significant amount of Ca olefins, including n-butenes, in the MTBE raffinate.
The C4 olefin stream preferably comprises at least about 75 wt.% n-butenes, moxe preferably greater than about 90 wt.°ia n-butenes.
Streams containing lower amounts of n-butenes are also acceptable, such as where a stream containing a significant amount of diolefins, such as butadiene, is employed. When the Ca olefin stream is injected into the reaction zone along with the naphtha feed, the C4 olefins undergo rapid disproportionation reactions with other olefins in the naphtha feed, followed by cracking reactions. These reactions increase propylene yields.
The process of the present invention is performed in a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feed is fed into the reaction zone where it contacts a source of hot, regenerated catalyst. The hot catalyst vaporizes and cracks the feed at a temperature from about 500°C to about 650°C, preferably from about 525°C to about 600°C. The cracking reaction deposits coke on the catalyst, thereby deactivating the catalyst. The cracked products are separated from the coked catalyst and sent to a fractionator. The coked catalyst passes through the stripping zone where a stripping medium, such as steam, strips volatiles from the catalyst particles. The stripping can be preformed under low-severity conditions to retain a greater fraction of adsorbed hydrocarbons for heat balance. The stripped catalyst is then passed to the regeneration zone where it is regenerated by burning coke on the catalyst in the presence of an oxygen containing gas, preferably air. Decoking restores catalyst activity and simultaneously heats the catalyst to a temperature from about 650°C to about 750°C. The hot regenerated catalyst is then recycled to the reaction zone to react with fresh naphtha feed. Flue gas formed by burning coke in the regenerator may be treated for removal of particulates and for conversion of carbon monoxide. The cracked products from the reaction zone are sent to a fractionation zone where various products are recovered, particularly a C3 fraction, a C4 fraction, and optionally a CS
fraction.
The Ca fraction and the Cs fraction will typically be rich in olefins. One or both of these fractions can be recycled to the reactor. They can be recycled to either the main section of the reactor, or a riser section, or a stripping section. It is preferred that they be recycled to the upper part of the stripping section, or stripping zone.
Recycling one or both of these fractions will convert at least a portion of these olefins to propylene.
It may also be desirable to inject a C4 olefin stream into the stripper section. Such a Ca olefin stream (not to be confused with a C4 fraction recycled from the cracked products of the cracking process) would be derived from one or more suitable sources such as conventional FCC units, coker units, steam crackers and other process units that produce Ca olefins, streams that can be recycled to the cracking unit. In one embodinnent, the C4 olefin stream may be a raffmate from a methyl-tert-butyl-ether (MTBE) process as previously described. In another embodiment, the C4 olefin stream injected into the stripper section also preferably comprises at least about 75 wt.% n-butenes, more preferably greater than about wt.% n-butenes. Streams containing lower amounts ofn-butcnes are also acceptable, such as where a stream containing a significant amount of diolefins, such as butadiene, is employed.
While attempts have been made to increase light olefins yields in the FCC
I 0 process unit itself, the present invention uses its own distinct process unit, as previously described, which receives naphtha from a suitable source in the refinery. The reaction zone is operated at process conditions that will maximize CZ to Ca olefins (particularly propylene) selectivity with relatively high conversion of CS+ olefins. Suitable catalysts used with the present invention contain a 15 crystalline zeolite having an a~rerage pore diameter less than about 0.7 nanometers (nm), said crystalline zeolite comprising from. about 10 wt. % to about 50 wt.
% of the total fluidized catalyst composition. It is preferred that the crystalline zeolite be selected from the family of medium-pore size (< 0.7 nm) crystalline aluminosilicates, otherwise referred to as zeolites. Of particular interest are the 20 medium-pore zeolites with a silica to alumina molar ratio of less than about 75:1, preferably less than about 50::1, and more preferably less than about 40:1, although some embodiments rnay incorporate a silica to alumina ratio greater than 40:1. The pore diameter, also referred to as el:fective pore diameter, is measured using standard adsorption tecrmiques and hyd~rocarbonaceous compounds of 25 known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 and Anderson et al., J. Catalysis 58, 114 ( 1979), both of which axe incorporated herein by reference.
Medium-pore size zeolites that can be used in the practice of the present invention are described in "Atlas of Zeolite Structure Types", eds. W. H.
Meier 30 and D. H. Olson, Butterworth-Heineman, Third Edition, 1992, which is hereby incorporated by reference. The medium-pore size zeolites generally have a pore size from about SA, to about 7~ and include for example, :MFI, MFS, MEL, WO 02/26628 PCT/iJSO1116036 MTW, EUO, MTT, HEU, FER, and TON structure type zeolites (IIJPAC
Commission of Zeolite Nomenclature). Non-limiting examples of such medium-pore size zeolites, include ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite, and silicalite 2. The most preferred is S ZSM-5, which is described in U.S. Patent Nos. 3,702,886 and 3,770,614. ZSM-is described in U.S. Patent No. 3,709,979; ZSM-12 in U.S. Patent No.
3,832,449;
ZSM-21 and ZSM-38 in U.S. Patent No. 3,948,758; ZSM-23 in U.S. Patent No.
4,076,842; and ZSM-35 in U.S. Patent No. 4,016,245. All of the above patents are incorporated herein by reference. Other suitable medium-pore size zeolites include the silicoaluminophosphates (SAPO), such as SAPO-4 and SAPO-11 which is described in U.S. Patent No. 4,440,871; chromosilicates; gallium silicates; iron silicates; aluminum phosphates (ALPO), such as ALPO-11 described in U.S. Patmt No. 4,310,440; titanium aluminosilicates (TASO), such as TASO-45 described in EP-A No. 229,295; boron silicates, described in U.S.
Patent No. 4,254,297; titanium aluminophosphates (TAPO), such as 'TAPO-11 described in U.S. Patent No. 4,500,651; and iron aluxninosilicates.
The medium-pore-size zeolites can include "crystalline admixtures" which are thought to be the result of faults occurring within the crystal or crystalline area during the synthesis of the zeolites. Examples of crystalline admixtures of and ZSM-11 are disclosed in U.S. Patent No. 4,229,424, which is incorporated herein by reference. The crystalline admixtures are themselves medium-pore-size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals of crystallites of different zeolites are physically present in the same catalyst composite or hydrotherrnal reaction mixtures.
'The catalysts of the present invention may be held together with an inorganic oxide matrix material component. The inorganic oxide matrix component binds the catalyst components together so that the catalyst product is hard enough to survive intcrparticle and reactor wall collisions. The inorganic oxide matrix can be made from an inorganic oxide sol or gel which is dried to "bind" the catalyst components together. Preferably, the inorganic oxide matrix is not catalytically active and will be comprised of oxides of silicon and aluminum. It is also preferred that separate alumina phases be incorporated into the inorganic oxide matrix. Species of WO 02/26628 PCT/i1S01116036 aluminum oxyhydroxides-g-alumina, boehnnite, diaspore, and transitional aluminas such as a-alumina, b-alumina, g-alumina, d-alumina, e-alumina, k-alumina, and r-alumina can be employed. Preferably, the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite. The matrix material may also contain phosphorous or aluminum phosphate.
Process conditions include temperatures from about 500°C to about 650°C, preferably from about 500°C to 600°C; hydrocarbon partial pressures from about to 40 psia (about 70-about 280 kPa) to about, preferably from about 20 to 35 psia (about 140- about 245 kPa); and a catalyst to naphtha (wt/wt) ratio from 10 about 3 to 12, preferably from about 4 to 10, where catalyst weight is total weight of the catalyst composite. Steam may be concurrently introduced with the naphtha stream into the reaction zone, with the steam comprising up to about wt. % of the naphtha feed. Preferably, the naphtha residence time in the reaction zone is less than about 10 seconds, for example from about 1 to 10 seconds.
The reaction conditions will be such that at least about 60 wt. % of the Cs+
olefins in the naphtha stream are converted to C4- products and less than about 25 wt. %, preferably less than about 20 wt. % of the paraffins are converted to Ca-products, and that propylene comprises at least about 90 mol.%, preferably greater than about 95 mol % of the total C3 reaction products with the weight ratio of propylene/total CZ- products greater than about 3.5.
Preferably, ethylene comprises at least about 90 mol.% of the CZ products, with the weight ratio of propylene:ethylenc being greater than about 4, and that the "full range" Cs+ naphtha product is enhanced in both motor and research octanes relative to the naphtha feed. It is within the scope of this invention to pre-coke the catalysts before introducing the feed to further improve the selectivity to propylene. It is also within the scope of this invention to feed an effective amount of single-ring aromatics to the reaction zone to also improve the selectivity of propylene versus ethylene. The aromatics may be from an external source such as a reforming process unit or they may consist of heavy naphtha recycle product from the instant process.
The following examples are presented for illustrative purposes only and arc not to be taken as limiting the present invention in any way.
Examples 1-12 The following examples illustrate the criticality of process operating conditions for maintaining chemical grade propylene purity with samples of cat naphtha cracked over ZCAT-40 (a catalyst that contains ZSM-5) which had been steamed at 1500°F 0815°C) for 16 hrs to simulate commercial equilibrium.
Comparison of Examples 1 and 2 show that increasing Cat/Oil ratio improves propylene yield, but sacrifices propylene purity. Comparison of Examples 3 and and S and 6 shows reducing oil partial pressure greatly improves propylene purity without compromising propylene yield. Comparison of Examples 7 and 8 and 9 and 10 shows increasing temperature improves both propylene yield and purity.
Comparison of Examples 11 and 12 shows decreasing cat residence time improves propylene yield and purity. Example 13 shows an example where both high propylene yield and purity are obtained at a reactor temperature and cat/oil ratio that can be achieved using a conventional FCC reactor/regenerator design for the second stage.
WO 02/26628 PCT/tISOl/16036 ° ° . ° ° ° ° ° °
° ° ° °
y v v y y W y o y v y y.
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.r N M V V1 ~D h 00 O~ ~ .~.. ..Nr ,.M-a' x WO 02/26628 PCT/~ISOII16036 Table 1 Continued Ratio of C3 Ratio of C3°
Example Wt.% C,' Wt % Ci to~' ° toto C; Wt.% C~
1 2.35 2.73 4.9 4.2 11.4 2 3.02 3.58 4.2 3.6 12.8 3 2.32 2.53 3.5 3.2 8.2 4 2.16 2.46 2.9 2.6 6.3 5 6.97 9.95 2.4 1.7 16.7 6 6.21 8.71 2.7 1.9 16.8 7 1.03 1.64 S.R 3.7 6.0 8 1.48 2.02 4.9 3.6 7.3 9 2.16 2.46 2.9 2.6 6.3 10 5.21 6.74 2.0 1.5 10.4 11 4.99 6.67 1.9 1.4 9.6 12 4.43 6.27 2.3 1.6 10.1 13 4.45 5.76 3.3 2.6 15.0 C2 - CH4 + C2H4 + C2H6 5 The above examples (1,2,7 and 8) show that C3-/CZ > 4 and C3~/CZ > 3.5 can be achieved by selection of suitable reactor conditions.
Examples 14 - 17 The cracking of olefins and paraffins contained in naphtha streams (e.g.
10 FCC naphtha, coker naphtha) over small or medium-pore zeolites such as ZSM-can produce significant amounts of ethylene and propylene. The selectivity to ethylene or propylene and selectivity of propylene to propane varies as a function of catalyst and process operating conditions. It has been found that propylene yield can be increased by co-feeding steam along with cat naphtha to the reactor.
The catalyst may be ZSM-5 or other small or medium-pore zeolites. Table 2 below illustrates the increase in propylene yield when 5 wt. % steam is co-fed with an FCC naphtha containing 38.8 wt. % olefins. Although propylene yield increased, the propylene purity is diminished. Thus, other operating conditions may need to be adjusted to maintain the targeted propylene selectivity.
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w Egam~les I8 - 21 ZCAT-40 was used to crack cat cracker naphtha as described for the above examples. The coked catalyst was then used to crack a Ca stream composed of 6 wt.% n-butane, 9 wt % i-butane, 47 wt.% 1-butene, and 38 wt.% i-butene in a reactor at the temperatures and space velocities indicated in the table below.
As can be seen from the results in the table below, a significant fraction of the feed stream was converted to propylene.
WHSV, Hr-1 35 18 12 6 Temperature C 575 575 575 575 Butylene Conversion wt.
Product Yields. wt.%
Ethylene 2.4 4.7 5.9 8.8 Propylene 20.5 27.1 28.8 27.4 Butylenes 39.7 29.0 25.5 19.2 C,-C4 Light Saturates 18.2 19.2 19.8 22.0 CS+ Products 19.3 20.0 20.0 22.6 Light olefins resulting from the preferred process may be used as feeds for processes such as oligimcrization, polymerization, co-polymerization, ter-polymerization, and related processes (hereinafter "polymerization") to form macromolecules. Such light olefins may be polymerized both alone and in combination with other species, in accordance with polymerization methods known in the art. In some cases it may be desirable to separate, concentrate, purify, upgrade, or otherwise process the light olefins prior to polymerization.
Propylene and ethylene are preferred polymerization feeds. Polypropylene and polyethylene are preferred polymerization products made therefrom.
Claims (16)
1. A process for producing propylene comprising the steps of:
(a) feeding a naphtha stream comprising from 10 to 30 wt.%
paraffins and between 15 to 70 wt.% olefins to a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone;
(b) feeding a stream comprising C4 olefins to said process unit;
(c) contacting the naphtha stream with a fluidized bed of catalyst in the reaction zone to form a cracked product, the catalyst comprising a zeolite having an average pore diameter of less than 0.7 nm and wherein the reaction zone is operated at a temperature from 500° to 650°C, a hydrocarbon partial pressure of 10 to 40 psia, a hydrocarbon residence time of 1 to 10 seconds, and a catalyst to feed weight ratio between 4 and 10, thereby producing a reaction product wherein no more than 20 wt. % of paraffins are converted to olefins and wherein propylene comprises at least 90 mol.% of the total C3 products;
(d) passing the catalyst through said stripping zone;
(e) passing the stripped catalyst from the stripping zone to the catalyst regeneration zone where the catalyst is regenerated in the presence of an oxygen-containing gas;
(f) recycling the regenerated catalyst to the reaction zone;
(g) fractionating the cracked product to produce a C3 fraction, a C4 fraction rich in olefins, and optionally a C5 fraction rich in olefins;
(h) recycling the C4 fraction rich in olefins to the reaction zone, stripping zone, or both.
(a) feeding a naphtha stream comprising from 10 to 30 wt.%
paraffins and between 15 to 70 wt.% olefins to a process unit comprising a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone;
(b) feeding a stream comprising C4 olefins to said process unit;
(c) contacting the naphtha stream with a fluidized bed of catalyst in the reaction zone to form a cracked product, the catalyst comprising a zeolite having an average pore diameter of less than 0.7 nm and wherein the reaction zone is operated at a temperature from 500° to 650°C, a hydrocarbon partial pressure of 10 to 40 psia, a hydrocarbon residence time of 1 to 10 seconds, and a catalyst to feed weight ratio between 4 and 10, thereby producing a reaction product wherein no more than 20 wt. % of paraffins are converted to olefins and wherein propylene comprises at least 90 mol.% of the total C3 products;
(d) passing the catalyst through said stripping zone;
(e) passing the stripped catalyst from the stripping zone to the catalyst regeneration zone where the catalyst is regenerated in the presence of an oxygen-containing gas;
(f) recycling the regenerated catalyst to the reaction zone;
(g) fractionating the cracked product to produce a C3 fraction, a C4 fraction rich in olefins, and optionally a C5 fraction rich in olefins;
(h) recycling the C4 fraction rich in olefins to the reaction zone, stripping zone, or both.
2. The process of claim 1 wherein the C4 olefin stream is fed into the reaction zone.
3 The process of claim 2 wherein the C4 olefin stream is also fed into the stripping zone.
4. The process of claim 1 wherein the C4 olefin stream is fed into the stripping zone.
5. The process of claim 1 wherein the C4 olefin stream is derived from a MTBE unit, an FCC unit, a stream cracker, or a coker unit.
6. The process of claim 1 wherein the C4 olefin stream is an MTBE
raffinate stream.
raffinate stream.
7. The process of claim 1 wherein the C4 olefin stream is passed to the process unit from a steam cracker.
8. The process of claim 1 wherein the C4 olefin stream comprises at least 75 wt.% n-butenes.
9. The process of claim 1 wherein the crystalline zeolite is selected from the ZSM series.
10. The process of claim 9 wherein the crystalline zeolite is ZSM-5.
11. The process of claim 10 wherein the reaction temperature is from 500°C to 600°C.
12. The process of claim 10 wherein at least 60 wt. % of the C5+ olefins in the feedstream is converted to C4- products and less than 25 wt. % of the paraffins are converted to C4- products.
13. The process of claim 12 wherein propylene comprises at least 95 mol. % of the total C3 products.
14. The process of claim 13 wherein the weight ratio of propylene to total C2- products is greater than 3.5.
15. The process of claim 1 further comprising the step of producing said C5 fraction and recycling said C5 fraction to the reaction zone, the stripping zone, or both.
16. The process of claim 1 further comprising the step of separating propylene from the C3 fraction and polymerizing the propylene to form polypropylene.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57426200A | 2000-05-19 | 2000-05-19 | |
| US09/574,262 | 2000-05-19 | ||
| PCT/US2001/016036 WO2002026628A1 (en) | 2000-05-19 | 2001-05-19 | Process for selectively producing c3 olefins in a fluid catalytic cracking process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2388605A1 true CA2388605A1 (en) | 2002-04-04 |
Family
ID=24295356
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002388605A Abandoned CA2388605A1 (en) | 2000-05-19 | 2001-05-19 | Process for selectively producing c3 olefins in a fluid catalytic cracking process |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1289887A1 (en) |
| JP (1) | JP2004509928A (en) |
| CN (1) | CN1383448A (en) |
| CA (1) | CA2388605A1 (en) |
| MX (1) | MXPA02000719A (en) |
| WO (1) | WO2002026628A1 (en) |
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| US7425258B2 (en) * | 2003-02-28 | 2008-09-16 | Exxonmobil Research And Engineering Company | C6 recycle for propylene generation in a fluid catalytic cracking unit |
| US7067597B2 (en) * | 2004-02-25 | 2006-06-27 | Exxonmobil Chemical Patents Inc. | Process of making polypropylene from intermediate grade propylene |
| CN101747129B (en) * | 2008-11-28 | 2013-09-04 | 中国石油化工股份有限公司 | Method for producing light olefins through catalytic conversion |
| US8940955B2 (en) | 2008-12-19 | 2015-01-27 | Uop Llc | Fluid catalytic cracking system and process |
| BR112012024901A2 (en) | 2010-03-31 | 2021-07-20 | Indian Oil Corporation Limited | process for the simultaneous cracking of lighter and heavier hydrocarbons and system for the same |
| JP2023508350A (en) * | 2019-12-23 | 2023-03-02 | シェブロン ユー．エス．エー． インコーポレイテッド | Circular Economy of Waste Plastics to Polypropylene and Lubricating Oils via Refining FCC and Isomerization Dewaxing Units |
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| US6093867A (en) * | 1998-05-05 | 2000-07-25 | Exxon Research And Engineering Company | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
-
2001
- 2001-05-19 MX MXPA02000719A patent/MXPA02000719A/en unknown
- 2001-05-19 WO PCT/US2001/016036 patent/WO2002026628A1/en not_active Application Discontinuation
- 2001-05-19 JP JP2002530418A patent/JP2004509928A/en not_active Withdrawn
- 2001-05-19 EP EP01939096A patent/EP1289887A1/en not_active Withdrawn
- 2001-05-19 CA CA002388605A patent/CA2388605A1/en not_active Abandoned
- 2001-05-19 CN CN01801862A patent/CN1383448A/en active Pending
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| JP2004509928A (en) | 2004-04-02 |
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| WO2002026628A1 (en) | 2002-04-04 |
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