CN114762836B - Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve - Google Patents

Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve Download PDF

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CN114762836B
CN114762836B CN202110030461.3A CN202110030461A CN114762836B CN 114762836 B CN114762836 B CN 114762836B CN 202110030461 A CN202110030461 A CN 202110030461A CN 114762836 B CN114762836 B CN 114762836B
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molecular sieve
phosphorus
aluminum
catalytic cracking
inorganic binder
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CN114762836A (en
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罗一斌
王成强
欧阳颖
邢恩会
舒兴田
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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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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to TW111101188A priority patent/TW202237269A/en
Priority to EP22736632.5A priority patent/EP4275789A1/en
Priority to CN202280009687.8A priority patent/CN116917234A/en
Priority to KR1020237027323A priority patent/KR20230130708A/en
Priority to US18/260,971 priority patent/US20240059630A1/en
Priority to PCT/CN2022/071280 priority patent/WO2022148471A1/en
Priority to JP2023541771A priority patent/JP2024502195A/en
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10G2400/26—Fuel gas
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a preparation method of a catalytic cracking catalyst, which is characterized by comprising the following steps: mixing and pulping the phosphorus modified MFI structure molecular sieve, the Y-type molecular sieve, the inorganic binder and the second clay which is optionally added, forming, and carrying out hydrothermal roasting treatment on the formed product under the atmosphere environment of externally applying pressure and externally adding aqueous solution; the phosphorus modified MFI structure molecular sieve is obtained by carrying out contact treatment on the MFI structure molecular sieve with the temperature of 0-150 ℃ and an aqueous solution of a phosphorus-containing compound with the temperature of 0-150 ℃ by an impregnation method; the apparent pressure of the hydrothermal roasting treatment is 0.01-1.0 Mpa and the water vapor is 1-100%; the hydrothermal roasting treatment is carried out at 200-800 ℃. The invention optimally shortens the flow of preparing the catalyst, can reduce the preparation cost, and the catalytic cracking catalyst provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbon, and simultaneously has higher liquefied gas yield.

Description

Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve
Technical Field
The invention relates to a preparation method and a preparation system of a catalytic cracking catalyst, in particular to a short-flow preparation method and a preparation system of a catalytic cracking catalyst of a phosphorus-containing modified MFI molecular sieve.
Background
ZSM-5 molecular sieve having MFI structure was a widely used zeolite molecular sieve catalytic material developed by Mobil company of America in 1972. The molecular sieve has a three-dimensional crossed pore canal structure, the pore canal along the axial direction a is a straight pore, the cross-sectional dimension of the pore canal along the axial direction b is 0.54 multiplied by 0.56nm, the pore canal along the axial direction b is a Z-shaped pore, the cross-sectional dimension of the pore canal along the axial direction b is 0.51 multiplied by 0.56nm, and the pore canal is elliptical. The pore opening is formed by ten-membered rings, and the size of the pore opening is between that of small pore zeolite and large pore zeolite, so that the molecular sieve has unique shape selective catalysis. ZSM-5 has unique pore structure, good shape selective catalysis and isomerization performance, high heat and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon formation, is widely used as a catalyst and a catalyst carrier, and is successfully used in alkylation, isomerization, disproportionation, catalytic cracking, methanol-to-gasoline, methanol-to-olefin and other production processes. ZSM-5 molecular sieve is introduced into catalytic cracking and carbon four hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin by utilizing the molecular shape selectivity of the molecular sieve.
Since 1983, ZSM-5 molecular sieves have been applied to catalytic cracking processes as an aid to the octane number of catalytic cracking, with the aim of increasing the octane number of catalytically cracked gasoline and the selectivity to lower olefins. US3758403 originally reported that ZSM-5 was used as an active component for propylene production along with REY to prepare FCC catalysts, and US5997728 discloses that the use of ZSM-5 molecular sieves without any modification as an auxiliary for propylene production is not high in propylene yields. Although ZSM-5 molecular sieves have good shape selectivity and isomerization properties, they have the disadvantage of poor hydrothermal stability and are susceptible to deactivation under severe high-temperature hydrothermal conditions, leading to a reduction in catalytic performance.
In the 80 s of the 20 th century, the Mobil company found that phosphorus can improve the hydrothermal stability of ZSM-5 molecular sieves, and that phosphorus can improve the yield of low-carbon olefins after modifying ZSM-5 molecular sieves. Conventional additives typically contain phosphorus-activated ZSM-5, which selectively converts primary cracked products (e.g., gasoline olefins) to C3 and C4 olefins. After the ZSM-5 molecular sieve is synthesized, a proper amount of inorganic phosphorus compound is introduced for modification, so that framework aluminum can be stabilized under severe hydrothermal conditions.
In CN 106994364A, a process for modifying ZSM-5 molecular sieve with phosphorus is disclosed, which is carried out by a method selected from phosphoric acid, diammonium hydrogen phosphate and phosphoric acidOne or more phosphorus-containing compounds of ammonium dihydrogen and ammonium phosphate are mixed with ZSM-5 molecular sieve having a high alkali metal ion content to give a mixture having phosphorus and P 2 O 5 At least 0.1wt% of the supported amount of the mixture, drying, roasting, and then performing an ammonium-exchange step and a water-washing step so that the alkali metal ion content thereof is reduced to less than 0.10wt%, and then performing the steps of drying and hydrothermal aging at 400-1000 ℃ and 100% steam. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity, and higher liquefied gas yield.
In CN1506161a, a method for modifying a hierarchical pore ZSM-5 molecular sieve is disclosed, which comprises the following conventional steps: synthesizing, filtering, carrying out ammonium exchange, drying and roasting to obtain a hierarchical pore ZSM-5 molecular sieve, modifying the hierarchical pore ZSM-5 molecular sieve by phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve. Wherein P is 2 O 5 The loading is generally in the range of 1 to 7 wt%. However, phosphoric acid or ammonium phosphate salts can self-polymerize to form phosphorus species with different aggregation states in the roasting process, and only phosphate radicals entering holes interact with framework aluminum to retain B acid centers in the hydrothermal treatment process, so that the distribution of the phosphorus species is reduced.
Although proper inorganic phosphide is adopted to modify ZSM-5 molecular sieve, which can slow down the dealumination of the framework and improve the hydrothermal stability, and phosphorus atoms can combine with distorted four-coordination framework aluminum to generate weak B acid centers, so that higher conversion rate of long-chain alkane pyrolysis and higher light olefin selectivity are achieved, excessive inorganic phosphide is used to modify ZSM-5 molecular sieve, which can block pore channels of molecular sieve, reduce pore volume and specific surface area and occupy a large amount of strong B acid centers. In addition, phosphoric acid or ammonium phosphate salt in the roasting process can self-polymerize to generate phosphorus species with different aggregation states, the coordination of phosphorus and framework aluminum is insufficient, the utilization efficiency of phosphorus is low, and the modification of phosphorus does not always obtain satisfactory hydrothermal stability improvement results. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus modified ZSM-5 molecular sieve and further improve the cracking activity.
In the industrial production of the prior art, the preparation flow of the catalytic cracking catalyst is shown in figure 1, and the MFI molecular sieve is subjected to phosphorus-containing solution impregnation, drying (flash evaporation drying), primary roasting, raw material (comprising a Y-type molecular sieve, an inorganic binder and the like) mixed forming (spraying agent) and secondary roasting to obtain a catalytic cracking catalyst finished product. In order to improve the hydrothermal stability of the phosphorus exchange modified MFI molecular sieve, the prior art needs to carry out two roasting processes, the preparation cost is high, and the process is complex.
Disclosure of Invention
The invention provides a preparation method of a cracking catalyst, which aims at solving the problems that a phosphorus modification process of a phosphorus modified MFI molecular sieve for improving the hydrothermal stability of the phosphorus modified MFI molecular sieve in the prior art is complex and a preparation process of the cracking catalyst is complex.
It is a second object of the present invention to provide a preparation system for the above simplified flow process preparation method.
In order to achieve one of the above objects, the present invention provides a method for preparing a catalytic cracking catalyst, which is characterized in that the method comprises: mixing and pulping the phosphorus modified MFI structure molecular sieve, the Y-type molecular sieve, the inorganic binder and the second clay which is optionally added, forming, and carrying out hydrothermal roasting treatment on the formed product under the atmosphere environment of externally applying pressure and externally adding aqueous solution; the phosphorus modified MFI structure molecular sieve is obtained by carrying out impregnation exchange on an MFI structure molecular sieve with the temperature of 0-150 ℃ and an aqueous solution of a phosphorus-containing compound with the temperature of 0-150 ℃; the apparent pressure of the hydrothermal roasting treatment is 0.01-1.0 Mpa and the water vapor is 1-100%; the hydrothermal roasting treatment is carried out at 200-800 ℃.
In the present invention, the catalytic cracking catalyst preferably comprises 1 to 25% by weight of a Y-type molecular sieve, 5 to 50% by weight of a phosphorus-modified MFI structure molecular sieve, 1 to 60% by weight of an inorganic binder, and optionally 0 to 60% by weight of a second clay, on a dry basis.
In the invention, the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.
In the invention, the binder is at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol, water glass and phosphorus-aluminum inorganic binder; the preferred binder comprises a phosphorus aluminum inorganic binder, and the more preferred binder is a phosphorus aluminum inorganic binder. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay. When the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, the phosphorus-aluminum inorganic binder containing first clay is based on dry basis, and the phosphorus-aluminum inorganic binder containing first clay contains Al 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio containing the first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth. The second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.
In the present invention, the phosphorus-containing compound used for phosphorus modification may be selected from organic phosphorus compounds and/or inorganic phosphorus compounds. The organic phosphorus compound may be selected from, for example, trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphorus bromide, triphenyl butyl phosphorus bromide, triphenyl benzyl phosphorus bromide, hexamethylphosphoric triamide, dibenzyldiethyl phosphorus, 1, 3-xylene bis triethyl phosphorus; the inorganic phosphide may be selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, boron phosphate, for example.
In the invention, in the MFI molecular sieve, na 2 O<0.1wt%. The phosphorus modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multistage pore ZSM-5 molecular sieve. The microporous ZSM-5 moleculesThe sieve has a silica/alumina molar ratio of 15 to 1000, preferably 20 to 200. The ratio of mesoporous volume to total pore volume of the multistage hole ZSM-5 molecular sieve is more than 10%, the average pore diameter is 2-20 nm, and the mol ratio of silicon oxide to aluminum oxide is 15-1000, preferably 20-200.
When the MFI molecular sieve is subjected to impregnation exchange by using the aqueous solution of the phosphorus-containing compound, the phosphorus-containing compound is calculated by phosphorus, the MFI molecular sieve is calculated by aluminum, and the molar ratio of the phosphorus-containing compound to the MFI molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2-1.5. The weight ratio of the water sieve is 0.5-1; the higher impregnation exchange temperature is advantageous in obtaining better effect, namely better dispersion of phosphorus species, more easy migration of phosphorus to the inside of the crystal of the molecular sieve to combine with framework aluminum during the subsequent pressure roasting process of the catalyst raw material mixture, further improving the coordination degree of phosphorus and framework aluminum and finally improving the hydrothermal stability of the molecular sieve, so that the impregnation exchange is preferably carried out at a higher temperature, preferably 50-150 ℃, more preferably 70-130 ℃ for 0.5-40 hours.
In the invention, the apparent pressure of the atmosphere environment is 0.1-0.8 Mpa, preferably 0.3-0.6 Mpa, and the atmosphere environment contains 30-100% of water vapor, preferably 60-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃. The external pressure is applied to the molded product of the auxiliary raw material mixture from the outside in the hydrothermal roasting treatment process, and for example, inert gas is introduced from the outside to maintain a certain back pressure. The external water is added in an amount which satisfies the condition that the atmosphere contains 1 to 100 percent of water vapor.
In the present invention, a specific embodiment of the composition of the binder includes 3 to 39 wt% of the phosphorus aluminum inorganic binder on a dry basis and 1 to 30 wt% of other inorganic binders including at least one of pseudo-boehmite, aluminum sol, silica alumina sol and water glass on a dry basis, based on the total amount of the catalytic cracking auxiliary.
The inventionIn the present invention, the phosphorus-aluminum inorganic binder containing the first clay is preferably prepared by the steps of: pulping and dispersing an alumina source, the first clay and water into slurry with a solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide is prepared by 15 to 40 weight parts of aluminum oxide 2 O 3 An alumina source in an amount of greater than 0 parts by weight and no more than 40 parts by weight, based on dry weight of the first clay; adding concentrated phosphoric acid to the slurry with stirring according to the weight ratio of P/Al=1-6, and reacting the obtained mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus in phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
In the present invention, the shaping is spray-dried granulation to give microspheres of 1-150um diameter, an operation well known to those skilled in the art and not described further herein.
The invention also provides a catalytic cracking catalyst prepared by the preparation method.
The invention further provides a method for catalytic cracking of hydrocarbon oil, which is characterized by comprising the following steps: and (3) under the condition of catalytic cracking, enabling the hydrocarbon oil to react with the catalytic cracking catalyst prepared by the preparation method. The catalytic cracking conditions include: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, direct-current wax oil, light/heavy propane deoiling, coker wax oil and coal liquefied products.
The invention further provides a preparation system of the catalytic cracking catalyst for the preparation method, which is characterized by mainly comprising a phosphorus modification device of an MFI molecular sieve, a raw material mixing device, a forming device and a pressurized water heating roasting device.
In the preparation system, the phosphorus modification device of the MFI molecular sieve is used for the dipping exchange operation of the phosphorus-containing compound solution and the MFI molecular sieve, and comprises phosphorus-containing compound solution introducing equipment.
In the preparation system of the invention, the raw material mixing device receives raw materials for preparing the cracking catalyst, wherein the raw materials comprise the impregnated and exchanged phosphorus modified MFI molecular sieve obtained from the phosphorus modification device of the MFI molecular sieve, the phosphorus-aluminum inorganic binder from the phosphorus-aluminum inorganic binder treatment device, the Y-type molecular sieve and the optionally added clay.
In the production system of the present invention, the forming device is not limited to but is preferably a spray drying forming device.
In the preparation system, the hydrothermal pressurized roasting device is provided with a water inlet and a gas pressurizing interface so as to meet the pressurized hydrothermal roasting condition of the formed product.
One particular form of the preparation system provided by the present invention is shown in fig. 2. As can be seen from fig. 2, in the phosphorus modification apparatus of the MFI molecular sieve, the MFI molecular sieve is subjected to impregnation exchange with a phosphorus-containing aqueous solution to obtain a phosphorus-modified MFI molecular sieve; in the raw material mixing device, mixing and pulping the phosphorus modified MFI molecular sieve, the Y-type molecular sieve and the binder with the optional second clay, and shaping (such as spray drying); the molded article is subjected to hydrothermal baking treatment under external pressure and in an atmosphere with external water.
The preparation method provided by the invention has the characteristics of short preparation flow, and the prepared catalytic cracking catalyst has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbon, and simultaneously has higher liquefied gas yield.
Drawings
FIG. 1 is a flow chart of a conventional catalyst preparation in the prior art.
FIG. 2 is a flow chart of a catalyst preparation system provided by the invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The apparatus and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The micro-reaction device is adopted to evaluate the influence of the catalytic cracking catalyst of the invention on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon.
And (3) carrying out 800 ℃ and 100% water vapor aging treatment on the prepared catalytic cracking catalyst sample on a fixed bed aging device for 17 hours, and evaluating on a micro-reaction device, wherein the raw oil is VGO or naphtha, and the evaluation condition is that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the catalyst-oil ratio is 3.2. Microreaction activity was measured using ASTM D5154-2010 standard method.
Some of the raw materials used in the examples were as follows:
pseudo-boehmite is an industrial product produced by Shandong aluminum company and has a solid content of 60 weight percent. The aluminum sol is an industrial product produced by the middle petrochemical catalyst Qilu division company, al 2 O 3 The content was 21.5% by weight. Silica sol is an industrial product produced by the middle petrochemical catalyst Qilu division company, siO 2 The content was 28.9 wt%, na 2 O content was 8.9%. The kaolin is special for the catalytic cracking catalyst produced by Suzhou kaolin company, and the solid content of the kaolin is 78 weight percent. The rectorite is produced by Hubei's lucky famous rectorite development Co., ltd<3.5 wt%, al 2 O 3 The content of Na is 39.0 wt.% 2 The O content was 0.03 wt% and the solid content was 77 wt%. SB aluminium hydroxide powder, produced by Condex, germany, al 2 O 3 The content was 75% by weight. Gamma-alumina, manufactured by Condex, germany, al 2 O 3 The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, produced by Beijing chemical plant.
PSRY molecular sieve is an industrial product produced by medium petrochemical catalyst, namely longline division company, na 2 O content<1.5 wt%, P 2 O 5 The content is 0.8 to 1.2 weight percent, and the unit cell constant is as follows<2.456nm, and the crystallinity is more than or equal to 64 percent. HRY-1 finished molecular sieve is an industrial product produced by China petrochemical catalyst, namely Changling Co., ltd., la 2 O 3 Content of 11-13 wt%, unit cell constant<2.464nm, and the crystallinity is more than or equal to 40 percent.
The phosphor-aluminum inorganic Binder1 used in the examples was prepared as follows: 1.91 kg of pseudo-thin water is addedAldrite (containing Al) 2 O 3 1.19 kg), 0.56 kg of kaolin (dry basis 0.5 kg) and 3.27 kg of decationized water are beaten for 30 minutes, 5.37 kg of concentrated phosphoric acid (mass concentration 85%) is added into the slurry under stirring, the phosphoric acid adding speed is 0.04 kg of phosphoric acid/min/kg of alumina source, the temperature is raised to 70 ℃, and then the reaction is carried out for 45 minutes at the temperature, so that the phosphorus-aluminum inorganic binder is prepared. The material ratios are shown in Table 1.
The inorganic binders Binder2, binder3 and Binder4 were also prepared as described above, except for the differences in the proportions of the materials, which are shown in Table 1.
TABLE 1
Examples 1-20 provide catalytic cracking catalysts of the present invention, and comparative examples 1-16 illustrate catalytic cracking catalysts as a comparison. Wherein the MFI molecular sieve in examples 1-10 is microporous ZSM-5 molecular sieve, and the MFI molecular sieve in examples 11-20 is hierarchical ZSM-5 molecular sieve. Comparative example 8 is a comparative catalytic cracking catalyst for preparing an MFI molecular sieve containing microporous ZSM-5 in the prior art, and comparative example 16 is a comparative catalytic cracking catalyst for preparing an MFI molecular sieve containing hierarchical pore ZSM-5 in the prior art.
Example 1-1
16.2g of diammonium phosphate (analytical grade, hereinafter referred to as "Sedrin light complex technology development Co., ltd.) was dissolved in 60g of deionized water, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, and 113g of HZSM-5 molecular sieve (supplied by Qilu Co., ltd., relative crystallinity of 91.1%, silica/alumina molar ratio of 24.1, na) was added 2 O content 0.039 wt%, specific surface area 353m 2 Per g, total pore volume of 0.177ml/g, the same applies below), modified by impregnation, impregnated for 2 hours at 20deg.C, and added with Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite, and decationized withPulping the son water and the aluminum sol for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to 3.0, then pulping for 45 minutes continuously, then adding a phosphorus-aluminum inorganic Binder1, stirring for 30 minutes, spray-drying the obtained slurry to form microspheres, externally applying pressure to the microspheres, adding water, and treating the microspheres for 0.5 hour in a steam atmosphere with the pressure of 500 ℃ and the pressure of 0.5Mpa and 50 percent to obtain a catalytic cracking catalyst sample, wherein the sample is numbered CFZY1-1, and the proportion of the sample is phosphorus-modified ZSM-5 molecular sieve 40%, PSRY molecular sieve 10%, kaolin 23%, binder1 is 18%, and pseudo-boehmite (with Al 2 O 3 5% by weight of aluminum sol (in terms of Al) 2 O 3 Calculated) 4%.
The catalytic cracking catalyst CFZY1-1 prepared in example 1-1 was subjected to reaction performance evaluation using a fixed bed micro-reactor with 100% of the balancing agent and the balancing agent incorporated therein to demonstrate the catalytic cracking reaction effect of the catalytic cracking catalyst provided in the present disclosure.
Catalyst CFZY1-1 was subjected to an aging treatment at 800℃under a 100% steam atmosphere for 17 hours. The aged CFZY1-1 was mixed with an industrial FCC balance catalyst (industrial brand DVR-3 FCC balance catalyst, light oil micro-reaction activity 63). The mixture of the balancing agent and the catalyst is filled into a fixed bed micro-reaction reactor, and the raw oil shown in the table 2 is subjected to catalytic cracking, wherein the evaluation condition is that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃, and the catalyst-oil ratio is 3.2. The results of the reaction are given in Table 3, which includes blank test reagents.
TABLE 2
Project Raw oil
Density (20 ℃), g/cm 3 0.9334
Refraction (70 ℃ C.) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Colloid 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
Carbon residue m% 1.77
Examples 1 to 2
The procedure is as in example 1-1 except that the phosphorus-modified molecular sieve is prepared by mixing diammonium hydrogen phosphate, HZSM-5 molecular sieve and water and slurrying, and then heating to 100deg.C and maintaining for 2 hr. A sample of the catalytic cracking catalyst was prepared, numbered CFZY1-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 3.
Comparative example 1
The same as in example 1-1 was distinguished in that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing was carried out in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 3.
TABLE 3 Table 3
Example 2-1
The same as in example 1-1 except that 16.2g of diammonium hydrogen phosphate was dissolved in 120g of deionized water at 50℃and stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated at 20℃for 2 hours; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 600 ℃ under 0.5Mpa and 30% steam atmosphere. A sample of the catalytic cracking catalyst was prepared, numbered CFZY2-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
Example 2-2
The procedure is as in example 2-1 except that the diammonium phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 70℃and maintained for 2 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY2-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
Comparative example 2
The procedure is as in example 2-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
TABLE 4 Table 4
Example 3-1
The same as in example 1-1 except that 10.4g phosphoric acid was dissolved in 60g deionized water at room temperature, stirred for 2 hours to obtain a phosphorus-containing aqueous solution, then 113g HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated at 20℃for 4 hours; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 400 ℃ under 0.3Mpa and 100% steam atmosphere. A sample of the catalytic cracking catalyst was prepared, numbered CFZY3-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
Example 3-2
The procedure is as in example 3-1, except that an aqueous solution of the phosphorus-containing compound at 80℃is contacted with the HZSM-5 molecular sieve heated to 80℃for 4 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY3-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
Comparative example 3
The procedure is as in example 3-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY3, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
TABLE 5
Example 4-1
The same as in example 1-1 except that 8.1g of diammonium hydrogen phosphate was dissolved in 120g of deionized water at room temperature, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, modified by an impregnation method, and impregnated for 2 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 300 ℃ under 0.4Mpa and 100% steam atmosphere. A sample of the catalytic cracking catalyst was prepared, numbered CFZY4-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
Example 4-2
The procedure is as in example 4-1 except that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 90℃and maintained for 2 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY4-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
Comparative example 4
The procedure of example 4-1 was repeated except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY4, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
TABLE 6
Example 5-1
The same as in example 1-1 except that 8.5g of trimethyl phosphate was dissolved in 80g of deionized water at 90℃and stirred for 1 hour to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated for 8 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 4 hours at 500 ℃ under 0.8Mpa and 80% steam atmosphere. A sample of the catalytic cracking catalyst was prepared, numbered CFZY5-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
Example 5-2
The procedure is as in example 5-1 except that trimethyl phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 120℃and maintained for 8 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY5-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
Comparative example 5
The procedure is as in example 5-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY5, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
TABLE 7
Example 6-1
The same as in example 1-1 except that 11.6g of boron phosphate was dissolved in 100g of deionized water at 100℃and stirred for 3 hours to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated for 2 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 4 hours at 400 ℃ under 0.3Mpa and 100% steam atmosphere. A sample of the catalytic cracking catalyst was prepared, numbered CFZY6-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
Example 6-2
The procedure is as in example 6-1 except that the boron phosphate, HZSM-5 molecular sieve and water are mixed and slurried and then heated to 150℃for 2 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY6-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
Comparative example 6
The procedure was as in example 6-1 except that the conditions for calcination were atmospheric (apparent pressure 0 MPa) and air-calcination in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY6, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
TABLE 8
Example 7-1
The same as in example 1-1 except that 14.2g of triphenylphosphine was dissolved in 80g of deionized water at 100deg.C, stirred for 2 hours to obtain a phosphorus-containing aqueous solution, and 113g of HZSM-5 molecular sieve was added to modify by impregnation, and impregnated for 4 hours at 20deg.C; externally applying pressure and adding water, and performing pressurized hydrothermal roasting at 600 ℃ under 1.0Mpa and 30% steam atmosphere for 2h. A sample of the catalytic cracking catalyst was prepared, numbered CFZY7-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
Example 7-2
The procedure is as in example 7-1 except that the boron phosphate, HZSM-5 molecular sieve and water are mixed and slurried and then heated to 150℃for 2 hours. A sample of the catalytic cracking catalyst was prepared, numbered CFZY7-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
Comparative example 7
The procedure of example 7-1 was repeated except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the catalytic cracking catalyst, numbered DCFZY7, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
TABLE 9
Comparative example 8
Comparative example 8 illustrates the conventional process of the prior art and the resulting phosphorus-containing modified ZSM-5 comparative sample.
The same as in example 1-2, except that 16.2g of diammonium phosphate was dissolved in 60g of deionized water, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, modified by an impregnation method, dried in an oven at 110 ℃ after 2 hours of impregnation at 100 ℃, and air-calcined in a muffle furnace at 550 ℃ under normal pressure (apparent pressure 0 Mpa), to obtain a phosphorus-modified ZSM-5 molecular sieve sample, then slurried with kaolin and pseudo-boehmite for 120 minutes with decationizing water and alumina sol to obtain a slurry with a solid content of 30 wt%, hydrochloric acid was added to adjust the pH of the slurry to 3.0, and then continued to slurry for 45 minutes, then phosphorus-alumina inorganic Binder1 was added, stirred for 30 minutes, and then the obtained slurry was spray-dried to obtain microspheres, which were calcined at 500 ℃ for 1 hour to obtain a catalytic cracking catalyst comparative sample, no. DCFZY8. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 10.
Table 10
Example 8-1
The same as in example 1-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. The catalytic cracking catalyst is prepared, with the number CFZY8-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 8-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. The catalytic cracking catalyst is prepared, with the number CFZY8-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-1
The same as in example 5-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. The catalytic cracking catalyst was prepared, numbered CFZY9-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. The catalytic cracking catalyst was prepared, numbered CFZY9-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 10-1
The same as in example 1-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst was prepared, numbered CFZY10-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 10-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst was prepared, numbered CFZY10-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
TABLE 11
Examples 11-20 illustrate the preparation of catalytic cracking catalysts for phosphorus-modified hierarchical pore ZSM-5 molecular sieves employed in the present invention.
Examples 11-1 to 17-1
Examples 11-1 to 17-1 correspond in sequence to examples 1-1 to 7-1, respectively, except that the HZSM-5 molecular sieve was a multi-pore ZSM-5 molecular sieve (Qilu division, china petrochemical catalyst Co., ltd., relative crystallinity 88.6%, silica/alumina mole ratio 20.8, na 2 O content of 0.017 wt% and specific surface area of 373m 2 Per gram, a total pore volume of 0.256ml/g, a mesoporous volume of 0.119ml/g, an average pore diameter of 5.8nm, the same applies below). Samples of the catalytic cracking catalyst were prepared, numbered CFZY11-1 to 17-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Examples 11-2 to 17-2
Examples 11-2 to 17-2 correspond in sequence to examples 1-2 to 7-2, respectively, except that the HZSM-5 molecular sieve was replaced with a multi-stage pore ZSM-5 molecular sieve. Samples of the catalytic cracking catalyst were prepared, numbered CFZY11-2 to 17-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Comparative example 9 to comparative example 15
Comparative examples 9 to 15 correspond in sequence to comparative examples 1 to 7, respectively, except that the HZSM-5 molecular sieve was replaced with a multi-pore ZSM-5 molecular sieve. The catalytic cracking catalyst samples are prepared, and the numbers are DCFZY 9-15.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Table 12
TABLE 13
TABLE 14
TABLE 15
Table 16
TABLE 17
TABLE 18
Comparative example 16
Comparative example 16 illustrates the conventional process of the prior art and the resulting phosphorus-containing modified hierarchical pore ZSM-5 comparative sample. The same as in comparative example 8, except that the HZSM-5 molecular sieve was replaced with a multi-stage pore ZSM-5 molecular sieve.
A catalytic cracking catalyst comparative sample number DCFZY16 was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 19.
TABLE 19
Example 18-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. The catalytic cracking catalyst was prepared, numbered CFZY18-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 18-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. The catalytic cracking catalyst was prepared, numbered CFZY18-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 19-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. A catalytic cracking catalyst, number CFZY19-1, was prepared. The evaluation was conducted in the same manner as in example 5-1, and the results are shown in Table 20.
Example 19-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. The catalytic cracking catalyst was prepared, numbered CFZY19-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared, with the number CFZY20-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared, with the number CFZY20-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Table 20
Example 21-1
The same as in example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A catalyst sample, number CFZY21-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 21.
Example 21-2
The same as in example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. Catalyst samples were prepared, numbered CFZY21-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 21.
Comparative example 17
The same as in example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A comparative sample of catalyst, numbered DCFZY17, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 21.
Table 21
Project Blank test case Example 21-1 Example 21-2 Comparative example 17
Balance and weight of materialsAmount%
Liquefied gas 18.54 37.32 44.57 30.15
Ethylene yield 1.39 4.00 4.89 2.98
Propylene yield 8.05 18.34 20.38 13.15
Example 22-1
The same as in example 1-1 was found to be different in that the addition of pseudo-boehmite and alumina sol was increased instead of the phosphor-alumina inorganic Binder1. A sample of catalytic cracking aid was prepared, numbered CFZ22-1. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 22.
Example 22-2
The same as in example 11-1 was found to be different in that the addition of pseudo-boehmite and alumina sol was increased instead of the phosphor-alumina inorganic Binder1. A sample of catalytic cracking aid was prepared, numbered CFZ22-2. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 22.
Table 22
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (31)

1. A preparation method of a catalytic cracking catalyst is characterized by comprising the following steps: mixing and pulping the phosphorus modified MFI structure molecular sieve, the Y-type molecular sieve, the inorganic binder and the optional second clay, forming, and carrying out hydrothermal roasting treatment on the formed product under the external pressure and the external aqueous solution adding atmosphere environment to obtain a catalytic cracking catalyst; wherein the phosphorus modified MFI structure molecular sieve is obtained by carrying out contact treatment on the MFI structure molecular sieve with the temperature of 50-150 ℃ and an aqueous solution of a phosphorus-containing compound with the temperature of 50-150 ℃ by an impregnation method; the apparent pressure of the hydrothermal roasting treatment is 0.1-1.0 MPa and the water vapor content is 1-100%; the hydrothermal roasting treatment is carried out at 200-800 ℃.
2. The process according to claim 1, wherein the catalyst comprises, on a dry basis, 1 to 25% by weight of the Y-type molecular sieve, 5 to 50% by weight of the phosphorus-modified MFI structure molecular sieve, 1 to 60% by weight of the inorganic binder, and optionally 0 to 60% by weight of the second clay.
3. The method of claim 1, wherein the Y-type molecular sieve is selected from at least one of a PSRY molecular sieve, a rare earth-containing PSRY 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.
4. The production method according to claim 1 or 2, wherein the inorganic binder is at least one selected from the group consisting of pseudo-boehmite, alumina sol, silica alumina sol, water glass and phosphorus-aluminum inorganic binder.
5. The production method according to claim 1 or 2, wherein the inorganic binder contains a phosphorus-aluminum inorganic binder.
6. The production method according to claim 1 or 2, wherein the inorganic binder is a phosphorus-aluminum inorganic binder.
7. The preparation method according to claim 4, wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay.
8. The process according to claim 7, wherein the first clay-containing phosphorus-aluminum inorganic binder contains, on a dry basis, an aluminum-based compound 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio containing the first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.
9. The preparation method according to claim 1, wherein the second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomaceous earth.
10. The preparation method according to claim 1, wherein the inorganic binder comprises 3 to 39 wt% of an inorganic binder of phosphorus-aluminum and 1 to 30 wt% of at least one inorganic binder selected from the group consisting of pseudo-boehmite, alumina sol, silica-alumina sol and water glass on a dry basis, based on the total amount of the catalytic cracking catalyst.
11. The method of manufacturing according to claim 7, further comprising: the phosphorus aluminum inorganic binder containing the first clay is prepared by the following steps: pulping and dispersing an alumina source, the first clay and water into slurry with a solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide is prepared by using 15-40 parts by weight of Al 2 O 3 An alumina source in an amount of greater than 0 parts by weight and no more than 40 parts by weight, based on dry weight of the first clay; adding concentrated phosphoric acid to the slurry with stirring according to the weight ratio of P/Al=1-6, and reacting the obtained mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus in phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
12. The process according to claim 1, wherein the shaping is spray-drying granulation.
13. The process according to claim 1, wherein the atmosphere has an apparent pressure of 0.1 to 0.8MPa and contains 30 to 100% of water vapor.
14. The process according to claim 1, wherein the apparent pressure of the atmosphere is 0.3 to 0.6MPa.
15. The process according to claim 1, wherein the atmosphere contains 60 to 100% of water vapor.
16. The process according to claim 1, wherein the hydrothermal baking treatment is carried out at 300 to 500 ℃.
17. The process according to claim 1, wherein the phosphorus-containing compound is selected from the group consisting of organic phosphides and/or inorganic phosphides.
18. The process according to claim 17, wherein the organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphine bromide, triphenyl butyl phosphine bromide, triphenyl benzyl phosphine bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphoric, 1, 3-xylyl ditriethylphosphorus; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
19. The process according to claim 1, wherein Na is contained in the MFI-structured molecular sieve 2 O<0.1 wt%。
20. The process according to claim 1, wherein the phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve.
21. The process according to claim 20, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15 to 1000; the ratio of mesoporous volume to total pore volume of the multistage hole ZSM-5 molecular sieve is more than 10%, the average pore diameter is 2-20 nm, and the mol ratio of silicon oxide to aluminum oxide is 15-1000.
22. The process according to claim 21, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 20 to 200; the mole ratio of silicon oxide/aluminum oxide of the multistage hole ZSM-5 molecular sieve is 20-200.
23. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to the aluminum is 0.01 to 2.
24. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to aluminum is 0.1 to 1.5.
25. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to aluminum is 0.2 to 1.5.
26. The process according to claim 1, wherein the contacting is carried out for 0.5 to 40 hours with a water sieve weight ratio of 0.5 to 1.
27. The process according to claim 1, wherein the contacting is carried out at 70 to 130 ℃.
28. A catalytic cracking catalyst prepared by the method of any one of claims 1-27.
29. A method for catalytic cracking of hydrocarbon oils, the method comprising: contacting a hydrocarbon oil with the catalytic cracking catalyst of claim 28 under catalytic cracking conditions.
30. The method of claim 29, wherein the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, straight-run wax oil, light/heavy propane deoiling, coker wax oil and coal liquefied products.
31. A preparation system for the preparation method of the catalytic cracking catalyst in claim 1, which is characterized in that the system mainly comprises a phosphorus modification device, a raw material mixing device, a forming device and a pressurized hydrothermal roasting device of an MFI molecular sieve;
the phosphorus modification device of the MFI molecular sieve comprises phosphorus-containing compound solution introducing equipment;
the raw material mixing device receives raw materials for preparing a catalyst, wherein the raw materials comprise an impregnated and exchanged MFI molecular sieve obtained from a phosphorus modification device of the MFI molecular sieve, a phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder treatment device, a Y-type molecular sieve and optionally added clay;
the forming device is a spray drying forming device;
the pressurized hydrothermal roasting device is provided with a water inlet and a gas pressurizing interface, and the apparent pressure of the hydrothermal roasting device is 0.1-1.0 Mpa and contains 1-100% of water vapor.
CN202110030461.3A 2021-01-11 2021-01-11 Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve Active CN114762836B (en)

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CN202110030461.3A CN114762836B (en) 2021-01-11 2021-01-11 Preparation method and preparation system of catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve
EP22736632.5A EP4275789A1 (en) 2021-01-11 2022-01-11 Catalytic cracking agent containing phosphorus modified molecular sieve, and preparation method therefor, preparation system thereof and use thereof
CN202280009687.8A CN116917234A (en) 2021-01-11 2022-01-11 Catalytic cracking agent of phosphorus-containing modified molecular sieve, preparation method and preparation system thereof, and application of catalytic cracking agent
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