CN107971013B - Catalytic cracking catalyst and preparation method thereof - Google Patents

Catalytic cracking catalyst and preparation method thereof Download PDF

Info

Publication number
CN107971013B
CN107971013B CN201610919769.2A CN201610919769A CN107971013B CN 107971013 B CN107971013 B CN 107971013B CN 201610919769 A CN201610919769 A CN 201610919769A CN 107971013 B CN107971013 B CN 107971013B
Authority
CN
China
Prior art keywords
molecular sieve
catalytic cracking
cracking catalyst
acid
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610919769.2A
Other languages
Chinese (zh)
Other versions
CN107971013A (en
Inventor
王丽霞
周翔
田辉平
袁帅
刘宇键
刘俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petrochemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610919769.2A priority Critical patent/CN107971013B/en
Publication of CN107971013A publication Critical patent/CN107971013A/en
Application granted granted Critical
Publication of CN107971013B publication Critical patent/CN107971013B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/084—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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/7007—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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

Abstract

The catalytic cracking catalyst comprises 5-65% of natural mineral substances, 10-60% of oxide binder, 24-75% of first molecular sieve and 0.1-15% of phosphorus additive, wherein the first molecular sieve is a material with the pore diameter smaller than that of the first molecular sieveThe molecular sieve and the Y-type molecular sieve have a pore diameter smaller than

Description

Catalytic cracking catalyst and preparation method thereof
Technical Field
The invention relates to a catalytic cracking catalyst, a preparation method and application thereof.
Background
The low-carbon olefin such as ethylene, propylene, butylene and the like is an essential chemical raw material and can be used for synthesizing resin, fiber, rubber and the like. Propylene is an important raw material for manufacturing petrochemical products, which is second only to ethylene, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide and the like. At present, propylene is mainly derived from the by-product of ethylene production by thermal cracking at home and abroad, and the second largest source of propylene is the FCC unit, which provides about 30% of the demand, and in the united states, the FCC unit provides half of the demand of propylene for petrochemical products.
In recent years, the demand for propylene has increased rapidly, and by the prediction of HIS, the global propylene consumption has increased by 2016 at an average rate of about 5% which is greater than the rate of ethylene increase by 3.4%. However, the steam cracking propylene/ethylene ratio cannot be flexibly adjusted. And the reaction temperature is up to 840-860 ℃, and the energy consumption accounts for about 40% of the energy consumption of the petrochemical industry. Thus, the large production of propylene by FCC is an effective and efficient way to meet the growing demand.
Beta molecular sieve is a high-silicon large-pore molecular sieve which was first synthesized by Mobil corporation in 1967. In 1988, Newsman and Kiggins determined the crystal structure of beta molecular sieves by electron diffraction, high resolution electron microscopy, and computer-generated technologies. The Beta molecular sieve has three 12-membered ring channels which are mutually crossed, the twelve-membered ring pore diameter of one-dimensional channel which is parallel to the (001) crystal plane is 0.57-0.75 nm, and the twelve-membered ring pore diameter of the other two-dimensional channel which is parallel to the (100) crystal plane is 0.56-0.65 nm. Due to the unique pore structure, high acidity and good hydrothermal stability of the Beta molecular sieve, the Beta molecular sieve has wide industrial application prospect and is successfully applied to the petrochemical fields of isomerization, catalytic cracking, alkylation of aromatic hydrocarbon and the like.
The Y molecular sieve is successfully synthesized in 1964, and shows good catalytic effect in alkane catalytic conversion reaction. The Y molecular sieve has a three-dimensional twelve-membered ring channel structure, the aperture is 0.74nm, and a super cage with the diameter of 1.3nm exists in the molecular sieve. Because of the structural characteristics, the Y molecular sieve is widely applied to catalytic cracking reaction and has excellent performance. Along with the demand of products such as low-carbon olefin and the like, the Y molecular sieve is compounded with other molecular sieves, such as ZSM-5 and the like, so that the distribution of the products can be adjusted more flexibly.
CN103785460A provides a catalyst for producing low-carbon olefins and a preparation method thereof, and a catalyst system compounded by an MFI structure molecular sieve and a phosphorus-modified beta molecular sieve is used for preparing propylene by catalytic cracking of naphtha, so that the yield of the low-carbon olefins is higher.
CN101837301A proposes a catalytic cracking catalyst for increasing propylene yield and a preparation method thereof, which mixes and homogenizes a shape selective molecular sieve (ZSM-5 or beta molecular sieve) and a Y-type molecular sieve with a substrate to form slurry, sprays and dries the slurry, and then obtains the catalytic cracking catalyst by acid solution treatment.
However, the existing cracking catalyst is not high in propylene yield and BTX yield in heavy oil conversion.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a fluidized bed catalytic cracking catalyst, which has excellent hydrothermal stability and higher propylene yield. The second purpose of the invention is to provide a preparation method and an application method of the catalyst.
The invention provides a catalytic cracking catalyst, which comprises (a) 5-64% of natural mineral substances in dry basis by taking the weight of the catalyst as a reference; (b) 10% -60% of oxide; and (c) 24-75% of a first molecular sieve based on a dry basis, wherein the first molecular sieve is a Y-type molecular sieve and has a pore diameter smaller than that of the first molecular sieveThe molecular sieve of (2), or the first molecular sieve is a molecular sieve with a pore diameter smaller than that ofTwo or more of the molecular sieves of (a); and D) with P2O50.1 to 15 percent of phosphorus additive; the proportion of the mesoporous protonic acid in the catalytic cracking catalyst in the total acid amount is 20-70%, for example 25-65%. The total specific surface area of the catalyst is preferably greater than 240m2/g。
Preferably, the proportion of the mesopore volume of the catalytic cracking catalyst in the total pore volume is 35-60%, for example 40-60%, or 45-58%, or 35-45%. The mesoporous volume of the catalyst is 0.25-0.4 ml/g, or 0.25-0.45 ml/g, or 0.35-0.42 ml/g. The mesoporous is a pore with the pore diameter of 2-100 nm.
Preferably, the proportion of the mesoporous volume of the catalytic cracking catalyst in the total pore volume is 35-60%. The mesoporous volume of the catalyst is 0.14-0.35 ml/g, such as 0.14-0.30 ml/g, or 0.25-0.35 ml/g, such as 0.15-0.32 ml/g. The mesoporous is a pore with the pore diameter of 2-100 nm.
Preferably, the total specific surface area (also called specific surface area) of the catalytic cracking catalyst is 240-350 m2A/g, for example, of 250 to 320m2/g。
The catalytic cracking catalyst provided by the invention has more mesoporous protonic acid, preferably, the proportion of the mesoporous protonic acid in the total acid is 20-70%, such as 25-65%, preferably, such as 25-50% or 30-55%.
The mesoporous pore volume and the total pore volume of the catalytic cracking catalyst are measured by adopting a nitrogen adsorption BET specific surface area method; the total specific surface area of the catalyst is measured by adopting a nitrogen adsorption BET specific surface area method; the mesoporous protonic acid of the catalyst has a kinetic diameter ofThe 2, 6-di-tert-butylpyridine molecule can contact with protonic acid. Measuring the amount of mesoporous protonic acid by adopting a 2, 6-di-tert-butylpyridine adsorption infrared acidity method; total acid content adopts NH3The TPD method is used for the measurement.
Preferably, the phosphorus additive content in the catalytic cracking catalyst is P2O5From 0.1 to 15% by weight, for example from 1 to 13% by weight or from 1.5 to 8% by weight or from 0.5 to 6.5% by weight or from 2 to 5% by weight.
The catalytic cracking catalyst provided by the invention contains natural minerals, wherein the natural minerals are one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; the oxide binder is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silica-alumina binder; the Y-type molecular sieve is DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, HY molecular sieveOne or more of molecular sieves having a pore size of less thanThe molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The aperture is smaller thanThe two or more molecular sieves are two or more of MFI structure molecular sieves, IMF structure molecular sieves, BEA structure molecular sieves and ferrierite. The MFI structure molecular sieve may be a sodium MFI structure molecular sieve, or may be a modified MFI structure molecular sieve obtained by modifying a sodium MFI structure molecular sieve, such as a hydrogen MFI structure molecular sieve, an ammonium MFI structure molecular sieve, and an MFI structure molecular sieve containing phosphorus and/or transition metals, wherein the transition metals are, for example, one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi, and Ga. The MFI structure molecular sieve, such as ZSM-5, may be NaZSM-5, or a molecular sieve modified from NaZSM-5 molecular sieve, such as HZSM-5, ammonium ZSM-5, ZSM-5 containing phosphorus and/or transition metals, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the IMF structure can be a sodium-type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve by various modification methods, such as an ammonium-type IMF structure molecular sieve, a hydrogen-type IMF structure molecular sieve, and one or more IMF structure molecular sieves containing phosphorus and/or transition metals, wherein the transition metals are one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The IMF structure molecular sieve such as IM-5 can be Na type IM-5, and can also be modified IM-5 molecular sieve obtained by modifying NaIM-5, such as IM-5 molecular sieve modified by one or more of hydrogen type IM-5, ammonium type IM-5 and phosphorus and/or transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the BEA structure can be a sodium type molecular sieve with the BEA structure, and can also be a sodium type molecular sieve with the BEA structureModified BEA structure molecular sieves obtained by modifying BEA structure molecular sieves, such as hydrogen BEA structure molecular sieves, ammonium BEA structure molecular sieves, and BEA structure molecular sieves containing phosphorus and/or transition metals, wherein the transition metals such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga, and the BEA structure molecular sieves are beta molecular sieves, can be sodium beta molecular sieves, and can be modified beta molecular sieves obtained by modifying sodium beta molecular sieves, such as H beta, NH beta, and the like4Beta molecular sieve, phosphorus, and/or one or more transition metals such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi, and Ga. The ferrierite such as Fer molecular sieve can be sodium type Fer molecular sieve, also can be modified Fer molecular sieve obtained by modifying sodium type Fer molecular sieve, such as HFer, NH4A Fer molecular sieve modified with one or more of a Fer molecular sieve, phosphorus and/or a transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.
Preferably, in the catalytic cracking catalyst, the Y-type molecular sieve and the pore diameter are smaller thanThe weight ratio of the molecular sieve (b) is 1: 8-4: 0.1 or 0.3: 1-20: 1 or 0.15: 1-1: 1 or 1: 4-4: 0.1 or 0.3: 1-20: 1 or 1: 6.5-1: 2.
the invention also provides a preparation method of the catalytic cracking catalyst, which comprises the steps of preparing the catalyst which comprises the Y-type molecular sieve and has the aperture smaller than that of the catalystThe microsphere composition of the molecular sieve, the natural mineral and the oxide binder, which is referred to as the microsphere of the first composition, is subjected to modification treatment; the microsphere modification treatment of the first composition comprises the following steps:
a. putting the first composition microspheres into an alkaline solution for treatment, filtering and washing to obtain alkali-treated first composition microspheres;
b. and c, treating the alkali-treated first composition microspheres obtained in the step a in a composite acid solution consisting of fluosilicic acid, organic acid and inorganic acid, filtering and washing, optionally carrying out ammonium exchange sodium washing treatment, optionally filtering and optionally washing, and optionally drying to obtain the composition microspheres rich in mesopores.
c. Introducing a phosphorus additive into the composition microspheres rich in mesopores;
d. roasting at 400-800 deg.c for at least 0.5 hr.
In the preparation method of the catalytic cracking catalyst provided by the invention, the alkaline solution comprises an alkaline compound, preferably, the alkaline compound is a strongly alkaline inorganic compound, for example, the alkaline compound is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide and high-alkali sodium metaaluminate. The alkaline solution used in step a is at least one selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonium hydroxide solution and high-alkali sodium metaaluminate solution. The alkaline solution is preferably an aqueous solution of an alkaline compound.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the alkaline solution used in the step a preferably comprises high-alkali sodium metaaluminate, preferably high-alkali sodium metaaluminate solution. Preferably, in the high-alkali sodium metaaluminate solution, Na2O content of 270-310 g/L, Al2O3The content is 30-50 g/L, and the solution density is 1.25-1.45 g/mL.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the treatment in the step a comprises the following steps: comprises contacting the microspheres of the first composition with an alkaline solution, wherein the alkaline solution comprises an alkaline compound, and the microspheres of the first composition are mixed with an alkali metal oxide (ammonium hydroxide as NH) based on the weight of the alkali metal oxide3The weight ratio of the basic compound is 1 (0.01-0.35). Preferably, the microspheres of the first composition are mixed with the alkali metal oxide (ammonium hydroxide as NH) on a dry weight basis3In terms of the weight ratio of the basic compounds) is 1: (0.05-0.25) or 1: (0.01-0.15).
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: the weight ratio of the first composition microspheres to water on a dry basis is 1: (5-20).
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: the temperature of the treatment is 25 to 100 ℃, preferably 30 to 80 ℃ or 45 to 65 ℃, and the treatment time is 10 minutes or more, for example, 0.2 to 6 hours or 0.2 to 4 hours or 0.3 to 3 hours.
In the preparation method of the catalytic cracking catalyst, in the step b, the alkali-treated first composition microspheres obtained in the step a are treated in a solution of a composite acid consisting of fluosilicic acid, organic acid and inorganic acid, wherein the treatment is to contact the alkali-treated first composition microspheres with a composite acid aqueous solution consisting of fluosilicic acid, organic acid and inorganic acid for 10 minutes or more, such as 0.2-10 hours or 0.5-6 hours, filter and optionally wash. The filter cake obtained by filtration or the filter cake after washing can also be contacted with an ammonium salt solution to carry out an ammonium exchange sodium washing treatment so that the sodium oxide in the obtained catalyst is not more than 0.2 wt%, preferably not more than 0.15 wt%. The ammonium salt may be a commonly used ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate, and ammonium nitrate.
In the step b, the treatment temperature is 25-100 ℃, for example, 30-80 ℃ or 45-65 ℃.
According to the preparation method of the catalytic cracking catalyst, at least one of the organic acid selected from ethylenediamine tetraacetic acid, oxalic acid, acetic acid, citric acid and sulfosalicylic acid in the step b is preferably oxalic acid, and at least one of the inorganic acid selected from hydrochloric acid, sulfuric acid and nitric acid is preferably hydrochloric acid.
In the preparation method of the catalytic cracking catalyst provided by the invention, the treatment conditions in the step b are as follows: the weight ratio of the first composition microspheres, the fluosilicic acid, the inorganic acid and the organic acid is 1 (0.003-0.3) to 0.01-0.45 to 0.01-0.55 on a dry basis.
Preferably, in the preparation method of the catalytic cracking catalyst provided by the invention, the treatment conditions in the step b are as follows: the weight ratio of the first composition microspheres, the fluosilicic acid, the organic acid and the inorganic acid is 1 (0.005-0.3): (0.02-0.3): or 1 (0.005-0.17): 0.015-0.15): 0.02-0.15): or 1 (0.005-0.1): 0.02-0.2): 0.02-0.15. The weight ratio of the fluosilicic acid to the first composition microspheres is preferably (0.005-0.3): 1 or (0.005-02): 1 or (0.005-0.17): 1 or (0.005-0.1): 1; the weight ratio of the organic acid to the first composition microspheres is preferably (0.02-0.3): 1 or (0.015 to 0.15): 1 or (0.02-0.2): 1; the weight ratio of the inorganic acid to the first composition microspheres is preferably (0.01-0.2): 1 (or 0.02-0.3): 1 or (0.02-0.15): 1 or (0.02-0.15): 1.
in the preparation method of the catalytic cracking catalyst provided by the invention, in the step b, the weight ratio of water to the first composition microspheres calculated on a dry basis is 3-20: 1 is, for example, 4 to 15:1 or 5-10: 1.
the preparation method of the catalytic cracking catalyst according to the present invention, wherein the ammonium exchange sodium wash exchange process of step b contacts the composition obtained by the complex acid treatment with an ammonium salt solution, wherein the ammonium salt may be a commonly used ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, sodium acetate and ammonium nitrate. Ammonium salt exchange sodium wash treatment followed by filtration, optionally washing, to wash out exchanged sodium and non-exchanged ammonium salts in the catalyst. For example, in ammonium exchange sodium washing, the weight ratio of an ammonium salt solution to the composition obtained by the complex acid treatment is 5-20: 1, the concentration of the ammonium salt solution is 1-10 wt%, the contact temperature is 30-80 ℃, and the contact time is 0.5-2 hours.
In the preparation method of the catalytic cracking catalyst provided by the invention, the washing in the step b is a conventional method, for example, according to a weight ratio of the first composition microspheres to water of 1: and leaching with water in a weight ratio of 5-10. In the washing, the washing liquid after washing is generally neutral, for example, the pH value is 6 to 8.
In the preparation method of the catalytic cracking catalyst provided by the invention, the step c of introducing the phosphorus additive comprises the step of contacting the composition microspheres rich in mesopores with a phosphorus-containing compound. The phosphorus additive is introduced into the catalyst by performing said contacting to effect impregnation and/or ion exchange. The phosphorus additive may be introduced into the mesopore-rich composition microspheres by one or more contacts with the composition. The composition after the additive is introduced can be dried and/or roasted, and then is subjected to another contact process of introducing the additive, wherein the drying and roasting method is the conventional method, and for example, the composition can be roasted at 350-650 ℃ for 0.5-8 hours.
In the preparation method of the catalytic cracking catalyst provided by the invention, the method for introducing the phosphorus additive in the step c comprises the step of impregnating and/or ion exchanging the composition microspheres rich in mesopores by using a phosphorus-containing compound. The phosphorus-containing compound may be selected from one or more of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
According to the preparation method of the catalytic cracking catalyst, the roasting treatment conditions in the step d comprise the following steps: the atmosphere of the roasting treatment is air atmosphere, nitrogen atmosphere or water vapor atmosphere or the mixture atmosphere of the above atmospheres; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours. Preferably, the roasting treatment is carried out at 500-600 ℃ for 0.5-8 hours.
According to the method of the present invention, the baking process in step d may be wet baking, and the wet baking is performed in an atmosphere of 1 to 100 vol% of water vapor (i.e., the atmosphere contains 1 to 100 vol% of water vapor), more preferably 100 vol% of water vapor.
The catalytic cracking catalyst provided by the invention can be used for producing low-carbon olefin by catalytic cracking of hydrocarbon oil, and the method for producing low-carbon olefin by catalytic cracking of hydrocarbon oil comprises the step of contact reaction of hydrocarbon oil and the catalytic cracking catalyst provided by the invention. The reaction conditions can refer to the existing conditions for producing the low-carbon olefin by catalytic cracking. The hydrocarbon oil may be petroleum hydrocarbon, partial fraction petroleum hydrocarbon, or whole fraction petroleum hydrocarbon. Such as one or more of atmospheric residue, vacuum residue, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, solvent deasphalted oil, refined lubricating oil and hydrotreated oil obtained by hydrotreating the above hydrocarbon oil.
The catalytic cracking catalyst provided by the invention has rich mesoporous structure and higher stability; the catalyst is used for the catalytic cracking reaction of heavy petroleum hydrocarbon, and has the advantages of higher conversion rate, high propylene yield and high BTX yield. The catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking, has higher hydrocarbon oil cracking activity, higher propylene yield and BTX yield and higher propylene selectivity compared with the existing cracking catalyst. The preparation method of the catalytic cracking catalyst provided by the invention adopts a molecular sieve with the pore diameter of less than 6.9 angstroms, a Y-type molecular sieve or more than two molecular sieves with the pore diameter of less than 6.9 angstroms, an oxide binder and natural minerals to prepare a microsphere composition, and then the pore structure and the acidity of the catalyst are further modulated by an alkali and acid coupling treatment method, so that the catalyst has larger specific surface area and higher mesoporous volume and proper mesoporous acidity, and phosphorus modification is carried out after the catalyst composition is prepared, so that the performance of the whole catalyst can be improved, the stability of the catalyst and the selectivity of propylene and BTX are improved, and the efficiency of phosphorus modification on the catalyst can also be improved.
Detailed Description
The catalytic cracking catalyst provided by the invention contains natural minerals, wherein the natural minerals comprise one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, rectorite and the like. The content of the natural mineral in the catalyst provided by the invention is 5-65 wt%, preferably 8-60 wt%, for example 15-60 wt%, or 8-45 wt%, or 20-55 wt%, calculated by weight percentage based on the total amount of the catalyst, on a dry basis.
The catalytic cracking catalyst provided by the invention contains an oxide binder component, wherein the oxide is one or a mixture of more than two of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, amorphous silica-alumina and aluminum phosphate material, and the oxide binder is prepared from a corresponding oxide precursor thereof, such as a sol-state substance of the oxide, such as one or more of silica sol, alumina sol, pepto-pseudo-boehmite, silicon-alumina sol and phosphorus-containing alumina sol. The content of the oxide binder is 10 to 60 wt%, preferably 15 to 55 wt%, for example 10 to 30 wt%, or 20 to 50 wt%, or 25 to 50 wt%, or 12 to 28 wt%, in terms of the weight percentage of the oxide based on the total amount of the catalyst.
The catalytic cracking catalyst provided by the invention contains a first molecular sieve, wherein the first molecular sieve is a Y-type molecular sieve and has a pore diameter smaller than that of the first molecular sieveThe Y-type molecular sieve is a molecular sieve used for a catalytic cracking catalyst, and the Y-type molecular sieve is at least one of a DASY molecular sieve, a rare earth-containing DASY molecular sieve, a USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, a REHY molecular sieve, and an HY molecular sieve. Preferably, the Y-type molecular sieve has a pore size smaller than that of the zeoliteThe weight ratio of the molecular sieve (b) is 1: 8-4: 0.1 or 0.3: 1-20: 1 or 0.15: 1-1: 1 or 1: 4-4: 0.1 or 1: 3-15: 1. the content of the first molecular sieve is preferably 25 to 65 wt%, for example 30 to 55 wt%, or 30 to 65 wt%, or 30 to 55 wt%, or 35 to 50 wt%.
The aperture is smaller thanThe molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The MFI structure molecular sieve can be a sodium type MFI structure molecular sieve, and can also be an MFI structure molecular sieve obtained by subjecting a sodium type MFI structure molecular sieve to various modification methods, such as an ammonium type MFI structure molecular sieve obtained by ammonium exchange, a hydrogen type MFI structure molecular sieve, and a modified MFI structure molecular sieve containing one or more of phosphorus and/or transition metals; the MFI structure molecular sieve is, for example, ZSM-5, and may be NaZSM-5, or may be formed by passing NaZSM-5 molecular sieve throughModified molecular sieves, e.g. HZSM-5, NH4ZSM-5, ZSM-5 containing phosphorus and/or transition metals; wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the IMF structure can be a sodium-type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve by various modification methods, such as an ammonium-type IMF structure molecular sieve, a hydrogen-type IMF structure molecular sieve, and one or more IMF structure molecular sieves containing phosphorus and/or transition metals, wherein the transition metals are one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with IMF structure such as IM-5 can be Na-type IM-5, or modified IM-5 molecular sieve obtained by modifying NaIM-5, such as hydrogen-type IM-5, NH4IM-5, IM-5 containing phosphorus and/or transition metals such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the BEA structure is, for example, a beta molecular sieve, can be a sodium type beta molecular sieve, and can also be a modified beta molecular sieve obtained by modifying the sodium type beta molecular sieve, such as H beta. The ferrierite such as Fer molecular sieve can be sodium type Fer molecular sieve, also can be modified Fer molecular sieve obtained by modifying sodium type Fer molecular sieve, such as HFer, NH4A Fer molecular sieve modified with one or more of a Fer molecular sieve, phosphorus and/or a transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The aperture is smaller thanThe molecular sieve is preferably in a sodium form, a hydrogen form or an ammonium form, and the pore diameter is smaller thanThe molecular sieve of (1).
The sodium-type IMF structure molecular sieve is well known to those skilled in the art and can be prepared commercially or by itself, for example, by the steps comprising: filtering and washing the slurry of the IMF structure molecular sieve obtained by amine crystallization to obtain a washed molecular sieve; wherein the washed molecular sieve has a sodium content of less than 3.0 wt.% as sodium oxide based on the total dry basis weight of the washed molecular sieve; and drying and air roasting the washed molecular sieve to obtain the sodium type IMF structure molecular sieve. The molecular sieve with the IMF structure is preferably a molecular sieve obtained by amine crystallization, wherein the amine crystallization refers to the preparation of the molecular sieve by hydrothermal crystallization by adopting a template agent, and specific documents can refer to Chinese patents CN102452667A, CN103708491A, CN102452666A and CN103723740A by taking the preparation of the IMF molecular sieve as an example. The air roasting is used for removing the template agent in the washed molecular sieve, and the temperature of the air roasting can be 400-700 ℃, and the time can be 0.5-10 hours.
The cracking catalyst provided by the invention can also contain an auxiliary component. The content of the auxiliary component is not more than 30% by weight, for example 0 to 30% by weight or 0.5 to 25% by weight, based on the dry basis. The additive component is at least one of a desulfurization additive component, a denitration additive component and a combustion improver component.
The cracking catalyst provided by the invention also can contain a second molecular sieve, wherein the second molecular sieve is other molecular sieves except the first molecular sieve, and the molecular sieves are used as active components of catalytic cracking catalysts. The content of the second molecular sieve is 0-20 wt%. Such as SAPO molecular sieves, MCM molecular sieves.
In the preparation method of the catalytic cracking catalyst provided by the invention, the catalyst is prepared by a Y-type molecular sieve with the aperture smaller than that of the catalystThe molecular sieve (also called molecular sieve with pore diameter less than 0.69 nm), natural mineral and oxide binder, and then carrying out modification treatment. The preparation comprises Y-type molecular sieve with pore diameter smaller thanThe microspheroidal composition of molecular sieve, natural mineral, oxide binder of (a) may be prepared by: will be the first toA molecular sieve, e.g. Y-type, having a pore size of less thanThe molecular sieve, the natural mineral, the precursor of the oxide binder component and water are pulped, spray dried and optionally roasted to obtain the microspherical composition, which is called as the first composition microsphere in the invention. The spray drying and roasting are prior art, and the invention has no special requirements. For example, the temperature of the calcination may be 300 to 650 ℃ or 350 to 500 ℃, and the calcination time may be 0.5 to 10 hours. The firing may be carried out in an air atmosphere, a nitrogen atmosphere, or an atmosphere containing water vapor.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of mixing and pulping the natural minerals, the first molecular sieve, the oxide binder such as oxide sol and/or oxide gel and water. Based on the total weight of the catalytic cracking catalyst, the amount of each component is such that the finally obtained catalytic cracking catalyst contains 5-65 wt% of natural mineral, 10-60 wt% of oxide and 24-75 wt% of first molecular sieve. More preferably, the components are used in amounts such that the composition of the final catalyst comprises: the natural mineral content is 5 to 50 wt% on a dry basis, for example 8 to 45 wt%, the first molecular sieve content is 30 to 65 wt% on a dry basis, for example 30 to 55 wt%, and the oxide binder content is 15 to 55 wt% on an oxide basis, for example 20 to 50 wt% or 25 to 45 wt% or 20 to 35 wt% or 12 to 28 wt%.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the natural mineral substances comprise one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, rectorite and the like. The amount of the natural mineral is 5 wt% to 65 wt%, for example 20 wt% to 55 wt%, or 8 wt% to 45 wt%, or 8 wt% to 60 wt%, or 15 wt% to 60 wt%, based on the total amount of the catalyst.
The invention provides a preparation method of the catalytic cracking catalyst, wherein the oxide binder precursor is selected from one or more of silica, alumina, zirconia, titania, amorphous silica-alumina and aluminum phosphate material sol or gel, and the oxide binder precursor is selected from one or more of silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol and phosphorus-containing alumina sol. The amount of the oxide binder precursor is such that the oxide binder content in the resulting catalytic cracking catalyst is 10 to 60 wt.%, for example 15 to 55 wt.%, or 15 to 35 wt.%, or 20 to 50 wt.%, or 12 to 28 wt.%, in terms of oxide weight percentage based on the total amount of the catalyst.
The preparation method of the catalytic cracking catalyst provided by the invention has the advantages that the dosage of the first molecular sieve (Y-type molecular sieve and the pore diameter smaller thanThe dosage of the molecular sieve or more than two pore diameters are less thanThe amount of the molecular sieve) is such that the content of the first molecular sieve in the resulting catalytic cracking catalyst is 24 to 75 wt%, preferably 30 to 70 wt% or 25 to 65 wt%, for example 30 to 55 wt% or 30 to 55 wt%, on a dry basis. Wherein the aperture of the Y-shaped molecular sieve is less thanThe weight ratio of the molecular sieve (b) is 1: 8-4: 0.1 or 0.3: 1-20: 1 or 0.15: 1-1: 1 or 1: 4-4: 0.1 or 1: 3-15: 1. the Y-type molecular sieve is one or more of DASY molecular sieve, DASY molecular sieve containing rare earth, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve and HY molecular sieve.
The preparation method of the catalytic cracking catalyst provided by the invention has the pore diameter smaller thanThe molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The MFI structure molecular sieve can be a sodium type MFI structure molecular sieve, and can also be an MFI structure molecular sieve obtained by carrying out various modification methods on the sodium type MFI structure molecular sieve, such as an ammonium type MFI structure molecular sieve obtained by ammonium exchange, a hydrogen type MFI structure molecular sieve, and a modified MFI structure molecular sieve containing one or more of phosphorus and/or transition metals; the MFI structure molecular sieve is one or more of ZSM-5, ZSP and ZRP molecular sieves, the ZSM-5 molecular sieve can be NaZSM-5 or a molecular sieve obtained by modifying NaZSM-5 molecular sieve, such as HZSM-5 and NH4ZSM-5, ZSM-5 containing phosphorus and/or a transition metal; wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the IMF structure can be a sodium-type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve by various modification methods, such as an ammonium-type IMF structure molecular sieve, a hydrogen-type IMF structure molecular sieve, and one or more IMF structure molecular sieves containing phosphorus and/or transition metals, wherein the transition metals are one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. For example, IM-5 can be Na type IM-5, or can be modified IM-5 molecular sieve obtained by modifying NaIM-5, such as hydrogen type IM-5, NH4IM-5, IM-5 containing phosphorus and/or transition metals such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the BEA structure is, for example, a beta molecular sieve, a sodium type beta molecular sieve, or a modified beta molecular sieve obtained by modifying the sodium type beta molecular sieve, such as H beta and NH4Beta molecular sieve, phosphorus, and/or one or more transition metals such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi, and Ga. The ferrierite such as the Fer molecular sieve can be a sodium type Fer molecular sieve or a modified ferrierite of the sodium type Fer molecular sieveTo modified Fer molecular sieves such as HFer, NH4A Fer molecular sieve modified with one or more of a Fer molecular sieve, phosphorus and/or a transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The aperture is smaller thanThe molecular sieve is preferably in a sodium form, a hydrogen form or an ammonium form, and the pore diameter is smaller thanThe molecular sieve of (1).
According to the preparation method of the catalyst provided by the invention, preferably, the weight ratio of the natural mineral substance in terms of dry basis, the first molecular sieve in terms of dry basis and the oxide binder in terms of oxide in the first composition microspheres is 5-65: 24-75: 10-60, preferably 8-55: 30-65: 15-55, more preferably 8-45: 30-55: 20 to 50. Preferably, the first composition microspheres contain 5 to 65% of natural mineral substance on a dry basis, 10 to 60% of oxide binder on an oxide basis and 24 to 75% of first molecular sieve on a dry basis, and preferably, the first composition microspheres contain 8 to 55% of natural mineral substance on a dry basis, 15 to 55% of oxide binder on an oxide basis and 25 to 55% of first molecular sieve on a dry basis, based on the weight of the first composition microspheres. More preferably, the first composition microspheres contain 8 to 45 wt%, such as 20 to 45 wt%, on a dry basis, of the natural mineral, 20 to 50 wt%, such as 10 to 30 wt%, on an oxide basis, of the oxide binder, and 30 to 55 wt%, such as 35 to 50 wt%, on a dry basis, of the first molecular sieve.
In one embodiment, a precursor of an inorganic oxide binder, such as pseudo-boehmite, alumina sol, silica-alumina gel, or a mixture of two or more thereof, is mixed with a natural mineral, such as kaolin, and water (e.g., decationized and/or deionized water) to prepare a slurry having a solid content of 10 to 50 wt%Uniformly stirring, optionally adjusting the pH of the slurry to 1-4, e.g., 2-3, with an inorganic acid, e.g., hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, uniformly stirring, optionally standing at 20-80 ℃ for 0-2 hours, e.g., 0.3-2 hours, and then adding a first molecular sieve, wherein the first molecular sieve has a pore diameter smaller than that of the first molecular sieveThe molecular sieve and the Y-type molecular sieve have a pore diameter smaller thanThe slurry of the first composition, which has a solid content of, for example, 20 to 45% by weight, is spray-dried to prepare a microspherical composition. And then roasting the microspherical composition for 0.5 to 6 hours at 300 to 650, preferably 350 to 550 ℃, for example, to obtain the first composition microsphere. If the catalytic cracking catalyst includes a promoter component and/or a second molecular sieve, the first composition slurry also contains the promoter component and the second molecular sieve, and the promoter component and the second molecular sieve can be introduced into the slurry at any step prior to spray drying.
The washing according to the present invention is well known to those skilled in the art and, without particular reference thereto, generally refers to water washing, for example, the molecular sieve may be rinsed with 5 to 10 times the weight of the molecular sieve.
In the preparation method of the catalytic cracking catalyst provided by the invention, in the step c, a phosphorus additive is introduced into the mesoporous-rich composition microspheres obtained in the step b. Preferably, the introduction is such that the phosphorus additive content in the resulting catalytic cracking catalyst is as P2O5From 0.1 to 15% by weight, for example from 1 to 13% by weight or from 1.5 to 8% by weight or from 0.5 to 6.5% by weight or from 2 to 5% by weight.
The catalytic cracking catalyst prepared by the preparation method provided by the invention has more mesoporous protonic acid, and the proportion of the mesoporous protonic acid in the total acid amount is 20-70%, such as 25-65%, preferably, such as 25-50% or 30-55%.
The total specific surface area of the catalytic cracking catalyst prepared by the method is more than 240m2A total specific surface area (also referred to as specific surface area) of 240 to 350m2The/g is, for example, 250 to 320m2/g。
According to the preparation method of the catalytic cracking catalyst provided by the invention, the proportion of the mesoporous volume of the catalytic cracking catalyst in the total pore volume is 35-60%, such as 40-60%, 45-58% or 35-45%. The mesoporous volume of the catalyst is 0.14-0.35 ml/g, such as 0.15-0.30 ml/g, or 0.25-0.35 ml/g, or 0.15-0.32 ml/g.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The influence of the catalytic cracking catalyst on the propylene yield and the BTX yield in the catalytic cracking of petroleum hydrocarbon is evaluated by using raw oil ACE. The method comprises the following steps: the catalyst was aged at 800 ℃ under 100% water vapor for 15 hours and evaluated on stationary fluidized bed micro-reaction ACE under conditions of reaction temperature 530 ℃ and regeneration temperature 620 ℃ with the raw oil as hydrotreated oil (see Table 3 for composition and properties) and a catalyst-to-oil ratio of 5 (weight ratio).
The specific surface area of the present invention was measured by the standard method of GBT 5816-1995.
The pore volume of the present invention was determined using standard methods of GB/T5816-1995.
The total acid content of the invention adopts NH3TPD method see research methods for solid catalysts, petrochemical, 30(12), 2001: 952.
the mesoporous protonic acid is determined by adopting a 2, 6-di-tert-butylpyridine adsorption infrared acidity method. The specific method comprises the following steps: the catalyst was pressed to 10mg/cm2Into a band of CaF2In the infrared bath of the window. Vacuumizing at 400 deg.C, cooling to 150 deg.C, adsorbing 2, 6-di-tert-butylpyridine for 15 min, and dryingVacuum was applied for 1 hour. And cooling to room temperature to collect the spectrogram. And calculating the amount of protonic acid. See Applied Catalysis A, General, 294, 2005: 92.
na of the invention2O、P2O5The content is determined by a GB/T30905-2014 standard method.
The RIPP standard method can be found in petrochemical analysis, Yangcui and other editions, 1990 edition.
The following examples illustrate the catalysts and the process for their preparation according to the invention, in which the raw materials used have the following properties: kaolin (Kaolin, China Suzhou, with a solid content of 75 wt%), montmorillonite (Red Stone Bentonite, Kogyo, Liaoning, Inc., with a solid content of 75 wt%), alumina sol (Qilu division, China petrochemical catalyst, Inc., with an alumina content of 22.5 wt%), silica sol (Qingdao ocean chemical, Inc., with a silica content of 25.5 wt%, pH 3.0), IM-5 molecular sieve (produced by Chang Ling division, China petrochemical catalyst, Inc., with an amine synthesis), sodium type (with a sodium oxide content of 2.5 wt%, a silica to alumina ratio of 30), ZSM-5 molecular sieve (Qilu division, China petrochemical catalyst, Inc., NaZSM-5, with a silica to alumina ratio of 45), Beta molecular sieve (produced by catalyst Qilu division, H β, a silica to alumina ratio of 30), REY molecular sieve (produced by China petrochemical catalyst, Inc., rare earth content of 10 mass%, Si/Al ratio of 4.9), USY molecular sieve (Qilu division, China petrochemical catalyst, Ltd., rare earth content (in RE)2O3Calculated) is 1.5 weight percent, and the silicon-aluminum ratio is SiO2/Al2O3The molar ratio was 5.8). ZRP-1 molecular sieve, a product of Qilu division of China petrochemical catalyst corporation, Si/Al ratio (the invention refers to SiO)2/Al2O3Molar ratio) was 40.
The solid content is the weight ratio of the solid product obtained by roasting the material at 800 ℃ for 1 hour to the material.
Example 1
267g of alumina sol and 180g of kaolin are mixed, and are prepared into slurry with the solid content of 30 weight percent by using decationized water, 15g of USY, 45g of beta molecular sieve and 45g of ZRP-1 molecular sieve are added after stirring for 2 hours to form composition slurry (the solid content is 35 weight percent), the mixture is uniformly stirred and spray-dried to prepare composition microspheres, and then the composition microspheres are roasted for 2 hours at 500 ℃ to prepare first composition microspheres A1.
200g of the first composition microspheres A1 (dry basis weight, the same applies hereinafter) prepared above were taken, water was added and slurried to obtain a slurry having a solid content of 10% by weight, and 15.1g of a high-alkali sodium metaaluminate solution (Na) was added2O is 290g/L, Al2O340g/L, the solution density is 1.353g/mL), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering, and washing to neutrality (the washing to neutrality means that the washing liquid after washing is neutral, and the pH is 6-8); adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 6.2g of oxalic acid while stirring, then adding 54g of hydrochloric acid (HCl with the mass fraction of 10%) and 33.4g of fluorosilicic acid solution (with the concentration of 3 wt%), heating to 50 ℃, stirring for 1h at constant temperature, filtering, and washing to be neutral to obtain a filter cake; adding water into the filter cake and pulping to obtain composite microsphere slurry which is rich in mesopores and has the solid content of 40 weight percent, and adding 14.6gH3PO4Dissolving (with the concentration of 85 weight percent) in 60g of water, mixing and soaking with the composition microsphere slurry rich in mesopores, and drying; and roasting the obtained sample at 550 ℃ for 2 hours to obtain the catalytic cracking catalyst A provided by the invention. The physicochemical properties of catalyst sample A are shown in Table 1, and the results of ACE evaluation of the feedstock after 100% steam aging at 800 ℃ for 15 hours are shown in Table 2, and the properties of the feedstock for evaluation are shown in Table 3.
Example 2
333.3g of alumina sol and 100g of montmorillonite are mixed, and prepared into slurry with the solid content of 21.5 weight percent by using decationized water, 20g of EY-type molecular sieve and 130g of ZSM-5 molecular sieve are added after stirring for 0.5 hour, the mixture is uniformly stirred to form first composition slurry (the solid content is 35 weight percent), the first composition slurry is prepared into composition microspheres by spray drying, and then the composition microspheres are roasted for 2 hours at 350 ℃ to obtain first composition microspheres B1.
200g of the first composition microspheres B1 (dry basis weight) prepared above were taken, water was added to prepare a first composition microsphere slurry having a solid content of 10% by weight, 20.5g of NaOH (purity: 96%) was added, and the temperature was raisedStirring at 70 deg.C for 0.3h, filtering, and washing to neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 25.1g of oxalic acid while stirring, then adding 38g of hydrochloric acid (the mass fraction of HCl is 10%) and 55g of fluosilicic acid solution (the concentration of fluosilicic acid is 3 wt%), heating to 80 ℃, stirring at constant temperature for 0.8h, filtering, and washing to obtain a filter cake; adding water into the filter cake and pulping to obtain slurry JY2 with the solid content of 40 wt%; at 11.37gH3PO4Adding 90g of water (with the concentration of 85 weight percent), mixing with the slurry JY2, soaking, drying and roasting at 550 ℃ for 2 hours; namely the catalytic cracking catalyst B provided by the invention. The physicochemical properties of catalyst sample B are shown in Table 1, and after aging at 800 ℃ for 15 hours with 100% steam, the raw oil ACE evaluation was performed using the raw oil shown in Table 3, and the results are shown in Table 2.
Example 3
353g of silica sol and 80g of montmorillonite are mixed, and are prepared into slurry with the solid content of 30 weight percent by using decationized water, 30g of ZRP-1 type molecular sieve, 75gIM-5 molecular sieve and 45g of beta molecular sieve are added, the mixture is uniformly stirred to form first composition slurry (the solid content is 35 weight percent), and the first composition slurry is prepared into the microsphere composition by spray drying. The microsphere composition was then calcined at 350 ℃ for 1-2 hours to obtain first composition microspheres C1.
Taking 200g of the prepared first composition microspheres C1 (dry basis weight), adding water to prepare first composition microsphere slurry with the solid content of 10 weight percent, adding 33.1g of KOH (purity of 96 percent), heating to 60 ℃, stirring for 1 hour at constant temperature, filtering, and washing to be neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 20 wt%, adding 34.2g of oxalic acid while stirring, slowly dropwise adding 120g of hydrochloric acid (HCl mass fraction is 10%) and 667g of fluorosilicic acid solution (concentration is 3 wt%), heating to 70 ℃, stirring for 2h at constant temperature, filtering, washing, drying to obtain the JY3 slurry with the solid content of 40 wt%, adding water, and pulping; 4.65g (NH)4)2HPO4Dissolving in 180g of water, mixing and soaking with the slurry JY3, and drying; the obtained sample is roasted for 2 hours at 550 ℃, and the catalyst C provided by the invention is obtained. Physicochemical properties of catalyst sample C; after aging at 800 deg.C for 15h with 100% steam, stock oil ACE evaluation was performed with stock oils shown in Table 3, conversionThe evaluation results of the gas yield, the coke amount and the like are shown in Table 2.
Example 4
Taking 200g of the prepared catalyst B1 (dry basis weight), adding water to prepare slurry with the solid content of 10 weight percent, adding 21.2g of NaOH (with the purity of 96 percent), heating to 90 ℃, stirring for 2 hours at constant temperature, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 5.6g of citric acid while stirring, then adding 188g of hydrochloric acid (the HCl mass fraction is 10 wt%) and 90g of fluorosilicic acid solution (the concentration of fluosilicic acid is 3 wt%), stirring at the constant temperature of 30 ℃ for 5.5h, filtering, washing and drying to obtain a composition DJ4 rich in mesopores; 21.13gH3PO4(concentration 85%) is added into 160g of water, mixed and soaked with the composition DJ4 rich in mesopores, and dried; and roasting the obtained sample at 550 ℃ for 2 hours in an atmosphere of 100% water vapor to obtain the catalytic cracking catalyst D provided by the invention. Physicochemical properties of catalyst sample D; after aging at 800 ℃ for 15 hours with 100% steam, the raw oil was evaluated by ACE, and the results of evaluation of conversion, gas yield, coke amount, etc. are shown in Table 2.
Example 5
353g of silica sol and 80g of montmorillonite are mixed, and are prepared into slurry with the solid content of 10-50 wt% by using decationized water, 45g of USY type molecular sieve, 75g of ferrierite and 30g of ZSM-5 molecular sieve are added after stirring for 1 hour, the mixture is uniformly stirred to form composition slurry (the solid content is 35 wt%), the slurry is prepared into a microspherical composition by spray drying, and the microspherical composition is roasted for 2 hours at 350 ℃ to obtain a first composition microspherical D1.
Taking 200g of the prepared first composition microspheres D1 (dry basis weight), adding water to prepare first composition microsphere slurry with the solid content of 10 weight percent, adding 38.1g of NaOH (with the purity of 96 percent), stirring at constant temperature of 30 ℃ for 3h, filtering, and washing to be neutral; adding water into the filter cake, pulping to obtain alkali treatment composition slurry with the solid content of 20 wt%, adding 7.1g of citric acid while stirring, adding 70g of hydrochloric acid (HCl with the mass fraction of 10 wt%) and 35g of fluosilicic acid (the concentration is 3 wt%), heating to 50 ℃, stirring at constant temperature for 1h, filtering, washing, drying to obtain dried filter cake, adding water, pulping to obtain alkali treatment composition slurry with the solid content of 40 wt%Slurry JY 5; 1.49g (NH)4)2HPO4Dissolving in 90g of water, mixing and soaking with the slurry JY5, and drying; the obtained sample is roasted for 2 hours at 550 ℃ in the atmosphere of 100 volume percent of water vapor, and the catalytic cracking catalyst E provided by the invention is obtained. The physicochemical properties of catalyst sample E are shown in Table 1, and the results of the ACE evaluation of the base oil after 100% steam aging at 800 ℃ for 15 hours, such as conversion, gas yield, coke amount, etc., are shown in Table 2.
Comparative example 1
The basic procedure in this comparative example was as in example 1 except that the reaming (i.e., without alkali and acid treatment) and phosphorus modification were not performed, sodium was exchanged and washed with ammonium sulfate solution, and the resulting sample was comparative sample i. The physicochemical properties are shown in Table 1, the ACE evaluation results of the feedstock are shown in Table 2, and the evaluation conditions are the same as those in the examples (the evaluation conditions of the comparative examples are the same as those below).
Comparative example 2
A catalyst was prepared by following the procedure of example 1 except that, in the acid treatment, only an organic acid and an inorganic acid were used without conducting the alkali treatment, and the fluorosilicic acid was replaced with an equimolar amount of hydrochloric acid.
Comparative example 3
The basic procedure in this comparative example follows the procedure of example 1 except that the complex acid dealumination treatment was not performed prior to phosphorus modification and the sodium was washed with an ammonium nitrate solution exchange and the resulting sample was comparative sample III. The physicochemical properties, ACE evaluation conversion of the raw oil, gas yield and coke content are shown in Table 2.
Comparative example 4
The basic procedure in this comparative example was as in example 1 except that the dealumination treatment with a complex acid was not conducted before the phosphorus modification, and the dealumination treatment was conducted with a fluorosilicic acid in a molar amount equivalent to that of the complex acid described in example 1, and the sample thus obtained was comparative sample IV whose physicochemical properties and formulation were shown in Table 1 and whose ACE evaluation results of the feedstock oil were shown in Table 2.
Comparative example 5
A catalytic cracking catalyst was prepared by following the procedure of example 1 except that the treatment with the complex acid was not conducted and the treatment with hydrochloric acid was conducted. The molar amount of hydrochloric acid (HCl) was equal to the molar amount of the complex acid, and the resulting sample was comparative sample V. The physicochemical properties and the ACE evaluation results of the raw oil are shown in Table 2.
TABLE 1
VMesoporous structure/VGeneral holeIs the ratio of mesopore volume to total pore volume.
TABLE 2
TABLE 3
Item Raw oil
Density (20 ℃ C.), g/cm3 0.9334
Dioptric light (70 degree) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Glue 14.4
Asphaltenes <0.1
Freezing point, DEG C 34
Metal content, ppm
Ca 3.9
Fe 1.1
Mg <0.1
Na 0.9
Ni 3.1
Pb <0.1
V 0.5
C m％ 86.88
H m％ 11.94
S m％ 0.7
M% of carbon residue 1.77
As can be seen from Table 2, compared with the contrast agent, the catalyst provided by the invention has high hydrocarbon oil cracking conversion rate and higher propylene yield and BTX yield. Therefore, the catalytic cracking catalyst provided by the invention has higher conversion rate, higher propylene yield and BTX (benzene, toluene and xylene) yield.

Claims (36)

1. A catalytic cracking catalyst comprising the following components in weight percent:
A) 5% ~ 65% natural minerals on a dry basis;
B) 10% ~ 60% oxide binder calculated as oxide;
C) ~ 74% on a dry basis of a first molecular sieve being a Y-type molecular sieve and a molecular sieve having a pore size of less than 6.9 Å, or two or more of the first molecular sieves being molecular sieves having a pore size of less than 6.9 Å, and
D) with P2O5~ 15% by weight of a phosphorus additive;
the proportion of the mesoporous protonic acid amount of the catalytic cracking catalyst in the total acid amount is 20% ~ 70%.
2. The catalytic cracking catalyst of claim 1, wherein the phosphorus additive is present in an amount of 0.5 ~ 6.5.5 wt%.
3. The catalytic cracking catalyst of claim 1, having a total specific surface area of 240 ~ 350m2The proportion of mesoporous protonic acid accounting for the total acid amount is 25 percent ~ 50 percent.
4. The catalytic cracking catalyst of claim 1, wherein the catalyst has a mesopore volume of 0.14 ~ 0.35.35 ml/g and a ratio of mesopore volume to total pore volume of 35% ~ 60%.
5. The catalytic cracking catalyst of claim 4, wherein the catalyst has a mesopore volume of 0.14 ~ 0.30.30 ml/g.
6. The catalytic cracking catalyst of claim 1, wherein the natural minerals comprise one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite, the oxides are one or more of silica, alumina, zirconia, titania and amorphous silica-alumina, the Y-type molecular sieve is at least one of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve and HY molecular sieve, and the molecular sieve with the pore size less than 6.9 Å is at least one of MFI-structure molecular sieve, IMF-structure molecular sieve, BEA-structure molecular sieve and ferrierite.
7. The catalytic cracking catalyst of claim 1, wherein the weight ratio of the Y-type molecular sieve to the molecular sieve having a pore size of less than 6.9 Å is 1:8 to 4: 0.1.
8. The catalytic cracking catalyst of claim 1, wherein the phosphorus additive content is 2 ~ 5 wt%.
9. The catalytic cracking catalyst of claim 7, wherein the weight ratio of the Y-type molecular sieve to the molecular sieve having a pore size of less than 6.9 Å is 0.3:1 ~ 20:1 or 0.15:1 ~ 1: 1.
10. The catalytic cracking catalyst of claim 7, wherein the weight ratio of the Y-type molecular sieve to the molecular sieve having a pore size of less than 6.9 Å is 1: 6.5 ~ 1: 2.
11. A method of preparing the catalytic cracking catalyst of any one of claims 1 ~ 10, comprising:
forming first composition microspheres comprising the first molecular sieve, natural minerals and oxide binders, and modifying the first composition microspheres; the modification treatment of the microspheres of the first composition comprises the following steps:
a. putting the first composition microspheres into an alkaline solution for treatment, filtering and washing to obtain alkali-treated first composition microspheres;
b. b, treating the alkali-treated first composition microspheres obtained in the step a in a composite acid solution consisting of fluosilicic acid, organic acid and inorganic acid, filtering, washing and optionally drying to obtain composition microspheres rich in mesopores; or treating the alkali-treated first composition microspheres obtained in the step a in a composite acid solution consisting of fluosilicic acid, organic acid and inorganic acid, filtering, optionally washing, performing ammonium exchange sodium washing treatment, filtering, optionally washing, and optionally drying to obtain composition microspheres rich in mesopores;
c. introducing a phosphorus additive into the composition microspheres rich in mesopores;
d. roasting at 400-800 deg.c for at least 0.5 hr.
12. The method of claim 11, wherein the catalytic cracking catalyst optionally comprises a second molecular sieve, optionally comprises a promoter component, and the step of forming microspheres of the first composition comprising the first molecular sieve, the natural mineral, and the oxide binder comprises:
mixing the first molecular sieve, the natural mineral substance, the precursor sol of the oxide, the optional second molecular sieve, the optional auxiliary agent component and water, pulping, spray drying and optional roasting.
13. The method for preparing a catalytic cracking catalyst according to claim 11, wherein the alkaline solution in step a comprises alkaline compounds, and the alkaline compounds are one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and high alkali sodium metaaluminate.
14. The method of claim 11, wherein the treating step a comprises contacting the microspheres of the first composition with an alkaline solution, wherein the alkaline solution comprises an alkaline compound, and the weight ratio of the microspheres of the first composition to the alkaline compound is 1 (0.01 ~ 0.35.35) on a dry basis, wherein the alkali metal compound is calculated as alkali metal oxide, and the ammonium hydroxide is calculated as NH3And (6) counting.
15. The catalytic cracking catalyst production method according to claim 11, wherein in the treatment in step a: the weight ratio of the microspheres of the first composition to water on a dry basis is 1: (5-20), wherein the treatment temperature is between room temperature and 100 ℃, and the treatment time is 0.2-4 hours.
16. The method for preparing a catalyst for catalytic cracking according to claim 11, wherein the treating in the step a is carried out under the condition that the weight ratio of the microspheres of the first composition to the alkali metal oxide in the basic compound is 1 (0.05 ~ 0.25.25) or 1 (0.01 ~ 0.15.15) based on the weight of the microspheres of the first composition on a dry basis.
17. The catalytic cracking catalyst preparation method of claim 11, wherein the organic acid in step b is at least one of ethylenediaminetetraacetic acid, oxalic acid, acetic acid, citric acid, and sulfosalicylic acid, and the inorganic acid is at least one of hydrochloric acid, sulfuric acid, and nitric acid.
18. The method for preparing a catalyst for catalytic cracking according to claim 11, wherein the treating in the step b is carried out under conditions such that the weight ratio of the microspheres of the first composition, the fluorosilicic acid, the organic acid and the inorganic acid is 1 (0.003 ~ 0.3.3) to (0.01 ~ 0.55.55) to (0.01 ~ 0.45.45) on a dry basis.
19. The method for preparing a catalytic cracking catalyst as claimed in claim 11, wherein the treating in step b is carried out under conditions such that the weight ratio of the microspheres of the first composition, the fluorosilicic acid, the organic acid and the inorganic acid is 1 (0.005 ~ 0.3.3) to (0.02 ~ 0.3.3) to (0.02 ~ 0.3.3) on a dry basis.
20. The method for preparing a catalytic cracking catalyst according to claim 11, wherein the temperature of the treatment in the step b is 25 to 100 ℃ and the time is 0.5 to 6 hours.
21. The method of claim 11, wherein the ammonium exchange sodium wash treatment process of step b comprises contacting an ammonium salt solution with the acid-treated microspheres of the first composition, wherein the ammonium exchange sodium wash treatment is performed such that the resulting catalytic cracking catalyst has a sodium oxide content of no more than 0.2 wt.%.
22. The method of preparing a catalytic cracking catalyst according to claim 11, wherein the introducing of the phosphorus additive in step c comprises a step of contacting the mesoporous rich composition microspheres with a phosphorus-containing compound for impregnation and/or ion exchange.
23. The catalytic cracking catalyst preparation method of claim 22, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate.
24. The catalytic cracking catalyst preparation method of claim 11, wherein the conditions of the calcination treatment in the step d include: the atmosphere of the roasting treatment is air atmosphere, nitrogen atmosphere or water vapor atmosphere or the mixture atmosphere of the above atmospheres; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
25. The method of preparing a catalytic cracking catalyst of claim 11, wherein forming microspheres of the first composition including the first molecular sieve, natural minerals, and oxide binder includes: the first molecular sieve, natural minerals, oxide binder precursor and water are slurried, spray dried, and optionally calcined.
26. The method for preparing a catalyst for catalytic cracking according to claim 11, wherein the microspheres of the first composition comprise, on a dry basis, 5% ~% of a natural mineral, 10% ~% of an oxide binder, and 24% ~% of a first molecular sieve, on a dry basis, based on the weight of the microspheres of the first composition.
27. The process for producing a catalytic cracking catalyst according to claim 11 or 26, wherein the catalytic cracking catalyst contains P based on the weight of the catalytic cracking catalyst2O50.1% ~ 15% phosphorus additive.
28. The catalytic cracking catalyst preparing method of claim 13, wherein the alkaline solution is at least one selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution, an ammonium hydroxide solution, and a high alkali sodium metaaluminate solution.
29. The method for preparing a catalyst for catalytic cracking of a hydrocarbon according to claim 19, wherein the weight ratio of the first composition microspheres, the fluorosilicic acid, the organic acid, and the inorganic acid is 1 (0.005 ~ 0.17) (0.015 ~ 0.15.15): 0.02 ~ 0.15.15).
30. The method for preparing a catalyst for catalytic cracking of a hydrocarbon according to claim 19, wherein the weight ratio of the microspheres of the first composition, the fluorosilicic acid, the organic acid, and the inorganic acid is 1 (0.005 ~ 0.1): (0.02 ~ 0.2.2): 0.02 ~ 0.15.15).
31. A method for preparing a catalytic cracking catalyst according to claim 21, wherein the ammonium salt is at least one selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate.
32. The method of preparing a catalytic cracking catalyst of claim 21, wherein the ammonium exchange sodium wash treatment results in a catalytic cracking catalyst having a sodium oxide content of no more than 0.15 wt.%.
33. The method of claim 25, wherein the oxide binder precursor is one or more of silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol, and phosphorus-containing alumina sol.
34. The method of preparing a catalytic cracking catalyst of claim 27, wherein the catalytic cracking catalyst contains 0.5 ~ 6.5.5 wt% phosphorus additive.
35. The method of preparing a catalytic cracking catalyst of claim 27, wherein the catalytic cracking catalyst contains 2 ~ 5 wt% of the phosphorus additive.
36. A method for producing lower olefins by catalytic cracking of hydrocarbons, comprising the step of contacting hydrocarbon oil with the catalytic cracking catalyst of claim 1 ~ 10.
CN201610919769.2A 2016-10-21 2016-10-21 Catalytic cracking catalyst and preparation method thereof Active CN107971013B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610919769.2A CN107971013B (en) 2016-10-21 2016-10-21 Catalytic cracking catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610919769.2A CN107971013B (en) 2016-10-21 2016-10-21 Catalytic cracking catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107971013A CN107971013A (en) 2018-05-01
CN107971013B true CN107971013B (en) 2019-12-27

Family

ID=62004512

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610919769.2A Active CN107971013B (en) 2016-10-21 2016-10-21 Catalytic cracking catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107971013B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111482198B (en) * 2020-04-26 2023-12-15 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN111482199B (en) * 2020-04-26 2023-12-15 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN113731477B (en) * 2020-05-27 2023-08-15 中国石油化工股份有限公司 Catalyst for preparing propylene and preparation method and application thereof
CN113181960B (en) * 2021-04-19 2023-09-12 中科合成油技术股份有限公司 IM-5 molecular sieve containing heteroatom boron and modification method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101837301A (en) * 2009-03-18 2010-09-22 中国石油天然气股份有限公司 Catalytic cracking propylene catalyst with yield increase and preparation method
CN103007986A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
CN104307560A (en) * 2014-10-20 2015-01-28 丁泳 Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101837301A (en) * 2009-03-18 2010-09-22 中国石油天然气股份有限公司 Catalytic cracking propylene catalyst with yield increase and preparation method
CN103007986A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
CN104307560A (en) * 2014-10-20 2015-01-28 丁泳 Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst

Also Published As

Publication number Publication date
CN107971013A (en) 2018-05-01

Similar Documents

Publication Publication Date Title
CN107971018B (en) Catalytic cracking catalyst and preparation method thereof
CN107971017B (en) Catalytic cracking catalyst and preparation method thereof
CN107970991B (en) Catalytic cracking catalyst and preparation method thereof
US9968918B2 (en) Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof
US9889439B2 (en) High light received heavy oil catalytic cracking catalyst and preparation method therefor
CN107971013B (en) Catalytic cracking catalyst and preparation method thereof
JP6486989B2 (en) Phosphorus-modified cracking catalyst with enhanced activity and hydrothermal stability
JP2011005489A (en) Catalyst for production of light olefin
US20140005032A1 (en) Catalyst containing a modified y-type zeolite and a preparaton process thereof
WO2020078434A1 (en) Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof
RU2509605C1 (en) Method of preparing catalyst with low content of rare-earth elements for cracking oil fractions
KR20210066927A (en) Mesopore-rich phosphorus-containing rare earth-containing MFI structure molecular sieve, method for preparing same, catalyst containing same, and use thereof
WO2020078437A1 (en) Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof
WO2018026313A1 (en) Method for manufacturing a cracking catalyst with alkaline-earth elements
CN107971014B (en) Catalytic cracking catalyst and preparation method thereof
CN107970986B (en) Catalytic cracking catalyst and preparation method thereof
CN107970987B (en) Catalytic cracking catalyst and preparation method thereof
CN107971004B (en) Catalytic cracking catalyst and preparation method thereof
CN109675616B (en) Catalytic conversion catalyst for producing more butene, preparation method of catalytic conversion catalyst and catalytic conversion method for producing more butene
CN107970995B (en) Catalytic cracking catalyst and preparation method thereof
CN107971012B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon
CN107974281B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon
CN107974285B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon
CN107971002B (en) Catalytic cracking auxiliary agent containing Beta molecular sieve rich in mesopores and preparation method thereof
CN107974282B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant