EP1049754A4 - Craquage catalytique destine a la production d'olefines - Google Patents

Craquage catalytique destine a la production d'olefines

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Publication number
EP1049754A4
EP1049754A4 EP99960387A EP99960387A EP1049754A4 EP 1049754 A4 EP1049754 A4 EP 1049754A4 EP 99960387 A EP99960387 A EP 99960387A EP 99960387 A EP99960387 A EP 99960387A EP 1049754 A4 EP1049754 A4 EP 1049754A4
Authority
EP
European Patent Office
Prior art keywords
catalyst
zsm
process according
matrix material
feed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99960387A
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German (de)
English (en)
Other versions
EP1049754A1 (fr
Inventor
Arthur W Chester
Thomas F Degnan
Ke Kiu
Hye Kyung Cho Timken
Mark F Mathias
Geoffrey L Woolery
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
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ExxonMobil Oil Corp
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Publication date
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Publication of EP1049754A1 publication Critical patent/EP1049754A1/fr
Publication of EP1049754A4 publication Critical patent/EP1049754A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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

Definitions

  • the present invention relates to the catalytic cracking of heavy hydrocarbon feeds over a catalyst to produce hydrocarbon compounds of lower molecular weight including, especially, light olefins such as ethylene and propylene.
  • the catalyst includes an intermediate pore size zeolite in a substantially inert matrix; a large pore molecular sieve may also be present.
  • Gasoline is the traditional high value product of fluid catalytic cracking (FCC).
  • FCC fluid catalytic cracking
  • ethylene and propylene are in higher demand and have higher value per pound than does gasoline.
  • conventional fluid catalytic cracking typically less than 2 wt.% ethylene in dry gas is obtained, and it is used as fuel gas.
  • the propylene yield is typically 3-6 wt.%.
  • Catalytic cracking operations are commercially employed in the petroleum refining industry to produce useful products, such as high quality gasoline and fuel oils from hydrocarbon - containing feeds.
  • the endothermic catalytic cracking of hydrocarbons is most commonly practiced using Fluid Catalytic Cracking (FCC) which has replaced the older moving bed catalytic cracking process.
  • FCC Fluid Catalytic Cracking
  • the cracking catalyst circulates cyclically between a cracking reactor and a catalyst regenerator.
  • hydrocarbon feedstock is contacted with hot, active, solid particulate catalyst in the absence of added hydrogen, for example at pressures up to 50 psig (4.4 bar) and temperatures typically from 425°C to 600°C.
  • a carbonaceous residue known as coke is deposited on the catalyst, deactivating the catalyst.
  • the cracked products are separated from the coked catalyst, the coked catalyst is stripped of volatiles, usually with steam in a catalyst stripper, after which the catalyst is regenerated. Decoking restores catalyst activity while the burning of the coke heats the catalyst.
  • the heated, regenerated catalyst is recycled to the cracking reactor to crack more feed.
  • the trend in FCC has been to dilute phase riser cracking with a brief hydrocarbon feed residence time of one to ten seconds.
  • a small amount of diluent e.g., steam up to 5 wt.% of the feed
  • the FCC process generally uses a cracking catalyst which includes a large pore zeolite such as USY or REY as the active cracking component.
  • the octane rating of the cracked FCC gasoline may be increased by the addition of a minor amount of ZSM-5 to the catalyst inventory, with commercial units believed to operate with less than 10 wt. % additive, usually considerably less.
  • U.S. Patent No. 5, 389,232 (Adewuyi) describes an FCC process in which the catalyst contains up to 90 wt.% conventional large pore cracking catalyst and an additive containing more than 3.0 wt.% ZSM-5 on a pure crystal basis on an amorphous support.
  • the patent indicates that although ZSM-5 increases C 3 and C 4 olefins, high temperatures degrade the effectiveness of ZSM-5. Therefore, a temperature of 950°F to 1100° F (510°C to 593°C) in the base of the riser is quenched with light cycle oil downstream of the base to lower the temperature in the riser 10°F- 100°F (5.6°C-55.6°C).
  • the ZSM-5 and the quench increase the production of C 3 /C 4 light olefins but there is no appreciable ethylene product.
  • U.S. Patent No. 5,456,821 (Absil) describes catalytic cracking over a catalyst composition which includes large pore molecular sieve, e.g., USY, REY or REUSY and an additive of ZSM-5, in organic oxide binder, e.g., colloidal silica with optional peptidized alumina, and clay.
  • organic oxide binder e.g., colloidal silica with optional peptidized alumina
  • the clay is treated with a phosphorus-containing compound.
  • the clay, source of phosphorus, zeolite and inorganic oxide are slurried together and spray-dried.
  • the catalyst can also contain metal such as platinum as an oxidation promoter.
  • the patent teaches that an active matrix material enhances the conversion.
  • the cracking products included gasoline, and C 3 and C 4 olefins but no appreciable ethylene.
  • European Patent Specifications Nos. 490,435-B and 372,632-B and European Patent Application No. 385,538-A describe processes for converting hydrocarbonaceous feedstocks to olefins and gasoline using fixed or moving beds.
  • the catalysts described include ZSM-5 in a matrix which includes a large proportion of alumina.
  • Catalysts include pentasil shaped molecular sieves and Y zeolites. Although the composition of the pentasil shape selective molecular sieve (CHP) is not particularly described, a table at column 3 indicates that the pentasil catalyst contains a high proportion of alumina, i.e., 50% alumina, presumably as a matrix.
  • DCC Deep Catalytic Cracking
  • the present invention includes a process for catalytically cracking heavy hydrocarbon feed to lighter hydrocarbon products comprising light olefins especially ethylene and propylene, by contacting the feed with a catalyst which comprises ZSM- 5 and/or ZSM-1 1 having a silica/alumina ratio above 12 and bound with a substantially inert matrix material. The contacting is under catalytic cracking conditions.
  • the cracking may also be carried out in the presence of a large pore size zeolite such as a faujasite, e.g. zeolite USY.
  • the substantially inert matrix material comprises silica, clay or mixtures of these materials.
  • Substantially inert means that the matrix preferably includes less than 10 wt.% active matrix material, more preferably less than 5 wt.% active material based on catalyst composition.
  • Active matrix materials are those which have catalytic activity for non-selective cracking and hydrogen transfer. The presence of active matrix material is minimized in the present invention. While the most commonly used active matrix material for catalyst manufacture is active alumina, the catalyst composition used in the invention preferably includes less than 10 wt.% active alumina, more preferably less than 5 wt.% active alumina, or essentially no active alumina.
  • non- acidic forms of alumina such as alpha alumina can be used in the matrix.
  • a small amount of alumina may be used to confer sufficient "hardness" in the catalyst particles for resistance to attrition and high temperatures but without introducing any appreciable non-selective cracking or hydrogen transfer.
  • the matrix comprises from zero to 60 wt.% silica and from 50 to 100 wt.% clay.
  • the catalyst composition may optionally include a large pore molecular sieve such as, preferably, the zeolites of the faujasite structure, preferably zeolite USY. When used, faujasites preferably contain less than 2.0 wt.% rare earth (RE) based on faujasite structure.
  • RE rare earth
  • the large pore molecular sieve is also preferably bound with a substantially inert matrix material.
  • the conditions used in the cracking process are selected to minimize hydrogen transfer and it is preferred to avoid hydrogen addition, hydroprocessing and the use of other catalyst components which would introduce excess hydrogen transfer activity. High temperature operation also increases the rate of cracking relative to hydrogen transfer and is therefore preferred.
  • Catalytic cracking conditions typically include a temperature from 510° to 704°C, a pressure from zero up to 8 bar (100 psig), a catalyst/oil ratio from 5 to 30, which corresponds under normal conditions to a WHSV from l to 20 hr "1 .
  • the products of the cracking process include gasoline boiling range products and olefins, and preferably less than 10 wt.% light gas product which includes methane, ethane, hydrogen and hydrogen sulfide.
  • Product olefins include ethylene and propylene, preferably in an amount of at least 13 wt.% based on total product; more preferably at least 20 wt.% or 25 wt.% up to 40 wt.% ethylene plus propylene.
  • the gasoline range product is preferably highly aromatic, containing from 20 wt % to 80 wt % BTX (benzene, toluene, xylenes) which are important petrochemical intermediates.
  • the process can be practiced in fluid catalytic cracking (FCC) although moving bed catalytic cracking is possible.
  • a heavy hydrocarbon feed is catalytically cracked in a catalytic cracking reactor operating at catalytic cracking conditions with a catalyst comprising ZSM-5 and/or ZSM-11 in the substantially inert matrix, optionally with a large pore molecular sieve component, preferably USY.
  • the cracked product effluent includes the desired olefins.
  • coke is formed on the catalyst.
  • the product effluent and the catalyst containing coke are separated from each other and the effluent recovered.
  • the coked catalyst is regenerated by contact with oxygen- containing gas to burn off the coke and produce hot, regenerated catalyst and to produce heat for the endothermic cracking reaction.
  • the hot, regenerated catalyst is recycled to the catalytic cracking reactor.
  • the process produces valuable olefin and aromatic gasoline range products useful as petrochemical feedstocks.
  • high molecular weight hydrocarbons are converted to lower molecular weight hydrocarbons.
  • the present process provides not only a high quality aromatic gasoline range product, but significantly more light olefins, especially ethylene and propylene.
  • the light olefins of the product can be separated as high quality petrochemical grade and may be used, for example, in the manufacture of valuable polymers such as polyethylene and polypropylene, and in the manufacture of ethers and/or alcohols, and as alkylating agents.
  • the feedstock typically have a 10% boiling point above 345°C (650°F) and usually a 50% boiling point of at least 750°F (400°C); feeds of this type normally include in whole or in part, gas oils such as vacuum gas oils, coker gas, thermally cracked oils, residual oils, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, or asphalts, as well as hydrotreated feedstocks derived from any of these stocks.
  • gas oils such as vacuum gas oils, coker gas, thermally cracked oils, residual oils, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, or asphalts, as well as hydrotreated feedstocks derived from any of these stocks.
  • the boiling temperatures specified in this specification are expressed in terms of the boiling point corrected to atmospheric pressure even though the distillation of higher boiling petroleum fractions above 400
  • Resids or deeper cut gas oils having an end point of up to 700°C, even with high metals, sulfur or nitrogen contents, can also be cracked using the present catalysts.
  • Catalytic cracking units which are amenable to the use of the present catalysts normally operate at temperatures from 950°F (510°C) to 1300°F (704°C) preferably from 1000°F (538°C) to 1200°F (649°C) and under atmospheric, or slightly uperatmospheric total pressure, usually from zero to 100 psig (1 to 8 bar), preferably from zero to 50 psig (1 to 4.5 bar).
  • the catalytic process can be either fixed bed, moving bed, transfer line, or fluidized bed, and the hydrocarbon flow can be either concurrent or countercurrent to the catalyst flow.
  • a process according to the invention is particularly applicable to the Fluid Catalytic Cracking (FCC) or the moving bed catalytic cracking processes.
  • a process according to the invention is particularly applicable to Fluid Catalytic Cracking.
  • the fluidizable catalyst is a fine powder of 20 to 140 micrometers. This powder is generally suspended in the feed and propelled upward in a reaction zone. Diluent such as steam up to 40% may be added to the feed at the bottom of the riser to lower hydrocarbon partial pressure.
  • a heavy hydrocarbon feedstock e.g., a gas oil
  • a suitable cracking catalyst is admixed with a suitable cracking catalyst to provide a fluidized suspension and cracked in an elongated reactor or riser, at elevated temperatures to provide a mixture of lighter hydrocarbon products.
  • the gaseous reaction products and spend catalyst are discharged from the riser into a separator, e.g.
  • a cyclone unit located within the upper section of an enclosed stripping vessel, or stripper, with the reaction products being conveyed to a product recovery zone and the spent catalyst entering a dense catalyst bed within the lower section of the stripper.
  • an inert stripping gas e.g., steam
  • the spent catalyst includes deposited coke which is burned off in an oxygen-containing atmosphere in a regenerator to produce hot, regenerated catalyst.
  • the fluidizable catalyst is continuously circulated between the riser and the regenerator and serves to transfer heat from the latter to the former thereby supplying the thermal needs of the cracking reaction which is endothermic.
  • the FCC conversion conditions typically include a temperature from 950°F (510°C) to 1250°F (677°C), preferably 1000°F (538°C) to 1200°F (649°C); catalyst/oil weight ratio from 5 to 30, preferably from 5 to 20; a catalyst riser residence time (contact time), of 0.5 to 10 seconds, preferably 1 to 5 seconds; and a weight hourly space velocity (WHSV) of 1 to 20 hr "1 , preferably 5 to 15 hr "1 .
  • WHSV weight hourly space velocity
  • the catalyst composition includes an intermediate pore zeolite component which is ZSM-5 (U.S. Pat. No. 3,702,886 and Re. 29,948) and/or ZSM-1 1 (U.S. Pat. No. 3,709,979). More preferred is ZSM-5.
  • relatively high silica zeolites ZSM-5 or ZSM-1 1 are used, i.e., those with a silica/alumina molar ratio above 5, and more preferably with a ratio of 12, 20, 70, 100, 500 or higher, even more preferably 12 to 100.
  • This ratio is meant to represent, as closely as possible, the molar ratio in the rigid framework of the zeolite crystal and to exclude silicon and aluminum in the matrix or in cationic or other form within the channels.
  • Other metals besides aluminum have been incorporated into the zeolite framework such as gallium which can be used in the invention.
  • the preparation of the zeolite may require reduction of the sodium content, as well as conversion to the protonated form. This can be accomplished, for example by employing the procedure of converting the zeolite to an intermediate ammonium form as a result of ammonium ion exchange followed by calcination to provide the hydrogen form. The operational requirements of these procedures are well known in the art.
  • the source of the ammonium ion is not critical; thus the source can be ammonium hydroxide or an ammonium salt such as ammonium nitrate, ammonium sulfate or ammonium chloride. Calcination of the ammonium exchanged zeolite will produce its hydrogen form. Calcination can be effected at temperatures up to 550°C.
  • the intermediate pore zeolite may be stabilized with phosphorus.
  • Phosphorus stabilization is well known and is described, for example, in U.S. Patent Nos. 3,911 ,041 to Kaeding et al., 3,972,832 to Butter et al., 4,423,266 to Young et al., 4,590,321 to Chu, and 5,456,821 to Absil et al.
  • the phosphorus can be added in an amount of zero to 10 wt.% of the total catalyst composition, preferably from 1 to 8 wt.%.
  • the catalyst composition may optionally include a large pore molecular sieve component with cracking activity.
  • the large-pore molecular sieve component of the catalyst composition may comprise any active component which has cracking activity and which has a pore opening of greater than 0.7 nm in effective diameter.
  • the active component may be a conventional large-pore zeolite molecular sieve X (U.S. Pat. No. 2,882,244); REX; zeolite Y (U.S. Pat. No. 3, 130,007); Ultrastable Y (USY) (U.S. Pat. No. 3, 449,070); Rare Earth exchanged Y (REY) (U.S. Pat. No. 4,415,438); Rare Earth exchanged USY (REUSY); Dealuminated Y (DeAI Y) (U.S. Pat. Nos.
  • Ultrahydrophobic Y UHPY
  • Ultrahydrophobic Y U.S. Pat. No. 4,401 ,556
  • dealuminated silicon-enriched zeolites e.g., LZ-210 (U.S. Pat. No. 4,678,765).
  • Naturally occurring zeolites such as faujasite, mordenite may also be used. These materials may be subjected to conventional treatments, such as impregnation or ion exchange with rare earths to increase stability.
  • large-pore zeolite molecular sieves include pillared silicates and/or clays; aluminophosphates e.g., ALPO 4 -5, ALPO 4 -8, VPI-5; silicoaluminophosphates, e.g., SAPO-5, SAPO-37, SAPO-40, MCM-9; and other metal aluminophosphates.
  • Mesoporous crystalline material for use as the molecular sieve includes MCM-41 .
  • the large-pore molecular sieve catalyst component may include phosphorus or a phosphorus compound for any of the functions generally attributed thereto, such as, for example, attrition resistance, stability, metals passivation, and coke reduction.
  • the preferred large-pore molecular sieve are zeolites of the faujasite structure with a silica/alumina ratio greater than 2, preferably a zeolite Y, more preferably USY.
  • the large pore molecular sieve contains less than 2.0 wt.% rare earth, preferably less than 1.0 wt. % rare earth (RE) based on faujasite, e.g., 0.3 wt % RE.
  • a slurry may be formed by deagglomerating the molecular sieve, preferably in an aqueous solution.
  • a slurry of the matrix material may be formed by mixing the desired matrix components such as clay and/or inorganic oxide in an aqueous solution.
  • the molecular sieve slurry and the matrix slurry are then well mixed and spray dried to form catalyst particles of, for example, less than 200 micrometers in diameter.
  • the large pore molecular sieve can be prepared in particles separately from the ZSM-5 and/or ZSM- 11 or together in the same particle with the ZSM-5 and/or ZSM-1 1 .
  • the binder matrix for the large pore molecular sieve is preferably substantially inert, containing, e.g., little if any active alumina, e.g., less than 10 wt.% active alumina, preferably less than 5 wt.% active alumina.
  • the catalyst composition preferably comprises from 1 wt.% to 50 wt % of the intermediate pores size component (ZSM-5 and/or ZSM-1 1 ) and, when used, from 1 wt.% to 50 wt % of the large-pore molecular sieve component. More preferably, the ratio of the large-pore molecular sieve/intermediate pore zeolite (ZSM-5 and/or ZSM-1 1 ) on a pure crystal basis is from 10: 1 to 1 : 10.
  • a zeolite For use in catalytic conversion processes a zeolite is usually compounded with a binder or matrix material, generally inorganic oxides, for increased resistance to temperatures and other conditions, e.g., mechanical attrition, which occur in various hydrocarbon conversion processes such as cracking. It is generally necessary for the catalysts to be resistant to mechanical attrition, that is, the formation of fines which are small particles, e.g., less than 20 micrometer.
  • the matrix materials used in the present compositions are substantially inert. i implying that the catalyst composition includes less than 10 wt.%, preferably less than 5 wt.%, active material.
  • the most commonly used active material is alumina in its active form. Active alumina is generally made by peptidizing a dispersable alumina (e.g., formed from the Bayer process or by controlled hydrolysis of aluminum alcoholates) with acid (e.g., formic, nitric). The dispersed alumina slurry is then mixed into the matrix.
  • the present catalyst composition includes less than 10 wt.%, preferably less than 5 wt.%, active alumina.
  • Matrix materials particularly useful for the present catalyst compositions include silica and clay.
  • the matrix can be in the form of a cogel or sol. A mixture of these components can also be used.
  • the sol can comprise zero to 60% by weight of the matrix.
  • the matrix comprises 50 to 100 wt.% clay, and zero to 50 wt.% sol.
  • the matrix can comprise up to 100% by weight clay.
  • Naturally occurring clays which can be composited with the catalyst include the montmorillonite and kaolin families which include the subbentonites, and the kaolins.
  • Clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Clay is generally used as a filler to produce denser catalyst particles.
  • catalyst can be composited with a porous matrix material such as silica- magnesia, silica-zirconia, silica-magnesia-zirconia.
  • the relative proportions of finely divided zeolite component and inorganic oxide matrix can vary widely, with the molecular sieve content ranging from 1 to 90 percent by weight, and more usually from 2 to 80 weight percent of the composite.
  • the zeolite makes up 5 to 75 wt. % of the catalyst and the matrix makes up 25 to 95 wt.% of the catalyst.
  • the total catalyst composition preferably comprises the large pore molecular sieve in an amount of 1 to 50 wt.%, preferably 10 to 40 wt. %; ZSM-5 and/or ZSM-1 1 in an amount of 1 to 50 wt %, preferably 10 to 40 wt.%; and matrix material in an amount of zero to 80 wt.%, preferably 20 to 60 wt.%. It is important to exclude catalyst components which could introduce excess hydrogen transfer activity such as rare earth stabilized faujasite, large amounts of active alumina or metals, such as platinum, palladium, rare earth, tin, etc., which supply an undesirable hydrogenation- dehydrogenation function.
  • the products of the catalytic cracking include gasoline range product and light olefins.
  • the gasoline range product preferably includes from 20 wt.% to 80 wt.% aromatics BTX (benzene, toluene, xylenes), preferably greater than 40 wt.% BTX.
  • the product also includes ethylene, e.g., over 1 wt.% ethylene or at least 2 or 3 wt.% ethylene. In favorable cases, the product includes greater than 5 wt.% ethylene, and it is possible to achieve greater than 8 wt.% ethylene, as a percentage of the feed based on the total product.
  • a substantial amount of propylene is also produced, and the amount of ethylene plus propylene may be greater than 13 wt.% or 15 wt % of the feed based on total product.
  • Ethylene plus propylene yields of greater than 20 wt.% or higher are possible, for example, greater than 25 wt.% (same basis).
  • Small amounts of light gas components including methane, ethane, hydrogen and hydrogen sulfide are also produced, e.g., less than 10 wt.%.
  • the product can include preferably less than 10 wt.% dry gas (methane, ethane, hydrogen, hydrogen sulfide and ethylene). At least 50% of dry gas product is ethylene.
  • the hydrocarbon conversion is from 50% to 95% of the feed, preferably 65% to 90%.
  • the amount of coke produced generally increases with conversion conditions.
  • Catalysts were prepared as follows with properties shown in Table 1 below: Catalyst A
  • a conventional FCC catalyst sampled from a refinery consisted of 35 wt.% rare earth exchanged ultrastablilized faujasite (REUSY) in a silica sol matrix (Davison,
  • Catalyst B This catalyst consisted of 40 wt % ZSM-5 (23: 1 Si ⁇ 2 /AI 2 0 3 ), 30% clay, 5% peptidized alumina, 25% silica sol. In addition, phosphorus (2.3 wt.% on finished catalyst) was added to the spray dryer slurry. The slurry containing all the catalyst components was spray dried.
  • Catalyst C This catalyst consisted of 40 wt.% ZSM-5 (55:1 SiO 2 /Al2 ⁇ 3) in an alumina sol matrix. TABLE 1
  • Catalyst A Catalyst B Catalyst C
  • Example 2 The catalysts prepared in Example 1 were used in a fixed-fluid-bed unit to process a mid Continent type Heavy Gas Oil with the properties listed in Table 2.
  • the liquid product was analyzed by Gas Chromatography to allow calculation of gasoline, LFO (light fuel oil), and HFO (heavy fuel oil) yields (ASTM D 2887-97).
  • the product was also analyzed by GC (Gas Chromatography) to identify C5- components. Runs with several catalyst/oil ratios between 1080°F (582°C) and 1200°F (649°) were done over the three catalysts. Based on this, yields at constant conversion were interpolated.
  • the reaction temperatures, conversion levels, catalyst/oil (C/O) ratios and products are listed in Table 3 below.
  • the zeolite to matrix balance in Catalyst C appears less favorable than that of Catalyst B for obtaining high ethylene and propylene yields.
  • the yield is seen to be primarily a function of conversion and not of temperature. This indicates that the ethylene is produced by catalytic cracking and not by thermal cracking.
  • the gas residence time has been held constant. It is expected that similar yields could be obtained by increasing the gas residence time and lowering either temperature or catalyst/oil ratio.
  • Catalyst D This catalyst consisted of ZSM-5 (silica/alumina ratio of 450/1) formulated like
  • Catalyst B (40% ZSM-5, 30% clay, 5% peptidized alumina, 25% silica sol, stabilized with phosphorus).
  • Catalyst E (40% ZSM-5, 30% clay, 5% peptidized alumina, 25% silica sol, stabilized with phosphorus).
  • This catalyst consisted of ZSM-5 in silica sol and clay with no alumina in the binder, stabilized with phosphorus, prepared as was Catalyst B but without the peptidized alumina.
  • Catalyst F Catalyst F
  • This catalyst consisted of ZSM-1 1 prepared as was Catalyst B with 40% ZSM-1 1 stabilized with phosphorus, with 30% clay, 5% peptidized alumina, 25% silica sol.
  • This catalyst consisted of ZSM-5 prepared as were Catalysts B and E but with 20% peptized alumina. Catalysts B, D, and F were used in a fixed-fluid-bed unit to process a Sour Heavy Gas Oil Feed. Process conditions included a temperature of 1200 ° F (650°C) and a WHSV of 12. The results are shown in Table 4 below.
  • Catalyst blends were prepared containing from zero to 100 wt% Catalyst H and a complementary amount of Catalyst I.
  • Catalyst H was a standard cracking catalyst (OctacatTM) including 40 wt% USY in a silica sol and clay matrix with no phosphorus.
  • Catalyst I was 40% ZSM-5 (26: 1 silica/alumina) in a silica sol matrix with 5% alumina (derived from pseudoboemite) and clay, phosphorus stabilized.
  • the catalyst blends were used in a fixed-fluid-bed unit to process a Mid Continent type heavy gas oil feed (Table 6) at 1200°F (650°C) and a WHSV of 12. Results are in Table 7. TABLE 1
  • 50-50 catalyst blends were prepared containing 50 wt.% USY-containing Catalyst H described in Example 5 and 50 wt.% each of the following:
  • phosphorus stabilized ZSM-11 (40% ZSM-11 in a silica sol matrix with 5% alumina and clay, P-stabilized);
  • Blends were prepared of 70 wt.% USY containing Catalyst H (40% USY in a silica sol matrix with no phosphorus) and 30 wt.% ZSM-5-containing Catalyst I.
  • Catalyst I was pre-steamed using the cyclic propylene steaming described above and in another blend, Catalyst I was calcined for 3 hours in air as previously decsribed but otherwise not steamed.
  • the blends containing steamed and unsteamed Catalyst I were used in fixed-fluid-bed unit to process a Sour Heavy Gas Oil Feed at 1200°F (649°C), and a WHSV of 12. The results are shown in Table 9.
  • a blend was prepared of 50 wt.% USY-containing Catalyst H and 50 wt.% ZSM-5- containing Catalyst I.
  • Another blend was prepared of 50 wt.% USY-containing Catalyst H and 50 wt.% ZSM-5-containing Catalyst J (no alumina).
  • the blends were used in a fixed-fluid-bed under conditions described in Example 1 but with 7.5 wt.% H 2 O cofeed. In another run, 15 wt.% water co-feed was added to the feed. Results are shown in Table 11.
  • a catalyst blend was prepared containing 50 wt.% USY-containing Catalyst H and 50 wt.% ZSM-5-containing catalyst J (no alumina).
  • the USY/ZSM-5 blend was used to process a paraffinic 760°F+ (405°C+) resid. Feed properties and results are summarized in Table 12 below. Table 12 also compares conversion results described by Fu et al., Oil & Gas Journal, Jan. 12, 1998, pp 49-53 for Deep Catalytic Cracking.
  • the Fu et al. catalyst is thought to contain rare earth (RE) ZSM-5 (pentasil) to process hydrotreated paraffinic feed.
  • RE rare earth

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  • Catalysts (AREA)

Abstract

Les charges d'hydrocarbures lourds subissent un craquage catalytique pour donner des produits plus légers par contact avec un catalyseur contenant un composant tamis moléculaire à larges pores et ZSM-5 et/ou ZSM-11, le catalyseur présentant une matière de matrice inerte, telle que de la silice et/ou de l'argile, et présentant une matière de matrice active inférieure à 10 % en masse, d'après la composition totale du catalyseur. Parmi ces produits figurent les oléfines légères à base d'éthylène et de propylène, la production d'oléfines légères croissant lorsque la matière de matrice est sensiblement inerte.
EP99960387A 1998-11-24 1999-11-17 Craquage catalytique destine a la production d'olefines Withdrawn EP1049754A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US19862598A 1998-11-24 1998-11-24
US19862498A 1998-11-24 1998-11-24
US198625 1998-11-24
US198624 1998-11-24
PCT/US1999/027137 WO2000031215A1 (fr) 1998-11-24 1999-11-17 Craquage catalytique destine a la production d'olefines

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EP1049754A1 EP1049754A1 (fr) 2000-11-08
EP1049754A4 true EP1049754A4 (fr) 2002-04-17

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JP (1) JP2002530514A (fr)
AU (1) AU1727800A (fr)
CA (1) CA2319263A1 (fr)
WO (1) WO2000031215A1 (fr)

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US8778170B2 (en) 2004-03-08 2014-07-15 China Petroleum Chemical Corporation Process for producing light olefins and aromatics
CN1301794C (zh) * 2004-08-06 2007-02-28 董家禄 一种催化热裂解制低碳烯烃的分子筛型催化剂
US7582203B2 (en) 2004-08-10 2009-09-01 Shell Oil Company Hydrocarbon cracking process for converting gas oil preferentially to middle distillate and lower olefins
KR20070056090A (ko) 2004-08-10 2007-05-31 쉘 인터내셔날 리써취 마트샤피지 비.브이. 탄화수소 원료로 중간 증류 제품 및 저급 올레핀을 만드는방법 및 장치
TWI379711B (en) * 2004-11-05 2012-12-21 Grace W R & Co Catalyst for light olefins and lpg in fluidized catalytic cracking units
JP2010523803A (ja) 2007-04-13 2010-07-15 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 炭化水素供給原料から中間蒸留物生成物及び低級オレフィンを製造するシステム及び方法
WO2009018722A1 (fr) 2007-08-09 2009-02-12 China Petroleum & Chemical Corporation Procédé de conversion catalytique
JP5213401B2 (ja) * 2007-09-20 2013-06-19 Ｊｘ日鉱日石エネルギー株式会社 重質石油類の流動接触分解方法
JP5390833B2 (ja) * 2008-11-06 2014-01-15 日揮触媒化成株式会社 炭化水素油の流動接触分解触媒
EP2877281B1 (fr) * 2012-07-24 2021-08-18 Indian Oil Corporation Ltd Composition de catalyseur pour craquage catalytique fluide, son procédé de préparation et son utilisation
US20150165427A1 (en) * 2013-12-13 2015-06-18 King Fahd University Of Petroleum And Minerals Metal-modified zeolite for catalytic cracking of heavy oils and process for producing light olefins
JP6234829B2 (ja) * 2014-01-24 2017-11-22 Ｊｘｔｇエネルギー株式会社 重質油の流動接触分解法
JP6329436B2 (ja) * 2014-05-30 2018-05-23 Ｊｘｔｇエネルギー株式会社 重質油の流動接触分解法
CN110272760B (zh) * 2018-05-29 2021-01-26 石宝珍 一种石油烃多级流化催化反应方法及反应器
CN115228506B (zh) * 2021-04-22 2023-09-26 中国科学院大连化学物理研究所 一种用于c4烯烃裂解制乙烯和丙烯的zsm-11催化剂及其制备方法
US11760943B1 (en) * 2022-11-08 2023-09-19 Saudi Arabian Oil Company Nano-ZSM-11 for direct conversion of crude oil to light olefins and aromatics

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Also Published As

Publication number Publication date
CA2319263A1 (fr) 2000-06-02
WO2000031215A1 (fr) 2000-06-02
JP2002530514A (ja) 2002-09-17
EP1049754A1 (fr) 2000-11-08
AU1727800A (en) 2000-06-13

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