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CN114433219B - Hydrocarbon oil catalytic cracking catalyst and application thereof - Google Patents

Hydrocarbon oil catalytic cracking catalyst and application thereof Download PDF

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Publication number
CN114433219B
CN114433219B CN202011197357.5A CN202011197357A CN114433219B CN 114433219 B CN114433219 B CN 114433219B CN 202011197357 A CN202011197357 A CN 202011197357A CN 114433219 B CN114433219 B CN 114433219B
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molecular sieve
oxide
catalytic cracking
content
cracking catalyst
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CN114433219A (en
Inventor
王丽霞
韩蕾
周翔
王鹏
郭瑶庆
王振波
赵留周
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The catalytic cracking catalyst comprises a matrix 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 pore opening diameters of 0.65-0.7 nm, and the molecular sieve comprises a catalyst layer, wherein the catalyst layer comprises a catalyst layer and a catalyst layer, and the catalyst layer comprises a catalyst layer, wherein the catalyst layer comprises a Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with pore opening diameters of 0.65-0.7 nm: the Y-type molecular sieve contains rare earth oxide, and the rare earth content is RE based on the total weight of the Y-type molecular sieve 2 O 3 Not more than 5% by weight, and not more than 1% by weight of sodium oxide; the unit cell constant of the Y-type molecular sieve is 2.430-2.450 nm, the proportion of non-framework aluminum content is not higher than 20wt% of the total aluminum content, 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 outer surface acid amount measured by a 2,4, 6-trimethylpyridine macromolecular probe molecule is 220-300 mu mol/g. The catalytic cracking catalyst can effectively improve the ratio of low-carbon olefin to coke, can improve the yield of the low-carbon olefin, and can reduce the yield of the coke, thereby having good application prospect in the catalytic cracking reaction of hydrocarbon oil.

Description

Hydrocarbon oil catalytic cracking catalyst and application thereof
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, including 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 the like. The butene is mainly used for producing sec-butyl alcohol, laminated gasoline, butyl rubber and the like.
In recent years, the demand for low-carbon olefins has increased rapidly, driving the production capacity to increase continuously. Currently, the main modes for producing low-carbon olefins are steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the ratio of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is as high as 840-860 ℃, and the energy consumption accounts for about 40% of the energy consumption in petrochemical industry. The catalytic cracking reaction is carried out under the action of the catalyst, the reaction temperature is greatly reduced, and the distribution of the product is flexible and adjustable. Therefore, the catalytic cracking of low-carbon olefins to increase the yield of low-carbon olefins is an efficient way for meeting the increase of demand. However, the catalytic cracking of raw oil is increasingly heavier and inferior, and the aromatic hydrocarbon and naphthene contents therein are gradually increased. Even if hydrotreated, the aromatic hydrocarbon is mostly converted into naphthene, the naphthene content in the raw oil is very high, and the conversion of the final naphthene is the key of catalytic cracking. If the catalyst is not suitable, the proportion of naphthenes for cracking reaction is low, most of the naphthenes are subjected to dehydrogenation and/or hydrogen transfer reaction to regenerate aromatic hydrocarbon, further generate coke precursors and finally generate coke. Therefore, the production of coke is reduced while the current various raw oil is converted into low-carbon olefin as much as possible, and high requirements are put on the development of catalytic cracking catalysts.
In catalytic cracking catalysts, Y-type molecular sieves are an important component. In recent years, 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 active centers in the Y-type molecular sieve is reduced, and the cracking activity is reduced. Along with the gradual and deep research on the relation between the Y-type molecular sieve and the catalyst performance, the Y-type molecular sieve with high silicon-aluminum ratio has more mesopores, so that the heavy oil conversion rate can be obviously improved, and the thermal and hydrothermal stability of the molecular sieve can be effectively improved, and therefore, the Y-type molecular sieve has become a main active component of the heavy oil catalytic cracking catalyst. In addition, with the heavy and poor quality of raw oil, it is important to improve accessibility of active center of catalytic cracking catalyst and raise its macromolecule cracking ability. The active sites exposed on the surface of the Y molecular sieve are greatly increased along with the reduction of crystal grains, the number of active sites on the outer surface of the Y molecular sieve is large, and the catalytic activity is improved along with the reduction of crystal grains; on the other hand, the pore canal of the small-grain Y molecular sieve communicated with the outside is shortened, thereby being beneficial to the diffusion of reactants and products, reducing the diffusion resistance and effectively reducing the reaction depth and 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 small-grain NaY molecular sieve by using NaY molecular sieve synthesis mother liquor, comprising (1) preparing NaY molecular sieve crystallization director; (2) Adding aluminate into NaY synthesis mother liquor to prepare silica-alumina gel slurry; (3) Filtering and washing the silica-alumina gel slurry obtained in the step (2) to obtain a gel filter cake; (4) Uniformly mixing the gel filter cake obtained in the step (3), the NaY molecular sieve crystallization directing agent obtained in the step (1) and alkali liquor to obtain a synthetic gel mixture; (5) Crystallizing the synthesis 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 synthetic mother liquor, realizes the complete recycling of silicon in the NaY mother liquor, and can stabilize the quality of small-grain NaY molecular sieve products. However, the disclosure does not relate to how the Y molecular sieve can be made to have a better conversion effect on the hydrogenated residuum.
CN106268918B provides a heavy oil catalytic cracking catalyst containing ultra-stable high silicon rare earth Y-zeolite in crystal grain gas phase, its preparation method and heavy oil catalytic cracking method. The catalyst comprises 10-40 wt% of small-grain gas-phase ultrastable 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 zeolite grains is 0.1-0.8 microns, the unit cell constant is 24.5-24.6 angstrom, and the silicon-aluminum ratio is 7-10; 6-16 wt% of rare earth oxide and less than 2 wt% of sodium oxide; the zeolite is prepared from small-grain Y-type zeolite through gas phase ultrastable treatment, washing and rare earth ion exchange in sequence; the average pore diameter of the activated alumina is 5-25nm. The catalytic cracking catalyst provided by the invention is mainly used for producing gasoline, and has high gasoline octane number product and good gasoline quality.
CN103509588A discloses a cracking method for producing low-carbon olefins and light aromatics from raw oil containing more naphthene rings, which comprises the steps of contacting a hydrocarbon oil raw material containing more naphthene rings with a catalyst in a reactor for reaction, wherein the catalyst mainly comprises 5-35 wt% of heat-resistant inorganic oxide, 0-65 wt% of clay, 5-50 wt% of modified mesoporous silica-alumina 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 higher propylene and isobutene yields and higher BTX proportion in the gasoline fraction aromatic hydrocarbon. In the disclosure, a modified mesoporous silica-alumina material is used, and the catalytic cracking effect of hydrogenated residual oil is still to be improved.
Based on this, there is a need in the art to provide a catalyst that significantly increases the yield of lower olefins and reduces coke formation.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the 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, which are used for solving 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 above purpose, the present invention adopts the following technical scheme:
the invention provides a catalytic cracking catalyst, which comprises a matrix and a molecular sieve, wherein the molecular sieve comprises a Y-shaped molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with pore opening diameter of 0.65-0.7 nm, wherein the molecular sieve comprises the following components in percentage by weight: the Y-type molecular sieve contains rare earth oxide and sodium oxide, and the rare earth content is RE based on the total weight of the Y-type molecular sieve 2 O 3 Not more than 5% by weight, and not more than 1% by weight of sodium oxide; the unit cell constant of the Y-type molecular sieve is 2.430-2.450 nm, the proportion of non-framework aluminum content is not higher than 20wt% of the total aluminum content, the lattice collapse temperature is not lower than 1050 ℃, the ratio of the B acid amount to the L acid amount measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 3, and the outer surface acid amount measured by a 2,4, 6-trimethylpyridine macromolecular probe molecule is 220-300 mu mol/g.
According to one embodiment of the present invention, the Y-type molecular sieve is a small-grain Y-type molecular sieve having an average grain size of 300nm to 900nm, preferably 400nm to 800nm.
According to one embodiment of the invention, the sodium oxide content is 0.1 to 0.7 percent based on the total weight of the Y-type molecular sieve.
According to one embodiment of the present invention, the ratio of the amount of B acid to the amount of L acid of the Y-type molecular sieve is 3.0 to 4.5 or 3.1 to 4.
According to one embodiment of the invention, the lattice collapse temperature of the Y-type molecular sieve is 1055 ℃ to 1085 ℃.
According to one embodiment of the present invention, the Y-type molecular sieve has a relative crystalline retention of 38% to 45% after 17 hours aging at 800℃under a pressure of 1atm and a 100% water vapor atmosphere.
According to one embodiment of the invention, the relative crystallinity of the Y-type molecular sieve is 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 Si/Al ratio of the framework is SiO 2 /Al 2 O 3 The 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 silicon to aluminum ratio of the metal oxide containing IM-5 molecular sieve is SiO 2 /Al 2 O 3 The molar ratio is 20-170.
According to one embodiment of the present invention, the IMF structure molecular sieve containing metal oxide has a content of metal oxide of 0.5wt% to 12wt%, and the metal oxide is one or more selected from the group consisting of zirconia, 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, the total weight of the dry basis of the catalytic cracking catalyst is taken as reference, the matrix content is 45% -75%, the Y-type molecular sieve content is 3% -13%, the IMF structure molecular sieve content containing metal oxide is 15% -30%, and the molecular sieve content with pore opening diameter of 0.65-0.7 nm is 1% -10%.
According to one embodiment of the present invention, the molecular sieve having pore opening diameters 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 small-grain NaY molecular sieve with rare earth salt and/or ammonium salt solution to perform ion exchange reaction to obtain molecular sieve with reduced sodium oxide content; roasting the molecular sieve with reduced sodium oxide content at 450-650 ℃ for 4.5-7 h to obtain a roasted molecular sieve; and contacting the baked molecular sieve with silicon tetrachloride gas to perform gas-phase ultrastable reaction to obtain the Y-type molecular sieve.
According to one embodiment of the present invention, further comprising: carrying out ammonium exchange treatment on a product obtained after the gas-phase superstable reaction so as to ensure that the sodium oxide content in the product is less than 1wt%; mixing the product with sodium oxide content less than 1wt% with water, adding ammonium fluosilicate solution with concentration of 0.05mol/L-0.4mol/L at 70-90 deg.C, stirring for 0.5-2 h, and roasting the obtained product at 400-600 deg.C for 1-5 h to obtain the Y-type molecular sieve.
According to one embodiment of the invention, the small-grain NaY molecular sieve has a grain size of no more than 1 μm.
According to one embodiment of the 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 not more than 12wt%.
According to one embodiment of the invention, the rare earth content in the molecular sieve with reduced sodium oxide content is RE 2 O 3 The content of sodium oxide is not more than 5wt%, the content of sodium oxide is 4wt% -11.5 wt%, and the unit cell constant is 2.465-2.472 nm.
According to one embodiment of the invention, the method further comprises drying the calcined molecular sieve to a moisture content of no more than 1wt%.
According to one embodiment of the invention, the ion exchange reaction comprises: according to small-grain NaY molecular sieve: rare earth salts and/or ammonium salts: h 2 O=1: (0.001-0.1): (5-15) forming a mixture by using small-grain NaY molecular sieve, rare earth salt and/or ammonium salt and water according to the weight ratio, and stirring; wherein the weight ratio of the total content of rare earth salt and/or 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 15-95 ℃ and the exchange time is 30-120 min.
According to one embodiment of the invention, the rare earth salt is selected from one or more of rare earth chloride, 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 ultrastable 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 ultrastable reaction, and comprises the following steps: mixing the product after the gas phase ultrastable reaction with water according to the weight ratio of 1:6-15, washing at 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, wherein the silica matrix is one or more of neutral, acidic or basic silica sols, the silica sol matrix being formed of SiO 2 The content is 1-15 wt%.
The invention also provides application of the catalytic cracking catalyst in catalytic cracking reaction of petroleum hydrocarbon.
According to the technical scheme, the beneficial effects of the invention are as follows:
The invention provides a novel catalytic cracking catalyst, which is prepared by using a molecular sieve formed by compounding a specific Y-shaped molecular sieve, an IMF structure molecular sieve containing metal oxide and a molecular sieve with a pore opening diameter of 0.65-0.7 nm as active components, and can obtain the catalytic cracking catalyst with good heavy oil conversion activity and low carbon olefin yield by utilizing the synergistic effect of the three components.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
One aspect of the present invention provides a catalytic cracking catalyst comprising a substrate and a molecular sieve, the molecular sieve comprising a Y-type molecular sieve, an IMF structure molecular sieve comprising 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 rare earth content is RE based on the total weight of the Y-type molecular sieve 2 O 3 Not more than 5% by weight, and not more than 1% by weight of sodium oxide; the unit cell constant of the Y-type molecular sieve is 2.430-2.450 nm, the proportion of non-framework aluminum content is not higher than 20wt% of the total aluminum content, the lattice collapse temperature is not lower than 1050 ℃, the ratio of the B acid amount to the L acid amount measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 3, and the outer surface acid amount measured by a 2,4, 6-trimethylpyridine macromolecular probe molecule is 220-300 mu mol/g.
According to the present invention, in the catalytic cracking process, for crude oil, especially heavy crude oil, the ultra-stable modification of Y-type molecular sieve by employing high silica-alumina ratio in the catalytic cracking catalyst is one of the main methods for improving the conversion rate of heavy oil at present. However, the existing catalytic cracking catalyst has great limitation, can not simultaneously achieve stability and conversion activity, and limits the development of the catalytic cracking process of hydrogenated heavy oil.
Therefore, the invention adopts the molecular sieve formed by compounding the specific Y-type molecular sieve, the IMF structure molecular sieve containing metal oxide and the molecular sieve with the pore opening diameter of 0.65 nm-0.7 nm as the catalytic cracking catalyst of the active components. Through the synergistic effect of the components, the heavy oil conversion activity can be effectively improved, and the selectivity of the low-carbon olefin and the coke is high. The catalytic cracking catalyst has good application prospect in hydrocarbon oil catalytic cracking reaction.
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 present invention comprises a matrix and a molecular sieve. Wherein 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, preferably silica sol. The content is 1 to 15wt%, preferably 5 to 15wt%, calculated as oxide, based on the total weight of the catalyst. (2) The inorganic oxide matrix is used for the cracking catalyst, and the content of the inorganic oxide matrix is 0-80 wt%, preferably 10-70 wt%, based on the total catalyst, and is one or more of inorganic oxide matrixes commonly used for cracking catalysts, preferably one or more of alumina, silica, amorphous silica-alumina and clay. The clay is selected from clay commonly used for cracking catalyst, such as one or more selected from kaolin, halloysite, montmorillonite, kieselguhr and rectorite, 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 precursor of silica 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 substrate, and other substrates conventional in the art may be selected.
In some preferred embodiments, the matrix is one or more of a natural clay, an alumina matrix, a silica matrix, wherein the silica matrix is one or more of a neutral, acidic, or basic silica sol, the silica sol being formed as SiO 2 The content is 1wt% to 15wt%, for example, 1wt%, 5wt%, 7wt%, 8wt%, 10wt%, 11wt%, 12wt%, 15wt%.
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 pore canal opening diameter of 0.65-0.7 nm. 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 rare earth content is RE based on the total weight of the Y-type molecular sieve 2 O 3 No more than 5%, e.g., 1%, 2%, 3%, 4%, 5%, etc., preferably no more than 3% by weight; the Y-type molecular sieve does not contain sodium oxide as much as possible, if 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%, still 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, for example, 2.432nm, 2.437nm, 2.442nm, 2.447nm, 2.449nm and the like, and the Si/Al ratio of the framework is SiO 2 /Al 2 O 3 The molar ratio is 8.7 to 20, for example, 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 low content of non-framework aluminum, the proportion of the non-framework aluminum content to the total aluminum content is not higher than 20wt%, for example, 10wt%, 13wt%, 15wt%, 16wt%, 18wt%, 19wt%, 20wt%, etc., preferably 13wt% to 19wt%. The lattice collapse temperature of the Y-type molecular sieve is not lower than 1050 ℃, preferably 1055-1085 ℃, more preferably 1060-1085 ℃.
The Y-type molecular sieve of the invention has more proper acid center type and strength, wherein the ratio of the B acid amount to the L acid amount measured by a pyridine adsorption infrared method at 200 ℃ of the Y-type molecular sieve is not less than 3, preferably 3.1-4.0. The external surface area is more than 30m 2 /g, e.g. 40m 2 /g～50m 2 The amount of acid on 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, as measured by the 2,4, 6-trimethylpyridine macromolecular probe molecule.
The Y-type molecular sieve of the present invention, in one embodiment, has a specific surface area of 600m 2 /g～750m 2 For example 650 m/g 2 /g～750m 2 /g or 680m 2 /g～750m 2 /g or 690m 2 /g～730m 2 /g。
In one embodiment, the mesoporous specific surface area of the Y-type molecular sieve is greater than 10m 2 /g, preferably greater than 15m 2 /g, e.g. 15m 2 /g～50m 2 /g or 20m 2 /g～50m 2 /g or 20m 2 /g～40m 2 /g or 40m 2 /g～50m 2 /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 0.25 mL/g-0.42 mL/g, preferably 0.275 mL/g-0.385 mL/g or 0.30 mL/g-0.4 mL/g, preferably 0.32 mL/g-0.39 mL/g or 0.35-0.39mL/g.
In some embodiments, the relative crystallinity of the Y-type molecular sieve is not less than 50%, preferably 50% to 70%, more preferably 61% to 69%, e.g., 65%, 66%, 67%, 68%, etc. The Y-type molecular sieve of the present invention has excellent hydrothermal stability, and after aging at 800℃under normal pressure (1 atm) and 100% steam atmosphere for 17 hours, the relative crystal retention of the Y-type molecular sieve 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 as follows. The method specifically comprises the following steps:
step (1): contacting small-grain NaY molecular sieve with rare earth salt and/or ammonium salt solution to perform ion exchange reaction, filtering, washing, and optionally drying to obtain NaY molecular sieve with reduced sodium oxide content; the NaY molecular sieve with reduced sodium oxide content is a Y-type molecular sieve with the size of a conventional unit cell;
Step (2): roasting the Y-type molecular sieve with the conventional unit cell size and reduced sodium oxide content at the temperature of 450-650 ℃ for 4.5-7 h, and optionally drying to obtain a roasted molecular sieve; and
Step (3): and contacting the baked molecular sieve with silicon tetrachloride gas to perform gas-phase ultrastable reaction to obtain the Y-type molecular sieve.
Optionally, further comprising step (4): and (3) 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 (3) 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 water: ammonium fluorosilicate: 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 process for preparing the Y-type molecular sieve is specifically described below.
In the step (1), a specific small-grain NaY molecular sieve is selected to be contacted with 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 is commercially available or prepared according to existing methods, and in one embodiment, the small-grain NaY molecular sieve has a unit cell constant of 2.465nm to 2.472nm, a framework silica to alumina ratio (SiO 2 /Al 2 O 3 Molar ratio) is 4.5 to 5.2, the relative crystallinity is more than 85%, for example, 85 to 95%, and the sodium oxide content is 13.0 to 13.8wt%. The small-grain NaY molecular sieve has a grain size of not more than 1 μm, preferably 300nm to 900nm, for example 400nm to 800nm.
In some embodiments, preferably, the synthesis method of the small-grain NaY molecular sieve comprises the following steps:
(s 1) preparing a NaY molecular sieve crystallization directing agent;
(s 2) SiO in molar ratio 2 ：Al 2 O 3 Aluminate is added into NaY synthetic mother liquor according to the proportion of (5-18), and pH value is adjusted to (5-12) to prepare silica-alumina gel slurry;
(s 3) filtering and washing the silica-alumina gel slurry of (s 2) to obtain a gel filter cake, wherein the molar composition of the gel filter cake accords with Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=0.5-2.5: 1:5-18:100-500 parts of a mixture ratio;
(s 4) uniformly mixing the gel filter cake in (s 3), the NaY molecular sieve crystallization directing agent in (s 1) and alkali liquor to obtain a synthetic gel mixture, wherein the composition of the synthetic gel mixture accords with Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=1.5-8: 1:5-18:100-500 mol ratio, wherein Al in the NaY molecular sieve crystallization directing agent 2 O 3 Is contained in the synthetic gel mixture 2 O 3 1% -20% of the total amount;
(s 5) crystallizing the synthetic gel mixture obtained in the step (s 4) at the temperature of 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 more of aluminum sulfate, aluminum chloride, aluminum nitrate and aluminum phosphate.
In the synthesis method of the small-grain NaY molecular sieve, the guiding agent is prepared from a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na 2 O:Al 2 O 3 :(15-17)SiO 2 :(280-380)H 2 Mixing the O in a molar ratio, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of between room temperature and 70 ℃.
In the synthesis method of the small-grain NaY molecular sieve, the silicon source can be sodium silicate, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.
In the synthesis method of the small-grain NaY molecular sieve, preferably, the SiO in the step (s 2) 2 ：Al 2 O 3 ＝7～10。
In the synthesis method of the small-grain NaY molecular sieve, the pH value in the step (s 2) is=7-10.
In the synthesis method of the small-grain NaY molecular sieve, the gel filter cake in the step (s 3) preferably comprises Na in molar composition ratio 2 O：Al 2 O 3 ：SiO 2 ：H 2 O＝1～2：1：6～10：150～400。
In the synthesis method of the small-grain NaY molecular sieve, the mixture ratio of the synthesis gel in the step (s 4) is preferably Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O＝2～6：1：7～10：150～400。
In the synthesis method of the small-grain NaY molecular sieve, preferably, in the step (s 4), al in the directing agent 2 O 3 Is contained in Al in the synthetic gel mixture 2 O 3 5-15 mole% of the total amount.
The synthesis method of the small-grain NaY molecular sieve can also comprise the process of collecting the synthetic mother liquor obtained in the step (s 5) after the step (s 5), and the collected synthetic mother liquor is mixed with the mother liquor of the conventional synthesis process to prepare the silica-alumina gel for the next cycle.
In accordance with the present invention, in some embodiments, small-grain NaY molecular sieves are dissolved with rare earthsThe solution and/or ammonium salt solution is subjected to ion exchange reaction at a temperature of preferably 15 to 95℃such as 65 to 95℃e.g. 65 to 70℃78℃80℃82℃90℃and the like, and a time of preferably 30 to 120 minutes such as 45 to 90 minutes. 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 by contacting with a solution containing both rare earth salt and ammonium salt. The ion exchange reaction may be carried out one or more times. Preferably, small-grain NaY molecular sieves (on a dry basis): rare earth salts and/or ammonium salts (rare earth salts in RE) 2 O 3 Water=1 (0.001-0.01): (5-15) weight ratio, 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 to 0.08:1. small grain NaY molecular sieves (on a dry basis) of rare earth salts and/or ammonium salts (rare earth salts on RE) 2 O 3 Meter (meter): H 2 O 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 to 0.05:1, the weight ratio of the ammonium salt to the NaY molecular sieve (based on dry basis) is 0 to 0.1:1. the rare earth salt and/or ammonium salt solution is an aqueous solution of rare earth salt and/or ammonium salt.
In some embodiments, the ion exchange reaction comprises: according to NaY molecular sieve, rare earth salt and/or ammonium salt and water (H) 2 O) =1 (0.001 to 0.1) 5 to 15 by weight of small-grain NaY molecular sieve (also called NaY zeolite), rare earth salt and/or ammonium salt and water are mixed to form a mixture, and the mixture is stirred at 15 to 95 ℃, for example 65 to 95 ℃, preferably for 30 to 120 minutes to exchange rare earth ions and/or ammonium ions with sodium ions, and the water is decationized water, deionized water or a mixture thereof. Small-grain NaY molecular sieve, rare earth salt and/or ammonium salt and water are mixed to form a mixture, naY molecular sieve and water can be formed into slurry in a ratio of 1:5-15, and then aqueous solution of rare earth salt and/or ammonium salt and/or aqueous solution of ammonium salt is added into the slurry. The solution of rare earth salt may be simply referred to as rare earth solution. The rare earth salt is preferably rare earth chloride and/or nitrate, and the ammonium salt is preferably nitric acid Ammonium, 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 mixed rare earth, preferably, the mixed rare earth contains one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), or at least one of rare earth except lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd).
In some embodiments, the rare earth is a misch metal, the misch metal comprises at least lanthanum and/or cerium, the lanthanum and/or cerium content is more than 40wt%, preferably more than 50wt% or 60wt% of the total misch metal content, and the rare earth element is effective to improve the stability of the catalyst.
The washing of step (1) is aimed at washing away exchanged sodium ions, for example, deionized water or decationized water may be used. 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 calculated as RE 2 O 3 For example, not more than 5wt%, for example, not more than 3wt%, the sodium oxide content is not more than 12wt%, for example, 4wt% to 11.5wt% or 4wt% to 9wt%, for example, 5.5wt% to 8.5wt% or 5.5wt% to 7.5wt%, and the unit cell constant is 2.465nm to 2.472nm.
According to the invention, in step (2), the Y-type molecular sieve with the conventional unit cell size containing rare earth is roasted for 4.5 to 7 hours at the temperature of 450 to 650 ℃, preferably, the roasting temperature in step (2) is 450 to 600 ℃ and the roasting time is 5 to 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 molecular sieve obtained by calcination so that the water content therein is preferably not more than 1wt%.
In step (3), siCl 4 : the weight ratio of the Y-type molecular sieve (based on dry basis) with the unit cell constant reduced obtained in the step (2) is 0.1-0.7: 1, preferably 0.3 to 0.6:1, the reaction temperature is 300-550 ℃, preferably 300-550 ℃. The step (3)The washing method may be a conventional washing method, and may be washing with water such as deionized water or deionized water, in order to remove Na remaining in the zeolite + ，Cl - Al and Al 3+ Such soluble byproducts, e.g., wash conditions, may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieves: h 2 O weight ratio=1:6-15, pH value is preferably 2.5-5.0, washing temperature is 30-60 ℃. Preferably, the washing is performed such that no free Na is detected in the washing liquid after washing + ，Cl - Al and Al 3+ Plasma, preferably Na in the washing water after washing + ，Cl - Al and Al 3+ The respective content is not more than 0.05wt%. The unit cell constant of the Y-type molecular sieve obtained in the step (3) is preferably 2.430nm to 2.450nm.
According to the present invention, if step (3) results in the modified Y-type molecular sieve sodium oxide having a reduced unit cell constant of greater than 1wt%, it preferably further comprises the aforementioned step (4): and (3) contacting the modified small-grain Y-type molecular sieve product obtained in the step (3) with an ammonium salt solution for ion exchange so that the sodium oxide content in the molecular sieve is not more than 1wt%. 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 can be used for preparing the catalyst after further processing the Y-type molecular sieve obtained in the step (3) or the step (4).
According to the present invention, preferably, the method further comprises the step (5): and (3) contacting the molecular sieve with the sodium oxide content of less than 1 weight percent obtained in the step (3) or the step (4) with an ammonium fluosilicate solution. Wherein water: ammonium fluorosilicate: the weight ratio of molecular sieves is preferably from 5 to 20:0.002 to 0.3:1, for example water: ammonium fluorosilicate: the weight ratio of the molecular sieve is 5-10:0.005-0.1:1 or 5-15:0.05-0.2:1. the step (5) can further improve the selectivity of the catalyst for the catalytic cracking of the hydrogenated heavy oil.
In some embodiments, the contact temperature in step (5) is preferably 70 ℃ to 90 ℃ and the contact time is preferably 0.5h to 2h.
In some embodiments, step (5) may further comprise calcination, preferably at a temperature of 400 to 600 ℃, and for a time of preferably 1 to 5 hours.
Preferably, in one embodiment, the preparation method of the Y-type molecular sieve comprises the step (5), mixing the modified Y-type molecular sieve I with the unit cell constant reduced obtained in the step (3) or the molecular sieve obtained in the step (4) with water, such as deionized water, according to the proportion of 1:5-10, adding ammonium fluosilicate solution with the concentration of 0.05mol/L to 0.4mol/L, such as 0.1mol/L to 0.3mol/L, at the temperature of 70 ℃ to 90 ℃, and stirring the formed mixture for 0.5h to 2h. Preferably, the ratio of ammonium fluorosilicate to water in the mixture is preferably from 0.01 to 0.1mol/L, for example from 0.03 to 0.08mol/L of ammonium fluorosilicate water; then filtering, drying and washing, roasting for 1-5 h at 400-600 ℃ to obtain the Y-type molecular sieve, 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, the average grain size of the Y-type molecular sieve is 300-900 nm, preferably 400-800 nm, and the Y-type molecular sieve has high crystallinity, high thermal stability and high hydrothermal stability, meanwhile, the aluminum in the molecular sieve is uniformly distributed, the non-framework aluminum content is low, the cracking activity of heavy oil is high when the Y-type molecular sieve is used for heavy oil conversion, and the yield of low-carbon olefin when the molecular sieve is used for heavy oil conversion can be improved.
The molecular sieve in the catalytic cracking catalyst of the invention comprises an IMF structure molecular sieve containing metal oxide and a molecular sieve with pore opening diameter of 0.65-0.7 nm besides the Y-type molecular sieve.
Based on the total weight of the dry basis of the catalytic cracking catalyst, the matrix content is 45% -75%, for example 45%, 50%, 55%, 60%, 65%, etc., the Y-type molecular sieve content is 3% -13%, for example 3%, 4%, 7%, 9%, 10%, 12%, etc., the IMF structure molecular sieve content containing metal oxide is 15% -30%, for example 15%, 18%, 20%, 24%, 28%, 30%, etc., and the molecular sieve content with pore opening diameters of 0.65 nm-0.7 nm is 1% -10%, for example 1%, 5%, 8%, 9%, 10%, etc.
In some embodiments, the metal oxide is present in the IMF structure molecular sieve comprising metal oxide in an amount of 0.5wt% to 12wt%, e.g., 0.5wt%, 1wt%, 2wt%, 4wt%, 5wt%, 7wt%, 9wt%, 10wt%, 11wt%, 12wt%, etc., the metal oxide being selected from one or more of zirconia, 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 heavy oil conversion activity is further improved by selecting molecular sieves with different acidity and different apertures to cooperate with the Y-type molecular sieve and the IMF structure molecular sieve containing metal oxide.
The Y-type molecular sieve, the IMF structure molecular sieve containing metal oxide and the molecular sieve with pore opening diameter of 0.65-0.7 nm are compounded according to a specific proportion to obtain a synergistic effect, and the obtained catalytic cracking catalyst can have good heavy oil conversion activity, and the obtained low-carbon olefin has high proportion of coke and higher thermal and hydrothermal stability.
In some embodiments, the catalysts provided herein can be prepared using the following methods: mixing and pulping a Y-type molecular sieve, an IMF structure molecular sieve containing metal oxide, a molecular sieve with pore opening diameter of 0.65-0.7 nm, an inorganic oxide matrix, a 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 50wt%, preferably 15 to 30wt%. The drying condition after beating 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℃and preferably from 200℃to 300 ℃. The drying may be by a drying, forced air drying or spray drying method, preferably a spray drying method. However, the method for preparing the catalyst of the present invention is not limited to the foregoing method, and may be adjusted to a certain extent according to actual needs.
The catalyst provided by the invention is used under the conditions of the conventional reaction conditions in the general hydrocarbon cracking process, such as the reaction temperature of 400-600 ℃, preferably 450-550 ℃ and the weight hourly space velocity of 5-30 hours －1 Preferably 8 to 25 hours －1 The ratio of the catalyst to the oil is 1 to 10, preferably 2 to 7. The catalyst to oil ratio refers to the weight ratio of catalyst to raw oil.
In summary, the specific Y-type molecular sieve, the IMF structure molecular sieve containing metal oxide and the molecular sieve with the specific pore opening diameter are compounded to be used as active components of the catalyst, so that the obtained catalytic cracking catalyst has good thermal and hydrothermal stability, the ratio of low-carbon olefin to coke can be improved, the yield of the low-carbon olefin is improved, and the yield of the coke is reduced. The catalytic cracking catalyst has good application prospect in petroleum hydrocarbon catalytic cracking reaction.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. The reagents, materials, etc. used in the present invention are commercially available unless otherwise specified. Wherein:
the "relative crystallinity" according to the present invention is the crystallinity obtained by comparing the zeolite product with the NaY starting material of example 1 (defining the crystallinity thereof as 100%), and the method for measuring the relative crystallinity is described in "petrochemical analysis method (RIPP test method)" (Yang Cuiding et al, scientific press, 1990, published standard method RIPP 146-90). The method comprises the following steps:
Figure BDA0002754399910000151
Examples and comparative examples, naY1 molecular sieves (also referred to as NaY zeolite) were provided by Qilu division, china petrochemical catalyst Co., ltd, and had a sodium oxide content of 13.5% by weight and a framework silica alumina ratio (SiO 2 /Al 2 O 3 Molar ratio) =4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; average grain ruler of NaY1 molecular sieveThe dimensions are approximately 600nm.
The average grain sizes of NaY2, naY3 and NaY4 are about 400nm, 800nm and 1000nm respectively, and are provided for Qilu division of China petrochemical catalyst Co.
The small-grain NaY1-NaY3 molecular sieves are synthesized according to the synthesis method of the small-grain NaY molecular sieves provided by the invention.
Rare earth chloride (RECl) 3 ) And rare earth nitrate (RE (NO) 3 ) 3 ) For Beijing chemical plant production, the weight ratio of La to Ce is 2:3, and the total content of La and Ce is 46wt% of the total rare earth content.
The analysis method comprises the following steps: in each of the comparative examples and examples, the elemental content of zeolite was determined by X-ray fluorescence spectrometry; the unit cell constant and the relative crystallinity of the zeolite are measured by an X-ray powder diffraction (XRD) method by using RIPP145-90 and RIPP146-90 standard methods (see, e.g., petrochemical analysis method (RIPP test method) Yang Cuiding, published by science Press, 1990), and the framework silica-alumina ratio of the zeolite is calculated by the following formula: siO (SiO) 2 /Al 2 O 3 ＝(2.5858-a 0 )×2/(a 0 2.4191) wherein a 0 Is 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 skeleton Al to total Al can be calculated according to the ratio of skeleton Si-Al measured by an XRD method to the ratio of total Si-Al measured by an XRF method, so that the ratio of non-skeleton Al to total Al is calculated. The collapse temperature of the crystal structure was determined by Differential Thermal Analysis (DTA).
The average grain size of zeolite is measured by SEM scanning electron microscope method, and the diameter of the largest circumcircle of 50 grains in SEM image is measured, and the average value is taken as the average grain size.
The relative crystallinity is measured by taking an external standard sample of RIPP 146-90 as a reference, and the measuring method of the relative crystallinity is referred to the RIPP 146-90 method in petrochemical analysis method (RIPP test method) (Yang Cuiding et al, scientific Press, 1990).
In each of the comparative examples and examples, the acid center type of the molecular sieve and the acid amount thereof were determined by infrared analysis of pyridine adsorption. Experimental instrumentThe device comprises: bruker company IFS113V type FT-IR (Fourier transform Infrared) spectrometer, U.S. The acid amount measurement experiment method by pyridine adsorption infrared method at 200 ℃ comprises the following steps: and (3) performing self-supporting tabletting on the sample, and sealing in an in-situ cell of an infrared spectrometer. Heating to 400 ℃, and vacuumizing to 10 DEG C -3 Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. Cooling to room temperature, and introducing pyridine vapor with the pressure of 2.67Pa for 30min to keep adsorption balance. Then heating to 200 ℃, vacuumizing to 10 DEG C -3 Desorbing for 30min under Pa, cooling to room temperature, photographing, and scanning the wave number range: 1400cm -1 -1700cm- 1 And obtaining a pyridine adsorption infrared spectrogram of the sample subjected to desorption at 200 ℃. According to 1540cm in pyridine adsorption infrared spectrogram -1 And 1450cm -1 The ratio of the intensities of the characteristic adsorption peaks to obtain the total molecular sieve
Figure BDA0002754399910000161
The relative amounts of acid centers (B acid centers) and Lewis acid centers (L acid centers).
In each of the comparative examples and examples, the measurement method of the pore structure was as follows: determining total pore volume of molecular sieve according to adsorption isotherm according to RIPP151-90 standard method (RIPP test method) (Yang Cuiding et al, scientific Press, 1990 publication), determining micropore volume of molecular sieve according to T-plot method from adsorption isotherm, subtracting micropore volume from total pore volume to obtain secondary pore volume, measuring specific surface area and specific surface area (total specific surface area), pore volume, pore size distribution by low temperature nitrogen adsorption capacity method, vacuum degassing sample at 100deg.C and 300deg.C for 0.5 hr and 6 hr respectively by ASAP2420 adsorbent of Micromeritics company, and vacuum degassing sample at 77.4K for N 2 Adsorption and desorption tests, wherein the adsorption quantity and desorption quantity of the test sample on nitrogen under different specific pressure conditions are used for obtaining N 2 Adsorption-desorption isotherms. BET specific surface area (total specific surface area) was calculated using the BET formula, and the micropore area was calculated by t-plot.
2,4, 6-trimethylpyridine testing instrument: CPCP-7070-B infrared in-situ transient analysis platform (Tianjin city proprietary industry and trade development Co., ltd.) infrared model: BRUKER TENSOR II, sample mass: 5mg, diameter of tablet: 7mm, resolution: 4cm -1 Scanning time: 32Scans, experimental procedure:
1. sample was pressed into tablets under high vacuum (pressure 5.4X10) -6 mbar) treatment at 350℃for 30min,
2. cooling to room temperature, adsorbing pyridine for 30min,
3. vacuum (6.3X10) -6 mbar) for 10min,
4. desorbing for 30min at 200 deg.C, measuring total acid quantity,
5. and (3) heating to 350 ℃ for desorption for 30min, and measuring the amount of the strong acid.
The chemical reagents used in the comparative examples and examples are not particularly noted and are chemically pure in specification.
Example 1
This example is a description of a method for preparing a Y-type molecular sieve according to one embodiment of the present invention
2000 g of NaY1 molecular sieve (dry basis) was added to 20L of decationized aqueous solution and stirred to mix well, 68ml of RE (NO) was added 3 ) 3 Solution (rare earth solution concentration with RE) 2 O 3 319 g/L), stirring, heating to 90-95deg.C, maintaining for 1 hr, filtering, washing, and drying the filter cake at 120deg.C to obtain powder with unit cell constant of 2.471nm, sodium oxide content of 8.9wt% and RE 2 O 3 Y-type molecular sieve having a rare earth content of 1wt%, followed by calcination in an air atmosphere at 450 ℃ for 6 hours to a water content of less than 1wt%, followed by SiCl 4 : y-type molecular sieve (dry basis) =0.5: 1 weight ratio, siCl vaporized by heating is introduced 4 Reacting gas at 350 ℃ for 2 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.455nm, washing with 20 liters of deionized water, filtering, washing, drying, exchanging with 20.0L of 2wt% ammonium sulfate solution at 70 ℃ for 1 hour, filtering, washing, drying, and repeating the exchanging, filtering, washing and drying steps for 1 time to obtain a QZ-1 molecular sieve with a sodium oxide content of less than 1.0wt%;
mixing a 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 a concentration of 0.1mol/L, stirring for 1h at 90 ℃, filtering, drying, washing, and roasting for 2h at 550 ℃, thereby obtaining the modified small-grain Y-type molecular sieve provided by the invention, which is denoted as SZ1. The physical and chemical properties are shown in Table 1, and after SZ1 is aged for 17 hours at 800 ℃ under 1atm with 100% steam, the relative crystallinity of the molecular sieve before and after the SZ1 is aged is analyzed by XRD method and the relative crystallinity retention after the aging is calculated, and the results are shown in Table 2, wherein:
Figure BDA0002754399910000171
Example 2
2000 g of NaY2 molecular sieve (dry basis) was added to 25 l of decationized aqueous solution and stirred to mix well, 138ml of RECl was added 3 Solution (in RE) 2 O 3 The solution concentration was: 319 g/L), stirring, heating to 90-95deg.C for 1 hr, filtering, washing, and drying the filter cake at 120deg.C to obtain powder with unit cell constant of 2.471nm, sodium oxide content of 7.1wt% and RE 2 O 3 Y-type molecular sieve with rare earth content of 2.0wt%, roasting at 550 deg.c for 5.5 hr to water content lower than 1wt%, and SiCl treatment 4 : y zeolite = 0.6:1 weight ratio, siCl vaporized by heating is introduced 4 The gas was reacted at 400℃for 1.5 hours to give a Y-type molecular sieve having a unit cell constant of 2.461nm, which was then washed with 20 liters of decationized water, filtered, washed and dried. Exchanging the dried molecular sieve with 2wt% ammonium sulfate solution at 80 ℃ for 1h, filtering, washing and drying, and repeating the steps for 1 time to ensure that the sodium oxide content 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 a weight ratio of water to 1:8, adding 10.0L of ammonium fluosilicate solution with a 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 modified small-grain Y-type molecular sieve provided by the invention, which is denoted as SZ2. The physical and chemical properties are shown in Table 1, SZ2 is aged in the naked state by 100% steam at 800℃for 17 hours, and then The XRD method analyzed the crystallinity of the zeolite before and after SZ2 aging and calculated the relative crystalline retention after aging, and the results are shown in table 2.
Example 3
2000 g NaY3 molecular sieve (dry basis) was added to 22L of decationized aqueous solution and stirred to mix well, and 50ml RECl was added 3 Solution (in RE) 2 O 3 The concentration of the calculated rare earth solution is 319 g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, filtering and washing, drying the filter cake at 120deg.C to obtain a unit cell constant of 2.471nm, sodium oxide content of 11.4wt%, RE 2 O 3 Y-type molecular sieve with rare earth content of 0.7wt% is baked at 600 ℃ for 5 hours to make the water content of the Y-type molecular sieve lower than 1 wt%, and SiCl is used as the raw material 4 : y zeolite = 0.4:1 weight ratio, siCl vaporized by heating is introduced 4 The gas was reacted at 540℃for 1 hour to give a Y-type molecular sieve having a unit cell constant of 2.458nm, which was then washed with 20 liters of decationized water, filtered, washed and dried. Exchanging the dried molecular sieve with an ammonium sulfate solution in a water bath at 80 ℃ to ensure that the sodium oxide content is less than 1.0wt%; obtaining a QZ-3 molecular sieve;
mixing QZ-3 molecular sieve and deionized water according to a weight ratio of 1:8, adding 10.0L of ammonium fluosilicate solution with a concentration of 0.2mol/L under a water bath condition at 85 ℃, stirring and heating for 0.5h, filtering, drying, washing, and roasting for 2h at 550 ℃ to obtain the modified small-grain Y-type molecular sieve provided by the invention, which is denoted as SZ3. The physical and chemical properties are shown in Table 1, and after SZ3 was aged in a bare state with 100% steam at 800℃for 17 hours, the crystallinity of the zeolite before and after SZ3 aging was analyzed by XRD and the relative crystallinity retention after aging was calculated, and the results are shown in Table 2.
Comparative example 1
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationizing aqueous solution and stirred to be evenly mixed, 1000 g (NH) is added 4 ) 2 SO 4 Stirring, heating to 90-95deg.C for 1 hr, filtering, washing, drying the filter cake at 120deg.C, performing hydrothermal modification (baking at 650deg.C under 100% water vapor for 5 hr), and dryingThen, the mixture was stirred in 20 liters of a decationized aqueous solution, and 1000 g (NH) 4 ) 2 SO 4 Stirring, heating to 90-95 ℃ for 1 hour, filtering, washing, drying the filter cake at 120 ℃ and then carrying out a second hydrothermal modification treatment, wherein the hydrothermal treatment condition is 650 ℃ and roasting is carried out for 5 hours under 100% water vapor, and the hydrothermal ultrastable Y-type molecular sieve which is twice ion exchange and is not rare earth-containing and is twice ion exchange is obtained and is marked as DZ1. The physical and chemical properties are shown in Table 1, and after DZ1 was subjected to 100% steam aging at 800℃for 17 hours in the bare state, the crystallinity of the zeolite before and after DZ1 aging was analyzed by XRD and the relative crystal retention after aging was calculated, and the results are shown in Table 2.
Comparative example 2
2000 g of NaY1 molecular sieve (dry basis) is added into 20L of decationizing aqueous solution and stirred to be evenly mixed, 1000 g (NH) is added 4 ) 2 SO 4 Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying filter cake at 120 deg.C, hydrothermal modifying, calcining at 650 deg.C and 100% water vapor for 5 hr, adding into 20L of decationizing water solution, stirring, mixing, adding 68ml RE (NO) 3 ) 3 Solution (in RE) 2 O 3 The concentration of the rare earth solution is as follows: 319 g/L) and 900 g (NH) 4 ) 2 SO 4 Stirring, heating to 90-95 ℃ for 1 hour, filtering, washing, drying the filter cake at 120 ℃ and then carrying out a second hydrothermal modification treatment (roasting for 5 hours at the temperature of 650 ℃ and 100% water vapor) to obtain the twice ion-exchange twice hydrothermal ultrastable rare earth-containing hydrothermal ultrastable Y-type molecular sieve, which is marked as DZ2. The physical and chemical properties are shown in Table 1, and after DZ2 was subjected to 100% steam aging at 800℃for 17 hours in the bare state, the crystallinity of the zeolite before and after DZ2 aging was analyzed by XRD and the relative crystal retention after aging was calculated, and the results are shown in Table 2.
Comparative example 3
2000 g of NaY1 molecular sieve (dry basis) was added to 20L of decationized aqueous solution and stirred to mix well, 820ml of RE (NO) was added 3 ) 3 The solution (319 g/L) is stirred, heated to 90-95 ℃ and kept for 1 hour, then filtered and washed, and then is dried by molecular sieve for 4 hours at 110 ℃ to make the water content lower than 1 weight percent, and then is subjected to gas phase ultrastable modification treatment and then is subjected to SiCl treatment 4 : y zeolite = 0.4:1 weight ratio, siCl vaporized by heating is introduced 4 The gas was reacted at 580℃for 1.5 hours, then washed with 20 liters of decationized water, and then filtered to give a gas phase high silicon ultrastable Y-type molecular sieve, designated DZ3. The physical and chemical properties are shown in Table 1, and after DZ3 was subjected to 100% steam aging at 800℃for 17 hours in the bare state, the crystallinity of the zeolite before and after DZ3 aging was analyzed by XRD and the relative crystal retention after aging was calculated, and the results are shown in Table 2.
Comparative example 4
2000 g of NaY4 molecular sieve (dry basis) was added to 20L of decationized aqueous solution and stirred to mix well, 68ml of RE (NO) was added 3 ) 3 Solution (rare earth solution concentration with RE) 2 O 3 319 g/L), stirring, heating to 90-95deg.C, maintaining for 1 hr, filtering, washing, and drying the filter cake at 120deg.C to obtain powder with unit cell constant of 2.471nm, sodium oxide content of 9.3 wt%, and RE 2 O 3 Y-type molecular sieve having rare earth content of 1.0 wt%, and then calcined in an air atmosphere at 450 ℃ for 6 hours to have water content of less than 1 wt%, and then according to SiCl 4 : y-type molecular sieve (dry basis) =0.5: 1 weight ratio, siCl vaporized by heating is introduced 4 The gas was reacted at a temperature of 350℃for 2 hours to give a Y-type molecular sieve having a unit cell constant of 2.455nm, which was then washed with 20 liters of decationized water, filtered, washed and dried. Exchanging the dried molecular sieve with ammonium sulfate solution at 70 ℃ for 1h, filtering, washing and drying, and repeating the steps of exchanging, filtering, washing and drying for 1 time to ensure that the sodium oxide content of the molecular sieve is less than 1.0 weight percent, thus obtaining DQZ-4; DQZ-4 molecular sieve and deionized water are mixed according to the weight ratio of 1:8, 10.0L of ammonium fluosilicate solution with the concentration of 0.1mol/L is added under the water bath condition of 90 ℃, after stirring and heating for 1h, the mixture is filtered, dried and washed, and baked for 2h at 550 ℃ to obtain the modified productThe Y-type molecular sieve is denoted as DZ4. The physical and chemical properties are shown in Table 1, and after DZ4 was aged in the bare state for 17 hours at 800℃under 1atm with 100% steam, the relative crystallinity of the molecular sieve before and after DZ4 aging was analyzed by XRD and the relative crystallinity retention after aging was calculated, and the results are shown in Table 2.
TABLE 1
Figure BDA0002754399910000201
As can be seen from Table 1, the high stability Y-type molecular sieve provided by the invention has the following advantages: the sodium oxide content is low, the non-framework aluminum content of the molecular sieve 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 amount to the L acid amount) is high, the crystallinity value measured when the unit cell constant of the molecular sieve is low and the rare earth content is low is high, the thermal stability is high, and the external surface acid amount is high.
TABLE 2
Figure BDA0002754399910000211
As shown in Table 2, the Y-type molecular sieve provided by the invention has higher relative crystallization retention degree compared with the existing conventional grain Y-type molecular sieve after being aged under severe conditions of 800 ℃ and 100 volume percent of steam for 17 hours in a naked state, which indicates that the Y-type molecular sieve provided by the invention has 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 respectively prepared into catalysts, and the serial numbers of the catalysts are as follows: a1, A2, 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, product of Beijing chemical plant) with the concentration of 36% under stirring, wherein the acid-aluminum ratio (the molar ratio of HCl to pseudo-boehmite calculated by alumina) is 0.19 mol ratio, heating the obtained mixture to 50 ℃, and aging for 1.5 hours to obtain the aged pseudo-boehmite. The alumina content of the bauxite slurry was 12%.
(2) And uniformly mixing a quantitative modified Y-type molecular sieve SZ1, SZ3 and QZ-1, a quantitative alumina sol or silica sol, a quantitative mesoporous molecular sieve, an IM-5 molecular sieve loaded with ferric oxide, a quantitative kaolin and the aged pseudo-boehmite with deionized water to prepare slurry with the solid content of 32 weight percent, and spray drying.
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 measured by adopting an X-ray fluorescence spectrometry.
In the examples, the kaolin is an industrial product of China Kaolin company, and the solid content of the kaolin is 75%; the pseudo-boehmite used is produced by Shandong aluminum factory, and the alumina content of the pseudo-boehmite is 65 weight percent; the alumina sol is obtained from catalyst plant in Shandong country, and has an alumina content of 21 wt%, and IM-5 molecular sieve (SiO 2 With Al 2 O 3 30 in molar ratio, hydrogen form) supplied by the medium petrochemical catalyst company, kaolin, beta zeolite SiO 2 With Al 2 O 3 25 in molar ratio, hydrogen form) is a commercial product of ziluta corporation, a medium petrochemical catalyst company. The silica sol is produced by Beijing chemical plant, and the silicon oxide content is 25%.
The IM-5 molecular sieve is loaded with 3.1 percent of ferric oxide, and comprises the following steps: 16.2g of Fe (NO) 3 ) 3 9H 2 O is dissolved in 100g of water, 100g of IM-5 molecular sieve is added for impregnation, then the mixture is dried at 110 ℃, and the obtained sample is roasted at 550 ℃ for 2 hours.
Table 3 shows the types and amounts of the Y-type zeolite, the alumina sol, the silica sol and the kaolin used in the step (2). The compositions of catalysts A1 to A3 (wherein the content of each component is based on the total weight of the catalyst) are given in Table 4.
After aging the A1, A2 and A3 catalysts with 100% steam at 800℃for 10 hours, the catalytic cracking reaction performance was evaluated on a small fixed fluidized bed reactor (ACE), and the cracked gas and product were collected separately and analyzed by gas chromatography. The properties of the raw oil in 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 was mixed with pseudo-boehmite, kaolin, mesoporous molecular sieve, iron-modified IM-5 molecular sieve (Fe/IM-5), water and alumina sol according to the catalyst preparation method of example 4, and spray-dried to prepare a microsphere catalyst. Catalyst number DB5. Table 3 shows the types and amounts of Y zeolite, alumina sol and kaolin used in the comparative example catalyst (1 kg catalyst was prepared). The composition of catalyst DB5 (wherein the amounts of the components are based on the total weight of the catalyst) is given in Table 4. The ACE evaluation method of the comparative example was the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 6
A microspheroidal catalyst was prepared according to the catalyst preparation procedure of example 4, except that no iron modified IM-5 molecular sieve (Fe/IM-5) was added. Catalyst number DB6. Table 3 shows the types and amounts of Y zeolite, alumina sol and kaolin used in the comparative example catalyst (1 kg catalyst was prepared). The composition of catalyst DB6 (wherein the amounts of the components are based on the total weight of the catalyst) is given in Table 4. The ACE evaluation method of the comparative example was the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 7
A microspheroidal catalyst was prepared according to the catalyst preparation procedure of example 4, except that the IM-5 molecular sieve was not modified. Catalyst number DB7. Table 3 shows the types and amounts of Y-type zeolite, IM-5 molecular sieve, alumina sol and kaolin used in the comparative example catalyst (1 kg catalyst was prepared). The composition of catalyst DB7 (wherein the amounts of the components are based on the total weight of the catalyst) is given in Table 4. The ACE evaluation method of the comparative example was the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 8
A microsphere catalyst was prepared according to the catalyst preparation method of example 4, except that the Y and iron modified IM-5 molecular sieves were not included. Catalyst number DB8. Table 3 shows the types and amounts of Y-type zeolite, iron-modified IM-5 molecular sieve (Fe/IM-5), alumina sol and kaolin used in the comparative example catalyst (1 kg catalyst was prepared). The composition of catalyst DB8 (wherein the amounts of the components are based on the total weight of the catalyst) is given in Table 4. The ACE evaluation method of the comparative example was the same as that of the example, and the evaluation results are shown in Table 6.
Comparative example 9
Microsphere 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, and the catalyst number was DB9. Table 3 shows the types and amounts of Y-type zeolite, iron-modified IM-5 molecular sieve (Fe/IM-5), alumina sol and kaolin used in the comparative example catalyst (1 kg catalyst was prepared). The composition of catalyst DB9 (wherein the amounts of the components are based on the total weight of the catalyst) is shown in Table 4. The ACE evaluation method of the comparative example was the same as that of the example, and the evaluation results are shown in Table 6.
TABLE 3 Table 3
Figure BDA0002754399910000231
Figure BDA0002754399910000241
The above was used to prepare 1kg of catalyst formulation.
TABLE 4 catalyst composition
Figure BDA0002754399910000242
TABLE 5
Hydro-upgrading heavy oil properties
Density (20 ℃ C.)/(kg/m) 3 ) 890.0
Sulfur/(micrograms/gram) <200
Ni+V/(micrograms/gram) <1
Hydrogen content/% 12.90
Naphthene content/% 44.67％
End point of distillation 630℃
TABLE 6
Figure BDA0002754399910000243
Figure BDA0002754399910000251
As can be seen from the results shown in Table 6, the catalytic cracking catalyst prepared by using the molecular sieve formed by compounding the Y-type molecular sieve, the IMF structure molecular sieve containing metal oxide and the molecular sieve with the pore opening diameter of 0.65-0.7 nm as active components has lower coke yield and high ratio of low-carbon olefin to coke yield when the low-carbon olefin yield is improved.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.

Claims (20)

1. The catalytic cracking catalyst is characterized by comprising a matrix 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 pore opening diameter of 0.65-0.7 nm, and the molecular sieve comprises the following components in percentage by weight:
the Y-type molecular sieve contains rare earth oxide, and the rare earth content is RE based on the total weight of the Y-type molecular sieve 2 O 3 Not more than 5% by weight, and not more than 1% by weight of sodium oxide; the unit cell constant of the Y-type molecular sieve is 2.430 nm-2.450 nm, the proportion of non-framework aluminum content to total aluminum content is not higher than 20wt%, 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 outer surface acid amount measured by a 2,4, 6-trimethylpyridine macromolecular probe molecule is 220 mu mol/g-300 mu mol/g;
the Y-shaped molecular sieve is a small-grain Y-shaped molecular sieve, and the average grain size of the small-grain Y-shaped molecular sieve is 300 nm-900 nm;
the ratio of the amount of B acid to the amount of L acid of the Y-type molecular sieve is 3.0-4.5;
after 17 hours aging at 800 ℃, 1atm pressure and 100% steam atmosphere, the relative crystallization retention degree of the Y-type molecular sieve is 38% -45%;
the relative crystallinity of the Y-type molecular sieve is 50% -70%;
the preparation method of the Y-type molecular sieve comprises the following steps:
contacting small-grain NaY molecular sieve with rare earth salt and/or ammonium salt solution to perform ion exchange reaction to obtain molecular sieve with reduced sodium oxide content;
roasting the molecular sieve with the reduced sodium oxide content at 450-650 ℃ for 4.5-7 hours to obtain a roasted molecular sieve; and
Contacting the baked molecular sieve with silicon tetrachloride gas to perform gas-phase ultrastable reaction to obtain the Y-type molecular sieve;
further comprises:
carrying out ammonium exchange treatment on the product obtained after the gas-phase superstable reaction so as to ensure that the sodium oxide content in the product is less than 1wt%;
mixing the product with the sodium oxide content of less than 1wt% with water, adding ammonium fluosilicate solution with the concentration of 0.05mol/L-0.4mol/L at 70-90 ℃ and stirring for 0.5-2 h, and roasting the obtained product at 400-600 ℃ for 1-5 h to obtain the Y-type molecular sieve;
the matrix is one or more of natural clay, aluminum oxide matrix and silicon oxide matrix.
2. The catalytic cracking catalyst of claim 1, wherein the ratio of the amount of B acid to the amount of L acid of the Y-type molecular sieve is 3.1 to 4.
3. The catalytic cracking catalyst of claim 1, wherein the sodium oxide content is 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 lattice collapse temperature of 1055 ℃ to 1085 ℃.
5. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve has a unit cell constant of 2.435nm to 2.445nm and a framework silica to alumina ratio of SiO 2 /Al 2 O 3 The molar ratio is 8.7-20.
6. 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 silicon to aluminum ratio of SiO 2 /Al 2 O 3 The molar ratio is 20-170.
7. The catalytic cracking catalyst of claim 1, wherein the IMF structure molecular sieve containing metal oxide has a content of metal oxide of 0.5wt% to 12wt%, and the metal oxide is one or more selected from the group consisting of zirconia, 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.
8. The catalytic cracking catalyst of claim 1, wherein the matrix content is 45% -75%, the Y-type molecular sieve content is 3% -13%, the IMF structure molecular sieve content containing metal oxide is 15% -30%, and the molecular sieve content with pore opening diameters of 0.65 nm-0.7 nm is 1% -10% based on the total dry weight of the catalytic cracking catalyst.
9. The catalytic cracking catalyst of claim 1, wherein the molecular sieves with pore opening diameters of 0.65nm to 0.7nm are selected from one or more of molecular sieves with AET, AFR, AFS, AFI, BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF and SAO structures.
10. The catalytic cracking catalyst of claim 1, wherein the small-crystallite NaY molecular sieve has a crystallite size of no more than 1 μm.
11. The catalytic cracking catalyst of claim 1, wherein 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 12wt%.
12. The catalytic cracking catalyst of claim 1, wherein the reduced sodium oxide molecular sieve has a rare earth content of RE 2 O 3 The content of sodium oxide is not more than 5wt%, the content of sodium oxide is 4wt% -11.5 wt%, and the unit cell constant is 2.465-2.472 nm.
13. The catalytic cracking catalyst of claim 1, further comprising drying the calcined molecular sieve to a moisture content of no more than 1wt%.
14. The catalytic cracking catalyst of claim 1, wherein the ion exchange reaction comprises: according to small-grain NaY molecular sieve: rare earth salts and/or ammonium salts: h 2 O=1: (0.001-0.1): (5-15) forming a mixture by using small-grain NaY molecular sieve, rare earth salt and/or ammonium salt and water according to the weight ratio, and stirring; wherein the weight ratio of the total content of the rare earth salt and/or ammonium salt to the small-grain NaY molecular sieve is not less than 0.001:1.
15. The catalytic cracking catalyst of claim 1, wherein the temperature of the ion exchange reaction is 15-95 ℃ and the exchange time is 30-120 min.
16. The catalytic cracking catalyst of claim 1, wherein the rare earth salt is selected from one or more of rare earth chloride, rare earth nitrate, and the ammonium salt is selected from one or more of ammonium sulfate, ammonium chloride, and ammonium nitrate.
17. The catalytic cracking catalyst according to claim 1, wherein the weight ratio of the calcined molecular sieve to the silicon tetrachloride gas is 1 (0.1-0.7), the gas phase ultrastable reaction temperature is 300-550 ℃, and the reaction time is 10-300 min.
18. The catalytic cracking catalyst of claim 1, further comprising washing and filtering the product after the gas phase ultrastable reaction, comprising: mixing the product after the gas phase superstable reaction with water according to the weight ratio of 1:6-15, washing at 30-60 ℃, and controlling the pH value to be 2.5-5.
19. According to the weightsThe catalytic cracking catalyst of claim 1, wherein the silica matrix is one or more of a neutral, acidic or basic silica sol, the silica sol being formed as SiO 2 The content is 1-15 wt%.
20. Use of the catalytic cracking catalyst according to any one of claims 1 to 19 in a hydrocarbon oil catalytic cracking reaction.
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