CN114433219A - Hydrocarbon oil catalytic cracking catalyst and application thereof - Google Patents
Hydrocarbon oil catalytic cracking catalyst and application thereof Download PDFInfo
- Publication number
- CN114433219A CN114433219A CN202011197357.5A CN202011197357A CN114433219A CN 114433219 A CN114433219 A CN 114433219A CN 202011197357 A CN202011197357 A CN 202011197357A CN 114433219 A CN114433219 A CN 114433219A
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- Prior art keywords
- molecular sieve
- catalytic cracking
- cracking catalyst
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 77
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- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- B01J35/40—
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- B01J35/613—
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- B01J35/617—
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- B01J35/633—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The catalytic cracking catalyst comprises a substrate and a molecular sieve, wherein the molecular sieve comprises a Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with a pore opening diameter of 0.65 nm-0.7 nm, wherein: the Y-type molecular sieve contains rare earth oxide, and the content of the rare earth is RE based on the total weight of the Y-type molecular sieve2O3Calculated by not more than 5 percent, and the content of sodium oxide is not more than 1 percent; the unit cell constant of the Y-type molecular sieve is 2.430-2.450 nm, and the non-framework aluminum content accounts for the total aluminum contentThe weight ratio is not higher than 20 wt%, the lattice collapse temperature is not lower than 1050 ℃, the ratio of the B acid amount to the L acid amount measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 3, and the external surface acid amount measured by 2,4, 6-trimethyl pyridine macromolecular probe molecules is 220-300 mu mol/g. The catalytic cracking catalyst can effectively improve the ratio of the low-carbon olefin to the coke, and reduce the yield of the coke while improving the yield of the low-carbon olefin, and has good application prospect when being used for hydrocarbon oil catalytic cracking reaction.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrocarbon oil catalytic cracking catalyst and application thereof.
Background
The low-carbon olefin is an indispensable chemical raw material and comprises ethylene, propylene and butylene. Wherein, ethylene is mainly used for producing polyethylene, ethylene oxide, dichloroethane and the like, and propylene is mainly used for producing polypropylene, acrylonitrile, propylene oxide and other products. The butene is mainly used for producing sec-butyl alcohol, superimposed gasoline, butyl rubber and the like.
In recent years, the demand of low-carbon olefins is rapidly increased, and the productivity is continuously improved. At present, the main modes for producing low-carbon olefins include steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the proportion of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is up to 840-860 ℃, and the energy consumption is about 40 percent of the energy consumption of the petrochemical industry. The catalytic cracking reaction is carried out under the action of a catalyst, the reaction temperature is greatly reduced, and the distribution of products is flexible and adjustable. Therefore, the method for increasing the yield of the low-carbon olefin in large quantity by catalytic cracking is an efficient way for meeting the demand increase. However, the catalytically cracked feedstock oil is increasingly heavy and deteriorated, and the aromatic and naphthenic hydrocarbon contents thereof are gradually increased. Even if the hydrogenation treatment is carried out, most of aromatics are converted into naphthenes, the content of the naphthenes in raw oil is very high, and the conversion of final naphthenes is the key of catalytic cracking. If the catalyst is not suitable, the proportion of the naphthenic hydrocarbon subjected to cracking reaction is low, and most of the naphthenic hydrocarbon is subjected to dehydrogenation and/or hydrogen transfer reaction to regenerate aromatic hydrocarbon, further generate coke precursors and finally generate coke. Therefore, various raw oil at present is converted into low-carbon olefin as much as possible, and simultaneously, the production of coke is reduced, and high requirements are put forward on the development of a catalytic cracking catalyst.
In catalytic cracking catalysts, Y-type molecular sieves are an important component. In recent years, along with the increase of the slag doping amount of the catalytic cracking raw material, the proportion of macromolecules in the raw material is gradually increased, so that the utilization rate of an active center in a Y-type molecular sieve is reduced, and the cracking activity is reduced. With the research on the relationship between the Y-type molecular sieve and the catalyst performance, the Y-type molecular sieve with high silica-alumina ratio has more mesopores, so that the conversion rate of heavy oil can be remarkably improved, and the thermal and hydrothermal stability of the molecular sieve can be effectively improved, thereby becoming the main active component of the heavy oil catalytic cracking catalyst. In addition, along with the heaviness and deterioration of the raw oil, the accessibility of the active center of the catalytic cracking catalyst is improved, and the macromolecular cracking capability of the catalytic cracking catalyst is improved. As the crystal grains are reduced, the exposed active sites on the surface of the Y molecular sieve are greatly increased, the number of active centers on the outer surface is large, and the catalytic activity is improved; on the other hand, the small crystal grain Y molecular sieve has shorter pore passage communicated with the outside, is beneficial to the diffusion of reactants and products, reduces the diffusion resistance and effectively reduces the reaction depth and the coking rate. Therefore, compared with the traditional Y-type molecular sieve, the small-grain Y-type molecular sieve has more excellent catalytic performance and becomes the key point of research and development of novel petrochemical catalytic materials.
CN110092393A provides a method for preparing a small-grain NaY molecular sieve by using a NaY molecular sieve synthesis mother solution, which comprises the steps of (1) preparing a NaY molecular sieve crystallization guiding agent; (2) adding aluminate into the NaY synthesis mother liquor to prepare silicon-aluminum gel slurry; (3) filtering and washing the silicon-aluminum gel slurry in the step (2) to obtain a gel filter cake; (4) uniformly mixing the gel filter cake in the step (3) with the NaY molecular sieve crystallization guiding agent in the step (1) and alkali liquor to obtain a synthetic gel mixture; (5) crystallizing the synthesized gel mixture in the step (4) to obtain the small-grain NaY molecular sieve. The method adopts a recycling mode different from the traditional NaY synthesis mother liquor, realizes the complete recycling of silicon in the NaY mother liquor, and can stabilize the quality of the small-crystal-grain NaY molecular sieve product. However, the disclosure does not relate to how to achieve better resid conversion for Y molecular sieves.
CN106268918B provides a heavy oil catalytic cracking catalyst containing crystal grain gas phase ultrastable high silicon rare earth Y-type zeolite, a preparation method thereof and a heavy oil catalytic cracking method. The catalyst comprises 10-40 wt% of small-crystal-grain gas-phase ultra-stable high-silicon rare earth Y-type zeolite, 10-60 wt% of clay and 13-60 wt% of inorganic oxide, wherein the inorganic oxide contains at least one active alumina; the average diameter of the crystal grains of the zeolite is 0.1-0.8 micron, the unit cell constant is 24.5-24.6 angstrom, and the ratio of silicon to aluminum is 7-10; 6-16 wt% of rare earth oxide and less than 2 wt% of sodium oxide; the zeolite is prepared by carrying out gas phase ultra-stable treatment, washing and rare earth ion exchange on small-grain Y-type zeolite in sequence; the average pore diameter of the activated alumina is 5-25 nm. The catalytic cracking catalyst provided by the invention is mainly used for producing gasoline, has high gasoline octane number product, and has good gasoline quality.
CN103509588A discloses a cracking method for increasing the yield of low-carbon olefin and light aromatic hydrocarbon aiming at raw oil containing more naphthenic rings, which comprises the step of carrying out contact reaction on a hydrocarbon oil raw material containing more naphthenic rings and a catalyst in a reactor, wherein the catalyst mainly comprises 5-35 wt% of heat-resistant inorganic oxide, 0-65 wt% of clay, 5-50 wt% of modified mesoporous silicon-aluminum material and 15-60 wt% of molecular sieve; wherein the molecular sieve comprises a beta molecular sieve and an MFI molecular sieve, and the weight ratio of the beta molecular sieve to the MFI molecular sieve is not less than 1/3. The method has high yield of propylene and isobutene, and high BTX ratio in gasoline fraction aromatic hydrocarbon. The catalytic cracking effect of the hydrogenated residual oil still needs to be improved by using the modified mesoporous silicon-aluminum material in the publication.
Based on this, there is a need in the art to provide a catalyst that can significantly improve the yield of light olefins and reduce coke formation.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention mainly aims to provide a catalytic cracking catalyst and application thereof, and aims to solve the problems that the existing catalytic cracking catalyst is insufficient in heavy oil conversion activity, the coke yield is increased when the low-carbon olefin yield is improved, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a catalytic cracking catalyst, which comprises a substrate and a molecular sieve, wherein the molecular sieve comprises a Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with the pore opening diameter of 0.65 nm-0.7 nm, wherein: the Y-type molecular sieve contains rare earth oxide and sodium oxide, and the content of the rare earth is RE based on the total weight of the Y-type molecular sieve2O3Calculated by not more than 5 percent, and the content of sodium oxide is not more than 1 percent; the unit cell constant of the Y-type molecular sieve is 2.430 nm-2.450 nm, the proportion of non-framework aluminum content in the total aluminum content is not higher than 20 wt%, the lattice collapse temperature is not lower than 1050 ℃, the ratio of B acid amount to L acid amount measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 3, and the acid amount on the outer surface measured by 2,4, 6-trimethyl pyridine macromolecular probe molecules is 220 mu mol/g-300 mu mol/g.
According to one embodiment of the invention, the Y-type molecular sieve is a small-grained Y-type molecular sieve having an average grain size of 300nm to 900nm, preferably 400nm to 800 nm.
According to one embodiment of the present invention, the sodium oxide content is 0.1% to 0.7% based on the total weight of the Y-type molecular sieve.
According to one embodiment of the invention, the ratio of the amount of B acid to the amount of L acid in the Y-type molecular sieve is 3.0 to 4.5 or 3.1 to 4.
According to one embodiment of the present invention, the lattice collapse temperature of the Y-type molecular sieve is 1055 ℃ to 1085 ℃.
According to one embodiment of the present invention, the relative crystal retention of the Y-type molecular sieve is 38% to 45% after aging at 800 ℃, 1atm pressure and 100% water vapor atmosphere for 17 hours.
According to one embodiment of the present invention, the Y-type molecular sieve has a relative crystallinity of 50% to 70%.
According to one embodiment of the invention, the unit cell constant of the Y-type molecular sieve is 2.435 nm-2.445 nm, and the framework silicon-aluminum ratio is SiO2/Al2O3The molar ratio is 8.7-20.
According to one embodiment of the invention, the metal oxide-containing IMF structure molecular sieve is a metal oxide-containing IM-5 molecular sieve, wherein the metal oxide-containing IM-5 molecular sieve has a silicon to aluminum ratio of SiO2/Al2O3The molar ratio is 20-170.
According to an embodiment of the present invention, the content of the metal oxide in the metal oxide-containing IMF structure molecular sieve is 0.5 wt% to 12 wt%, and the metal oxide is selected from one or more of zirconium oxide, tungsten oxide, iron oxide, molybdenum oxide, niobium oxide, cobalt oxide, copper oxide, zinc oxide, boron oxide, tin oxide, manganese oxide, bismuth oxide, lanthanum oxide, and cerium oxide.
According to one embodiment of the invention, based on the total weight of the catalytic cracking catalyst on a dry basis, the content of the matrix is 45-75%, the content of the Y-type molecular sieve is 3-13%, the content of the IMF structure molecular sieve containing metal oxide is 15-30%, and the content of the molecular sieve with the pore opening diameter of 0.65-0.7 nm is 1-10%.
According to one embodiment of the invention, the molecular sieve having a pore opening diameter of 0.65nm to 0.7nm is selected from one or more of molecular sieves having AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF and SAO structures.
According to one embodiment of the present invention, a method for preparing a Y-type molecular sieve comprises the steps of: contacting the small-crystal NaY molecular sieve with a rare earth salt and/or ammonium salt solution to perform an ion exchange reaction to obtain the molecular sieve with reduced sodium oxide content; roasting the molecular sieve with the reduced sodium oxide content at the temperature of 450-650 ℃ for 4.5-7 h to obtain a roasted molecular sieve; and contacting the roasted molecular sieve with silicon tetrachloride gas to perform gas-phase superstable reaction to obtain the Y-type molecular sieve.
According to an embodiment of the present invention, further comprising: performing ammonium exchange treatment on a product obtained after the gas phase hyperstable reaction to ensure that the content of sodium oxide in the product is less than 1 wt%; mixing a product with the sodium oxide content of less than 1 wt% with water, adding an ammonium fluosilicate solution with the concentration of 0.05-0.4 mol/L at the temperature of 70-90 ℃, stirring for 0.5-2 h, and roasting the obtained product at the temperature of 400-600 ℃ for 1-5 h to obtain the Y-type molecular sieve.
According to one embodiment of the invention, the small-grained NaY molecular sieve has a grain size of no more than 1 μm.
According to one embodiment of the present invention, the molecular sieve having a reduced sodium oxide content has a unit cell constant of from 2.465nm to 2.472nm and a sodium oxide content of no more than 12 wt%.
According to one embodiment of the invention, the rare earth content in the molecular sieve having a reduced sodium oxide content is RE2O3Not more than 5 wt%, sodium oxide content of 4-11.5 wt%, and unit cell constant of 2.465-2.472 nm.
According to one embodiment of the invention, the method further comprises drying the calcined molecular sieve so that the water content of the calcined molecular sieve is not more than 1 wt%.
According to one embodiment of the invention, the ion exchange reaction comprises: according to the small crystal grain NaY molecular sieve: rare earth and/or ammonium salts: h2O is 1: (0.001-0.1): (5-15) mixing the small-crystal NaY molecular sieve, rare earth salt and/or ammonium salt and water in a weight ratio to form a mixture, and stirring; wherein the weight ratio of the total content of the rare earth salt and/or the ammonium salt to the small-grain NaY molecular sieve is preferably not less than 0.001: 1.
according to one embodiment of the invention, the temperature of the ion exchange reaction is 15 ℃ to 95 ℃, and the exchange time is 30min to 120 min.
According to one embodiment of the invention, the rare earth salt is selected from one or more of rare earth chloride and rare earth nitrate, and the ammonium salt is selected from one or more of ammonium sulfate, ammonium chloride and ammonium nitrate.
According to one embodiment of the invention, the weight ratio of the molecular sieve after roasting to the silicon tetrachloride gas is 1 (0.1-0.7), the gas phase ultra-stable reaction temperature is 300-550 ℃, and the reaction time is 10-300 min.
According to one embodiment of the invention, the method further comprises washing and filtering the product after the gas-phase ultra-stable reaction, and comprises the following steps: mixing the product after the gas phase hyperstable reaction with water according to the weight ratio of 1: 6-15, washing at the temperature of 30-60 ℃, and controlling the pH value to be 2.5-5.
According to one embodiment of the invention, the matrix is one or more of a natural clay, an alumina matrix, a silica matrix.
According to one embodiment of the invention, the silica sol in which the silica matrix is one or more of neutral, acidic or basic, is based on SiO2The content is 1wt percent to 15wt percent.
The invention also provides the application of the catalytic cracking catalyst in the catalytic cracking reaction of petroleum hydrocarbons.
According to the technical scheme, the invention has the beneficial effects that:
the invention provides a novel catalytic cracking catalyst, which is prepared by using a molecular sieve formed by compounding a specific Y-type molecular sieve, an IMF (intrinsic mode function) structure molecular sieve containing metal oxide and a molecular sieve with a pore opening diameter of 0.65-0.7 nm as an active component, and can be used for preparing the catalytic cracking catalyst with good heavy oil conversion activity and low carbon olefin yield by utilizing the synergistic effect of the Y-type molecular sieve, the IMF structure molecular sieve and the molecular sieve.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
One aspect of the present invention provides a catalytic cracking catalyst, which comprises a substrate and a molecular sieve, wherein the molecular sieve comprises a Y-type molecular sieve, an IMF structure molecular sieve containing a metal oxide, and a molecular sieve having a pore opening diameter of 0.65nm to 0.7nm, wherein: the Y-type molecular sieve contains rare earth oxide, and the content of the rare earth is RE based on the total weight of the Y-type molecular sieve2O3Calculated by not more than 5 percent, and the content of sodium oxide is not more than 1 percent; the unit cell constant of the Y-type molecular sieve is 2.430 nm-2.450 nm, the proportion of non-framework aluminum content in the total aluminum content is not higher than 20 wt%, the lattice collapse temperature is not lower than 1050 ℃, the ratio of B acid amount to L acid amount measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 3, and the acid amount on the outer surface measured by 2,4, 6-trimethyl pyridine macromolecular probe molecules is 220 mu mol/g-300 mu mol/g.
According to the invention, in the catalytic cracking process, for crude oil, particularly heavy crude oil, the ultra-stable modified Y-type molecular sieve with high silica-alumina ratio is adopted in the catalytic cracking catalyst, which is one of the main methods for improving the conversion rate of heavy oil at present. However, the existing catalytic cracking catalyst has great limitations, cannot simultaneously consider stability and conversion activity, and limits the development of the catalytic cracking process of hydrogenated heavy oil.
Therefore, the invention adopts a molecular sieve which is formed by compounding a specific Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with a pore opening diameter of 0.65 nm-0.7 nm as an active component of the catalytic cracking catalyst. Through the synergistic effect among the components, the heavy oil conversion activity can be effectively improved, and the low-carbon olefin and coke have high selectivity. The catalytic cracking catalyst has good application prospect when being used for catalytic cracking reaction of hydrocarbon oil.
The structure, principle, preparation process and the like of the catalytic cracking catalyst of the present invention are further specifically described below.
The catalytic cracking catalyst of the invention comprises a substrate and a molecular sieve. Among them, the matrix of the present invention may optionally contain the following components: (1) a binder comprising an aluminum binder and a silicon binder, the precursor of the aluminum binder being selected from pseudo-boehmite and/or an aluminum sol; the precursor of the silicon binder is one or more of acidic, neutral and alkaline silica sol and water glass, and the silica sol is preferred. The content is 1 wt% -15 wt%, preferably 5 wt% -15 wt% calculated by oxide based on the total weight of the catalyst. (2) Inorganic oxide matrix, the content of the inorganic oxide matrix is 0-80 wt%, preferably 10-70 wt% based on the total weight of the catalyst, and the inorganic oxide matrix is selected from one or more of inorganic oxide matrices commonly used by cracking catalysts, preferably one or more of alumina, silica, amorphous silica-alumina and clay. The clay is selected from clay commonly used in cracking catalysts, such as one or more selected from kaolin, halloysite, montmorillonite, diatomite and montmorillonite, preferably kaolin. The precursor of amorphous silica-alumina may be selected from one or more of silica-alumina sol, a mixture of silica sol and alumina sol, silica-alumina gel. The silica precursor may be selected from one or more of silica sol, silica gel and water glass. Of course, the substrate of the present invention is not limited to the above-mentioned substrate, and other substrates conventional in the art may be selected.
In some preferred embodiments, the matrix is one or more of natural clay, alumina matrix, silica matrix, wherein the silica matrix is one or more of neutral, acidic or basic silica sol, the silica sol being SiO2The content is 1 to 15% by weight, for example, 1, 5, 7, 8, 10, 11, 12, 15% by weight.
The molecular sieve in the catalyst comprises a Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with the pore opening diameter of 0.65 nm-0.7 nm. Wherein, the Y-type molecular sieve used in the invention has obviously improved thermal stability and hydrothermal stability.
Specifically, the Y-type molecular sieve contains rare earth oxide, and the content of the rare earth is based on the total weight of the Y-type molecular sieve and RE2O3The content of the active carbon is not more than 5%,e.g., 1%, 2%, 3%, 4%, 5%, etc., preferably no more than 3 wt%; the Y-type molecular sieve contains no sodium oxide as much as possible, and if it contains sodium oxide, the content of sodium oxide is not more than 1%, preferably 0.1% to 0.7%, for example, 0.1%, 0.3%, 0.4%, 0.5%, 0.7%, etc., more preferably 0.3% to 0.7%, more preferably 0.35% to 0.60% or 0.4% to 0.55%; the unit cell constant of the Y-type molecular sieve is 2.430 nm-2.450 nm, such as 2.432nm, 2.437nm, 2.442nm, 2.447nm, 2.449nm, etc., and the framework Si/Al ratio is SiO2/Al2O3The molar ratio is 8.7 to 20, such as 9.05, 10.25, 10.59, 11.77, 12.48, 14, etc., preferably 8.8 to 10.9. The Y-type molecular sieve also has a relatively low amount of non-framework aluminum, which is not more than 20 wt% of the total aluminum content, for example, 10 wt%, 13 wt%, 15 wt%, 16 wt%, 18 wt%, 19 wt%, 20 wt%, etc., preferably 13 wt% to 19 wt%. The lattice collapse temperature of the Y-type molecular sieve is not lower than 1050 ℃, preferably 1055-1085 ℃, and more preferably 1060-1085 ℃.
The Y-type molecular sieve has a more suitable acid center type and strength, wherein the ratio of the B acid amount to the L acid amount of the Y-type molecular sieve measured at 200 ℃ by using a pyridine adsorption infrared method is not less than 3, and preferably 3.1-4.0. The external surface area is more than 30m2G, e.g. 40m2/g～50m2The acid amount of the outer surface of the probe molecule is 220 to 300 mu mol/g, preferably 240 to 280 mu mol/g or 250 to 275 mu mol/g, measured by 2,4, 6-trimethyl pyridine macromolecular probe molecule.
The Y-type molecular sieve of the present invention has a specific surface area of 600m in one embodiment2/g～750m2G is, for example, 650m2/g～750m2(iv)/g or 680m2/g～750m2(iv)/g or 690m2/g～730m2/g。
In one embodiment, the mesoporous specific surface area of the Y-type molecular sieve is greater than 10m2A/g, preferably greater than 15m2G, e.g. 15m2/g～50m2G or 20m2/g～50m2G or 20m2/g～40m2G or 40m2/g～50m2/g。
In some embodiments, the Y-type molecular sieves of the present invention have a more optimized pore size structure. Wherein the total pore volume of the Y-type molecular sieve is 0.25mL/g to 0.42mL/g, preferably 0.275mL/g to 0.385mL/g or 0.30mL/g to 0.4mL/g, preferably 0.32mL/g to 0.39mL/g or 0.35 to 0.39 mL/g.
In some embodiments, the Y-type molecular sieve has a relative crystallinity of no less than 50%, preferably from 50% to 70%, more preferably from 61% to 69%, e.g., 65%, 66%, 67%, 68%, etc. The Y-type molecular sieve of the present invention has good hydrothermal stability, and the relative crystal retention of the Y-type molecular sieve after aging at 800 ℃ under normal pressure (1atm) and 100% steam atmosphere for 17 hours is 38% or more, for example, 38%, 39%, 40%, 42%, 43%, 48%, etc., preferably 38% to 45%.
According to the present invention, the aforementioned Y-type molecular sieve having a specific structure can be prepared by the following method. The method specifically comprises the following steps:
step (1): contacting the small-crystal grain NaY molecular sieve with a rare earth salt and/or ammonium salt solution to perform an ion exchange reaction, filtering, washing and optionally drying to obtain the NaY molecular sieve with reduced sodium oxide content; the NaY molecular sieve with the reduced sodium oxide content is a Y-type molecular sieve with the conventional unit cell size;
step (2): roasting the Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size at the temperature of 450-650 ℃ for 4.5-7 h, and optionally drying to obtain a roasted molecular sieve; and
and (3): and contacting the roasted molecular sieve with silicon tetrachloride gas to perform gas phase ultra-stable reaction to obtain the Y-type molecular sieve.
Optionally, further comprising step (4): and (4) carrying out ammonium exchange treatment on the molecular sieve obtained in the step (3) to obtain the Y-type molecular sieve with the sodium oxide content of less than 1.0 wt%.
Optionally, further comprising step (5): and (4) contacting the Y-type molecular sieve obtained in the step (3) or the Y-type molecular sieve obtained in the step (4) with an ammonium fluosilicate solution, and roasting to obtain the Y-type molecular sieve. Wherein, the water: ammonium fluosilicate: the weight ratio of the Y-type molecular sieve obtained in the step (3) or the Y-type molecular sieve obtained in the step (4) is (5-20): 0.002-0.3): 1.
The preparation process of the Y-type molecular sieve is specifically described below.
In the step (1), a specific small-grain NaY molecular sieve is selected to contact with a rare earth salt and/or ammonium salt solution for ion exchange reaction, so that the NaY molecular sieve with reduced sodium oxide content is obtained.
Wherein the small-grain NaY molecular sieve can be purchased or prepared according to the prior method, and in one embodiment, the unit cell constant of the small-grain NaY molecular sieve is 2.465 nm-2.472 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85% to 95%, and a sodium oxide content of 13.0% to 13.8%. The small-grained NaY molecular sieves have a grain size of not more than 1 μm, preferably from 300nm to 900nm, for example from 400nm to 800 nm.
In some embodiments, preferably, the method for synthesizing the small-grained NaY molecular sieve comprises the following steps:
(s1) preparing a NaY molecular sieve crystallization guiding agent;
(s2) by mol ratio SiO2：Al2O3Adding aluminate into the NaY synthetic mother liquor according to the proportion of 5-18, and adjusting the pH value to 5-12 to prepare silicon-aluminum gel slurry;
(s3) filtering and washing the silica-alumina gel slurry obtained in the step (s2) to obtain a gel filter cake, wherein the molar composition of the gel filter cake meets Na2O：Al2O3：SiO2：H2O ═ 0.5 to 2.5: 1: 5-18: 100-500;
(s4) uniformly mixing the gel filter cake of (s3) with the NaY molecular sieve crystallization guiding agent of (s1) and alkali liquor to obtain a synthetic gel mixture, wherein the composition of the synthetic gel mixture is Na2O：Al2O3：SiO2：H21.5-8: 1: 5-18: 100-500 mol ratio, wherein Al in the NaY molecular sieve crystallization guiding agent2O3In an amount of Al in said synthetic gel mixture2O31% -20% of the total amount;
(s5) crystallizing the synthesized gel mixture of (s4) at 70-120 ℃ for 10-50 h to obtain the small-grain NaY molecular sieve.
In the synthesis method of the small-grain NaY molecular sieve, the aluminate can be one or a mixture of aluminum sulfate, aluminum chloride, aluminum nitrate or aluminum phosphate.
In the method for synthesizing the small-grain NaY molecular sieve, the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na2O:Al2O3:(15-17)SiO2:(280-380)H2Mixing the components according to the molar ratio of O, uniformly stirring, standing and aging for 0.5-48 h at the temperature of room temperature to 70 ℃.
In the method for synthesizing the small-grain NaY molecular sieve, the silicon source can be water glass, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.
In the method for synthesizing the small-grain NaY molecular sieve, preferably, the SiO is formed in the step (s2)2：Al2O3＝7～10。
In the method for synthesizing the small-grain NaY molecular sieve, the pH value in the step (s2) is 7-10.
In the method for synthesizing the small-grain NaY molecular sieve, the molar composition ratio of the gel filter cake in the step (s3) is preferably Na2O：Al2O3：SiO2：H2O＝1～2：1：6～10：150～400。
In the method for synthesizing the small-grain NaY molecular sieve, the proportion of the synthetic gel mixture in the step (s4) is preferably Na2O：Al2O3：SiO2：H2O＝2～6：1：7～10：150～400。
In the method for synthesizing the small-grain NaY molecular sieve, the Al in the directing agent in the step (s4) is preferred2O3In an amount of Al in the resultant gel mixture2O35-15 mol% of the total amount.
The method for synthesizing the small-grain NaY molecular sieve can also comprise the step of collecting the synthetic mother liquor obtained in the step (s5) after the step (s5), and the collected synthetic mother liquor is mixed with the mother liquor of the conventional synthesis process and then used for preparing the silica-alumina gel for the next cycle.
According to the present invention, in some embodiments, the small-grained NaY molecular sieve is ion-exchanged with a rare earth solution and/or an ammonium salt solution, preferably at a temperature of 15 ℃ to 95 ℃, e.g., 65 ℃, 70 ℃, 78 ℃, 80 ℃, 82 ℃, 90 ℃, etc., for a time of 30min to 120min, e.g., 45min to 90 min. The ion exchange reaction can be carried out by contacting with a solution containing rare earth salt (namely rare earth salt solution) and a solution containing ammonium salt (namely ammonium salt solution) respectively, or can be carried out by contacting with a solution containing both rare earth salt and ammonium salt to carry out the ion exchange reaction. The ion exchange reaction may be carried out one or more times. Preferably, small crystallite NaY molecular sieve (on a dry basis): rare earth salts and/or ammonium salts (rare earth salts in RE)2O3The weight ratio of water to water is 1 (0.001-0.01) to 5-15, wherein the weight ratio of the total content of rare earth salt and ammonium salt to the small-grain NaY molecular sieve is not less than 0.001: 1, rare earth salts and/or ammonium salts: the weight ratio of the small-grain NaY molecular sieve is, for example, 0.01-0.08: 1. small crystal NaY molecular sieve (dry basis) rare earth salt and/or ammonium salt (rare earth salt is RE)2O3Meter) H2O is, for example, 1:0.005 to 0.10:5 to 15. Preferably, the weight ratio of the rare earth salt to the NaY molecular sieve (on a dry basis) is 0-0.05: 1, the weight ratio of ammonium salt to NaY molecular sieve (calculated on a dry basis) is 0-0.1: 1. the rare earth salt and/or ammonium salt solution is a water solution of rare earth salt and/or ammonium salt.
In some embodiments, the ion exchange reaction comprises: according to the NaY molecular sieve, rare earth salt and/or ammonium salt and water (H)2And O) 1, wherein (0.001-0.1) 5-15 parts by weight of small-grain NaY molecular sieve (also called NaY zeolite), rare earth salt and/or ammonium salt and water, such as decationized water, deionized water or a mixture thereof, are mixed and stirred at 15-95 ℃, such as 65-95 ℃, preferably 30-120 min to exchange rare earth ions and/or ammonium ions with sodium ions. The method comprises the steps of mixing a small-grain NaY molecular sieve, a rare earth salt and/or an ammonium salt and water to form a mixture, forming slurry by mixing the NaY molecular sieve and the water in a ratio of 1: 5-15, and adding a rare earth salt and/or an ammonium salt and/or a rare earth salt water solution into the slurryAnd/or an aqueous solution of an ammonium salt. The solution of rare earth salt may be referred to simply as a rare earth solution. The rare earth salt is preferably rare earth chloride and/or rare earth nitrate, and the ammonium salt is one or more of ammonium nitrate, ammonium sulfate and ammonium chloride.
In some embodiments, the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and a mixed rare earth, and preferably, the mixed rare earth contains one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd), or further contains at least one of rare earths other than lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd).
In some embodiments, the rare earth is a mixed rare earth comprising at least lanthanum and/or cerium, the content of lanthanum and/or cerium being more than 40 wt%, preferably more than 50 wt% or more than 60 wt% of the total content of the mixed rare earth, and the rare earth elements have the effect of improving the stability of the catalyst well.
The washing in step (1) is intended to wash out exchanged sodium ions, and for example, deionized water or decationized water may be used for washing. Preferably, the rare earth content of the rare earth-containing conventional unit cell size Y-type molecular sieve with reduced sodium oxide content obtained in step (1) is as RE2O3In an amount of not more than 5% by weight, for example not more than 3% by weight, and a sodium oxide content of not more than 12% by weight, for example from 4% by weight to 11.5% by weight or from 4% by weight to 9% by weight, for example from 5.5% by weight to 8.5% by weight or from 5.5% by weight to 7.5% by weight, with a cell constant of from 2.465nm to 2.472 nm.
According to the invention, in the step (2), the Y-type molecular sieve containing rare earth and having a conventional unit cell size is roasted at the temperature of 450-650 ℃ for 4.5-7 hours for treatment, preferably, the roasting temperature in the step (2) is 450-600 ℃, and the roasting time is 5-6.5 hours. Further preferably, the roasting temperature in the step (2) is 500-600 ℃, and the roasting time is 5-6 hours.
Preferably, step (2) further comprises drying the calcined molecular sieve so that the water content therein preferably does not exceed 1 wt%.
In the step (3), SiCl4: reduced unit cell constant obtained in step (2)The weight ratio of the Y-type molecular sieve (calculated on a dry basis) is 0.1-0.7: 1, preferably 0.3-0.6: 1, the reaction temperature is 300-550 ℃, and preferably 300-550 ℃. The washing method in step (3) may be a conventional washing method, and may be a washing with water such as decationized water or deionized water, in order to remove Na remaining in the zeolite+，Cl-And Al3+Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h2The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, and the washing temperature is 30-60 ℃. Preferably, the washing is such that no free Na is detectable in the wash liquor after washing+，Cl-And Al3+Plasma, preferably Na, in the washed washing water+，Cl-And Al3+The respective contents do not exceed 0.05 wt%. The unit cell constant of the Y-type molecular sieve obtained in the step (3) is preferably 2.430 nm-2.450 nm.
According to the invention, if the modified Y-type molecular sieve sodium oxide with reduced unit cell constant obtained in step (3) is higher than 1 wt%, preferably, the method further comprises the step (4): and (3) contacting the product of the step (3) for preparing the modified small-grain Y-type molecular sieve with an ammonium salt solution for ion exchange so that the content of sodium oxide in the molecular sieve is not more than 1 wt%. Such as one or more of ammonium chloride, ammonium nitrate, ammonium sulfate.
According to the invention, the Y-type molecular sieve obtained in the step (3) or the step (4) can be used as the Y-type molecular sieve for preparing the catalytic cracking catalyst, and the Y-type molecular sieve obtained in the step (3) or the step (4) can be further processed for preparing the catalyst.
According to the present invention, preferably, the method further comprises the aforementioned step (5): and (4) contacting the molecular sieve with the sodium oxide content of less than 1 wt% obtained in the step (3) or the step (4) with an ammonium fluosilicate solution. Wherein, the water: ammonium fluosilicate: the weight ratio of molecular sieve is preferably 5-20:0.002-0.3:1, for example water: ammonium fluosilicate: the weight ratio of the molecular sieve is 5-10: 0.005-0.1: 1 or 5-15: 0.05-0.2: 1. the method comprises the step (5), so that the selectivity of the catalyst for the low-carbon olefin of the hydrogenated heavy oil catalytic cracking can be further improved.
In some embodiments, the contacting temperature in step (5) is preferably 70 ℃ to 90 ℃, and the contacting time is preferably 0.5h to 2 h.
In some embodiments, step (5) may further comprise roasting, wherein the roasting temperature is preferably 400 ℃ to 600 ℃, and the roasting time is preferably 1h to 5 h.
Preferably, in one embodiment, the preparation method of the Y-type molecular sieve comprises a step (5), mixing the modified Y-type molecular sieve I with reduced unit cell constant obtained in the step (3) or the molecular sieve obtained in the step (4) with water, such as deionized water, according to a ratio of 1:5-10, adding ammonium fluorosilicate solution with a concentration of 0.05mol/L-0.4mol/L, such as 0.1 mol/L-0.3 mol/L, at 70-90 ℃, and stirring the mixture at 70-90 ℃ for 0.5-2 h. Preferably, the ratio of the ammonium fluosilicate to the water in the mixture is preferably 0.01-0.1 mol/L, for example, 0.03-0.08 mol/L; then filtering, drying, washing, and roasting at 400-600 ℃ for 1-5 h to obtain the Y-type molecular sieve of the invention, wherein the unit cell constant of the Y-type molecular sieve is preferably 2.330-2.450 nm.
The Y-type molecular sieve is a small-grain Y-type molecular sieve, has the average grain size of 300-900 nm, preferably 400-800 nm, has high crystallinity, high thermal stability and high hydrothermal stability, is uniform in aluminum distribution, has low non-framework aluminum content, is high in heavy oil cracking activity when used for heavy oil conversion, and can improve the yield of low-carbon olefin when the molecular sieve is used for heavy oil conversion.
The molecular sieve in the catalytic cracking catalyst of the invention comprises a molecular sieve with an IMF structure containing metal oxide and a molecular sieve with a pore opening diameter of 0.65 nm-0.7 nm besides the Y-type molecular sieve.
The content of the matrix is 45% to 75%, for example, 45%, 50%, 55%, 60%, 65%, etc., the content of the Y-type molecular sieve is 3% to 13%, for example, 3%, 4%, 7%, 9%, 10%, 12%, etc., the content of the metal oxide-containing IMF-structure molecular sieve is 15% to 30%, for example, 15%, 18%, 20%, 24%, 28%, 30%, etc., and the content of the molecular sieve having a pore opening diameter of 0.65nm to 0.7nm is 1% to 10%, for example, 1%, 5%, 8%, 9%, 10%, etc., based on the total weight of the catalytic cracking catalyst on a dry basis.
In some embodiments, the content of the metal oxide in the foregoing metal oxide-containing IMF structure molecular sieve is 0.5 wt% to 12 wt%, for example, 0.5 wt%, 1 wt%, 2 wt%, 4 wt%, 5 wt%, 7 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, etc., and the metal oxide is selected from one or more of zirconium oxide, tungsten oxide, iron oxide, molybdenum oxide, niobium oxide, cobalt oxide, copper oxide, zinc oxide, boron oxide, tin oxide, manganese oxide, bismuth oxide, lanthanum oxide, and cerium oxide.
In some embodiments, the molecular sieve having pore opening diameters of 0.65nm to 0.7nm is preferably one or more of molecular sieves having AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF, and SAO structures. More preferably at least one of Beta, SAPO-5, SAPO-40, SSZ-13, CIT-1, ITQ-7, ZSM-18, mordenite and gmelinite. The molecular sieves with different acidity and different pore diameters are selected to act with the Y-type molecular sieve and the molecular sieve with the IMF structure containing metal oxide in a synergistic way, so that the heavy oil conversion activity is further improved.
The Y-type molecular sieve, the IMF structure molecular sieve containing the metal oxide and the molecular sieve with the pore opening diameter of 0.65 nm-0.7 nm are compounded according to a specific proportion to obtain a synergistic effect, and the obtained catalytic cracking catalyst has good heavy oil conversion activity, high proportion of the obtained low-carbon olefin and coke and higher thermal and hydrothermal stability.
In some embodiments, the catalyst provided by the present invention may be prepared by the following method: mixing and pulping Y-type molecular sieve, IMF structure molecular sieve containing metal oxide, molecular sieve with pore opening diameter of 0.65-0.7 nm, inorganic oxide matrix, precursor of silicon or aluminum binder and deionized water, and drying to obtain the cracking catalyst. The solid content of the slurry formed by beating is generally 10 to 50 weight percent, and preferably 15 to 30 weight percent. The drying condition after pulping is the drying condition commonly used in the preparation process of the catalytic cracking catalyst. In general, the drying temperature is from 100 ℃ to 350 ℃, preferably from 200 ℃ to 300 ℃. The drying may be by oven drying, air drying or spray drying, preferably by spray drying. However, the method for preparing the catalyst of the present invention is not limited to the above method, and may be adjusted to a certain extent according to actual needs.
The catalyst provided by the invention is used under the conventional reaction conditions of a common hydrocarbon cracking process, such as the reaction temperature of 400-600 ℃, preferably 450-550 ℃, and the weight hourly space velocity of 5-30 hours－1Preferably 8 to 25 hours－1The ratio of the solvent to the oil is 1 to 10, preferably 2 to 7. The catalyst-to-oil ratio refers to the weight ratio of the catalyst to the feedstock oil.
In conclusion, the specific Y-type molecular sieve, the IMF structure molecular sieve containing the metal oxide and the molecular sieve with the specific pore channel opening diameter are compounded to be used as the active components of the catalyst, so that the obtained catalytic cracking catalyst has good thermal and hydrothermal stability, the ratio of the low-carbon olefin to the coke can be improved, and the yield of the low-carbon olefin is reduced while the yield of the low-carbon olefin is improved. The catalytic cracking catalyst has good application prospect when being used for the catalytic cracking reaction of petroleum hydrocarbon.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available. Wherein:
the "relative crystallinity" referred to herein is the crystallinity of the zeolite product as compared with the NaY raw material (defined as 100%) in example 1, and is determined by the RIPP146-90 standard method in "analytical methods for petrochemical industry" (RIPP test method) (eds. "yang cui et al, published 1990). The method comprises the following specific steps:
in the examples and comparative examples, the NaY1 molecular sieve (also known as NaY zeolite) was supplied by Qilu division, China petrochemical catalyst, Inc., and had a sodium oxide content of 13.5wt%, framework Si/Al ratio (SiO)2/Al2O3Molar ratio) of 4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; the average grain size of the NaY1 molecular sieve was about 600 nm.
The average grain sizes of NaY2, NaY3 and NaY4 are about 400nm, 800nm and 1000nm respectively, and are provided by Qilu division of China petrochemical catalyst, Inc.
The small-grain NaY1-NaY3 molecular sieve is synthesized according to the synthesis method of the small-grain NaY molecular sieve provided by the invention.
Rare earth chloride (RECl)3) And rare earth nitrate (RE (NO)3)3) For the production of Beijing chemical plant, the weight ratio of La to Ce is 2:3, and the total content of La and Ce is 46 wt% of the total rare earth content.
The analysis method comprises the following steps: in each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy; the unit cell constants and relative crystallinity of the zeolite were measured by X-ray powder diffraction (XRD) using RIPP145-90 and RIPP146-90 standard methods (compiled by petrochemical analysis method (RIPP test method), Yankee et al, scientific Press, published in 1990), and the framework silica-alumina ratio of the zeolite was calculated from the following formula: SiO 22/Al2O3＝(2.5858-a0)×2/(a0-2.4191) wherein, a0Is the unit cell constant in nm; the total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated. The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).
The average grain size of the zeolite is measured by adopting an SEM (scanning Electron microscope) method, the diameter of the maximum circumscribed circle of 50 grains of an SEM image is measured, and the average value is taken to be the average grain size.
The relative crystallinity is measured by using an RIPP146-90 external standard sample as a reference, and the relative crystallinity is measured by referring to the RIPP146-90 method in petrochemical analysis (RIPP test method), compiled by Yangshui et al, published by scientific publishing company, 1990.
In each comparative example and example, the acid center type of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption. An experimental instrument: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. Experimental method for measuring acid content at 200 ℃ by using pyridine adsorption infrared method: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 200 ℃, and vacuumizing to 10 DEG C-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400cm-1-1700cm-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 200 ℃. According to pyridine absorption infrared spectrogram of 1540cm-1And 1450cm-1The ratio of the intensities of the characteristic adsorption peaks is obtained to obtain the total adsorption peak in the molecular sieve
Relative amount of acid center (B acid center) to Lewis acid center (L acid center).
In each of the comparative examples and examples, the pore structure was determined as follows: measuring total pore volume of the molecular sieve according to adsorption isotherm, measuring micropore volume of the molecular sieve from the adsorption isotherm according to T plot method, subtracting the micropore volume from the total pore volume to obtain secondary pore volume, measuring specific surface area of mesopores, specific surface area (total specific surface area), pore volume and pore size distribution by low temperature nitrogen adsorption volumetric method, vacuum degassing samples at 100 deg.C and 300 deg.C for 0.5h and 6h, and N at 77.4K2Adsorption and desorption tests are carried out, the adsorption quantity and the desorption quantity of the test sample to the nitrogen under the conditions of different specific pressures are tested, and N is obtained2Adsorption-desorption isotherm curve. The BET specific surface area (total specific surface area) was calculated using the BET formula, and the micropore area was calculated using t-plot.
2,4, 6-trimethylpyridine test instrument: CPCP-7070-B Infrared in situ transient analysis platform (Tianjin City pioneer trade development Co., Ltd.), infrared model: BRUKER (brukes) TENSOR II, sample mass: 5mg, pellet diameter: 7mm, resolution: 4cm-1The scanning time is as follows: 32Scans, Experimental procedure:
1. the samples were pressed into tablets under high vacuum (pressure 5.4X 10)-6mbar) at 350 ℃ for 30min,
2. cooling to room temperature, adsorbing pyridine for 30min,
3. vacuum pumping (6.3X 10)-6mbar) for 10min of desorption,
4. heating to 200 deg.C for desorption for 30min, measuring total acid amount,
5. and (4) heating to 350 ℃, desorbing for 30min, and measuring the strong acid content.
The chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.
Example 1
This example illustrates the preparation of a Y-type molecular sieve according to one embodiment of the present invention
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, and 68ml of RE (NO) is added3)3Solution (rare earth solution concentration in RE)2O3319g/L), stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, and drying at 120 deg.C to obtain crystal cell constant of 2.471nm, sodium oxide content of 8.9 wt%, and RE2O3Y-type molecular sieve with 1 wt% of rare earth content is calculated, then the Y-type molecular sieve is roasted for 6 hours in air atmosphere with the temperature of 450 ℃ to ensure that the water content is lower than 1 wt%, and then the Y-type molecular sieve is prepared according to SiCl4: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating4Reacting gas at 350 deg.C for 2 hr to obtain Y-type molecular sieve with unit cell constant of 2.455nm, washing with 20L deionized water, filtering, washing, drying, exchanging with 20.0L ammonium sulfate solution with concentration of 2 wt% at 70 deg.C for 1 hr, filtering, washing, drying, repeating the above steps for 1 time to obtain QZ-1 molecular sieve,the sodium oxide content is less than 1.0 wt%;
mixing the QZ-1 molecular sieve and deionized water according to a weight ratio of 1:8, heating to 90 ℃, adding 10.0L of ammonium fluosilicate solution with the concentration of 0.1mol/L, stirring for 1h at 90 ℃, filtering, drying, washing, and roasting for 2h at 550 ℃ to obtain the modified small-crystal-grain Y-type molecular sieve, which is marked as SZ 1. The physicochemical properties are shown in Table 1, and the results of the XRD analysis of the relative crystallinity of the molecular sieve before and after aging of SZ1 in the exposed state at 800 deg.C under 1atm under 100% steam for 17 hours and the calculation of the relative crystallinity retention after aging are shown in Table 2, wherein:
example 2
2000 g of NaY2 molecular sieve (dry basis) was added to 25L of decationized aqueous solution and mixed well, 138ml of RECl was added3Solutions (with RE)2O3The solution concentration is measured as: 319g/L), stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, and drying the filter cake at 120 deg.C to obtain crystal cell constant of 2.471nm, sodium oxide content of 7.1 wt%, RE2O3Y-type molecular sieve with 2.0 wt% of rare earth, roasting at 550 deg.C for 5.5 hr to make its water content less than 1 wt%, and then making into SiCl4: y-type zeolite 0.6: 1, by weight, introducing SiCl vaporized by heating4Gas was reacted at 400 ℃ for 1.5 hours to obtain a Y-type molecular sieve having a unit cell constant of 2.461nm, which was then washed with 20 liters of decationized water, and then filtered, washed and dried. Exchanging the dried molecular sieve for 1h at 80 ℃ by using an ammonium sulfate solution with the concentration of 2 wt%, filtering, washing and drying, and repeating the steps for 1 time to ensure that the content of sodium oxide is less than 1.0 wt% to obtain the QZ-2 molecular sieve; according to the molecular sieve: mixing QZ-2 molecular sieve and deionized water in the weight ratio of 1 to 8, adding 10.0L ammonium fluorosilicate solution with the concentration of 0.2mol/L at 85 ℃, stirring and heating for 0.5h, filtering, drying, washing, and roasting at 550 ℃ for 2h to obtain the catalystThe modified small-grain Y-type molecular sieve provided by the invention is marked as SZ 2. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ2 is analyzed by XRD method after aging of SZ2 in an exposed state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.
Example 3
2000 g of NaY3 molecular sieve (dry basis) is added into 22L of decationized aqueous solution and stirred to be mixed evenly, and 50ml of RECl is added3Solutions (with RE)2O3Calculated rare earth solution concentration is 319g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, drying filter cake at 120 ℃, obtaining crystal cell constant of 2.471nm, sodium oxide content of 11.4 wt%, RE2O3Y-type molecular sieve with 0.7 wt% of rare earth, roasting at 600 deg.C for 5 hr to make its water content less than 1 wt%, and then making into SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4Reacting the gas at 540 deg.C for 1 hr to obtain Y-type molecular sieve with unit cell constant of 2.458nm, washing with 20L decationized water, filtering, washing, and drying. Exchanging the dried molecular sieve with ammonium sulfate solution in water bath at 80 deg.C to make sodium oxide content less than 1.0 wt%; obtaining the QZ-3 molecular sieve;
mixing the QZ-3 molecular sieve and deionized water according to a weight ratio of 1:8, adding 10.0L of ammonium fluosilicate solution with the concentration of 0.2mol/L under the condition of water bath at 85 ℃, stirring and heating for 0.5h, filtering, drying, washing, and roasting for 2h at 550 ℃ to obtain the modified small-crystal-grain Y-type molecular sieve, which is marked as SZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ3 in the exposed state is analyzed by XRD method after aging at 800 deg.C for 17 hr and 100% water vapor, and the relative crystal retention after aging is calculated.
Comparative example 1
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 1000 g of (NH) is added4)2SO4Stirring the mixtureHeating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification treatment (at 650 deg.C, calcining with 100% water vapor for 5 hr), adding into 20L of decationized water solution, stirring, mixing, adding 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment, wherein the hydrothermal treatment conditions are that the temperature is 650 ℃ and the roasting is carried out for 5 hours under 100% water vapor, so as to obtain the rare earth-free hydrothermal ultrastable Y-shaped molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and is marked as DZ 1. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ1 is analyzed by XRD method after aging DZ1 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
Comparative example 2
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification treatment, calcining at 650 deg.C under 100% steam for 5 hr, adding into 20L of decationized aqueous solution, stirring, mixing, adding 68ml RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth solution is measured as follows: 319g/L) and 900 g (NH)4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying the filter cake at 120 deg.C, and performing second hydrothermal modification treatment (at 650 deg.C, roasting with 100% water vapor for 5 hr) to obtain twice ion exchange twice hydrothermal ultrastable rare earth-containing hydrothermal ultrastable Y-type molecular sieve, which is recorded as DZ 2. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, in which the crystallinity of zeolite before and after aging of DZ2 was analyzed by XRD after aging DZ2 in the bare state at 800 ℃ for 17 hours with 100% steam and the relative crystal retention after aging was calculated.
Comparative example 3
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 820ml of RE (NO) is added3)3Stirring the solution (319g/L), heating to 90-95 deg.C, maintaining for 1 hr, filtering, washing, drying with molecular sieve at 110 deg.C for 4 hr to make water content lower than 1 wt%, gas phase ultra-stable modifying, and performing SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at 580 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to obtain a gas phase high silicon ultrastable Y-type molecular sieve designated as DZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ3 is analyzed by XRD method after aging DZ3 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
Comparative example 4
2000 g of NaY4 molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, and 68ml of RE (NO) is added3)3Solution (rare earth solution concentration in RE)2O3319g/L), stirring, heating to 90-95 deg.C for 1 hr, filtering, washing, and drying at 120 deg.C to obtain crystal cell constant of 2.471nm, sodium oxide content of 9.3 wt%, and RE2O3Y-type molecular sieve with 1.0 wt% of rare earth content is calculated, then the Y-type molecular sieve is roasted for 6 hours in air atmosphere with the temperature of 450 ℃ to ensure that the water content is lower than 1 wt%, and then SiCl is adopted4: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating4Reacting the gas at 350 deg.C for 2 hr to obtain Y-type molecular sieve with unit cell constant of 2.455nm, washing with 20L decationized water, filtering, washing, and drying. Exchanging the dried molecular sieve with ammonium sulfate solution at 70 deg.C for 1h, filtering, washing, and drying, repeating the exchanging, filtering, washing, and drying steps for 1 time to make the sodium oxide content of the molecular sieve less than 1.0 wt% to obtain DQZ-4; DQZ-4 molecular sieve and deionized water according to the weight ratio of 1:8Mixing, adding 10.0L ammonium fluosilicate solution with the concentration of 0.1mol/L under the condition of water bath at 90 ℃, stirring and heating for 1h, filtering, drying, washing, and roasting at 550 ℃ for 2h to obtain the modified Y-type molecular sieve, which is recorded as DZ 4. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the relative crystallinity of the molecular sieve before and after aging DZ4 is analyzed by XRD method after aging DZ4 in naked state at 800 deg.C, 1atm and 100% water vapor for 17 hours, and the relative crystallinity retention after aging is calculated.
TABLE 1
As shown in table 1, the high-stability Y-type molecular sieve provided by the present invention has the following advantages: the sodium oxide content is low, the non-framework aluminum content is low when the silicon-aluminum content of the molecular sieve is high, the external specific surface area is high, the B acid/L acid (the ratio of the total B acid content to the L acid content) is high, the crystallinity value measured when the unit cell constant of the molecular sieve is small and the rare earth content is low is high, the thermal stability is high, and the external surface acid content is high.
TABLE 2
As can be seen from table 2, the Y-type molecular sieve provided by the present invention has a higher relative crystal retention compared to the conventional Y-type molecular sieve with crystal grains after being aged under the harsh conditions of 800 ℃, 100 vol% of steam and 17 hours in an exposed state, which indicates that the Y-type molecular sieve provided by the present invention has a higher hydrothermal stability.
Examples 4 to 6
The modified Y-type molecular sieves SZ1, SZ3 and QZ-1 prepared in examples 1 and 3 are prepared into catalysts, and the catalyst numbers are as follows in sequence: a1, A2 and A3. The preparation method of the catalyst comprises the following steps:
(1) weighing a certain amount of pseudo-boehmite and a certain amount of water, uniformly mixing, adding concentrated hydrochloric acid (chemical purity, produced by Beijing chemical plant) with the concentration of 36% under stirring, wherein the acid-aluminum ratio (the molar ratio of HCl to the pseudo-boehmite calculated by alumina) is 0.19 molar ratio, heating the obtained mixture to 50 ℃, and aging for 1.5 hours to obtain the aged pseudo-boehmite. The alumina content of the aluminum oxide slurry was 12%.
(2) Quantitative modified Y-type molecular sieves SZ1, SZ3 and QZ-1, quantitative alumina sol or silica sol, quantitative mesoporous molecular sieve, IM-5 molecular sieve loaded with ferric oxide, quantitative kaolin, the aged pseudo-boehmite and deionized water are mixed uniformly to prepare slurry with the solid content of 32 weight percent, and the slurry is sprayed and dried.
The contents of Y-type zeolite, binder, IM-5 molecular sieve loaded with ferric oxide, third molecular sieve and kaolin in the catalyst composition are calculated, and the content of rare earth oxide is determined by adopting an X-ray fluorescence spectrometry.
In the examples, kaolin is an industrial product of China Kaolin company, and the solid content of the kaolin is 75 percent; the pseudoboehmite is produced by Shandong aluminum factories and has the alumina content of 65 percent by weight; the alumina sol is produced by Shandong Zhoucun catalyst factory, and has alumina content of 21 wt% and IM-5 molecular Sieve (SiO)2With Al2O3In the hydrogen form) from zeolite Beta SiO supplied by Changig division, China petrochemical catalyst corporation2With Al2O3Is 25, hydrogen form) is a commercial product of the company zilu, middle petrochemical catalyst. The silica sol is produced by Beijing chemical plant, and the content of silica is 25 percent.
The step of loading 3.1% of ferric oxide on the IM-5 molecular sieve comprises the following steps: 16.2g Fe (NO)3)3 9H2Dissolving O in 100g of water, adding 100g of IM-5 molecular sieve for impregnation, drying at 110 ℃, and roasting the obtained sample at 550 ℃ for 2 hours.
The kind and amount of Y-type zeolite used in step (2), and the amounts of alumina sol, silica sol and kaolin are shown in Table 3. The compositions of catalysts A1 to A3 are given in Table 4 (the contents of the individual components are based on the total weight of the catalyst).
The catalytic cracking performance of catalysts A1, A2 and A3 was evaluated in a small fixed fluidized bed reactor (ACE) after aging at 800 deg.C for 10 hours with 100% steam, and cracked gas and product oil were collected separately and analyzed by gas chromatography. The properties of the raw oil in the ACE test are shown in Table 5, the catalyst loading is 9g, and the evaluation conditions and the evaluation results are shown in Table 6.
Comparative example 5
The Y-type molecular sieve DZ3 prepared in comparative example 3, pseudo-boehmite, kaolin, a mesoporous molecular sieve, an iron-modified IM-5 molecular sieve (Fe/IM-5), water and alumina sol were mixed according to the catalyst preparation method of example 4, and spray-dried to prepare a microspherical catalyst. Catalyst No. DB 5. The kind and amount of Y-type zeolite used in the comparative catalyst, and the amounts of alumina sol and kaolin (for example, 1kg of catalyst) are shown in Table 3. The composition of catalyst DB5 is given in Table 4 (with the contents of each component being based on the total weight of the catalyst). The ACE evaluation method of the comparative example is the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 6
A microspherical catalyst was prepared according to the catalyst preparation method of example 4, except that iron-modified IM-5 molecular sieve (Fe/IM-5) was not added. Catalyst number DB 6. The kind and amount of Y-type zeolite used in the comparative catalyst, and the amounts of alumina sol and kaolin (for example, 1kg of catalyst) are shown in Table 3. The composition of catalyst DB6 is given in Table 4 (with the contents of each component being based on the total weight of the catalyst). The ACE evaluation method of the comparative example is the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 7
A microspherical catalyst was prepared according to the catalyst preparation method of example 4, except that the IM-5 molecular sieve was not modified. Catalyst No. DB 7. Table 3 shows the type and amount of Y-type zeolite used in the comparative catalyst, and the amounts of IM-5 molecular sieve, alumina sol and kaolin (for example, 1kg of catalyst was prepared). The composition of catalyst DB7 is given in Table 4 (with the amounts of the components being based on the total weight of the catalyst). The ACE evaluation method of the comparative example is the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 8
A microspherical catalyst was prepared according to the catalyst preparation method of example 4, except that no other molecular sieve was included except the Y and iron modified IM-5 molecular sieves. Catalyst number DB 8. Table 3 shows the type and amount of Y-type zeolite used in the comparative catalyst, the amount of iron-modified IM-5 molecular sieve (Fe/IM-5), the amount of alumina sol and kaolin (for the preparation of 1kg of catalyst). The composition of catalyst DB8 is given in Table 4 (with the contents of each component being based on the total weight of the catalyst). The ACE evaluation method of the comparative example is the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 9
A microspherical catalyst was prepared according to the catalyst preparation method of example 4, except that the Y-type molecular sieve used was the Y-type molecular sieve of comparative example 4, catalyst number DB 9. Table 3 shows the type and amount of Y-type zeolite used in the comparative catalyst, the amount of iron-modified IM-5 molecular sieve (Fe/IM-5), the amount of alumina sol and kaolin (for the preparation of 1kg of catalyst). The composition of catalyst DB9 is given in Table 4 (with the contents of each component being based on the total weight of the catalyst). The ACE evaluation method of the comparative example is the same as that of the example, and the evaluation results are shown in Table 6.
TABLE 3
The above is to prepare 1kg of catalyst charge.
TABLE 4 catalyst composition
TABLE 5
| Hydro-upgrading heavy oil properties | |
| Density (20 ℃ C.)/(kg/m)3) | 890.0 |
| Sulfur/(microgram/gram) | <200 |
| Ni + V/(microgram/gram) | <1 |
| Content of hydrogen/%) | 12.90 |
| Content of naphthenic ring hydrocarbons/%) | 44.67％ |
| End point of distillation | 630℃ |
TABLE 6
As can be seen from the results listed in table 6, when the catalytic cracking catalyst prepared by using the molecular sieve formed by compounding the Y-type molecular sieve, the metal oxide-containing IMF-structured molecular sieve, and the molecular sieve having a pore opening diameter of 0.65nm to 0.7nm as an active component improves the yield of the low-carbon olefins, the coke yield is low, and the ratio of the low-carbon olefins to the coke yield is high.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (26)
1. A catalytic cracking catalyst is characterized by comprising a substrate and a molecular sieve, wherein the molecular sieve comprises a Y-type molecular sieve, an IMF (intrinsic mode function) structure molecular sieve containing metal oxide and a molecular sieve with the pore opening diameter of 0.65-0.7 nm, and the molecular sieve comprises:
the Y-type molecular sieve contains rare earth oxide, and the content of the rare earth is RE based on the total weight of the Y-type molecular sieve2O3Calculated by not more than 5 percent, and the content of sodium oxide is not more than 1 percent; the unit cell constant of the Y-type molecular sieve is 2.430-2.450 nm, the proportion of non-framework aluminum content in the total aluminum content is not higher than 20 wt%, the lattice collapse temperature is not lower than 1050 ℃, the ratio of B acid amount to L acid amount measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 3, and the external surface acid amount measured by 2,4, 6-trimethyl pyridine macromolecular probe molecules is 220-300 mu mol/g.
2. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve is a small-grained Y-type molecular sieve having an average grain size of 300nm to 900 nm.
3. The catalytic cracking catalyst of claim 1, wherein the sodium oxide is present in an amount of 0.1 to 0.7% based on the total weight of the Y-type molecular sieve.
4. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve has a ratio of the amount of the B acid to the amount of the L acid of 3.0 to 4.5 or 3.1 to 4.
5. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve has a lattice collapse temperature of 1055 ℃ to 1085 ℃.
6. The catalytic cracking catalyst of claim 1, wherein the relative crystal retention of the Y-type molecular sieve is 38-45% after aging at 800 ℃, 1atm pressure and 100% steam atmosphere for 17 hours.
7. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve has a relative crystallinity of 50% to 70%.
8. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve has a unit cell constant of 2.435-2.445 nm and a framework Si/Al ratio of SiO2/Al2O3The molar ratio is 8.7-20.
9. The catalytic cracking catalyst of claim 1, wherein the metal oxide-containing IMF structure molecular sieve is a metal oxide-containing IM-5 molecular sieve, wherein the metal oxide-containing IM-5 molecular sieve has a silica to alumina ratio of SiO2/Al2O3The molar ratio is 20-170.
10. The catalytic cracking catalyst of claim 1, wherein the metal oxide-containing IMF structure molecular sieve contains 0.5 wt% to 12 wt% of metal oxide selected from one or more of zirconium oxide, tungsten oxide, iron oxide, molybdenum oxide, niobium oxide, cobalt oxide, copper oxide, zinc oxide, boron oxide, tin oxide, manganese oxide, bismuth oxide, lanthanum oxide, and cerium oxide.
11. The catalytic cracking catalyst of claim 1, wherein the matrix content is 45-75%, the Y-type molecular sieve content is 3-13%, the metal oxide-containing IMF-structured molecular sieve content is 15-30%, and the molecular sieve having a pore opening diameter of 0.65-0.7 nm is 1-10%, based on the total weight of the catalytic cracking catalyst on a dry basis.
12. The catalytic cracking catalyst of claim 1, wherein the molecular sieve having pore opening diameters of 0.65nm to 0.7nm is selected from one or more molecular sieves having AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF, and SAO structures.
13. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve is prepared by the following steps:
contacting the small-crystal NaY molecular sieve with a rare earth salt and/or ammonium salt solution to perform an ion exchange reaction to obtain the molecular sieve with reduced sodium oxide content;
roasting the molecular sieve with the reduced sodium oxide content at 450-650 ℃ for 4.5-7 h to obtain a roasted molecular sieve; and
and contacting the roasted molecular sieve with silicon tetrachloride gas to perform gas phase ultra-stable reaction to obtain the Y-type molecular sieve.
14. The catalytic cracking catalyst of claim 13, further comprising:
performing ammonium exchange treatment on a product obtained after the gas-phase hyperstable reaction to ensure that the content of sodium oxide in the product is less than 1 wt%;
and mixing the product with the sodium oxide content of less than 1 wt% with water, adding an ammonium fluosilicate solution with the concentration of 0.05-0.4 mol/L at the temperature of 70-90 ℃, stirring for 0.5-2 h, and roasting the obtained product at the temperature of 400-600 ℃ for 1-5 h to obtain the Y-type molecular sieve.
15. The catalytic cracking catalyst of claim 13, wherein the small-crystallite NaY molecular sieve has a crystallite size of no more than 1 μ ι η.
16. The catalytic cracking catalyst of claim 13, wherein the molecular sieve having a reduced sodium oxide content has a unit cell constant of 2.465nm to 2.472nm and a sodium oxide content of no more than 12 wt%.
17. The catalytic cracking catalyst of claim 13, wherein the molecular sieve with reduced sodium oxide content has a rare earth content as RE2O3Not more than 5 wt%, sodium oxide content of 4-11.5 wt%, and unit cell constant of 2.465-2.472 nm.
18. The catalytic cracking catalyst of claim 13, further comprising drying the calcined molecular sieve to a moisture content of not more than 1 wt%.
19. The catalytic cracking catalyst of claim 13, wherein the ion exchange reaction comprises: according to the small crystal grain NaY molecular sieve: rare earth and/or ammonium salts: h2O is 1: (0.001-0.1): (5-15) mixing the small-crystal NaY molecular sieve, rare earth salt and/or ammonium salt and water in a weight ratio to form a mixture, and stirring; wherein the weight ratio of the total content of the rare earth salt and/or the ammonium salt to the small-grain NaY molecular sieve is not less than 0.001: 1.
20. the catalytic cracking catalyst according to claim 13, wherein the temperature of the ion exchange reaction is 15 to 95 ℃ and the exchange time is 30 to 120 min.
21. The catalytic cracking catalyst of claim 13, wherein the rare earth salt is selected from one or more of rare earth chloride and rare earth nitrate, and the ammonium salt is selected from one or more of ammonium sulfate, ammonium chloride and ammonium nitrate.
22. The catalytic cracking catalyst of claim 13, wherein the weight ratio of the calcined molecular sieve to the silicon tetrachloride gas is 1 (0.1-0.7), the gas-phase superstable reaction temperature is 300-550 ℃, and the reaction time is 10-300 min.
23. The catalytic cracking catalyst of claim 13, further comprising washing and filtering the product after the gas phase superstable reaction, including: and mixing the product after the gas phase hyperstable reaction with water according to the weight ratio of 1: 6-15, washing at the temperature of 30-60 ℃, and controlling the pH value to be 2.5-5.
24. The catalytic cracking catalyst of claim 1, wherein the matrix is one or more of natural clay, alumina matrix, and silica matrix.
25. The catalytic cracking catalyst of claim 24, wherein the silica matrix is one or more of a neutral, acidic or basic silica sol, the silica sol being SiO2The content is 1wt percent to 15wt percent.
26. The use of the catalytic cracking catalyst according to any one of claims 1 to 25 in catalytic cracking reactions of hydrocarbon oils.
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