CN114762836A - Preparation method and preparation system of catalytic cracking catalyst containing phosphorus-modified MFI structure molecular sieve - Google Patents
Preparation method and preparation system of catalytic cracking catalyst containing phosphorus-modified MFI structure molecular sieve Download PDFInfo
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- CN114762836A CN114762836A CN202110030461.3A CN202110030461A CN114762836A CN 114762836 A CN114762836 A CN 114762836A CN 202110030461 A CN202110030461 A CN 202110030461A CN 114762836 A CN114762836 A CN 114762836A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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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Abstract
The invention provides a preparation method of a catalytic cracking catalyst, which is characterized by comprising the following steps: mixing, pulping and forming the phosphorus-modified MFI structure molecular sieve, the Y-type molecular sieve and the inorganic binder with the second clay which is optionally added, and carrying out hydrothermal roasting treatment on the formed product under the external pressure and the external water solution adding atmosphere environment; the phosphorus-modified MFI structure molecular sieve is obtained by carrying out contact treatment on an MFI structure molecular sieve with the temperature of 0-150 ℃ and a phosphorus-containing compound aqueous solution with the temperature of 0-150 ℃ by an impregnation method; the hydrothermal roasting treatment is carried out, wherein the apparent pressure is 0.01-1.0 Mpa, and the hydrothermal roasting treatment contains 1-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃. The invention optimizes and 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 yield of low-carbon olefin in the catalytic cracking reaction of petroleum hydrocarbon, and simultaneously has higher yield of liquefied gas.
Description
Technical Field
The invention relates to a preparation method and a preparation system of a catalytic cracking catalyst, and further relates to a short-process preparation method and a preparation system of a catalytic cracking catalyst containing a phosphorus-modified MFI molecular sieve.
Background
ZSM-5 molecular sieves with the MFI structure were a widely used zeolitic molecular sieve catalytic material developed in 1972 by Mobil corporation, USA. The molecular sieve has a three-dimensional crossed pore channel structure, wherein the pore channel along the axial direction a is a straight pore, the cross section dimension of the pore channel is 0.54 multiplied by 0.56nm and is approximately circular, and the pore channel along the axial direction b is a Z-shaped pore, the cross section dimension of the pore channel is 0.51 multiplied by 0.56nm and is oval. The pore opening is composed of ten-membered rings, and the size of the molecular sieve is between that of the small-pore zeolite and that of the large-pore zeolite, so that the molecular sieve has a unique shape-selective catalytic action. ZSM-5 has a unique pore channel structure, has the characteristics of good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like. The 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 shape selectivity of the molecule.
Since 1983, ZSM-5 molecular sieve was applied to catalytic cracking process as an octane number promoter for catalytic cracking, aiming at improving the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefin. US3758403 originally reported that ZSM-5 was used as an active component for increasing propylene yield to prepare an FCC catalyst together with REY, and US5997728 disclosed that ZSM-5 molecular sieve without any modification was used as an aid for increasing propylene yield, and their propylene yields were not high. Although the ZSM-5 molecular sieve has good shape-selective performance and isomerization performance, the defects are that the hydrothermal stability is poor, and the catalyst is easy to inactivate under severe high-temperature hydrothermal conditions, so that the catalytic performance is reduced.
In the 80 s of the 20 th century, Mobil company found that phosphorus can improve the hydrothermal stability of the ZSM-5 molecular sieve, and meanwhile, phosphorus can improve the yield of low-carbon olefin after modifying the ZSM-5 molecular sieve. Conventional additives typically contain ZSM-5 activated with phosphorus, which selectively converts primary cracking products (e.g., gasoline olefins) to C3 and C4 olefins. After being synthesized, the ZSM-5 molecular sieve is modified by introducing a proper amount of inorganic phosphorus compound, and can stabilize framework aluminum under severe hydrothermal conditions.
CN 106994364A discloses a method for modifying ZSM-5 molecular sieve by phosphorus, which comprises mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with ZSM-5 molecular sieve with high alkali metal ion content to obtain a mixture containing P and P2O5At least 0.1 wt% of the mixture, drying, calcining, ammonium exchange step and water washing step to reduce the alkali metal ion content to below 0.10 wt%, drying and hydrothermal aging at 400-1000 deg.C and 100% water vapor. 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 → ammonium exchange → drying → roasting to obtain the hierarchical pore ZSM-5 molecular sieve, then modifying the hierarchical pore ZSM-5 molecular sieve by using phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve. Wherein, P2O5The loading capacity is usually in the range of 1 to 7% by weight. However, phosphoric acid or ammonium phosphate can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, and only phosphate radical entering pores is interacted with framework aluminum in the hydrothermal treatment process to keep B acid centers and reduce the distribution of the phosphorus species.
Although the ZSM-5 molecular sieve is modified by adopting a proper amount of inorganic phosphide, the framework dealumination can be slowed down, the hydrothermal stability is improved, and phosphorus atoms can be combined with distorted four-coordination framework aluminum to generate weak B acid centers, so that the higher conversion rate of long paraffin cracking and the higher selectivity of light olefin are achieved, the excessive inorganic phosphide is used for modifying the ZSM-5 molecular sieve, so that the pore channels of the molecular sieve can be blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, in the prior art, phosphoric acid or ammonium phosphate salts can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, phosphorus is insufficiently coordinated with framework aluminum, the utilization efficiency of phosphorus is low, and phosphorus modification does not always obtain a satisfactory hydrothermal stability improvement result. 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 in the prior art, the preparation process of the catalytic cracking catalyst is shown in fig. 1, and the finished catalytic cracking catalyst is obtained by dipping the MFI molecular sieve in a phosphorus-containing solution, drying (flash drying), primary roasting, mixing and molding (spraying) raw materials (including Y-type molecular sieve, inorganic binder and the like) and secondary roasting. In order to improve the hydrothermal stability of the phosphorus exchange modified MFI molecular sieve, the prior art needs to carry out twice roasting processes, the preparation cost is high, and the flow is complex.
Disclosure of Invention
One of the purposes of the present invention is to provide a preparation method of a cracking catalyst with a simplified process, which aims at solving the problems of complex phosphorus modification process and complex preparation process of the cracking catalyst in the catalytic cracking catalyst in the prior art, wherein the phosphorus modification process is performed on the phosphorus-modified MFI molecular sieve in order to improve the hydrothermal stability of the phosphorus-modified MFI molecular sieve.
Another object of the present invention is to provide a production system for the production method of the simplified flow.
In order to achieve one of the above objects, the present invention provides a method for preparing a catalytic cracking catalyst, comprising: mixing, pulping and forming the phosphorus-modified MFI structure molecular sieve, the Y-type molecular sieve and the inorganic binder with the second clay which is optionally added, and carrying out hydrothermal roasting treatment on the formed product under the external pressure and the external water solution adding atmosphere environment; the phosphorus-modified MFI structure molecular sieve is obtained by carrying out immersion exchange on an MFI structure molecular sieve with the temperature of 0-150 ℃ and a phosphorus-containing compound aqueous solution with the temperature of 0-150 ℃; the hydrothermal roasting treatment is carried out, wherein the apparent pressure is 0.01-1.0 Mpa, and the hydrothermal roasting treatment contains 1-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃.
In the invention, the catalytic cracking catalyst preferably contains 1-25 wt% of Y-type molecular sieve, 5-50 wt% of phosphorus modified MFI structure molecular sieve, 1-60 wt% of inorganic binder and 0-60 wt% of optional 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 selected from at least one of pseudo-boehmite, alumina sol, silica-alumina sol, water glass and phosphor-aluminum inorganic binder; preferred binders contain a phosphor-aluminum inorganic binder, and more preferred binders are phosphor-aluminum inorganic binders. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a 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 the first clay takes Al as the basis of dry basis2O315-40% by weight calculated as P of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing the first clay is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60 wt%; the first clay comprises 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 organophosphates may be selected, for example, from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bistrietyl phosphonium; the inorganic phosphide may be selected from, for example, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, boron phosphate.
In the MFI molecular sieve, Na is contained2O<0.1 wt%. The phosphorus modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve. The microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, preferably 20-200. The multi-stage pore ZSM-5 molecular sieve has the advantages that the proportion of mesoporous volume to total pore volume is more than 10%, the average pore diameter is 2-20 nm, and the molar 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 a phosphorus-containing compound aqueous solution, 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 to 1.5. The weight ratio of the water sieve in the immersion exchange is 0.5-1; the higher impregnation exchange temperature is favorable for obtaining a better effect, namely, phosphorus species are better dispersed, phosphorus is easier to migrate into molecular sieve crystals and combine with framework aluminum in the subsequent pressure roasting process of the catalyst raw material mixture, the coordination degree of the phosphorus and the framework aluminum is further improved, and the hydrothermal stability of the molecular sieve is finally improved, so that the impregnation exchange is preferably carried out for 0.5-40 hours at a higher temperature, preferably 50-150 ℃, and more preferably 70-130 ℃.
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 application means applying a certain pressure to the formed product of the auxiliary raw material mixture from the outside in the hydrothermal roasting treatment process, and for example, the external pressure application may be performed by introducing an inert gas from the outside to maintain a certain back pressure. The amount of the externally added water is determined to satisfy the requirement that the atmosphere contains 1-100% of water vapor.
In the invention, based on the total amount of the catalytic cracking assistant, one specific embodiment of the composition of the binder comprises 3-39 wt% of the phosphorus-aluminum inorganic binder on a dry basis and 1-30 wt% of other inorganic binders on a dry basis, wherein the other inorganic binders comprise at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass.
In the present invention, preferably, the first clay-containing aluminophosphate inorganic binder is prepared by the following steps: pulping an alumina source, the first clay and water to disperse into slurry with 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 source is 15-40 parts by weight of Al2O3(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid into the slurry according to the weight ratio of P/Al to 1-6 under stirring, and reacting the mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the 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 molding is spray drying granulation molding to obtain microspheres with a diameter of 1-150um, which is well known to those skilled in the art and will not be described herein.
The invention also provides the 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: under the condition of catalytic cracking, the hydrocarbon oil is in contact reaction 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 residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, direct current wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction products.
Aiming at the preparation method of the invention, the invention further provides a preparation system of the catalytic cracking catalyst, which is characterized in that the system mainly comprises a phosphorus modification device of the MFI molecular sieve, a raw material mixing device, a forming device and a pressurized hydrothermal roasting device.
In the preparation system, the phosphorus modification device of the MFI molecular sieve is used for the impregnation exchange operation of a phosphorus compound solution and the MFI molecular sieve, and comprises phosphorus compound solution introduction equipment.
In the preparation system, the raw material mixing device receives raw materials for preparing the cracking catalyst, wherein the raw materials comprise the phosphorus-modified MFI molecular sieve which is obtained by a phosphorus modification device from the MFI molecular sieve and is subjected to impregnation exchange, a phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder treatment device, a Y-type molecular sieve and optionally added clay.
In the preparation system of the present invention, the forming device is not limited, but is preferably a spray drying forming device.
In the preparation system, the hydrothermal pressurized roasting device is provided with a water input port and a gas pressurization interface so as to meet the pressurized hydrothermal roasting condition of the formed product.
One embodiment of the preparation system of the present invention is shown in FIG. 2. As can be seen from fig. 2, in the phosphorus modification device 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-shaped molecular sieve and the binder with the optional second clay, and forming (for example, spray drying); and (3) carrying out hydrothermal roasting treatment on the formed product under the atmosphere environment of externally applying pressure and externally adding water.
The preparation method provided by the invention has the characteristic of short preparation process, 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 has higher liquefied gas yield.
Drawings
FIG. 1 is a flow diagram of a conventional catalyst preparation of the prior art.
FIG. 2 is a flow diagram of a catalyst preparation system provided by the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
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 micro-reaction device is adopted to evaluate the influence of the catalytic cracking catalyst on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon.
The prepared catalytic cracking catalyst sample is aged for 17 hours at 800 ℃ under 100 percent water vapor on a fixed bed aging device, and is evaluated on a micro-reaction device, wherein the raw material oil is VGO or naphtha under the conditions of reaction temperature of 620 ℃, regeneration temperature of 620 ℃ and agent-oil ratio of 3.2. Microreaction activity was measured using ASTM D5154-2010 standard method.
Some of the raw materials used in the examples had the following properties:
the pseudoboehmite is an industrial product produced by Shandong aluminum industry company, and has the solid content of 60 percent by weight. The aluminum sol is an industrial product, Al, produced by the Qilu division of the medium petrochemical catalyst2O3The content was 21.5% by weight. The silica sol is an industrial product, SiO, produced by Qilu division of medium petrochemical catalyst2The content was 28.9% by weight, Na2The O content is 8.9%. The kaolin is kaolin specially used for a catalytic cracking catalyst produced by Suzhou kaolin company, and has the solid content of 78 weight percent. The rectorite is produced by Hubei Zhongxiang Mingliu rectorite development Limited company and the content of the quartz sand<3.5 wt.% of Al2O339.0 wt.% of Na2The O content was 0.03% by weight and the solids content was 77% by weight. SB aluminum hydroxide powder, manufactured by Condex, Germany, Al2O3The content was 75% by weight. Gamma-alumina, manufactured by Condex, Germany, Al2O3The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, and is produced in Beijing chemical plant.
The PSRY molecular sieve is an industrial product produced by Chang Ling division company of medium petrochemical catalyst, Na2Content of O<1.5 wt.%, P2O5The content is 0.8 to 1.2 wt%, and the unit cell constant<2.456nm and crystallinity not less than 64%. The HRY-1 molecular sieve is an industrial product produced by Chang Ling division of medium petrochemical catalyst, La2O3The content is 11 to 13 wt%, and the unit cell constant<2.464nm and the crystallinity is more than or equal to 40 percent.
The phosphorus-aluminum inorganic Binder1 used in the examples was prepared as follows: 1.91 kg of pseudoboehmite (containing Al)2O31.19 kg), 0.56 kg kaolin (0.5 kg on a dry basis) and 3.27 kg decationized water, stirring and adding 5.37 kg concentrated phosphoric acid (85% by mass) into the slurry, wherein the adding speed of the phosphoric acid is 0.04 kg phosphoric acid/min/kg alumina source, heating to 70 ℃, and then reacting for 45 minutes at the temperature to obtain the phosphorus-aluminum inorganic binder. The material ratios are shown in table 1.
The phosphorus-aluminum inorganic binders Binder2, Binder3 and Binder4 are also prepared by the above method, and the differences are that the material proportions are different, and the material proportions are shown in Table 1.
TABLE 1
Examples 1-20 provide catalytic cracking catalysts of the present invention and comparative examples 1-16 illustrate comparative catalytic cracking catalysts. Among them, the MFI molecular sieves in examples 1-10 were microporous ZSM-5 molecular sieves, and the MFI molecular sieves in examples 11-20 were hierarchical porous ZSM-5 molecular sieves. Comparative example 8 is a comparative catalytic cracking catalyst of the prior art for preparing an MFI molecular sieve containing microporous ZSM-5, and comparative example 16 is a comparative catalytic cracking catalyst of the prior art for preparing an MFI molecular sieve containing hierarchical pore ZSM-5.
Examples 1 to 1
Dissolving 16.2g diammonium phosphate (analytically pure, the same below) in 60g deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g HZSM-5 molecular sieve (provided by Qilu division, petrochemical catalyst, Inc. in China, with a relative crystallinity of 91.1%, a silica/alumina molar ratio of 24.1, and Na2O content 0.039 wt% and specific surface area 353m2(iv)/g, total pore volume is 0.177ml/g, the same is shown below), the catalyst is modified by an impregnation method, the catalyst is impregnated for 2 hours at 20 ℃, then is mixed with Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite, decationized water and alumina sol are added for pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, hydrochloric acid is added for adjusting the pH value of the slurry to be 3.0, then the slurry is continuously pulped for 45 minutes, then a phosphoaluminate inorganic Binder Binder1 is added, after stirring for 30 minutes, the obtained slurry is spray-dried and formed to obtain microspheres, the microspheres are externally pressurized and added with water, and are treated for 0.5 hour in the atmosphere of 500 ℃, 0.5Mpa and 50 percent water vapor to obtain a catalytic cracking catalyst sample with the serial number of CFZY1-1, the mixture ratio is that the phosphorus is 40 percent modified ZSM-5 molecular sieve, 10 percent PSRY molecular sieve, 23 percent kaolin, 18 percent Binder1 and the pseudo-boehmite (prepared by Al2O3Calculated by Al) 5%, alumina sol (calculated by Al)2O3Calculated) is 4 percent.
The reaction performance evaluation of 100% of the balancing agent and the catalytic cracking catalyst CFZY1-1 prepared by blending the balancing agent in example 1-1 was performed by using a fixed bed micro-reactor to demonstrate the catalytic cracking reaction effect of the catalytic cracking catalyst provided by the present disclosure.
The catalyst CFZY1-1 was subjected to an aging treatment at 800 ℃ for 17 hours in a 100% steam atmosphere. Mixing the aged CFZY1-1 with industrial FCC equilibrium catalyst (industrial FCC equilibrium catalyst of DVR-3, light oil with micro-reverse activity of 63). The mixture of the balancing agent and the catalyst is loaded into a fixed bed micro-reactor, and the raw oil shown in Table 2 is subjected to catalytic cracking under the evaluation conditions of the reaction temperature of 620 ℃, the regeneration temperature of 620 ℃ and the catalyst-to-oil ratio of 3.2. The results of the reactions are given in table 3, which includes the blank test agent.
TABLE 2
| 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 |
Examples 1 to 2
The difference from example 1-1 is that the phosphorus-modified molecular sieve is prepared by mixing diammonium phosphate, HZSM-5 molecular sieve and water, beating into slurry, and heating to 100 deg.C for 2 h. A sample of catalytic cracking catalyst was prepared under the accession number CFZY 1-2. The evaluation was made 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 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 3.
TABLE 3
Example 2-1
The method is the same as the example 1-1, except that 16.2g of diammonium phosphate is dissolved in 120g of deionized water at 50 ℃, the mixture is stirred for 0.5 hour to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve is added, the modification is carried out by adopting an impregnation method, and the impregnation is carried out for 2 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 600 deg.C under 0.5Mpa in 30% steam atmosphere for 2 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 2-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 4.
Examples 2 to 2
The procedure of example 2-1 was repeated except that diammonium phosphate, HZSM-5 molecular sieve and water were mixed and slurried, and the temperature was raised to 70 ℃ and the slurry was maintained for 2 hours. A sample of catalytic cracking catalyst was prepared, code CFZY 2-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 4.
Comparative example 2
The same as in example 2-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 4.
TABLE 4
Example 3-1
The method is the same as the example 1-1, except that 10.4g of phosphoric acid is dissolved in 60g of deionized water at normal temperature, the mixture is stirred for 2 hours to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve is added, the solution is modified by an impregnation method, and the solution is impregnated for 4 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 400 deg.C and 0.3Mpa in 100% steam atmosphere for 2 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 3-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 5.
Example 3-2
The same as example 3-1, except that the aqueous solution of the phosphorus-containing compound at 80 ℃ was contacted with the HZSM-5 molecular sieve heated to 80 ℃ for 4 hours. A sample of catalytic cracking catalyst was prepared under the accession number CFZY 3-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 5.
Comparative example 3
The same as in example 3-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 3.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 5.
TABLE 5
Example 4-1
The method is the same as the example 1-1, except that 8.1g of diammonium phosphate is dissolved in 120g of deionized water at normal temperature, the mixture is stirred for 0.5 hour to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve is added, the mixture is modified by an impregnation method, and the impregnation is carried out for 2 hours at the temperature of 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 300 deg.C and 0.4Mpa in 100% steam atmosphere for 2 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 4-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 6.
Example 4 to 2
The procedure of example 4-1 was repeated, except that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water were mixed and slurried, and the temperature was raised to 90 ℃ and the mixture was held for 2 hours. A sample of catalytic cracking catalyst was prepared, code CFZY 4-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 6.
Comparative example 4
The same as in example 4-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 4.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 6.
TABLE 6
Example 5-1
The method is the same as example 1-1, except that 8.5g trimethyl phosphate is dissolved in 80g deionized water at 90 ℃, stirred for 1h to obtain a phosphorus-containing aqueous solution, 113g HZSM-5 molecular sieve is added, the solution is modified by an impregnation method, and the solution is impregnated for 8 hours at 20 ℃; externally applying pressure, adding water, and performing pressurized hydrothermal roasting treatment at 500 deg.C and 0.8Mpa in 80% steam atmosphere for 4 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 5-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 7.
Examples 5 and 2
The procedure of example 5-1 was repeated, except that trimethyl phosphate, HZSM-5 molecular sieve and water were mixed and slurried, and the temperature was raised to 120 ℃ and the mixture was held for 8 hours. A sample of catalytic cracking catalyst was prepared under the accession number CFZY 5-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 7.
Comparative example 5
The same as in example 5-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 5.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 7.
TABLE 7
Example 6-1
The method is the same as that of example 1-1, except that 11.6g of boron phosphate is dissolved in 100g of deionized water at 100 ℃, the mixture is stirred for 3 hours to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve is added, the modification is carried out by adopting an impregnation method, and the mixture is impregnated for 2 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 400 deg.C and 0.3Mpa in 100% steam atmosphere for 4 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 6-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 8.
Example 6-2
The procedure of example 6-1 was repeated except that the mixture of boron phosphate, HZSM-5 molecular sieve and water was slurried and the temperature was raised to 150 ℃ for 2 hours. A sample of catalytic cracking catalyst was prepared under the accession number CFZY 6-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 8.
Comparative example 6
The same as example 6-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 6.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 8.
TABLE 8
Example 7-1
The method is the same as the example 1-1, except that 14.2g of triphenylphosphine is dissolved in 80g of deionized water at 100 ℃, the mixture is stirred for 2 hours to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve is added, the solution is modified by adopting an impregnation method, and the solution is impregnated for 4 hours at 20 ℃; externally applying pressure, adding water, and performing pressurized hydrothermal roasting treatment at 600 deg.C under 1.0Mpa in 30% steam atmosphere for 2 hr. A sample of catalytic cracking catalyst was prepared, code CFZY 7-1.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 9.
Example 7-2
The procedure of example 7-1 was repeated, except that the mixture of boron phosphate, HZSM-5 molecular sieve and water was slurried and the temperature was raised to 150 ℃ for 2 hours. A sample of catalytic cracking catalyst was prepared under the accession number CFZY 7-2.
The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 9.
Comparative example 7
The same as in example 7-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of catalytic cracking catalyst was prepared, code DCFZY 7.
The evaluation was made 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 current industry conventional process and the resulting phosphorus-containing modified ZSM-5 comparative sample.
The method is the same as the example 1-2, except that 16.2g diammonium hydrogen phosphate is dissolved in 60g deionized water, the mixture is stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g HZSM-5 molecular sieve is added, the mixture is modified by an impregnation method, the mixture is immersed for 2h at 100 ℃ and then dried in an oven at 110 ℃, the roasting conditions are atmospheric pressure (apparent pressure 0Mpa) and air roasting in a muffle furnace at 550 ℃ to obtain a phosphorus-modified ZSM-5 molecular sieve sample, then decationized water and alumina sol are added to the mixture to pulp kaolin and pseudo-boehmite for 120 min to obtain a pulp with a solid content of 30 wt%, hydrochloric acid is added to adjust the pH value of the pulp to 3.0, the pulp is continuously pulped for 45 min, then a phosphoaluminate inorganic Binder Binder1 is added, the obtained pulp is sprayed and dried after stirring for 30 min to obtain microspheres, the microspheres are roasted for 1h at 500 ℃ to obtain a catalytic cracking catalyst comparison sample, numbered DCFZY 8. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 10.
Watch 10
Example 8-1
The difference from example 1-1 is that the phosphorus-aluminum inorganic Binder was replaced with Binder 2. The catalytic cracking catalyst is prepared with the code CFZY 8-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 11.
Example 8 to 2
The difference from example 1-2 is that the phosphorus-aluminum inorganic Binder is replaced by Binder 2. The catalytic cracking catalyst is prepared with the code CFZY 8-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-1
The difference from example 5-1 is that the phosphorus-aluminum inorganic Binder was replaced with Binder 3. A catalytic cracking catalyst was prepared, code CFZY 9-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-2
The difference from example 1-2 is that the phosphorus-aluminum inorganic Binder is replaced by Binder 3. The catalytic cracking catalyst is prepared with the code CFZY 9-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 11.
Example 10-1
The difference from example 1-1 is that the phosphorus-aluminum inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared with the code CFZY 10-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 11.
Example 10-2
The difference from example 1-2 is that the aluminophosphate inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared with the code CFZY 10-2. The evaluation was made 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 multi-stage pore ZSM-5 molecular sieves employed in the present invention.
Example 11-1 to example 17-1
Example 11-1 to example 17-1 correspond to example 1-1 to example 7-1, respectively, in order, except that the HZSM-5 molecular sieve is composed of a multi-pore ZSM-5 molecular sieve (chinese petrochemical)Supplied by Zillus, a catalyst having a relative crystallinity of 88.6%, a silica/alumina molar ratio of 20.8, Na2The O content is from 0.017 percent by weight, and the specific surface area is 373m2/g, total pore volume of 0.256ml/g, mesoporous volume of 0.119ml/g, average pore diameter of 5.8nm, the same applies below). Preparing a catalytic cracking catalyst sample, and numbering CFZY 11-1-17-1.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Example 11-2 to example 17-2
Example 11-2 to example 17-2 correspond in sequence to example 1-2 to example 7-2, respectively, except that the HZSM-5 molecular sieve is replaced by a hierarchical pore ZSM-5 molecular sieve. And preparing a catalytic cracking catalyst sample with the number of CFZY 11-2-17-2.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Comparative examples 9 to 15
Comparative examples 9 to 15 correspond in sequence to comparative examples 1 to 7, respectively, except that the HZSM-5 molecular sieve is replaced by a hierarchical pore ZSM-5 molecular sieve. And preparing a catalytic cracking catalyst sample with the number of 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
Watch 13
TABLE 14
Watch 15
TABLE 16
TABLE 17
Watch 18
Comparative example 16
Comparative example 16 illustrates the prior art process and the resulting phosphorus-containing modified hierarchical pore ZSM-5 comparative sample. The difference from comparative example 8 is that the HZSM-5 molecular sieve is replaced by a hierarchical pore ZSM-5 molecular sieve.
Comparative sample No. DCFZY16 was prepared as a catalytic cracking catalyst. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 19.
Watch 19
Example 18-1
The difference from example 11-1 is that the aluminophosphate inorganic Binder was replaced with Binder 2. A catalytic cracking catalyst was prepared, code CFZY 18-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 20.
Example 18-2
The difference from example 11-2 is that the aluminophosphate inorganic Binder was replaced with Binder 2. A catalytic cracking catalyst was prepared, code CFZY 18-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 20.
Example 19-1
The difference from example 11-1 is that the aluminophosphate inorganic Binder was replaced with Binder 3. A catalytic cracking catalyst was prepared, code CFZY 19-1. The evaluation was made in the same manner as in example 5-1, and the results are shown in Table 20.
Example 19-2
The difference from example 11-2 is that the aluminophosphate inorganic Binder was replaced with Binder 3. The catalytic cracking catalyst is prepared with the code CFZY 19-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-1
The difference from example 11-1 is that the aluminophosphate inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared with the code CFZY 20-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-2
The difference from example 11-2 is that the aluminophosphate inorganic Binder was replaced with Binder 4. The catalytic cracking catalyst is prepared with the code CFZY 20-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 20.
Watch 20
Example 21-1
The same as example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A catalyst sample was prepared, code CFZY 21-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 21.
Example 21-2
The same as example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A catalyst sample was prepared, code CFZY 21-2. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 21.
Comparative example 17
The same as example 1-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A comparative catalyst sample was prepared, code DCFZY 17. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 21.
TABLE 21
| Item | Example of blank test | Example 21-1 | Example 21-2 | Comparative example 17 |
| Balance of materials, weight% | ||||
| Liquefied gas | 18.54 | 37.32 | 44.57 | 30.15 |
| Ethylene yield | 1.39 | 4.00 | 4.89 | 2.98 |
| Yield of propylene | 8.05 | 18.34 | 20.38 | 13.15 |
Example 22-1
The difference from example 1-1 is that the amount of pseudo-boehmite and alumina sol added is increased instead of the aluminophosphate inorganic Binder Binder 1. A sample of catalytic cracking aid was prepared, code CFZ 22-1. The evaluation was made in the same manner as in example 1-1, and the results are shown in Table 22.
Example 22-2
The difference from example 11-1 is that the amount of the pseudoboehmite and the alumina sol added was increased instead of the aluminophosphate inorganic Binder Binder 1. A sample of catalytic cracking aid was prepared, code CFZ 22-2. The evaluation was made 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, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (26)
1. A method for preparing a catalytic cracking catalyst, characterized in that the method comprises: mixing, pulping and forming the phosphorus-modified MFI structure molecular sieve, the Y-type molecular sieve and the inorganic binder with the second clay which is optionally added, and carrying out hydrothermal roasting treatment on the formed product under the external pressure and the external water solution adding atmosphere environment; the phosphorus-modified MFI structure molecular sieve is obtained by carrying out contact treatment on an MFI structure molecular sieve with the temperature of 0-150 ℃ and a phosphorus-containing compound aqueous solution with the temperature of 0-150 ℃ by an impregnation method; the hydrothermal roasting treatment is carried out, wherein the apparent pressure is 0.01-1.0 Mpa, and the hydrothermal roasting treatment contains 1-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃.
2. The process according to claim 1, wherein the catalyst for catalytic cracking comprises 1 to 25 wt% of the Y-type molecular sieve, 5 to 50 wt% of the phosphorus-modified MFI structure molecular sieve, 1 to 60 wt% of the inorganic binder, and optionally 0 to 60 wt% of the second clay, on a dry basis.
3. The method according to claim 1, wherein the Y-type molecular sieve is selected from 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.
4. The 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 phospho-alumina inorganic binders; preferably, the binder contains a phosphor-aluminum inorganic binder, and more preferably, a phosphor-aluminum inorganic binder.
5. The process according to claim 4, wherein the aluminophosphate inorganic binder is an aluminophosphate glue and/or a first clay-containing aluminophosphate inorganic binder.
6. The method of claim 5 wherein the first clay-containing aluminophosphate inorganic binder comprises Al on a dry basis2O315-40% by weight calculated as P of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing first clay is 1.0-6.0,pH of 1-3.5, solid content of 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth.
7. The 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.
8. The production method according to claim 1, wherein the inorganic binder comprises 3 to 39% by weight of a aluminophosphate inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from the group consisting of pseudoboehmite, alumina sol, silica-alumina sol and water glass on a dry basis, based on the total amount of the catalytic cracking catalyst.
9. The process according to claim 5, which further comprises: preparing the first clay-containing phosphorus-aluminum inorganic binder by adopting the following steps: pulping an alumina source, the first clay and water to disperse into slurry with 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 source is 15-40 parts by weight of Al2O3(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid into the slurry according to the weight ratio of P/Al to 1-6 under stirring, and reacting the mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
10. The process according to claim 1, wherein the molding is spray-drying granulation.
11. The method according to claim 1, wherein the atmosphere has an apparent pressure of 0.1 to 0.8MPa, preferably 0.3 to 0.6MPa, and contains 30 to 100% of water vapor, preferably 60 to 100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.
12. The process according to claim 1, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.
13. The process according to claim 12, wherein the organophosphate is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
14. The process according to claim 1, wherein in the MFI structure molecular sieve, Na is contained2O<0.1wt％。
15. The process of claim 1 wherein said phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve.
16. The catalytic cracking catalyst of claim 15, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15 to 1000, preferably 20 to 200; the multi-stage pore ZSM-5 molecular sieve has the advantages that the proportion of the mesopore volume to the total pore volume is more than 10%, the average pore diameter is 2-20 nm, and the molar ratio of silicon oxide to aluminum oxide is 15-1000, preferably 20-200.
17. The preparation method according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve is 0.01-2 in terms of phosphorus and aluminum; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5.
18. The method according to claim 1, wherein the contacting is carried out at 50 to 150 ℃, preferably 70 to 130 ℃ for 0.5 to 40 hours at a water-sieve weight ratio of 0.5 to 1.
19. A catalytic cracking catalyst prepared by the method of any one of claims 1 to 18.
20. A method for catalytic cracking of hydrocarbon oil, comprising: a hydrocarbon oil is brought into contact with the catalytic cracking catalyst according to claim 19 under catalytic cracking conditions.
21. The method of claim 20, 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 residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, direct current wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction products.
22. A preparation system of a catalytic cracking catalyst 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 hydrothermal roasting device.
23. The manufacturing system of claim 22 wherein the means for phosphorus modification of the MFI molecular sieve comprises a phosphorus compound solution introduction device.
24. The system of claim 22 wherein the feed mixing means receives feed for catalyst preparation including impregnated exchanged MFI molecular sieve from a phosphorus modification unit for the MFI molecular sieve, aluminophosphate inorganic binder from a aluminophosphate inorganic binder processing unit, Y-type molecular sieve, and optionally added clay.
25. The manufacturing system of claim 22, wherein said forming device is a spray drying forming device.
26. The system for preparing as claimed in claim 22, wherein the pressurized hydrothermal roasting apparatus is provided with a water inlet and a gas pressurizing port.
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| KR1020237027323A KR20230130708A (en) | 2021-01-11 | 2022-01-11 | Catalytic cracking agent comprising phosphorus-modified molecular sieve, manufacturing method thereof, manufacturing system and use thereof |
| US18/260,971 US20240059630A1 (en) | 2021-01-11 | 2022-01-11 | Catalytic cracking agent containing phosphorus-modified molecular sieve, preparation process thereof, preparation system and use thereof |
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