CN114425431B - Catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve - Google Patents

Catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve Download PDF

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CN114425431B
CN114425431B CN202011175729.4A CN202011175729A CN114425431B CN 114425431 B CN114425431 B CN 114425431B CN 202011175729 A CN202011175729 A CN 202011175729A CN 114425431 B CN114425431 B CN 114425431B
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phosphorus
molecular sieve
catalytic cracking
catalyst
mfi structure
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CN114425431A (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 US17/996,187 priority patent/US20230191380A1/en
Priority to JP2022562487A priority patent/JP2023523558A/en
Priority to TW110113300A priority patent/TW202138301A/en
Priority to PCT/CN2021/086824 priority patent/WO2021208885A1/en
Priority to EP21788715.7A priority patent/EP4137457A1/en
Priority to KR1020227039668A priority patent/KR20230002701A/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
    • 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
    • B01J35/647—
    • B01J35/695—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a catalytic cracking catalyst of a phosphorus-containing modified MFI structure molecular sieve, which comprises a Y-type molecular sieve and a phosphorus-modified MFI structure molecular sieve, wherein the K value of the phosphorus-modified MFI structure molecular sieve meets the following conditions: k is more than or equal to 70% and less than or equal to 90%, wherein K=P1/P2×100%, P1 represents phosphorus mass content in a region area of 100 square nanometers in any crystal plane vertical depth of 0-2 nm of the molecular sieve crystal grain measured by adopting an XPS method, and P2 represents phosphorus mass content in a region area of 100 square nanometers in a thickness interval of 5-10 nm in any crystal plane vertical depth of the molecular sieve crystal grain measured by adopting an EPMA method.

Description

Catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve
Technical Field
The invention relates to a catalytic cracking catalyst, in particular to a catalytic cracking catalyst containing an MFI structure 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 preparing ZSM-5 molecular sieve modified by phosphorus is disclosed, which features that the phosphorus-contained compound(s) chosen from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is (are) mixed with ZSM-5 molecular sieve with high content of alkali metal ions to obtain P-contained phosphorus 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 method can obtain the productThe phosphorus ZSM-5 molecular sieve 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.
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst based on a phosphorus-modified MFI structure molecular sieve with high dispersity of phosphorus species as one of active components.
In order to achieve the above object, the present invention provides a catalytic cracking catalyst of a phosphorus-containing modified MFI structure molecular sieve, which comprises 1 to 25 wt% of a Y-type molecular sieve, 5 to 50 wt% of a phosphorus-modified MFI structure molecular sieve, 1 to 60 wt% of an inorganic binder, and optionally 0 to 60 wt% of a second clay, based on the dry basis of the catalyst, wherein the phosphorus-modified MFI structure molecular sieve has a K value of: k is more than or equal to 70% and less than or equal to 90%, K=P1/P2×100%, wherein P1 represents phosphorus mass content in a region area of 100 square nanometers in any crystal plane vertical depth of a molecular sieve crystal grain measured by an XPS method within 0-2 nm, P2 represents phosphorus mass content in a region area of 100 square nanometers in a thickness interval of 5-10 nm in any crystal plane vertical depth of the molecular sieve crystal grain measured by an EPMA method, and the inorganic binder comprises a phosphorus-aluminum inorganic binder and/or other inorganic binders.
Preferably, said K value of said phosphorus-modified MFI structure molecular sieve satisfies: k is more than or equal to 75% and less than or equal to 90%, preferably, the K value satisfies the following conditions: k is more than or equal to 78% and less than or equal to 85%.
The phosphorus-modified MFI structure molecular sieve has the phosphorus content of P 2 O 5 The molar ratio of the alumina to the alumina is more than or equal to 0.01, the preferred molar ratio is more than or equal to 0.2, more preferably more than or equal to 0.3, and most preferably between 0.4 and 0.7.
Preferably, the phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a multistage pore ZSM-5 molecular sieve. The mole ratio of silicon oxide/aluminum oxide of the microporous ZSM-5 molecular sieve is 15-1000, preferably 20-200. 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.
Preferably, the Y-type molecular sieve comprises 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.
Preferably, the inorganic binder comprises a phosphorus aluminum inorganic binder. More preferably, the phosphorus aluminum inorganic binder is phosphorus aluminum glue and/or phosphorus aluminum inorganic binder containing first clay.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the steps of mixing and pulping a Y-type molecular sieve, a phosphorus-modified MFI structure molecular sieve, an inorganic binder and optionally added second clay, and performing spray drying to obtain the catalytic cracking catalyst, wherein the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with the temperature of 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃ and an MFI structure molecular sieve with the temperature of 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃ at the same temperature for at least 0.1 hour by using an impregnation method, drying and roasting the mixture at the temperature of 200-600 ℃ under an air or water vapor atmosphere for at least 0.1 hour; alternatively, the phosphorus-containing compound, MFI structure molecular sieve and water are mixed and slurried, then heated to 40 to 150 ℃, preferably 50 to 150 ℃, more preferably 70 to 130 ℃ for at least 0.1 hour, dried and then calcined at 200 to 600 ℃ in an air or steam atmosphere for at least 0.1 hour.
The phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphorus compound is selected from 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 and 1, 3-dimethylbenzene bis triethyl phosphorus; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
The mole ratio of the phosphorus-containing compound to the MFI structure molecular sieve to aluminum 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.
More preferably, the phosphorus-containing compound is a mixture of boron phosphate and one or more selected from trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, wherein the weight ratio of the boron phosphate in the mixture is 10-80%, and the preferred weight ratio of the boron phosphate is 20-40%.
The weight ratio of the contact and the water screen is 0.5-1; the roasting is carried out at the temperature of 450-550 ℃ and in an air atmosphere.
The said adhesiveThe binder is a phosphor-aluminum inorganic binder. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay; the first clay-containing phosphorus-aluminum inorganic binder contains, based on the dry weight of the first clay-containing phosphorus-aluminum inorganic binder, al 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of a phosphorus component and not more than 0 and not more than 40 wt% of a first clay on a dry basis, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio 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 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 preparation method, the binder comprises 3-39 wt% of the phosphorus-aluminum inorganic binder based on the catalytic cracking catalyst and 1-30 wt% of other inorganic binders based on the dry basis, wherein the other inorganic binders comprise at least one of pseudo-boehmite, aluminum sol, silicon-aluminum sol and water glass.
The preparation method also comprises the following steps: carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting is 300-650 ℃ and the roasting time is 0.5-8 h; the temperature of the drying treatment is 100-200 ℃, and the drying time is 0.5-24 h.
The preparation method can further comprise the following steps of preparing the phosphorus-aluminum inorganic binder containing the first clay: 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 not based on dry weight of the first clayMore than 40 parts by weight; 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.
The invention provides a catalytic cracking catalyst which is in contact reaction with hydrocarbon oil under the catalytic cracking condition. 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 catalytic cracking catalyst provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in petroleum hydrocarbon catalytic cracking reaction, and simultaneously has higher liquefied gas yield.
Detailed Description
The invention provides a catalytic cracking catalyst of a phosphorus-containing modified MFI structure molecular sieve, which comprises 1-25 wt% of a Y-type molecular sieve, 5-50 wt% of a phosphorus-modified MFI structure molecular sieve, 1-60 wt% of an inorganic binder and optionally 0-60 wt% of second clay, wherein the dry basis of the catalyst is taken as a reference, and the K value of the phosphorus-modified MFI structure molecular sieve is as follows: k is more than or equal to 70% and less than or equal to 90%, K=P1/P2×100%, wherein P1 represents phosphorus mass content in a region area of 100 square nanometers in any crystal plane vertical depth of a molecular sieve crystal grain measured by an XPS method within 0-2 nm, P2 represents phosphorus mass content in a region area of 100 square nanometers in a thickness interval of 5-10 nm in any crystal plane vertical depth of the molecular sieve crystal grain measured by an EPMA method, and the inorganic binder comprises a phosphorus-aluminum inorganic binder and/or other inorganic binders.
The catalytic cracking catalyst of the invention, wherein the Y-type molecular sieve comprises at least one of PSRY molecular sieve, PSRY molecular sieve containing rare earth, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve and HY molecular sieve.
The K value in the phosphorus modified MFI structure molecular sieve of the catalytic cracking catalyst disclosed by the invention is as follows: k is more than or equal to 75% and less than or equal to 90%, preferably, the K value satisfies the following conditions: k is more than or equal to 78% and less than or equal to 85%.
The phosphorus-modified MFI structure molecular sieve has the phosphorus content of P 2 O 5 The molar ratio of the alumina to the alumina is more than or equal to 0.01, the preferred molar ratio is more than or equal to 0.2, more preferably more than or equal to 0.3, and most preferably between 0.4 and 0.7.
Preferably, the phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a multistage pore ZSM-5 molecular sieve. The mole ratio of silicon oxide/aluminum oxide of the microporous ZSM-5 molecular sieve is 15-1000, preferably 20-200. 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.
Preferably, in the catalytic cracking catalyst of the present invention, the catalytic cracking catalyst may contain 1 to 40% by weight of an inorganic binder and 0 to 50% by weight of a second clay in addition to 2 to 20% by weight of a Y-type molecular sieve, 10 to 40% by weight, preferably 20 to 40% by weight of a phosphorus-modified MFI structure molecular sieve, based on the dry basis of the catalytic cracking catalyst. More preferably, the catalyst comprises 3 to 40 wt.% of an inorganic binder of phosphorus-aluminum or comprises 3 to 40 wt.% of an inorganic binder of phosphorus-aluminum and 1 to 30 wt.% of other inorganic binders, based on the dry basis of the catalyst.
The phosphorus aluminum inorganic binder is phosphorus aluminum glue and/or phosphorus aluminum inorganic binder containing first clay. The first clay-containing phosphorus-aluminum inorganic binder contains, based on the dry basis, a mixture of Al and 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of phosphorus component and not more than 0 and not more than 40 wt% of first clay on a dry basis, 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.
In one specific embodiment of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder can comprise, based on the dry weight of the phosphorus-aluminum inorganic binder, an alloy of the following components 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of a phosphorus component and 0-40 wt% of a first clay based on dry weight, and having a P/Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solids content of 15-60 wt%; for example, containing Al 2 O 3 15-35 wt% of aluminum component, P 2 O 5 50 to 75 wt% of the phosphorus component and 8 to 35 wt% of the first clay, and the P/Al weight ratio thereof is preferably 1.2 to 6.0, more preferably 2.0 to 5.0, and the pH is preferably 2.0 to 3.0.
In another specific embodiment of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder comprises, based on the dry weight of the phosphorus-aluminum inorganic binder, al 2 O 3 20-40 wt.% of an aluminium component and P 2 O 5 60 to 80% by weight of a phosphorus component.
The other inorganic binder may be selected from one or more of inorganic oxide binders conventionally used for catalytic cracking catalysts or catalyst binder components other than the phosphoalumina gel and phosphoalumina inorganic binder, preferably from at least one of pseudo-boehmite, alumina sol, silica alumina sol and water glass, more preferably from at least one of pseudo-boehmite and alumina sol.
The catalytic cracking catalyst of the present invention further comprises 0 to 65 wt%, preferably 5 to 55 wt%, of a second clay on a dry basis. The second clay is also well known to those skilled in the art, and is, for example, at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the steps of mixing and pulping a Y-type molecular sieve, a phosphorus-modified MFI structure molecular sieve, an inorganic binder and optionally added second clay, and performing spray drying to obtain the catalytic cracking catalyst, wherein the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with the temperature of 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃ and an MFI structure molecular sieve with the temperature of 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃ at the same temperature for at least 0.1 hour by using an impregnation method, drying and roasting the mixture in an air or steam atmosphere at 200-600 ℃ for at least 0.1 hour; alternatively, the phosphorus-containing compound, MFI structure molecular sieve and water are mixed and slurried, then heated to 40 to 150 ℃, preferably 50 to 150 ℃, more preferably 70 to 130 ℃ for at least 0.1 hour, dried and then calcined at 200 to 600 ℃ in an air or steam atmosphere for at least 0.1 hour.
In the preparation of the phosphorus modified MFI structure molecular sieve, the MFI structure molecular sieve can be a hydrogen type microporous ZSM-5 molecular sieve or a hydrogen type hierarchical pore ZSM-5 molecular sieve. They are reduced in sodium to Na by ammonium exchange 2 O<The silicon-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide) obtained after 0.1wt% is more than or equal to 10, and is usually 10 to 200.
In the preparation of the phosphorus-modified MFI structure molecular sieve, the phosphorus-containing compound is calculated by phosphorus, the hydrogen ZSM-5 molecular sieve or the hydrogen multi-level pore ZSM-5 molecular sieve is calculated by aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen multi-level pore ZSM-5 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 phosphorus-containing compound is selected from organic phosphorus such as trimethyl phosphate, triphenyl phosphorus, 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, dibenzyldiethyl phosphorus, 1, 3-dimethylbenzene bis-triethyl phosphorus and the like, and inorganic phosphorus such as phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, boron phosphate or a mixture thereof and the like. The inventors have found that when boron phosphate is used as one of the phosphorus-containing compounds and a hydrothermal calcination is carried out at 300-500 ℃, phosphorus has a better dispersivity in the molecular sieve, and therefore, a preferred combination of phosphorus-containing compounds is a mixture of boron phosphate with a compound selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate. The weight ratio of the boron phosphate in the mixture containing the boron phosphate is 10-80%, preferably 20-40%, more preferably 25-35%.
In the preparation of the phosphorus-modified MFI structure molecular sieve, the contacting is to contact an aqueous solution of a phosphorus-containing compound at a temperature of 0-150 ℃ with a hydrogen-type MFI structure molecular sieve at a temperature of 0-150 ℃ for at least 0.1 hour by an impregnation method. For example, the contact may be performed at a normal temperature range of 0 to 30 ℃, preferably at a higher temperature range of 40 ℃ or higher, for example, 50 to 150 ℃, more preferably 70 to 130 ℃, and a better effect is obtained in that the phosphorus species are better dispersed, the phosphorus migrates more easily into the hydrogen form MFI structure molecular sieve to be bonded with framework aluminum, the degree of coordination of phosphorus and framework aluminum is further improved, and finally the improvement of the hydrothermal stability of the molecular sieve is contributed. The substantially same temperature means that the temperature difference between the aqueous solution of the phosphorus-containing compound and the temperature of each of the hydrogen-type MFI structure molecular sieves is + -5 deg.c. For example, the aqueous solution of the phosphorus-containing compound is at a temperature of 80℃and the HZSM-5 molecular sieve is heated to 75 to 85 ℃.
In the preparation of the phosphorus-modified MFI structure molecular sieve, the contacting may be performed by mixing a phosphorus-containing compound, a hydrogen-type MFI structure molecular sieve, and water, and then maintaining the mixture at 0 to 150 ℃ for at least 0.1 hour. For example, the mixing is followed by maintaining the mixture at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, in order to obtain a better effect, i.e., better dispersion of phosphorus species, more easy migration of phosphorus into the molecular sieve crystal to bond with framework aluminum, further improving the coordination degree of phosphorus and framework aluminum, and finally improving the hydrothermal stability of the molecular sieve, the phosphorus-containing compound, the hydrogen-type MFI structure molecular sieve and water are maintained at a higher temperature range of 40 ℃ or higher for 0.1 hour, for example, a temperature range of 50 to 150 ℃ and more preferably a temperature range of 70 to 130 ℃.
In the preparation of the phosphorus modified MFI structure molecular sieve, the weight ratio of the water sieve is 0.5-1, and the time is 0.5-40 hours. The calcination is preferably carried out at 450 to 550 ℃ in an air atmosphere. .
The preparation method provided by the invention can also comprise the following steps: washing and optionally drying the product obtained by the roasting treatment to obtain the catalytic cracking catalyst; wherein the calcination temperature of the calcination may be 300 to 650 ℃, for example 400 to 600 ℃, preferably 450 to 550 ℃, and the calcination time may be 0.5 to 12 hours; the washing can be performed by adopting one of ammonium sulfate, ammonium nitrate and ammonium chloride, and the washing temperature can be 40-80 ℃; the temperature of the drying treatment may be 110 to 200 ℃, for example 120 to 150 ℃, and the drying time may be 0.5 to 18 hours, for example 2 to 12 hours.
In one embodiment of the preparation method provided by the invention, an inorganic binder (such as pseudo-boehmite, alumina sol, silica-alumina gel or a mixture of two or more of them) can be mixed with a second clay (such as kaolin clay) and water (such as deionized water and/or deionized water) to prepare a slurry with a solid content of 10-50 wt%, the slurry is stirred uniformly, the pH of the slurry is adjusted to 1-4 by using an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, the pH is maintained, the mixture is left to stand and age at 20-80 ℃ for 0-2 hours, for example, 0.3-2 hours, then the alumina sol and/or silica sol are added, stirring is carried out for 0.5-1.5 hours to form a colloid, then a molecular sieve is added, the molecular sieve comprises the phosphorus-modified ZSM-5 molecular sieve and Y-type molecular sieve, the solid content of the catalyst slurry is for example, the solid content of 20-45 wt% and the catalyst slurry is continuously stirred and then spray-dried to prepare the microsphere catalyst. The microspheroidal catalyst is then calcined, for example at 350 to 650 ℃ or 400 to 600 ℃, preferably 450 to 550 ℃ for 0.5 to 6 hours or 0.5 to 2 hours, washed with ammonium sulphate (wherein the washing temperature may be 40 to 70 ℃, ammonium sulphate: microspheroidal catalyst: water=0.2 to 0.8:1:5 to 15 weight ratio) until the sodium oxide content is less than 0.25 weight%, washed with water and filtered, and then dried.
In another embodiment of the preparation method provided by the invention, the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve, the phosphorus aluminum inorganic binder and other inorganic binders can be mixed, and the second clay is added or not added, pulped and spray-dried.
The inorganic binder comprises the phosphorus aluminum inorganic binder and the other inorganic binders, and the weight ratio of the phosphorus aluminum inorganic binder to the other inorganic binders can be (3-40): (1-30), preferably (5-35): (5-28), more preferably (10-30): (5-25); wherein the phosphorus-aluminum inorganic binder can be phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay; the other inorganic binder may include at least one of pseudo-boehmite, an alumina sol, a silica alumina sol, and water glass.
According to the preparation method of the catalytic cracking catalyst, the phosphorus-containing modified ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders can be mixed and pulped, the feeding sequence is not particularly required, for example, the phosphorus-aluminum inorganic binder, other inorganic binders, the molecular sieve and the second clay can be mixed (when the second clay is not contained, the relevant feeding steps can be omitted), and preferably, the second clay, the molecular sieve and the other inorganic binders are mixed and pulped before the phosphorus-aluminum inorganic binder is added, so that the activity and the selectivity of the catalyst are improved.
The preparation method of the catalytic cracking catalyst further comprises the step of spray drying the slurry obtained by pulping. Methods of spray drying are well known to those skilled in the art and are not particularly required by the present disclosure.
Further, the method of the present invention may further comprise preparing the first clay-containing phosphorus aluminum inorganic binder by: 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. The alumina source may be selected from the group consisting of rho-alumina, x-alumina, eta-alumina, gamma-alumina, kappa-alumina, sigma-alumina, theta-alumina,At least one of gibbsite, surge, nodiaspore, diaspore, boehmite, and pseudo-boehmite, the aluminum component of the first clay-containing aluminophosphate inorganic binder being derived from the alumina source. The first clay may be one or more of high bauxite, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth, preferably rectorite. The concentrated phosphoric acid may be present in a concentration of 60 to 98 wt.%, more preferably 75 to 90 wt.%. The phosphoric acid is preferably fed at a rate of 0.01 to 0.10kg phosphoric acid/min/kg alumina source, more preferably 0.03 to 0.07kg phosphoric acid/min/kg alumina source.
In the embodiment, the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer between materials in the preparation process due to the introduction of the clay, avoids the binder solid state caused by heat release superstable of uneven local instantaneous violent reaction of the materials, and has the binding performance equivalent to that of the phosphorus-aluminum binder prepared by a method without introducing clay; in addition, the clay, especially the rectorite with layered structure, is introduced to improve the heavy oil converting capacity of the catalyst, so that the obtained catalyst has better selectivity.
The invention also provides a catalytic cracking catalyst obtained by adopting the preparation method.
The invention further provides application of the catalytic cracking catalyst, namely a method for catalytic cracking of hydrocarbon oil, which comprises the following steps: and (3) under the catalytic cracking condition, the hydrocarbon oil is contacted and reacted with the catalytic cracking catalyst. 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 hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium and sulfur and nitrogen impurities, for example, the sulfur content in the hydrocarbon oil may be up to 3.0 wt%, the nitrogen content may be up to 2.0 wt%, and the vanadium and nickel metal impurities may be up to 3000ppm.
In one embodiment for use in a catalytic cracking process, the catalytic cracking catalyst may be added separately to the catalytic cracking reactor, for example, by contacting hydrocarbon oil with the catalytic cracking catalyst of the present invention under catalytic cracking conditions; in another embodiment for use in a catalytic cracking process, the catalyst may be used in combination with a catalytic cracking catalyst, for example, hydrocarbon oils may be reacted in contact with a catalytic mixture comprising the catalytic cracking catalyst of the present invention and other catalytic cracking catalysts. The catalyst provided by the present invention may comprise not more than 30% by weight, preferably 1 to 25% by weight, more preferably 3 to 15% by weight of the total amount of the above-mentioned mixture.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The quantitative analysis of phosphorus content is carried out by adopting an EPMA/SEM combined method to carry out the correspondence of chemical components of a micro-area and a depth structure, the dispersity K value refers to the percentage of phosphorus content on the surface of a molecular sieve grain and the phosphorus mass content on the depth interface of the molecular sieve grain, wherein K=P1 (XPS)/P2 (EPMA)%, P1 (XPS) represents the phosphorus mass content of any crystal face depth of the molecular sieve grain which is quantitatively measured by adopting the XPS method and is smaller than 2nm micro-area, P2 (EPMA) represents the phosphorus content of the depth interface micro-area which is quantitatively measured by adopting the EPMA method and is cut by utilizing a Focused Ion Beam (FIB) to obtain the thickness of 5-10 m, and instruments and reagents adopted in the embodiment of the invention are all instruments and reagents commonly used by a person in the field 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.
The RIPP standard method of the invention can be seen in petrochemical analysis method, yang Cuiding et al, 1990 edition.
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 wt%; 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 8.9%; the kaolin is special for the catalytic cracking catalyst produced by Suzhou kaolin company, and has the solid content of 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 is 75 wt%; 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.
Examples 1-13 illustrate the preparation and use of phosphorus modified, hierarchical pore ZSM-5 molecular sieves in the catalytic cracking catalysts of the invention.
Example 1-1
Taking 18.5g of diammonium hydrogen phosphate and 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve (provided by Qilu division of China petrochemical catalyst company, with relative crystallinity of 88.6%, silica/alumina molar ratio of 20.8, na) 2 O content of 0.017 wt% and specific surface area of 373m 2 Per gram, total pore volume of 0.256ml/g, mesoporous volume of 0.119ml/g, average pore diameter of 5.8nm, the same applies below) and 60g deionized water, heating to 100deg.C and maintaining After 2 hours, the mixture was dried in an oven at 110℃and air-calcined at 550℃for 2 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ1-1.
Comparative examples 1 to 1
The procedure of example 1-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D1-1.
Examples 1 to 2
The procedure of example 1-1 was repeated except that the sample was dried and then treated at 450℃under a 60% steam atmosphere for 0.5 hours to obtain a phosphorus-containing, multistage pore ZSM-5 molecular sieve sample designated as GPZ1-2.
Comparative examples 1 to 2
The same procedure as in examples 1-2 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D1-2.
The phosphorus dispersions K of GPZ-1, D1-1, GPZ1-2 and D1-2 are shown in Table 1.
TABLE 1
Figure BDA0002748632620000131
Example 2-1
18.5g of diammonium hydrogen phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 70 ℃ for 2 hours, dried in an oven at 110 ℃, and then air roasted at 550 ℃ for 2 hours, and the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ2-1.
Comparative example 2-1
The procedure of example 2-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D2-1.
Example 2-2
The procedure of example 2-1 was repeated except that the sample was dried and then treated at 600℃under 50% steam atmosphere for 2 hours to obtain a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve sample designated as GPZ2-2.
Comparative examples 2 to 2
The procedure is as in example 2-2 except that a hydrogen-type hierarchical pore ZSM-5 molecular sieve, designated D2-2, is impregnated with an aqueous solution containing phosphorus at 20℃using an impregnation method.
The phosphorus dispersions K for GPZ2-1, D2-1, GPZ2-2 and D2-2 are shown in Table 2.
TABLE 2
Figure BDA0002748632620000141
Example 3-1
Example 3-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and method of the invention.
Dissolving 11.8g of phosphoric acid in 60g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve; the aqueous solution containing phosphorus and the hydrogen type hierarchical pore ZSM-5 molecular sieve are heated to 80 ℃ respectively, then mixed and contacted for 4 hours, dried in an oven at 110 ℃, and then air roasted for 2 hours at 550 ℃, and the obtained phosphorus modified hierarchical pore ZSM-5 molecular sieve is named as GPZ3-1.
Comparative example 3-1
The procedure of example 3-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D3-1.
Example 3-2
The procedure of example 3-1 was repeated except that the sample was dried and then treated at 430℃under a 100% steam atmosphere for 2 hours to give a phosphorus-containing, hierarchical pore ZSM-5 molecular sieve sample designated as GPZ3-2.
Comparative example 3-2
The procedure is as in example 3-2 except that the hydrogen form of the hierarchical pore ZSM-5 molecular sieve is impregnated with an aqueous solution containing phosphorus at 20℃using an impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D3-2.
The phosphorus dispersions K of GPZ3-1, D3-1, GPZ3-2 and D3-2 are shown in Table 3.
TABLE 3 Table 3
Figure BDA0002748632620000151
Example 4-1
Example 4-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and method of the invention.
9.3g of diammonium hydrogen phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, then the slurry is kept at 90 ℃ for 2 hours, dried in an oven at 110 ℃, and then air roasted for 2 hours at 550 ℃, and the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve is named GPZ4-1.
Comparative example 4-1
The procedure of example 4-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D4-1.
Example 4-2
The procedure of example 4-1 was repeated except that the sample was dried and then treated at 350℃under a 100% steam atmosphere for 2 hours to give a phosphorus-containing, hierarchical pore ZSM-5 molecular sieve sample designated as GPZ4-2.
Comparative example 4-2
The procedure of example 4-2 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D4-2. The phosphorus dispersions K for GPZ4-1, D4-1, GPZ4-2 and D4-2 are shown in Table 4.
TABLE 4 Table 4
Figure BDA0002748632620000161
Example 5-1
9.7g of trimethyl phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 80g of deionized water are taken, mixed and beaten into slurry, then heated to 120 ℃ and kept for 8 hours, dried in an oven at 110 ℃, and then air roasted for 2 hours at 550 ℃, and the obtained phosphorus type hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ5-1.
Comparative example 5-1
The procedure of example 5-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D5-1.
Example 5-2
The procedure of example 5-1 was repeated except that the sample was calcined at 500℃under 40% steam for 4 hours after drying to give a phosphorus-containing, hierarchical pore ZSM-5 molecular sieve sample designated as GPZ5-2.
Comparative example 5-2
The procedure is as in example 5-2 except that the hydrogen form of the hierarchical pore ZSM-5 molecular sieve is impregnated with an aqueous solution containing phosphorus at 20℃using an impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D5-2.
The phosphorus dispersions K for GPZ5-1, D5-1, GPZ5-2 and D5-2 are shown in Table 5.
TABLE 5
Figure BDA0002748632620000171
Example 6-1
13.2g of boron phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 100g of deionized water are mixed and beaten into slurry, the slurry is kept at 150 ℃ for 2 hours, dried in an oven at 110 ℃, and then air roasted for 2 hours at 550 ℃, and the obtained phosphorus type hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ6-1.
Comparative example 6-1
The procedure of example 6-1 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D6-1.
Example 6-2
The procedure of example 6-1 was repeated except that the sample was subjected to hydrothermal calcination at 350℃under a 60% steam atmosphere for 4 hours after drying to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample designated as GPZ6-2.
Comparative example 6-2
The procedure of example 6-2 was followed except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D6-2. The phosphorus dispersions K for GPZ6-1, D6-1, GPZ6-2 and D6-2 are shown in Table 6.
TABLE 6
Figure BDA0002748632620000181
Example 7-1
Dissolving 16.3g of triphenylphosphine in 80g of deionized water, and stirring for 2h to obtain a phosphorus-containing aqueous solution; taking 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve; the above aqueous solution containing phosphorus and the above hydrogen type multi-stage pore ZSM-5 molecular sieve are heated to 80 ℃ respectively, then mixed and contacted for 4 hours, dried in an oven at 110 ℃, and then air roasted for 2 hours at 550 ℃, and the obtained sample of the multi-stage pore ZSM-5 molecular sieve containing phosphorus is named as GPZ7-1.
Comparative example 7-1
The procedure of example 7-1 was followed, except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D7-1.
Example 7-2
The procedure of example 7-1 was repeated except that the sample was dried and calcined at 600℃in a 50% steam atmosphere for 2 hours to give a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve sample designated as GPZ7-2.
Comparative example 7-2
The procedure of example 7-2 was followed, except that the hydrogen type hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃by the impregnation method. The obtained comparative sample of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is marked as D7-2.
The phosphorus dispersions K for GPZ7-1, D7-1, GPZ7-2 and D7-2 are shown in Table 7.
TABLE 7
Figure BDA0002748632620000191
Example 8-1
The same as in example 4-1, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 3:1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ8-1.
Example 8-2
The same as in example 4-2, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 3:1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ8-2.
Example 9-1
Same embodiment4-1The difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 2:2. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ9-1.
Example 9-2
Same embodiment4-2The difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 2:2. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ9-2.
Example 10-1
Same embodiment4-1, wherein the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 1:3. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ10-1.
Example 10-2
Same embodiment4-2, wherein the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 1:3. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ10-2.
The phosphorus dispersions K of GPZ8-1, GPZ8-2, GPZ9-1, GPZ9-2, GPZ10-1, GPZ10-2 are listed in Table 8-1.
TABLE 8
Figure BDA0002748632620000201
Example 11-1
Same embodiment8-1, differing in that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 3:1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sampleAnd is designated as GPZ11-2.
Example 11-2
Same embodiment8-2, differing in that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 3:1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ11-2.
Example 12-1
Same embodiment9--1, differing in that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 2:2. The resulting phosphorus-containing, multi-pore ZSM-5 molecular sieve sample was designated GPZ12-1.
Example 12-2
Same embodiment9-2, with the difference that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 2:2 equal to or near the ratio of example 9-1. The resulting phosphorus-containing, multi-pore ZSM-5 molecular sieve sample was designated GPZ12-2.
Example 13-1
Same embodiment10-1, differing in that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 1:3. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ13-2.
Example 13-2
Same embodiment 10-2, differing in that the phosphorus source is phosphoric acid and crystalline boron phosphate in a weight ratio of 1:3. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is named as GPZ13-2.
The phosphorus dispersions K for GPZ11-1, GPZ11-2, GPZ12-1, GPZ12-2, GPZ13-1, GPZ13-2 are listed in Table 9.
TABLE 9
Figure BDA0002748632620000211
As can be seen from the data in tables 1-1 through 9-1 above, the phosphorus-modified hierarchical pore ZSM-5 molecular sieves of the invention have higher dispersities for phosphorus, for example, the sample GPZ8-1 modified with a biphosphoric source of phosphoric acid and crystalline boron phosphate of example 8-1 achieves a dispersity K value of 85%.
Examples 14-26 illustrate phosphorus modified microporous ZSM-5 molecular sieves and methods of preparation employed in the catalytic cracking catalysts of the invention.
Example 14-1
16.2g of diammonium hydrogen phosphate and 113g of HZSM-5 molecular sieve (provided by Qilu division of China petrochemical catalyst company, with a relative crystallinity of 91.1%, a silica/alumina molar ratio of 24.1 and Na) 2 The O content is 0.039 wt% and the specific surface area is 353m 2 Per gram, total pore volume of 0.177ml/g, the same applies below) and 60g deionized water, heating to 100deg.C, maintaining for 2 hours, drying at 110deg.C, and treating at 550deg.C under air atmosphere for 0.5h. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ14-1.
Comparative example 14-1
Comparative example 14-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 14-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃for 2 hours by the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is designated as D14-1.
Example 14-2
The procedure of example 14-1 was repeated except that the air atmosphere at 550℃was changed to 500℃and the treatment was carried out in a 50% water vapor atmosphere for 0.5 hour. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ14-2. (high temperature impregnation, water baking)
Comparative example 14-2
The procedure of example 14-2 was followed, except that the hydrogen form of the hierarchical pore ZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃for 2 hours by the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D14-2.
The phosphorus dispersions K for GPZ14-1, D14-1, GPZ14-2 and D14-2 are shown in Table 14.
TABLE 14
Figure BDA0002748632620000221
Example 15-1
16.2g of diammonium phosphate, 113g of HZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 70 ℃ for 2 hours, and is dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and a phosphorus modified ZSM-5 molecular sieve sample is obtained and is marked as GPZ15-1.
Comparative example 15-1
Comparative example 15-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 15-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is denoted as D15-1.
Example 15-2
The procedure of example 15-1 was repeated except that the air atmosphere at 550℃was changed to 600℃and the treatment was carried out in a 30% water vapor atmosphere for 2 hours. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ15-2.
Comparative example 15-2
The procedure of example 15-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D15-2.
The phosphorus dispersions K for GPZ15-1, D15-1, GPZ15-2 and D15-2 are shown in Table 15.
TABLE 15
Figure BDA0002748632620000231
Example 16-1
Dissolving 10.4g of phosphoric acid in 60g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 113g of HZSM-5 molecular sieve; the above aqueous solution containing phosphorus and the above HZSM-5 molecular sieve are heated to 80 ℃ respectively, then mixed and contacted for 4 hours, dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and the obtained phosphorus modified ZSM-5 molecular sieve sample is named GPZ16-1.
Comparative example 16-1
Comparative example 16-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 16-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is designated as D16-1.
Example 16-2
Example 16-2 illustrates the microporous ZSM-5 molecular sieve containing phosphorus and method of the invention.
The procedure is as in example 16-1, except that the air atmosphere at 550℃is changed to 400℃and the treatment is carried out for 2 hours in a 100% water vapor atmosphere. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ16-2.
Comparative example 16-2
The procedure of example 16-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D16-2.
The phosphorus dispersions K for GPZ16-1, D16-1, GPZ16-2 and D15-2 are shown in Table 16.
Table 16
Figure BDA0002748632620000241
Example 17-1
8.1g of diammonium hydrogen phosphate, 113g of HZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 90 ℃ for 4 hours, and is dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and a phosphorus modified ZSM-5 molecular sieve sample is obtained and is marked as GPZ17-1.
Comparative example 17-1
Comparative example 17-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 17-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is designated as D17-1.
Example 17-2
The procedure of example 17-1 was repeated except that the air atmosphere at 550℃was changed to 300℃and the treatment was carried out in a 100% water vapor atmosphere for 2 hours. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ17-2.
Comparative example 17-2
The procedure of example 17-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated as D17-2.
The phosphorus dispersions K for GPZ17-1, D17-1, GPZ17-2 and D17-2 are shown in Table 17.
TABLE 17
Figure BDA0002748632620000251
Example 18-1
8.5g of trimethyl phosphate, 113g of HZSM-5 molecular sieve and 80g of deionized water are mixed and pulped, then the mixture is heated to 120 ℃ for 8 hours, the mixture is dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and the obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ18-1.
Comparative example 18-1
Comparative example 18-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 18-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is denoted as D18-1.
Example 18-2
The procedure was as in example 18-1, except that the air atmosphere at 550℃was changed to 500℃and the treatment was carried out in an 80% water vapor atmosphere for 4 hours. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ18-2.
Comparative example 18-2
The procedure of example 18-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D18-2.
The phosphorus dispersions K for GPZ18-1, D18-1, GPZ18-2 and D18-2 are shown in Table 18.
TABLE 18
Figure BDA0002748632620000261
Example 19-1
11.6g of boron phosphate, 113g of HZSM-5 molecular sieve and 100g of deionized water are mixed and beaten into slurry, the slurry is kept at 150 ℃ for 2 hours, dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and a phosphorus modified ZSM-5 molecular sieve sample is obtained and is marked as GPZ19-1.
Comparative example 19-1
Comparative example 19-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 19-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is designated as D19-1.
Example 19-2
The procedure of example 19-1 was repeated except that the air atmosphere at 550℃was changed to 400℃and the treatment was carried out in a 100% water vapor atmosphere for 4 hours. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ19-2.
Comparative example 19-2
The procedure of example 19-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D19-2.
The phosphorus dispersions K for GPZ19-1, D19-1, GPZ19-2 and D19-2 are shown in Table 19.
TABLE 19
Figure BDA0002748632620000262
Example 20-1
Dissolving 14.2g of triphenylphosphine in 80g of deionized water, and stirring for 2h to obtain a phosphorus-containing aqueous solution; taking 113g of HZSM-5 molecular sieve; the above aqueous solution containing phosphorus and the above HZSM-5 molecular sieve are heated to 80 ℃ respectively, then mixed and contacted for 4 hours, dried at 110 ℃ and treated for 2 hours in an air atmosphere at 550 ℃, and the obtained phosphorus modified ZSM-5 molecular sieve sample is named as GPZ20-1.
Comparative example 20-1
Comparative example 20-1 illustrates the conventional process of the prior art and the resulting phosphorus modified ZSM-5 comparative sample.
The procedure of example 20-1 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. The comparative sample of the obtained phosphorus-modified ZSM-5 molecular sieve is denoted as D20-1.
Example 20-2
The procedure is as in example 20-1, except that the air atmosphere at 550℃is changed to 600℃and the treatment is carried out for 4 hours in a 30% water vapor atmosphere. The resulting phosphorus-modified ZSM-5 molecular sieve sample was designated GPZ20-2.
Comparative example 20-2
The procedure of example 20-2 was followed except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20℃using the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and designated D20-2.
The phosphorus dispersions K for GPZ20-1, D20-1, GPZ20-2 and D20-2 are shown in Table 20.
Table 20
Figure BDA0002748632620000271
Example 21-1
The same as in example 17-1, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 3:1. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ21-1.
Example 21-2
The same as in example 17-2, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 3:1. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ21-2.
Example 22-1
Same embodiment17-1, with the difference that for example, the source of biphosphorus is diammonium phosphate and crystalline boron phosphate in a weight ratio of 2:2. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ22-1.
Example 22-2
The same as in example 17-2, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 2:2. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ23-2.
Example 23-1
The same as in example 17-1, except that the phosphorus source was diammonium phosphate and crystalline boron phosphate in a weight ratio of 1:3. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ23-1.
Example 23-2
Same embodiment17-2, wherein the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 1:3. The resulting phosphorus-containing ZSM-5 molecular sieve sample was designated GPZ23-2.
The phosphorus dispersions K of GPZ21-1, GPZ21-2, GPZ22-1, GPZ22-2, GPZ23-1, GPZ23-2 are set forth in Table 21.
Table 21
Figure BDA0002748632620000281
Examples 24-1 to 26-2
The phosphorus source in examples 21-1 to 23-2 was replaced with phosphoric acid and crystalline boron phosphate in the order of 3:1, 2:2, 1:3, and the phosphorus dispersity K of the obtained samples, GPZ24-1, GPZ24-2, GPZ25-1, GPZ25-2, GPZ26-1, and GPZ26-2, was shown in Table 22.
Table 22
Figure BDA0002748632620000291
Examples 27-30 illustrate the phosphorus aluminum inorganic binders employed in the catalytic cracking catalysts of the present invention.
Example 27
1.91 kg of pseudo-boehmite (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 23, sample number Binder1.
Examples 28 to 30
An inorganic Binder of phosphorus and aluminum was prepared as in example 27, the material ratios are shown in Table 23, and the sample numbers Binder2, binder3 and Binder4 were used.
Table 23
Figure BDA0002748632620000301
Examples 31-56 provide catalytic cracking catalysts of the present invention, and comparative examples 31-56 illustrate catalytic cracking comparative catalysts as a comparison. Wherein examples 31-43 contain phosphorus modified hierarchical pore ZSM-5 molecular sieves, and examples 44-56 contain phosphorus modified microporous ZSM-5 molecular sieves.
Example 31-1
Taking phosphorus modified molecular sieve GPZ1-1 prepared in example 1-1, Y type molecular sieve (PSRY molecular sieve) kaolin and pseudo-boehmite, adding deionized water and alumina sol, pulping for 120 minutes to obtain slurry with solid content of 30 wt%, adding hydrochloric acid to adjust pH value of the slurry to 3.0, then pulping for 45 minutes continuously, then adding phosphorus aluminum inorganic Binder1 prepared in example 27, stirring for 30 minutes, spray drying the obtained slurry to obtain microspheres, roasting the microspheres at 500 ℃ for 1 hour to obtain a catalytic cracking catalyst sample, wherein the mixture ratio is phosphorus modified ZSM-5 molecular sieve 40%, PSRY molecular sieve 10%, kaolin 18%, binder1 is 18%, pseudo-boehmite (with Al 2 O 3 5% by weight of aluminum sol (in terms of Al) 2 O 3 Calculated) 9%.
And (3) carrying out reaction performance evaluation on 100% of the balancing agent and the balancing agent doped with CAZY1-1 by adopting a fixed bed micro-reaction device so as to show the catalytic cracking reaction effect.
The catalyst CAZY1-1 was subjected to an aging treatment at 800℃under a 100% steam atmosphere for 17 hours. The aged CAZY1-1 was mixed with an industrial FCC equilibrium catalyst (industrial brand DVR-3 FCC equilibrium 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 table 24 is subjected to catalytic cracking under the evaluation condition that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the catalyst-oil ratio is 3.2. Table 25 shows the reaction results, including blank test reagents.
Table 24
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
Example 31-2
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in example 1-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY1-2.
The results of the evaluation in example 31-1 are shown in Table 25.
Comparative example 31-1
The same as in example 12-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D1-1 of comparative example 1-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY1-1.
The results of the evaluation in example 31-1 are shown in Table 25.
Comparative example 31-2
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D1-2 of comparative example 1-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY1-2.
The results of the evaluation in example 31-1 are shown in Table 25.
Table 25
Figure BDA0002748632620000321
Example 32-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ2-1 prepared in example 2-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY2-1.
The results of the evaluation in example 31-1 are shown in Table 26.
Example 32-2
The same as in example 32-1 except that the phosphorus-modified molecular sieve GPZ2-1 was replaced with the phosphorus-modified molecular sieve GPZ2-2 prepared in example 2-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY2-2.
The results of the evaluation in example 31-1 are shown in Table 26.
Comparative example 32-1
The same as in example 32-1 except that the phosphorus-modified molecular sieve GPZ2-1 was replaced with the comparative sample D2-1 of comparative example 2-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY2-1.
The results of the evaluation in example 31-1 are shown in Table 26.
Comparative example 32-2
The same as in example 32-1 except that the phosphorus-modified molecular sieve GPZ2-1 was replaced with the comparative sample D2-2 of comparative example 2-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY2-2.
The results of the evaluation in example 31-1 are shown in Table 26.
Table 26
Figure BDA0002748632620000331
Example 33-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ3-1 prepared in example 3-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY3-1.
The results of the evaluation in example 31-1 are shown in Table 27.
Example 33-2
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ3-2 prepared in example 3-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY3-2.
The results of the evaluation in example 31-1 are shown in Table 27.
Comparative example 33-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D3-1 of comparative example 3-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY3-1.
The results of the evaluation in example 31-1 are shown in Table 27.
Comparative example 33-2
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D3-2 of comparative example 3-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY3-2.
The results of the evaluation in example 31-1 are shown in Table 27.
Table 27
Figure BDA0002748632620000341
Example 34-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ4-1 prepared in example 4-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY4-1.
The results of the evaluation in example 31-1 are shown in Table 28.
Example 34-2
The same as in example 34-1 except that the phosphorus-modified molecular sieve GPZ4-1 was replaced with the phosphorus-modified molecular sieve GPZ4-2 prepared in example 4-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY4-2.
The results of the evaluation in example 31-1 are shown in Table 28.
Comparative example 34-1
The same as in example 34-1 except that the phosphorus-modified molecular sieve GPZ4-1 was replaced with the comparative sample D4-1 of comparative example 4-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY4-1.
The results of the evaluation in example 31-1 are shown in Table 28.
Comparative example 34-2
The same as in example 34-1 except that the phosphorus-modified molecular sieve therein was replaced with comparative sample D4-2 of comparative example 4-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY4-2.
The results of the evaluation in example 31-1 are shown in Table 28.
Table 28
Figure BDA0002748632620000351
Example 35-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ5-1 prepared in example 5-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY5-1.
The results of the evaluation in example 31-1 are shown in Table 29.
Example 35-2
The same as in example 35-1 except that the phosphorus-modified molecular sieve GPZ5-1 was replaced with the phosphorus-modified molecular sieve GPZ5-2 prepared in example 5-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY5-2.
The results of the evaluation in example 35-1 are shown in Table 29.
Comparative example 35-1
The same as in example 35-1 except that the phosphorus-modified molecular sieve GPZ5-1 was replaced with the comparative sample D5-1 of comparative example 5-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY5-1.
The results of the evaluation in example 35-1 are shown in Table 29.
Comparative example 35-2
The same as in example 35-1 except that the phosphorus-modified molecular sieve GPZ5-1 was replaced with the comparative sample D5-2 of comparative example 5-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY5-2.
The results of the evaluation in example 35-1 are shown in Table 29.
Table 29
Figure BDA0002748632620000361
Example 36-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ6-1 prepared in example 6-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY6-1.
The results of the evaluation in example 31-1 are shown in Table 30.
Example 36-2
The same as in example 36-1 except that the phosphorus-modified molecular sieve GPZ6-1 was replaced with the phosphorus-modified molecular sieve GPZ6-2 prepared in example 6-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY6-2.
The results of the evaluation in example 36-1 are shown in Table 30.
Comparative example 36-1
The same as in example 36-1 except that the phosphorus-modified molecular sieve GPZ6-1 was replaced with the comparative sample D6-1 of comparative example 6-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY6-1.
The results of the evaluation in example 36-1 are shown in Table 30.
Comparative example 36-2
The same as in example 36-1 except that the phosphorus-modified molecular sieve GPZ6-1 was replaced with the comparative sample D6-2 of comparative example 6-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY6-2.
The results of the evaluation in example 36-1 are shown in Table 30.
Table 30
Figure BDA0002748632620000371
Example 37-1
The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ7-1 prepared in example 7-1. A sample of the catalytic cracking catalyst was prepared, numbered CAZY7-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 31.
Example 37-2
The same as in example 37-1 except that the phosphorus-modified molecular sieve GPZ7-1 was replaced with the phosphorus-modified molecular sieve GPZ7-2 prepared in example 7-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY7-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 31.
Comparative example 37-1
The same as in example 37-1 except that the phosphorus-modified molecular sieve GPZ7-1 was replaced with the comparative sample D7-1 of comparative example 7-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY7-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 31.
Comparative example 37-2
The same as in example 37-1 except that the phosphorus-modified molecular sieve GPZ7-1 was replaced with the comparative sample D7-2 of comparative example 7-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY7-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 31.
Table 31
Figure BDA0002748632620000381
Examples 38 to 43
The same as in example 31-1 except that the phosphorus-modified molecular sieves GPZ1-1 were replaced with the phosphorus-modified molecular sieves GPZ8-1 to GPZ13-2 prepared in examples 8-1 to 13-2, respectively. The catalytic cracking catalyst samples are prepared and are numbered CAZY8-1 to CAZY13-2 in sequence.
The results of the evaluation in example 31-1 are shown in Table 32 and Table 33, respectively.
Table 32
Figure BDA0002748632620000391
Table 33
Figure BDA0002748632620000392
Examples 44 to 56
Examples 44-56 are catalysts CAZY 14-CAZY 26 sequentially containing microporous ZSM-5 (GPZ 14-GPZ 26), respectively, the material ratios correspond to examples 31-43, respectively, for example, in example 44-1, GPZ1-1 is replaced with GPZ14-1, in example 44-2, GPZ1-2 is replaced with GPZ14-2, and so on, until in example 56-1, GPZ14-1 is replaced with GPZ26-1, in example 56-2, GPZ14-2 is replaced with GPZ 26-2.
The results of the evaluation in example 31-1 are shown in tables 34 to 46, respectively.
Comparative examples 44 to 56
Comparative examples 44-56 are comparative catalysts DCAZY-14 to DCAZY-26 containing microporous ZSM-5 (D14-D26), respectively, in that order, the material ratios correspond to examples 44-50, respectively, for example, in comparative example 44-1, GPZ1-1 was replaced with D14-1, in comparative example 44-2, GPZ1-2 was replaced with D4-2, and so on, until GPZ14-1 in comparative example 50-1 was replaced with D26-1, and GPZ14-2 in comparative example 50-2 was replaced with D26-2.
The results of the evaluation in example 31-1 are shown in tables 34 to 46, respectively.
Watch 34
Figure BDA0002748632620000401
Table 35
Figure BDA0002748632620000402
Table 36
Figure BDA0002748632620000411
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Table 37
Figure BDA0002748632620000412
Table 38
Figure BDA0002748632620000413
Table 39
Figure BDA0002748632620000421
Table 40
Figure BDA0002748632620000422
Table 41
Figure BDA0002748632620000423
Table 42
Figure BDA0002748632620000431
Table 43
Figure BDA0002748632620000432
Table 44
Figure BDA0002748632620000433
Table 45
Figure BDA0002748632620000441
Watch 46
Figure BDA0002748632620000442
Examples 57 to 62
The same as in example 31-1 except that the phosphorus-modified molecular sieves GPZ1-1 were replaced with the phosphorus-modified molecular sieves GPZ21-1 to GPZ26-2 prepared in examples 21-1 to 26-2, respectively, in this order. The catalytic cracking catalyst samples are prepared and are numbered CAZY27-1 to CAZY32-2 in sequence.
The results of the evaluation in example 31-1 are shown in Table 47 and Table 48, respectively.
Table 47
Figure BDA0002748632620000451
Table 48
Figure BDA0002748632620000452
Example 63-1
The same as in example 31-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder2 prepared in example 28. The catalytic cracking catalyst is prepared, and the number is CAZY32-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Example 63-2
The same as in example 31-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder2 prepared in example 28. The catalytic cracking catalyst is prepared, and the number is CAZY32-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Example 64-1
The same as in example 31-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder3 prepared in example 29. The catalytic cracking catalyst was obtained, number CAZY33-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Example 64-2
The same as in example 31-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder3 prepared in example 29. The catalytic cracking catalyst was obtained, number CAZY33-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Example 65-1
The same as in example 31-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder4 prepared in example 30. The catalytic cracking catalyst was obtained, number CAZY34-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Example 65-2
The same as in example 31-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder4 prepared in example 30. The catalytic cracking catalyst was prepared, numbered CAZY34-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 49.
Table 49
Figure BDA0002748632620000461
Example 66-1
The same as in example 31-1 was found to differ in the phosphorus modified multi-pore ZSM-5 molecular sieve sample GPZ1-1 35 wt.%, PSRY10 wt.%, kaolin 18 wt.%, phosphorus aluminum inorganic Binder3 22 wt.%, pseudo-boehmite 10 wt.%, and alumina sol 5 wt.%. The catalytic cracking catalyst is prepared, and the number is CAZY35-1.
The results of the evaluation in example 31-1 are shown in Table 50.
Example 66-2
The same as in example 66-1 except that GPZ1-1 was replaced with GPZ 1-2. The catalytic cracking catalyst is prepared, and the number is CAZY35-2.
The results of the evaluation in example 31-1 are shown in Table 50.
Comparative example 66-1
The same as in example 66-1 except that GPZ1-1 was replaced with D1-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY35-1. The evaluation was conducted in the same manner as in example 12-1, and the results are shown in Table 50.
Comparative example 66-2
The same as in example 66-1 except that GPZ1-1 was replaced with D1-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY35-2. The evaluation was conducted in the same manner as in example 12-1, and the results are shown in Table 50.
Table 50
Figure BDA0002748632620000471
Example 67-1
The same as in example 44-1 was conducted except that the phosphorus-modified microporous ZSM-molecular sieve sample was GPZ 14-1.30 wt%, PSRY16 wt%, kaolin 24 wt%, phosphorus-aluminum inorganic Binder4 20 wt%, pseudo-boehmite 6 wt% and silica sol 10 wt%. The catalytic cracking catalyst is prepared, and the number is CAZY36-1. The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 51.
Example 67-2
The same as in example 67-1 except that GPZ14-1 was replaced with GPZ 14-2. The catalytic cracking catalyst was prepared, numbered CAZY36-2. The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 51.
Comparative example 67-1
The same as in example 67-1 except that GPZ14-1 was replaced with D14-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY36-1. The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 51.
Comparative example 67-2
The same as in example 67-1 except that GPZ14-1 was replaced with D14-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY36-2. The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 51.
Table 51
Figure BDA0002748632620000481
Example 68-1
Mixing binder aluminum sol with kaolin, preparing slurry with deionized water, stirring uniformly, regulating pH value of the slurry to 2.8 with hydrochloric acid, standing and aging at 55deg.C for 1 hr, adding phosphorus modified molecular sieve GPZ1-1 and Y-type molecular sieve (PSRY) prepared in example 1-1 to form catalyst slurry (with solid content of 35% by weight), stirring continuously, and spray drying to obtain microsphere catalyst. The microspherical catalyst was then calcined at 500 ℃ for 1 hour, then washed with ammonium sulfate at 60 ℃ (wherein ammonium sulfate: microspherical catalyst: water = 0.5:1:10) until sodium oxide content was less than 0.25 wt%, then rinsed with deionized water and filtered, then dried at 110 ℃ to obtain catalyst CAZY37-1. The proportion is 1-140% of phosphorus modified ZSM-5 molecular sieve GPZ, 10% of PSRY molecular sieve, 25% of kaolin and aluminum sol (Al is used) 2 O 3 Calculated) 25%.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 52.
Example 68-2
The same as in example 68-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in example 1-2. A sample of the catalytic cracking catalyst was prepared, numbered CAZY37-2.
The results of the evaluation in example 31-1 are shown in Table 20.
Comparative example 68-1
The same as in example 68-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D1-1 of comparative example 1-1. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY37-1.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 52.
Comparative example 68-2
The same as in example 68-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the comparative sample D1-2 of comparative example 1-2. A comparative sample of the catalytic cracking catalyst was prepared, numbered DCAZY37-2.
The evaluation was conducted in the same manner as in example 31-1, and the results are shown in Table 52.
Watch 52
Figure BDA0002748632620000501
Example 69-1, example 69-2
The catalytic cracking catalysts CAZY1-1 and CAZY1-2 of example 31-1 and example 31-2 were used in example 69-1 and example 69-2, respectively. The catalytically cracked feed oil was naphtha as shown in table 53.
The evaluation condition is that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃, and the catalyst-to-oil ratio is 3.2.
Table 54 shows the weight composition and reaction results for each catalyst mixture containing the catalytic cracking catalyst.
Comparative example 69-1, comparative example 69-2
The same as in example 69-1 was conducted except that the catalytic cracking comparative catalysts DCAZY1-1 and DCAZY1-2 of comparative example 31-1 and comparative example 31-2 were used, respectively.
The weight composition and reaction results of each catalyst mixture containing a comparative sample of the catalytic cracking catalyst are shown in Table 54.
Table 53
Raw materials Naphtha (naphtha)
Density (20 ℃ C.)/(g.m) -3 ) 735.8
Vapor pressure/kPa 32
Mass group composition/%
Paraffin hydrocarbons 51.01
N-alkanes 29.40
Cycloalkane (CNS) 38.24
Olefins 0.12
Aromatic hydrocarbons 10.52
Distillation range/. Degree.C
Primary distillation 45.5
5％ 72.5
10％ 86.7
30％ 106.5
50％ 120.0
70％ 132.7
90％ 148.5
95％ 155.2
End point of distillation 166.5
Watch 54
Figure BDA0002748632620000511
Examples 70-1 and 70-2
The catalytic cracking catalysts CAZY14-1 and CAZY14-2 of example 44-1 and example 44-2 were used in example 70-1 and example 70-2, respectively. The catalytically cracked feed oil was naphtha as shown in table 53.
The evaluation condition is that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃, and the catalyst-to-oil ratio is 3.2.
Table 55 shows the weight composition and reaction results of the respective catalyst mixtures containing the catalytic cracking catalyst.
Comparative example 70-1, comparative example 70-2
The same as in example 70-1 was conducted except that the catalytic cracking comparative catalysts DCAZY14-1 and DCAZY14-2 of comparative example 44-1 and comparative example 44-2 were used, respectively.
The weight composition and reaction results of the catalyst mixtures for each comparative sample containing the catalytic cracking catalyst are shown in Table 55.
Table 55
Figure BDA0002748632620000521
Example 71-1
The same as in example 31-1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A sample of the catalyst was prepared, numbered CAZY15-1.
The results of the evaluation in example 31-1 are shown in Table 56.
Example 71-2
The same as in example 31-1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A sample of the catalyst was prepared, numbered CAZY15-2.
The results of the evaluation in example 31-1 are shown in Table 56.
Comparative example 71-1
The same as in example 31-1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A comparative sample of the catalyst was prepared, numbered DCAZY15-1.
The results of the evaluation in example 31-1 are shown in Table 56.
Comparative example 71-2
The same as in example 31-1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A comparative sample of the catalyst was prepared, numbered DCAZY15-2.
The results of the evaluation in example 31-1 are shown in Table 56.
Watch 56
Project Blank test case Example 71-1 Example 71-2 Comparative example 71-1 Comparative example 71-2
Balance of materials, weight percent
Liquefied gas 18.54 36.75 39.43 25.58 26.84
Ethylene yield 1.39 3.98 4.45 2.89 2.98
Propylene yield 8.05 16.87 17.95 11.96 12.23
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 (38)

1. A catalytic cracking catalyst containing phosphorus-modified MFI structure molecular sieve, based on the dry basis of the catalyst, the catalytic cracking catalyst 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 optionally 0-60 wt% of second clay, wherein the phosphorus-modified MFI structure molecular sieve has a K value of: k is more than or equal to 70% and less than or equal to 90%, K=P1/P2×100%, wherein P1 represents phosphorus mass content in a region area of 100 square nanometers in any crystal plane vertical depth of a molecular sieve crystal grain measured by an XPS method within 0-2 nm, P2 represents phosphorus mass content in a region area of 100 square nanometers in a thickness interval of 5-10 nm in any crystal plane vertical depth of the molecular sieve crystal grain measured by an EPMA method, and the inorganic binder comprises a phosphorus-aluminum inorganic binder and/or other inorganic binders.
2. The catalyst of claim 1 wherein said K value of said phosphorus-modified MFI structure molecular sieve satisfies: k is more than or equal to 75% and less than or equal to 90%.
3. The catalyst of claim 2, wherein the K value satisfies: k is more than or equal to 78% and less than or equal to 85%.
4. The catalyst of claim 1 wherein the phosphorus modifies the MFI structure molecular sieve and the phosphorus content is P 2 O 5 The molar ratio of the alumina to the alumina is more than or equal to 0.01.
5. The catalyst of claim 4 wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P 2 O 5 The molar ratio of the alumina to the alumina is more than or equal to 0.2.
6. The catalyst of claim 5 wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P 2 O 5 The molar ratio of the alumina to the alumina is more than or equal to 0.3.
7. The catalyst of claim 6 wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P 2 O 5 The molar ratio of the alumina to the alumina is 0.4 to 0.7.
8. The catalyst of 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.
9. The catalyst of claim 8 wherein the microporous ZSM-5 molecular sieve has a silica/alumina mole ratio of 15 to 1000.
10. The catalyst of claim 9, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 20 to 200.
11. The catalyst of claim 8, wherein the multistage pore ZSM-5 molecular sieve has a mesopore volume greater than 10% of the total pore volume, an average pore diameter of 2-20 nm, and a silica/alumina mole ratio of 15-1000.
12. The catalyst of claim 8, wherein the multistage pore ZSM-5 molecular sieve has a silica/alumina molar ratio of 20 to 200.
13. The catalyst of claim 1, wherein the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a rare earth-containing PSRY-S molecular sieve, a USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, and an HY molecular sieve.
14. The catalyst of claim 1, wherein the phosphorus-aluminum inorganic binder is a phosphorus-aluminum gel and/or a phosphorus-aluminum inorganic binder comprising a first clay.
15. The method for preparing the catalytic cracking catalyst according to claim 1, which comprises mixing and pulping a Y-type molecular sieve, a phosphorus-modified MFI structure molecular sieve, an inorganic binder and optionally a second clay, and spray-drying to obtain the catalytic cracking catalyst, wherein the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with a temperature of 40-150 ℃ with the MFI structure molecular sieve with a temperature of 40-150 ℃ at the same temperature for at least 0.1 hour by an impregnation method, drying and roasting at 200-600 ℃ in an air or steam atmosphere for at least 0.1 hour; or mixing and pulping the phosphorus-containing compound, the MFI structure molecular sieve and water, heating to 40-150 ℃ and keeping at least 0.1 hour, drying and roasting at 200-600 ℃ for at least 0.1 hour in air or water vapor atmosphere.
16. The process for preparing as claimed in claim 15, wherein the phosphorus-modified MFI structure molecular sieve is prepared by bringing an aqueous solution of a phosphorus-containing compound having a temperature of 50 to 150 ℃ into mixed contact with the MFI structure molecular sieve having a temperature of 50 to 150 ℃ at substantially the same temperature by an impregnation method.
17. The process for preparing as claimed in claim 15, wherein the phosphorus-modified MFI structure molecular sieve is prepared by bringing an aqueous solution of a phosphorus-containing compound having a temperature of 70 to 130 ℃ into mixed contact with the MFI structure molecular sieve having a temperature of 70 to 130 ℃ at substantially the same temperature by an impregnation method.
18. The process according to claim 15, wherein the phosphorus compound, MFI structure molecular sieve and water are mixed and slurried and then heated to 50 to 150 ℃.
19. The preparation method of claim 15, wherein the phosphorus-containing compound, the MFI structure molecular sieve and water are mixed and pulped and then heated to 70-130 ℃.
20. The process according to claim 15, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.
21. The process according to claim 20, 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.
22. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to the MFI structure molecular sieve to aluminum is 0.01 to 2.
23. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to the MFI structure molecular sieve to aluminum is 0.1 to 1.5.
24. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to the MFI structure molecular sieve to aluminum is 0.2 to 1.5.
25. The process according to claim 15, wherein the phosphorus-containing compound is a mixture of boron phosphate and one or more selected from the group consisting of trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, and the weight ratio of boron phosphate in the mixture is 10% to 80%.
26. The method of claim 25, wherein the boron phosphate comprises 20% to 40% by weight of the mixture.
27. The preparation method according to claim 15, wherein the contact and water sieve weight ratio is 0.5-1.
28. The process according to claim 15, wherein the calcination is carried out at 450 to 550℃under an air atmosphere.
29. The method of claim 15, wherein the inorganic binder is a phosphorus aluminum inorganic binder.
30. The method of claim 29, wherein the inorganic binder is a glue and/or a first clay-containing inorganic binder; the first clay-containing phosphorus-aluminum inorganic binder contains, based on the dry weight of the first clay-containing phosphorus-aluminum inorganic binder, al 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of a phosphorus component and not more than 0 and not more than 40 wt% of a first clay on a dry basis, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio 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 includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.
31. The process according to claim 15, 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.
32. The production method according to claim 15, wherein the inorganic binder comprises 3 to 39% by weight of the phosphorus aluminum inorganic binder on a dry basis and 1 to 30% by weight of other inorganic binder on a dry basis, based on the catalytic cracking catalyst, the other inorganic binder being at least one selected from pseudo-boehmite, alumina sol, silica alumina sol and water glass.
33. The method of manufacturing of claim 15, wherein the method further comprises: carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting is 300-650 ℃ and the roasting time is 0.5-8 h; the temperature of the drying treatment is 100-200 ℃, and the drying time is 0.5-24 h.
34. The method of preparing according to claim 30, 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 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.
35. A catalytic cracking catalyst obtainable by the process of any one of claims 15 to 34.
36. A method for catalytic cracking of hydrocarbon oils, the method comprising: contacting a hydrocarbon oil with the catalytic cracking catalyst of any one of claims 1-14 and claim 35 under catalytic cracking conditions.
37. The method of claim 36, wherein the method comprises: contacting the hydrocarbon oil with the catalytic cracking catalyst under the catalytic cracking conditions, wherein the catalytic cracking reaction conditions include: the reaction temperature is 500-800 ℃.
38. The method of claim 36 or 37, wherein the hydrocarbon oil is selected from one or more of crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, straight run wax oil, propane light/heavy deoiling, coker wax oil, and coal liquefaction products.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171921A (en) * 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
CN1465527A (en) * 2002-06-27 2004-01-07 中国石油化工股份有限公司 MFI structure molecular sieve containing phosphorus and transition metal
CN102838130A (en) * 2011-06-23 2012-12-26 中国石油化工股份有限公司 MFI structure molecular sieve containing phosphorus and transition metals, and preparation method thereof
CN103007991A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking assistant for improving low-carbon olefin concentration
CN103007990A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking assistant for improving low-carbon olefin concentration
CN107971015A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof
CN107974274A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 MFI structure molecular sieve a kind of phosphorous and containing carried metal and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171921A (en) * 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
CN1465527A (en) * 2002-06-27 2004-01-07 中国石油化工股份有限公司 MFI structure molecular sieve containing phosphorus and transition metal
CN102838130A (en) * 2011-06-23 2012-12-26 中国石油化工股份有限公司 MFI structure molecular sieve containing phosphorus and transition metals, and preparation method thereof
CN103007991A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking assistant for improving low-carbon olefin concentration
CN103007990A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking assistant for improving low-carbon olefin concentration
CN107971015A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of catalytic cracking catalyst and preparation method thereof
CN107974274A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 MFI structure molecular sieve a kind of phosphorous and containing carried metal and preparation method thereof

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