CN113546672A - Catalytic cracking catalyst, preparation method and application thereof, and catalytic cracking method - Google Patents
Catalytic cracking catalyst, preparation method and application thereof, and catalytic cracking method Download PDFInfo
- Publication number
- CN113546672A CN113546672A CN202110342883.4A CN202110342883A CN113546672A CN 113546672 A CN113546672 A CN 113546672A CN 202110342883 A CN202110342883 A CN 202110342883A CN 113546672 A CN113546672 A CN 113546672A
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- molecular sieve
- zsm
- catalyst
- modified zsm
- acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 73
- 238000002360 preparation method Methods 0.000 title description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 221
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- 239000004927 clay Substances 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
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- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
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- 239000002253 acid Substances 0.000 claims description 88
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 229910021472 group 8 element Inorganic materials 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- 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 relates to the field of catalytic cracking of hydrocarbon oil, and discloses a catalytic cracking catalyst, which comprises: modified ZSM-5 molecular sieve and binder and optionally clay; based on the dry weight of the catalyst, the content of the modified ZSM-5 molecular sieve is 20-60 wt% in terms of dry basis, the content of the clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide; the modified ZSM-5 molecular sieve comprises ZSM-5Molecular sieves and alkaline earth elements; on the basis of the dry weight of the modified ZSM-5 molecular sieve, the content of the alkaline earth metal element is 10-30 wt% calculated by oxide; SiO of the modified ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50. When the catalyst is applied to cracking reaction, the cracking capability is stronger, the yield of low-carbon olefin is higher and the propylene selectivity is higher.
Description
Technical Field
The invention relates to the field of catalytic cracking of hydrocarbon oil, in particular to a catalytic cracking catalyst, a preparation method and application thereof, and a catalytic cracking method.
Background
The propylene capacity of China is rapidly increased in recent years, crude oil is heavier and light hydrocarbon and naphtha resources are poor in China, so that the development of a catalytic cracking technology for producing more propylene is suitable for the requirements of the national conditions of China.
Some domestic research units attach great importance to the research of the low-carbon olefin production technology. At the end of the 20 th century and the 80 s, the petrochemical research institute (abbreviated as "Shikoyao") developed a catalytic cracking technology (DCC) for producing low-carbon olefins from heavy oil, which employs a modified five-membered ring medium pore zeolite catalyst and utilizes a riser plus a fluidized bed or a riser reactor to increase the yield of propylene under a more severe condition than catalytic cracking; when paraffin base is used as raw material, the yield of propylene can reach 23%, and the yield of propylene of intermediate base raw material is about 17%; the process is successfully applied to more than 10 sets of devices at home and abroad. In the 90 s of the 20 th century, a catalytic Cracking (CPP) process technology for directly preparing ethylene and propylene from heavy oil was developed, wherein heavy oil or wax oil is used as a raw material, a specially-developed acid zeolite catalyst with double functions of carbonium ion reaction and free radical reaction is adopted, and the process is operated at the reaction temperature of 580-640 ℃, a large catalyst-oil ratio and a high water injection steam amount, and by taking Daqing atmospheric residue as an example, the ethylene yield reaches 10-14%, and the propylene yield reaches 19-21%. After the 21 st century, the shipments developed successively a new technology for producing propylene, namely, enhanced catalytic cracking (DCC-plus) and selective cracking of heavy oil (MCP), on the basis of DCC technology, and achieved the purpose of increasing propylene yield and reducing dry gas and coke yield by zone control. The research institute of petrochemical science also focuses on the research of propylene catalytic materials with high yield, develops new silicon-aluminum materials with high yield of propylene in ZRP series and ZSP series in sequence, plays an important role in the development of catalysts and auxiliaries for increasing the yield of propylene by catalytic cracking in China, but the performance of the developed silicon-aluminum materials still needs to be further improved so as to meet the requirement of heavy deterioration of crude oil.
In order to solve the limitations of conventional ZSM-5 zeolite in macromolecular catalytic reaction, researchers have conducted different approaches.
CN101380591A discloses a method for preparing an alkali-treated modified ZSM-5 zeolite catalyst for toluene disproportionation, which comprises the steps of adding a binder into raw zeolite powder of which the active component is ZSM-5 for molding, treating the raw zeolite powder at 25-75 ℃ by using 0.01-0.4mol/L alkali solution, exchanging the raw zeolite powder into hydrogen-type zeolite, washing the hydrogen-type zeolite powder by using an organic acid, drying the catalyst, performing chemical liquid phase deposition modification by using a cyclohexane solution of ethyl orthosilicate, and drying and roasting the catalyst to obtain the catalyst. The obtained catalyst is especially suitable for preparing benzene and p-xylene by shape-selective disproportionation of toluene.
CN102464336A discloses a modification method of ZSM-5 zeolite, which comprises the steps of firstly treating the ZSM-5 zeolite with an alkali solution in a closed system containing a low molecular weight organic solvent; then treating the ZSM-5 zeolite with an acid solution, and finally separating, washing and drying to obtain the modified ZSM-5 zeolite. The organic solvent added in the alkali treatment process can promote the generation of a mesoporous structure, so that the microporous structure is more efficiently converted into mesopores, and meanwhile, the microporous structure is stably protected; the amorphous aluminum in the zeolite crystal can be eluted in the subsequent acid treatment process, so that the aims of dredging the pore passage and increasing the total specific surface area are fulfilled.
CN102910644A relates to a hierarchical pore ZSM-5 molecular sieve and a preparation method thereof, wherein the method is to prepare the hierarchical pore ZSM-5 molecular sieve from a ZSM-12 molecular sieve through crystal transformation. The preparation method of the molecular sieve comprises the following steps: adding ZSM-12 molecular sieve powder into a solution containing sodium hydroxide and tetrapropylammonium bromide at room temperature, stirring uniformly, slowly adding an additional silicon source, stirring uniformly to obtain a reaction mixture gel system, and filling the reaction mixture gel into a stainless steel reaction kettle. Crystallizing the reaction mixture under a closed condition to obtain the hierarchical pore ZSM-5 molecular sieve. The molecular sieve provided by the method has micropores and a concentrated mesoporous structure, and can be used for various catalytic processes.
CN103011193A discloses a preparation method of high catalytic activity iron-containing mesoporous ZSM-5, relating to a preparation method of mesoporous ZSM-5. The method aims to solve the technical problem that the mesoporous ZSM-5 prepared by the existing method has low catalytic performance in the catalytic Friedel-crafts alkylation reaction, and is applied to the field of preparation of ferrous mesoporous ZSM-5.
CN104324746A discloses a metal modified ZSM-5 molecular sieve catalyst and application thereof, wherein the metal modified ZSM-5 molecular sieve catalyst can be used in preparation of acrylic acid by lactic acid dehydration.
CN104492476A discloses a modified ZSM-5 molecular sieve and a preparation method thereof, wherein the modified ZSM-5 molecular sieve is obtained by loading metal oxides on desilicated ZSM-5 molecular sieve, and the metal oxides are MgO, CoO and La2O3NiO or CeO2The metal oxide loading is calculated according to the mass ratio, and the metal oxide loading is as follows: the desiliconized ZSM-5 molecular sieve is 0.04-0.05: 1. method for preparing the sameNamely, the ZSM-5 zeolite molecular sieve is sequentially subjected to desiliconization treatment through alkali to obtain a desiliconized ZSM-5 zeolite molecular sieve, then is treated through an ammonium salt solution to obtain a hydrogenated ZSM-5 molecular sieve, and then is loaded with a metal oxide to obtain the modified ZSM-5 molecular sieve. When the catalyst is used for catalyzing benzene and methanol to alkylate and prepare p-xylene, the catalyst shows higher benzene conversion rate, excellent p-xylene selectivity and better activity stability.
CN106140258A provides a catalyst using modified ZSM-5 molecular sieve as carrier, its preparation method and its application in preparing isobutene. The preparation method of the catalyst comprises the following steps: (1) respectively dipping hydrogen type ZSM-5 molecular sieve carrier in an alkali solution, an acid solution and a magnesium salt solution, wherein the alkali solution is NaOH, KOH or Na2CO3One or more aqueous solutions, wherein the concentration of the alkali solution is 0.1-2 mol/L; the acid solution is one or more of hydrochloric acid, nitric acid or sulfuric acid solution, and the concentration of the acid solution is 0.1-5 mol/L; in the obtained modified ZSM-5 molecular sieve carrier, the weight content of magnesium in the carrier is 0.5-10% in terms of elements; (2) introducing zinc oxide into the treated hydrogen type ZSM-5 molecular sieve carrier; (3) and (2) carrying out bromination treatment on the hydrogen type ZSM-5 molecular sieve carrier introduced with the zinc oxide until the zinc oxide content in the catalyst is 0.5-20%, preferably 1-15%, and more preferably 1-9%, and the zinc bromide content is 10-50%, preferably 15-45%, and more preferably 18-39% by weight. The catalyst prepared by the method can improve the selectivity of isobutene.
In conclusion, the existing ZSM-5 molecular sieve modification technology carries out acid-base or metal modification to different degrees, however, the pore structure and acidity of the obtained modified ZSM-5 molecular sieve need to be further improved, the cracking performance needs to be improved when the modified ZSM-5 molecular sieve is applied to the catalytic cracking reaction of heavy inferior oil, and the effect of improving the yield of low-carbon olefin is not obvious.
Disclosure of Invention
The invention aims to overcome the problems of insufficient cracking capability of a catalyst on heavy and poor crude oil and low yield of low-carbon olefin in the prior art, and provides a catalytic cracking catalyst, a preparation method and application thereof and a catalytic cracking method.
In order to achieve the above object, a first aspect of the present invention provides a catalytic cracking catalyst comprising: modified ZSM-5 molecular sieve and binder and optionally clay; based on the dry weight of the catalyst, the content of the modified ZSM-5 molecular sieve is 20-60 wt% in terms of dry basis, the content of the clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
The modified ZSM-5 molecular sieve comprises a ZSM-5 molecular sieve and an alkaline earth metal element; on the basis of the dry weight of the modified ZSM-5 molecular sieve, the content of the alkaline earth metal element is 10-30 wt% calculated by oxide;
SiO of the modified ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50;
the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 25-60% of the total pore volume of the modified ZSM-5 molecular sieve;
the ratio of the B acid amount to the L acid amount of the modified ZSM-5 molecular sieve is 8-45.
Preferably, in the modified ZSM-5 molecular sieve, the volume of mesopores with a pore diameter of 5nm to 20nm accounts for 85% or more, more preferably 90% or more, for example 90 to 96% of the total mesopore volume.
Preferably, the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 30-50% of the total pore volume of the modified ZSM-5 molecular sieve.
Preferably, the modified ZSM-5 molecular sieve has SiO2/Al2O3The molar ratio is 20-40.
Preferably, the content of the alkaline earth metal element is 12 to 20% by weight, more preferably 14 to 20% by weight, in terms of oxide.
The proportion of the strong acid amount of the modified ZSM-5 molecular sieve in the total acid amount is 35-55%, preferably 40-50%.
Preferably, the modified ZSM-5 molecular sieve has a ratio of the amount of the B acid to the amount of the L acid of 8 to 30, preferably 10 to 28.
Preferably, the modified ZSM-5 molecular sieve further contains an auxiliary element, and the content of the auxiliary element is 1-15 wt%, preferably 6-12 wt%, and more preferably 7-10 wt% calculated by oxide based on the dry weight of the modified ZSM-5 molecular sieve; the auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
Preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 5-9 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%.
In a second aspect, the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting a ZSM-5 molecular sieve with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain a modified ZSM-5 molecular sieve;
(4) pulping the modified ZSM-5 molecular sieve, the binder and the optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
The modified ZSM-5 molecular sieve, the binder and the optional clay are used in amounts such that the prepared catalyst has a modified ZSM-5 molecular sieve content of 20-60 wt% on a dry basis, a clay content of 0-50 wt% on a dry basis and a binder content of 10-40 wt% on an oxide basis, based on the dry weight of the catalyst;
the ZSM-5 molecular sieve and the alkaline earth metal compound are used in an amount such that the modified ZSM-5 molecular sieve contains 10-30 wt% of the alkaline earth metal element in terms of oxide based on the dry weight of the modified ZSM-5 molecular sieve;
SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50.
Preferably, the method further comprises modifying the product obtained by the acid treatment in the step (2) after the step (2) and before the step (3), wherein the modification comprises: and (3) carrying out modification reaction on the product obtained by the acid treatment in the step (2) and a soluble compound of the auxiliary agent in the presence of a second solvent.
Preferably, the soluble compound of the auxiliary agent is used in an amount such that the content of the auxiliary agent element in the prepared modified ZSM-5 molecular sieve is 1-15 wt%, preferably 6-12 wt%, and more preferably 7-10 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve. The auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
Preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 5-9 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%.
Preferably, step (4) comprises pulping the filtrate obtained by filtration in step (1), the modified ZSM-5 molecular sieve, the binder and optionally the clay.
In a third aspect, the present invention provides a catalyst prepared by the above method. The catalyst has the characteristic of strong cracking capability, and can improve the yield of low-carbon olefin while keeping the high yield of liquefied gas in the catalytic cracking reaction.
Accordingly, a fourth aspect of the invention provides the use of a catalyst as described above in catalytic cracking.
In a fifth aspect, the present invention provides a method of catalytic cracking, the method comprising: under the condition of catalytic cracking, the hydrocarbon oil is in contact reaction with a catalyst; the catalyst is as described above.
Through the technical scheme, the ZSM-5 molecular sieve is modified by adopting the alkaline earth metal, part of silicon in the ZSM-5 molecular sieve is removed, and a framework and a surface vacancy are formed, so that the mesoporous structure of the ZSM-5 molecular sieve is enriched, wherein the alkaline earth metal has an alkaline site which can reduce the strong acidity of the ZSM-5 molecular sieve, thereby inhibiting the generated olefin from generating a hydrogen transfer reaction and stabilizing the generated low-carbon olefin. The modification is carried out by using acid, so that part of amorphous aluminum and impurities are removed, the pore structure of the ZSM-5 molecular sieve is favorably improved, and the stability is improved.
The embodiment of the invention shows that when the catalyst prepared by the modified ZSM-5 molecular sieve is used for catalytic cracking, the cracking capability of the catalyst is stronger, the liquefied gas yield, the ethylene yield and the propylene yield are higher, and the propylene selectivity is higher. Under the preferable condition, the product obtained by acid treatment in the step (2) is modified by adopting the auxiliary agent element, so that the cracking performance of the catalyst is improved, and the yield of the low-carbon olefin is improved; under the preferable condition, the invention adopts the filtrate generated in the preparation process of the modified ZSM-5 molecular sieve to prepare the catalyst, thereby improving the utilization rate of raw materials, avoiding environmental pollution, reducing the preparation cost of the catalyst and simultaneously improving the problem of higher coke selectivity of the cracking catalyst.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the pore diameter refers to a diameter unless otherwise specified.
In the present invention, the dry weight refers to the weight after burning at 800 ℃ for 1 hour.
In a first aspect, the present invention provides a catalytic cracking catalyst comprising: modified ZSM-5 molecular sieve and binder and optionally clay; based on the dry weight of the catalyst, the content of the modified ZSM-5 molecular sieve is 20-60 wt% in terms of dry basis, the content of the clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
the modified ZSM-5 molecular sieve comprises a ZSM-5 molecular sieve and an alkaline earth metal element; on the basis of the dry weight of the modified ZSM-5 molecular sieve, the content of the alkaline earth metal element is 10-30 wt% calculated by oxide;
SiO of the modified ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50;
the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 25-60% of the total pore volume of the modified ZSM-5 molecular sieve;
the ratio of the B acid amount to the L acid amount of the modified ZSM-5 molecular sieve is 8-45.
In the invention, the mesoporous volume and the total pore volume are measured by AS-3 and AS-6 static nitrogen adsorbers produced by Quantachrome instruments.
According to the present invention, preferably, the modified ZSM-5 molecular sieve is present in an amount of 25 to 50 wt% on a dry basis, the clay is present in an amount of 12 to 45 wt% on a dry basis, and the binder is present in an amount of 12 to 38 wt% on an oxide basis, based on the dry weight of the catalyst.
Further preferably, the modified ZSM-5 molecular sieve is present in an amount of 25 to 40 wt% on a dry basis, the clay is present in an amount of 25 to 40 wt% on a dry basis and the binder is present in an amount of 20 to 35 wt% on an oxide basis, based on the dry weight of the catalyst.
In one embodiment, the modified ZSM-5 molecular sieve content on a dry basis, the clay content on a dry basis, and the binder content on an oxide basis add up to 100% by weight of the catalyst on a dry basis.
In the present invention, the optional clay means that the catalyst may or may not contain clay, and preferably contains clay. The clay is selected from a wide range of materials known to those skilled in the art. Preferably, the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, and further preferably kaolin and/or halloysite.
According to the present invention, the selection of the binder is not particularly limited, and may be a material known to those skilled in the art. Preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, which is at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphor-alumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
According to a preferred embodiment of the present invention, in the modified ZSM-5 molecular sieve, the volume of mesopores with a pore diameter of 5nm to 20nm accounts for 85% or more, more preferably 90% or more, for example 90 to 96% of the total mesopore volume. In the preferable condition, the pore channel structure of the modified ZSM-5 molecular sieve is beneficial to improving the catalytic performance of the modified ZSM-5 molecular sieve in the catalytic cracking reaction.
According to the invention, the mesoporous volume of the modified ZSM-5 molecular sieve is 30-50% of the total pore volume of the modified ZSM-5 molecular sieve. In the preferable case, the generation and diffusion of the intermediate and the product of the isomerization reaction and the aromatization reaction are facilitated, thereby avoiding the coking and deactivation of the modified ZSM-5 molecular sieve.
According to a preferred embodiment of the present invention, the modified ZSM-5 molecular sieve has SiO2/Al2O3The molar ratio is 20-40. In this preferred embodiment, it is more advantageous to improve the cracking performance of the catalyst prepared.
According to a preferred embodiment of the present invention, the content of the alkaline earth metal element is 12 to 20% by weight, more preferably 14 to 20% by weight, in terms of oxide. The inventor of the invention finds that under the preferable condition, the strong acidity of the ZSM-5 molecular sieve is more favorably reduced, so that the hydrogen transfer reaction of the generated olefin is inhibited, and the yield of the low-carbon olefin is more favorably improved.
According to a preferred embodiment of the present invention, the modified ZSM-5 molecular sieve has a strong acid content of 35 to 55%, more preferably 40 to 50%, based on the total acid content. Under the preferable mode, the hydrogen transfer reaction generated by the generated olefin is favorably inhibited, so that the yield of the low-carbon olefin is favorably improved.
In the invention, NH is adopted as the proportion of the acid amount of the strong acid to the total acid amount3TPD method.
In the present invention, the strong acid means that the acid center is NH without specific description3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
According to a preferred embodiment of the present invention, the modified ZSM-5 molecular sieve has a ratio of the amount of the acid B to the amount of the acid L of 8 to 30, preferably 10 to 28. Under the preferred embodiment, the hydrogen transfer reaction generated by the generated olefin is inhibited, so that the yield of the low-carbon olefin is improved.
In the invention, the ratio of the B acid amount to the L acid amount is determined by a pyridine adsorption infrared acidity method.
In a preferred embodiment of the present invention, the modified ZSM-5 molecular sieve further contains an auxiliary element, and the content of the auxiliary element is 1 to 15 wt%, more preferably 6 to 12 wt%, and still more preferably 7 to 10 wt%, calculated as an oxide, based on the dry weight of the modified ZSM-5 molecular sieve. In the preferred embodiment, the cracking performance of the catalyst is improved, so that the yield of the low-carbon olefin in the cracking reaction product is improved.
According to the catalytic cracking catalyst provided by the invention, the selection range of the auxiliary element is wide, and preferably, the auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
The first auxiliary element is selected from a wide range, such as a metal element, and preferably, the first auxiliary element is selected from at least one of group IB, group IIB, group IVB, group VIIB, group VIII and rare earth elements. Further preferably, the first auxiliary element is at least one element selected from Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn, more preferably at least one element selected from Ti, Zr and Ce. Under the preferable condition, the cracking performance of the catalyst is stronger, and the yield of the low-carbon olefin is improved.
The second auxiliary element is selected in a wide range, such as a nonmetal element, preferably, the second auxiliary element is at least one element selected from B, P and an N element, and preferably, the second auxiliary element is a B element and/or a P element. Under the preferable condition, the cracking performance of the catalyst is stronger, and the yield of the low-carbon olefin is improved.
The content of the first auxiliary element and the second auxiliary element is selected in a wide range, and preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 5-9 wt% in terms of oxide based on the dry weight of the modified ZSM-5 molecular sieve; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%. Under the preferable condition, the cracking performance of the catalyst is stronger, and the yield of the low-carbon olefin is improved.
According to a preferred embodiment of the present invention, the alkaline earth metal element is at least one element selected from Mg, Ca, Sr and Ba elements, and is further preferably an Mg element. Under the preferred embodiment, the method is beneficial to improving the yield of the low-carbon olefin.
In a second aspect, the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting a ZSM-5 molecular sieve with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain a modified ZSM-5 molecular sieve;
(4) pulping the modified ZSM-5 molecular sieve, the binder and the optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the modified ZSM-5 molecular sieve, the binder and the optional clay are used in amounts such that the prepared catalyst has a modified ZSM-5 molecular sieve content of 20-60 wt% on a dry basis, a clay content of 0-50 wt% on a dry basis and a binder content of 10-40 wt% on an oxide basis, based on the dry weight of the catalyst;
The ZSM-5 molecular sieve and the alkaline earth metal compound are used in an amount such that the modified ZSM-5 molecular sieve contains 10-30 wt% of the alkaline earth metal element in terms of oxide based on the dry weight of the modified ZSM-5 molecular sieve;
SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50.
According to a preferred embodiment of the present invention, the method for preparing the catalytic cracking catalyst comprises:
(1) in the presence of a first solvent, contacting a ZSM-5 molecular sieve with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain a modified ZSM-5 molecular sieve;
(4) pulping the modified ZSM-5 molecular sieve, the binder and the optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the modified ZSM-5 molecular sieve, the binder and the optional clay are used in amounts such that the prepared catalyst has a modified ZSM-5 molecular sieve content of 20-60 wt% on a dry basis, a clay content of 0-50 wt% on a dry basis and a binder content of 10-40 wt% on an oxide basis, based on the dry weight of the catalyst;
The amount of the alkaline earth metal compound in terms of oxide is 10 to 35 parts by weight, preferably 12 to 20 parts by weight, and more preferably 14 to 20 parts by weight, relative to 100 parts by weight of the ZSM-5 molecular sieve;
SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50.
The inventor of the invention finds that the alkaline earth metal is adopted to modify the ZSM-5 molecular sieve, so that part of silicon in the ZSM-5 molecular sieve can be removed to form a framework and surface vacancies, and the mesoporous structure of the ZSM-5 molecular sieve is favorably improved; the alkaline-earth metal has an alkaline position which is beneficial to reducing the strong acidity of the ZSM-5 molecular sieve, so that the hydrogen transfer reaction of the generated olefin is inhibited, and the yield of the low-carbon olefin is improved.
In the present invention, the term "soluble" means soluble in the solvent under the action of a co-solvent.
The selection range of the first solvent in the step (1) is wide as long as the environment for contacting the ZSM-5 molecular sieve with alkali and alkaline earth metal elements can be provided. Preferably, the first solvent is water. The water used in the present invention is not particularly limited, and may be any water having various hardness, and any of tap water, distilled water, purified water and deionized water can be used. In one embodiment of the present invention, the first solvent is neutral water, which is also called distilled water.
The amount of the first solvent used in the present invention is selected from a wide range, and may be appropriately selected according to the amounts of the ZSM-5 molecular sieve and the compounds of alkali and alkaline earth metals, as long as an environment allowing the contact in step (1) is provided. Preferably, the first solvent is used in an amount of 100-1000 parts by weight with respect to 100 parts by weight of the ZSM-5 molecular sieve.
In the present invention, in the step (1), the order of contacting the ZSM-5 molecular sieve with the alkali and alkaline earth metal compounds is not particularly limited, and the ZSM-5 molecular sieve may be contacted with the alkali first, the alkaline earth metal compound first, or both the alkali and the alkaline earth metal compound simultaneously.
In the present invention, the first solvent may be introduced alone or together with the alkali or alkaline earth metal compound. According to an embodiment of the present invention, the step (1) comprises: contacting the first solvent, the ZSM-5 molecular sieve, with a basic solution and a compound of an alkaline earth metal.
According to the present invention, preferably, the contacting conditions of step (1) include: the temperature is 50-90 ℃ and the time is 1-5 h; further preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
In the present invention, the filtration and drying in step (1) are all operations well known to those skilled in the art, and the present invention is not particularly limited.
According to an embodiment of the present invention, the method may further comprise, in the step (1), washing the solid product obtained after the filtration. The washing conditions are selected in a wide range, and preferably, the pH of the filtrate obtained after washing is 6.5-7.5, and preferably, the pH of the filtrate obtained after washing is more than 7.
According to a preferred embodiment of the present invention, the amounts of the ZSM-5 molecular sieve and the compound of an alkaline earth metal are such that the modified ZSM-5 molecular sieve is produced with an alkaline earth metal element content of 12 to 20 wt%, more preferably 14 to 20 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve. Under the preferred embodiment, the method is more beneficial to inhibiting the generated olefin from generating hydrogen transfer reaction and improving the yield of the low-carbon olefin.
According to the invention, preferably, the SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 20-40.
The ZSM-5 molecular sieve is selected in a wide range, preferably, the ZSM-5 molecular sieve is selected from at least one of an ammonium type ZSM-5 molecular sieve, a Na type ZSM-5 molecular sieve and a hydrogen type ZSM-5 molecular sieve, and preferably, the Na type ZSM-5 molecular sieve.
In the present invention, the ZSM-5 molecular sieve may be commercially available or may be prepared by itself according to any of the methods of the prior art.
According to the present invention, preferably, the base is selected from at least one of sodium hydroxide, potassium carbonate, and sodium carbonate. From the viewpoint of cost reduction, the alkali is further preferably sodium hydroxide.
According to the present invention, preferably, in step (1), the base is introduced in the form of an alkaline solution. The concentration of the alkali solution is selected in a wide range, and the molar concentration of the alkali solution is preferably 0.1 to 2mol/L, and more preferably 0.3 to 0.9 mol/L.
According to the present invention, preferably, the alkali solution is used in an amount of 1 to 100 parts by weight, preferably 5 to 20 parts by weight, relative to 100 parts by weight of the ZSM-5 molecular sieve.
In the present invention, the selection range of the alkaline earth metal is as described above, and the present invention will not be described herein again.
The compound of the alkaline earth metal can be selected from a wide range, and the compound can be dissolved in a solvent or dissolved in the solvent under the action of a cosolvent. Preferably, the compound of the alkaline earth metal is selected from at least one of an oxide, a chloride, a nitrate and a sulfate of the alkaline earth metal, more preferably at least one of magnesium oxide, magnesium chloride, magnesium sulfate and magnesium nitrate.
The acid of the present invention can be selected from a wide range of acids, and can be any of those conventionally used in the art. Specifically, the acid is an organic acid and/or an inorganic acid. Preferably, the acid in step (2) is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid and acetic acid, preferably sulfuric acid and/or oxalic acid, and more preferably sulfuric acid and oxalic acid. Under the optimal condition, part of amorphous aluminum and impurities are removed, and the pore structure of the ZSM-5 molecular sieve is improved, so that the stability is improved, and the catalytic performance of the prepared catalyst is improved.
According to the invention, preferably, the weight ratio of the sulfuric acid to the oxalic acid is 1: 1-4.
According to the present invention, preferably, the acid treatment is such that the modified ZSM-5 molecular sieve is produced with a sodium content of not more than 0.5 wt% calculated as oxide.
The weight content of the acid solution is selected from a wide range, and preferably, the weight content of the acid solution is 5 to 98 wt%, and more preferably, 10 to 30 wt%.
According to the present invention, preferably, the weight ratio of the acid to the solid product obtained in step (1) on a dry basis is from 0.1 to 5, more preferably from 0.5 to 2. In this preferred case, it is more advantageous to improve the catalytic performance of the catalyst.
In a specific embodiment, in the step (2), the solid product obtained in the step (1) is pulped with a solvent (preferably water), and then the solid product is subjected to acid treatment by using an acid solution.
In the present invention, the acid treatment in step (2) is not particularly limited, and preferably, the reaction conditions of the acid treatment in step (2) include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
According to a preferred embodiment of the present invention, the method further comprises modifying the product obtained by the acid treatment in step (2) after step (2) and before step (3), wherein the modification comprises: and (3) carrying out modification reaction on the product obtained by the acid treatment in the step (2) and a soluble compound of the auxiliary agent in the presence of a second solvent. Under the preferred embodiment, the cracking performance of the catalyst is improved, and the yield of the low-carbon olefin is improved.
According to a particular embodiment of the invention, the modification comprises: and (3) contacting the product obtained by acid treatment in the step (2), the second solvent and a soluble compound of an auxiliary agent for modification reaction. The order of the contacting is not particularly limited in the present invention, and the product obtained by the acid treatment in the step (2) may be contacted with the second solvent first and then contacted with the soluble compound of the auxiliary agent; the product obtained by the acid treatment in the step (2) can also be contacted with the second solvent before being contacted with the soluble compound of the auxiliary agent. In the present invention, the introduction of the second solvent is not particularly limited, and specifically, for example, the second solvent may be introduced alone or may be introduced together with the soluble compound of the auxiliary.
In the present invention, the second solvent is selected from a wide range as long as the soluble compound of the product obtained by the acid treatment in the step (2) and the auxiliary agent can be used for the purpose of the modification reaction. Preferably, the second solvent is water. The water used in the present invention is not particularly limited, and may be any water having various hardness, and any of tap water, distilled water, purified water and deionized water can be used. In one embodiment of the present invention, the second solvent is neutral water, which is also called distilled water.
The amount of the second solvent is selected from a wide range, and may be appropriately selected according to the amounts of the soluble compound of the product obtained by the acid treatment in the step (2) and the auxiliary agent, as long as the modification reaction in the step (2) can be smoothly performed. Preferably, the second solvent is used in an amount of 100-1000 parts by weight based on 100 parts by weight of the product (dry basis weight) obtained in step (2).
According to the invention, preferably, the auxiliary element comprises a first auxiliary element and/or a second auxiliary element.
In the present invention, the selection ranges of the first auxiliary element and the second auxiliary element are as described above, and the present invention is not described herein again.
According to the invention, the soluble compound of the auxiliary agent is preferably used in an amount such that the content of the auxiliary agent element in the modified ZSM-5 molecular sieve obtained is 1 to 15 wt%, more preferably 6 to 12 wt%, and even more preferably 7 to 10 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve. Under the preferable condition, the cracking performance of the catalyst is improved, so that the yield of the low-carbon olefin is improved.
According to a preferred embodiment of the present invention, the soluble compound of the auxiliary agent is used in an amount such that the content of the first auxiliary agent element in the modified ZSM-5 molecular sieve obtained is 1 to 10 wt%, preferably 5 to 10 wt%, and more preferably 5 to 9 wt%, calculated as oxide; the content of the second auxiliary element is 0.1 to 10, preferably 0.1 to 5 wt%, and more preferably 1 to 3 wt%. Under the preferred embodiment, the cracking performance of the catalyst is improved, so that the yield of the low-carbon olefin is improved.
According to the present invention, preferably, the conditions of the modification reaction include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
According to an embodiment of the present invention, the method may further include: and (3) after the step (2), filtering, washing and drying the product obtained by the acid treatment in sequence before modifying the product obtained by the acid treatment in the step (2) to obtain the product after the acid treatment. The filtration, washing and drying are all operations well known to those skilled in the art, and the present invention is not particularly limited.
According to the present invention, it is preferable that after the modification reaction is carried out, the product obtained by the modification reaction is sequentially filtered and dried before the calcination in step (3). The filtration and drying are procedures well known to those skilled in the art, and the present invention is not particularly limited.
According to the present invention, preferably, the roasting conditions of step (3) include: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
In the present invention, the optional clay in step (4) means that the clay may or may not be introduced during the beating.
In the present invention, the optional calcination in the step (4) means that the slurry may or may not be calcined after spray-drying. Preferably, the slurry is spray-dried and then calcined in step (4).
According to a preferred embodiment of the present invention, the step (4) comprises: pulping the modified ZSM-5 molecular sieve, the binder and the clay to obtain slurry, and performing spray drying and roasting on the slurry.
The conditions for the calcination in the step (4) are not particularly limited in the present invention, and may be conventionally selected in the art. Specifically, for example, the conditions for the calcination in the step (4) include: the temperature is 300-880 ℃, preferably 400-700 ℃; the time is 0.5-10h, preferably 1-6 h.
According to the present invention, preferably, the modified ZSM-5 molecular sieve, binder, and optionally clay are used in amounts such that the resulting catalyst has a modified ZSM-5 molecular sieve content of 25 to 50 wt% on a dry basis, a clay content of 12 to 45 wt% on a dry basis, and a binder content of 12 to 38 wt% on an oxide basis, based on the dry weight of the catalyst.
Further preferably, the modified ZSM-5 molecular sieve is present in an amount of 25 to 40 wt% on a dry basis, the clay is present in an amount of 25 to 40 wt% on a dry basis and the binder is present in an amount of 20 to 35 wt% on an oxide basis, based on the dry weight of the catalyst.
In the present invention, the selection ranges of the clay and the binder are as described above, and the present invention will not be described herein.
According to a preferred embodiment of the present invention, step (4) comprises pulping the filtrate obtained by filtration in step (1), the modified ZSM-5 molecular sieve, the binder and optionally the clay. In the preferred embodiment, the filtrate generated in the preparation process of the modified ZSM-5 molecular sieve is reused in the preparation process of the catalyst, and the filtrate contains Al, Si and Mg elements, so that the utilization rate of raw materials is improved, the environmental pollution is reduced, the energy consumption for preparing the catalyst is reduced, and the coke selectivity of the cracking reaction is reduced.
According to the present invention, it is preferred that the filtrate obtained by filtration in step (1) has a total content of aluminum in terms of oxide and silicon in terms of oxide of 1 to 20% by weight, preferably 5 to 10% by weight.
According to the present invention, it is preferred that the filtrate obtained by filtration in step (1) is used in such an amount that the resultant catalyst contains Al introduced from the filtrate obtained by filtration in step (1) on a dry basis based on the weight of the catalyst2O3And SiO2The total content of (B) is 5-10 wt%.
According to the present invention, preferably, the solid content of the slurry in the step (4) is 15 to 45% by weight, and more preferably 30 to 40% by weight.
According to a specific embodiment of the invention, the binder in step (4) is pseudo-boehmite and alumina sol, and the pulping process in step (4) comprises: mixing the aluminum sol and the pseudo-boehmite, then adding the clay, adding acid for acidification, and finally adding the modified ZSM-5 molecular sieve.
The acidification in step (4) is not particularly limited in the present invention, and may be carried out according to a conventional technique in the art. The present invention has a wide choice of the acid used for the acidification in step (4), and may be, for example, a mineral acid conventionally used in the art, including but not limited to hydrochloric acid. The weight ratio of the acid to the pseudoboehmite in the step (4) is preferably 0.01 to 1.
The spray drying in the invention is the prior art, and the invention has no special requirements, and is not described in detail herein.
In a third aspect, the present invention provides a catalyst prepared by the method described above. When the catalyst is applied to cracking reaction, the cracking capability is stronger, the yield of low-carbon olefin is higher and the propylene selectivity is higher.
Accordingly, a fourth aspect of the invention provides the use of a catalyst as described above in catalytic cracking.
In a fifth aspect, the present invention provides a method of catalytic cracking, the method comprising: under the condition of catalytic cracking, the hydrocarbon oil is contacted with a catalyst to react; the catalyst is as described above.
In the present invention, the selection range of the hydrocarbon oil is wide, and the hydrocarbon oil can be selected conventionally in the field, and the present invention is not described herein again.
The reaction conditions for the catalytic cracking in the present invention are widely selected, and specifically, for example, the reaction conditions may include: the temperature is 400-650 ℃, preferably 580-640 ℃; the ratio of agent to oil (by weight) is 3-10, preferably 4-8.
According to the present invention, preferably, the method for catalytic cracking further comprises: the catalyst is subjected to hydrothermal aging before the reaction is carried out. The invention has wider selection range of the conditions of the hydrothermal aging, and preferably, the hydrothermal aging is carried out by adopting 90-100% of water vapor. Further preferably, the hydrothermal aging conditions further include: the temperature is 700-900 ℃, preferably 750-850 ℃ and the time is 5-24h, preferably 10-16 h.
The present invention will be described in detail below by way of examples.
In the following examples, room temperature means 25 ℃ unless otherwise specified;
the specifications of the raw materials used in the examples are as follows:
kaolin: with a solids content of 72% by weight, manufactured by china kaolin, inc (suzhou).
Sulfuric acid, oxalic acid: analyzing and purifying;
aluminum sol: al (Al)2O322 wt%, produced by Qilu Branch of China petrochemical catalyst, Inc.;
pseudo-boehmite: solid content 72 wt%, Shandong aluminum industries, China;
ZSM-5 molecular sieve: produced by Qilu division of China petrochemical catalyst, Inc. (amine-free synthesis);
CGP catalyst: re produced by Qilu division, China petrochemical catalyst, Inc2O3Content 3.2 wt.%, Al 2O3Content 51.2 wt.%, Na2The O content was 0.15% by weight.
The composition of the catalyst is determined by calculating the feeding amount of each raw material.
In the examples, the following methods were used to evaluate relevant parameters of the catalysts prepared:
(1) total pore volume:
the measurement was carried out by the RIPP151-90 method in "analytical methods in petrochemical industry, RIPP test method" (edited by Yangchi, scientific Press, 1990).
(2) Abrasion index:
the determination was carried out by the RIPP29-90 method in "analytical methods in petrochemical industry, RIPP test methods" (edited by Yangchi, scientific Press, 1990).
(3) Microreflective activity (i.e., heavy oil conversion):
the measurement was carried out by using the ASTM D5154-2010 standard method.
(4) Hydrocarbon composition of reaction product:
the determination was carried out by the RIPP85-90 method in "analytical methods in petrochemical industry, RIPP test methods" (edited by Yangchi, scientific Press, 1990).
(5) Specific surface area of catalyst:
the samples were degassed at 300 ℃ for 6 hours before testing as determined by GB/T5816-;
in the examples, the following methods were used to evaluate relevant parameters of the modified ZSM-5 molecular sieves prepared:
(1) degree of crystallinity:
measured using the standard method of ASTM D5758-2001(2011) e 1.
(2)SiO2/Al2O3The molar ratio is as follows:
the content of the silicon oxide and the aluminum oxide is calculated, and the content of the silicon oxide and the aluminum oxide is measured by a GB/T30905-2014 standard method.
(3) Comprises the following components:
and (3) adopting fluorescence spectrum analysis, and referring to the GB/T30905-2014 standard method for determination.
(4) Total specific surface area (SBET), mesopore volume, total pore volume, mesopore volume of 5-20 nm:
the determination is carried out by adopting AS-3 and AS-6 static nitrogen adsorption instruments produced by Congta Quantachrome company of America, and the instrument parameters are AS follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 300 deg.C-2Pa, keeping the temperature and the pressure for 4h, and purifying the sample. Testing the purified samples at different specific pressures P/P at a liquid nitrogen temperature of-196 DEG C0The adsorption quantity and the desorption quantity of the nitrogen under the condition are obtained to obtain N2Adsorption-desorption isotherm curve. Then, calculating the total specific surface area by utilizing a BET formula of two parameters; proportional pressure P/P0The adsorption capacity of 0.98 or less is the total pore volume of the sample; the pore size distribution of the mesoporous part is calculated by a BJH formula, and the mesoporous volume (5-50nm) and the mesoporous volume (5-20 nm) are calculated by an integration method.
(5) Acid amount of B acid and acid amount of L acid:
the measurement is carried out by adopting FTS3000 type Fourier infrared spectrometer manufactured by BIO-RAD company in America, and the test conditions are as follows: pressing the sample into tablet, sealing in an in-situ cell of an infrared spectrometer, and vacuumizing to 10 deg.C at 350 deg.C -3Pa, keeping for 1h to enable gas molecules on the surface of the sample to be desorbed completely, and cooling to room temperature. Leading to the in-situ pondAdding pyridine vapor with pressure of 2.67Pa, balancing for 30min, heating to 200 deg.C, and vacuumizing to 10 deg.C-3Pa, keeping for 30min, cooling to room temperature at 1400-1700cm-1Scanning in wave number range, and recording infrared spectrogram of pyridine adsorption at 200 ℃. Then the sample in the infrared absorption cell is moved to a heat treatment area, the temperature is raised to 350 ℃, and the vacuum is pumped to 10 DEG-3Pa, keeping for 30min, cooling to room temperature, and recording the infrared spectrogram of pyridine adsorption at 350 ℃. And automatically integrating by an instrument to obtain the acid content of the B acid and the acid content of the L acid.
(6) Total acid amount and strong acid amount:
the determination is carried out by adopting an Autochem II 2920 programmed temperature desorption instrument of Michman, USA, and the test conditions are as follows: weighing 0.2g of a sample to be detected, putting the sample into a sample tube, placing the sample tube in a thermal conductivity cell heating furnace, taking He gas as carrier gas (50mL/min), raising the temperature to 600 ℃ at the speed of 20 ℃/min, and purging for 60min to remove impurities adsorbed on the surface of the catalyst. Then cooling to 100 ℃, keeping the temperature for 30min, and switching to NH3-He mixed gas (10.02% NH)3+ 89.98% He) for 30min, and then continuing to purge with He gas for 90min until the baseline is stable, so as to desorb the physically adsorbed ammonia gas. And (4) heating to 600 ℃ at the heating rate of 10 ℃/min for desorption, keeping for 30min, and finishing desorption. Detecting gas component change by TCD detector, and automatically integrating by instrument to obtain total acid amount and strong acid amount, wherein acid center of strong acid is NH 3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
Example 1
The method for preparing the catalytic cracking catalyst comprises the following specific steps:
(1) taking ZSM-5 molecular Sieve (SiO)2/Al2O3The molar ratio is 27), 100g (dry basis weight), 600g of neutral water (also called distilled water in the invention), 20g of NaOH solution (the molar concentration is 0.833mol/L) and 20g of MgO are added, the temperature is raised to 70 ℃, after contact reaction is carried out for 2 hours, the mixture is cooled to the room temperature, and then the solid product is obtained by filtering, washing and drying in sequence; the filtrate was obtained for future use, and the content of elements in the filtrate was measured by the ICP analytical method, and the total weight content of aluminum in terms of oxides and silicon in terms of oxides in the filtrate was 7% by weight, and the specific ingredients are shown in table 1.
(2) Taking 80g (dry basis weight) of the solid product obtained in the step (1), pulping with 640g of water, and then adding 40g of H with the weight content of 20 wt%2SO460g of oxalic acid, heating to 70 ℃, carrying out acid treatment for 2 hours, and then sequentially carrying out filtration, washing and drying;
(3) taking 50g (dry basis weight) of the product obtained in the step (2), adding 200g of neutral water, 5.23g of zirconium oxychloride, 4.33g of cerous chloride and 1.86g of diammonium hydrogen phosphate, heating to 70 ℃, carrying out modification reaction for 2h, sequentially filtering and drying, and roasting at 650 ℃ for 2.5h to obtain a modified ZSM-5 molecular sieve S1, wherein the specific physicochemical property data are listed in Table 4;
(4) Pulping the modified ZSM-5 molecular sieve, the pseudo-boehmite, the alumina sol and the kaolin obtained in the step (3) with hydrochloric acid with the weight concentration of 22 wt% to obtain slurry, wherein the solid content of the slurry is 35 wt%; spray drying the slurry to obtain a microspherical catalyst, roasting the microspherical catalyst at 500 ℃ for 2 hours to obtain a catalytic cracking catalyst C1, wherein the specific physicochemical properties are listed in Table 5;
the amount of hydrochloric acid having a weight concentration of 22% by weight was 10.28 parts by weight relative to 100 parts by weight of the modified ZSM-5 molecular sieve;
calculated by alumina, the weight ratio of the used amount of the pseudo-boehmite to the used amount of the alumina sol is 2.25: 1; the modified ZSM-5 molecular sieve, the pseudo-boehmite, the alumina sol and the kaolin are used in amounts such that, in the prepared catalyst, the content of the modified ZSM-5 molecular sieve is 35 wt% on a dry basis, the content of the clay is 39 wt% on a dry basis and the content of the binder is 26 wt% on an oxide basis, based on the dry basis weight of the catalyst.
Examples 1 to 1
A catalytic cracking catalyst was prepared according to the method of the present invention, and steps (1), (2) and (3) were the same as in example (1), except that step (4) was performed according to the following procedure:
(4) pulping the filtrate obtained in the step (1), the modified ZSM-5 molecular sieve obtained in the step (3), the pseudo-boehmite, the alumina sol and the kaolin with hydrochloric acid with the weight concentration of 22 wt% to obtain slurry, wherein the solid content of the slurry is 33 wt%; spray drying the slurry to obtain a microspherical catalyst, and roasting the microspherical catalyst at 500 ℃ for 1h to obtain a catalytic cracking catalyst C1-1;
The amount of hydrochloric acid having a weight concentration of 22% by weight was 10.28 parts by weight relative to 100 parts by weight of the modified ZSM-5 molecular sieve; the amount of filtrate used was such that in the catalyst C1-1 obtained, Al was introduced from the filtrate on a dry weight basis of the catalyst2O3And SiO2The total content of (a) is 7% by weight;
calculated by alumina, the weight ratio of the used amount of the pseudo-boehmite to the used amount of the alumina sol is 2.25: 1;
in the preparation process of the catalyst, the weight ratio of the modified ZSM-5 molecular sieve, the total amount of the pseudoboehmite and the alumina sol counted by alumina and the kaolin counted by dry basis is 35: 26: 39.
comparative example 1
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that 20g of MgO was not added in the step (1);
the steps (2), (3) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve SD1, and the specific physicochemical property data are listed in Table 4; catalyst D1 was obtained, and the specific physicochemical properties are shown in Table 5.
Comparative example 2
The modified ZSM-5 molecular sieve is prepared according to the preparation method of example 1 in CN107973317A to obtain a modified ZSM-5 molecular sieve SD2, and the specific physicochemical property data are listed in Table 4;
catalyst D2 was obtained according to the procedure of step (4) in example 1, and the specific physicochemical properties are shown in Table 5.
Example 2
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that, in the step (2), H was contained in an amount of 20% by weight2SO4The dosage of the oxalic acid is 80g, and the dosage of the oxalic acid is 120 g;
the steps (1), (3) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve S2, and the specific physicochemical property data are listed in Table 4; catalyst C2 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 3
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate was replaced with 13.08g of zirconium oxychloride;
the steps (1), (2) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve S3, and the specific physicochemical property data are listed in Table 4; catalyst C3 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 4
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate were replaced with 10.83g of cerous chloride;
the steps (1), (2) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve S4, and the specific physicochemical property data are listed in Table 4; catalyst C4 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 5
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate was replaced with 9.3g of diammonium hydrogen phosphate;
the steps (1), (2) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve S5, and the specific physicochemical property data are listed in Table 4; catalyst C5 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 6
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that in step (3), 5.23g of zirconium oxychloride, 4.33g of cerous chloride, 1.86g of diammonium hydrogen phosphate were replaced with 2.62g of zirconium oxychloride, 2.17g of cerous chloride, 1g of titanium dioxide, 1.40g of diammonium hydrogen phosphate and 1.33g of boric acid;
the steps (1), (2) and (4) are carried out according to the method of the embodiment 1 to obtain the modified ZSM-5 molecular sieve S6, and the specific physicochemical property data are listed in Table 4; catalyst C6 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 7
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that the molar ratio of Si to Al of the ZSM-5 molecular sieve in step (1) was different and the SiO of the ZSM-5 molecular sieve was different2/Al2O3The molar ratio is 45;
the steps (1), (2), (3) and (4) are carried out according to the method of the example 1 to obtain the modified ZSM-5 molecular sieve S7, and the specific physicochemical property data are listed in Table 4; catalyst C7 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 8
A catalytic cracking catalyst was prepared in the same manner as in example 1, and steps (1), (2) and (4) were carried out in the same manner as in example 1, except that the modification reaction was not carried out in step (3), i.e., 50g of the product obtained in step (2) was calcined at 650 ℃ for 2 hours to obtain modified ZSM-5 molecular sieve S8, and the specific physicochemical property data are shown in Table 4; catalyst C8 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 9
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that MgO was replaced with the same mass of CaO in terms of oxides. Obtaining the modified ZSM-5 molecular sieve S9, wherein the specific physicochemical property data are listed in Table 4; catalyst C9 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 10
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that the amount of the NaOH solution used in step (1) was 5g and the amount of MgO was 12 g. Obtaining the modified ZSM-5 molecular sieve S10, wherein the specific physicochemical property data are listed in Table 4; catalyst C10 was obtained, the physical and chemical properties of which are shown in Table 5.
Example 11
A catalytic cracking catalyst was prepared in the same manner as in example 1, except that MgO was replaced with MgCl of the same quality in terms of oxide 2. Obtaining the modified ZSM-5 molecular sieve S11, wherein the specific physicochemical property data are listed in Table 4; catalyst C11 was obtained, the physical and chemical properties of which are shown in Table 5.
TABLE 1
| Element(s) | Al | Si | Na | Mg |
| content/(g.L)-1) | 0.23 | 3.05 | 1.12 | 0.22 |
Test example 1
This test example was used to evaluate the performance of the catalytic cracking catalysts prepared in the above examples.
Wherein the catalysts of the examples and the CGP catalyst were blended in a weight ratio of 3: 1.
The mixed catalyst is aged and deactivated by 100 percent water vapor at 800 ℃ for 12 hours by adopting a fixed fluidized bed device. The loading of the catalyst is 9g, the reaction raw material is Wu-MI-Sanyuan oil, and the raw materials are shown in Table 2. The reaction temperature was 560 ℃ and the catalyst oil ratio (by weight) was 6, and the measured catalyst performance parameters are shown in Table 5.
Conversion rate of gasoline, liquefied gas, dry gas and coke
Coke selectivity-coke yield/conversion
TABLE 2
Test example 2
This test example was used to evaluate the performance of the catalytic cracking catalysts prepared in the above examples.
The catalyst is aged and deactivated by 100 percent water vapor at 800 ℃ for 12 hours by adopting a fixed fluidized bed device. The reaction raw material is Shanghai hydrogenated tail oil, and the raw material is shown in Table 3. The reaction temperature is 620 ℃, the catalyst-oil ratio (weight) is 10, and the space velocity is 4h -1And the water injection amount (measured according to the weight ratio of the reaction raw materials to the water vapor) is 37.5 percent. The measured catalyst performance parameters are listed in table 6.
Conversion rate of gasoline, liquefied gas, dry gas and coke
Propylene selectivity ═ propylene yield/liquefied gas yield
Ethylene selectivity ═ ethylene yield/dry gas yield
Coke selectivity-coke yield/conversion
TABLE 3
TABLE 4
| Modified ZSM-5 molecular sieve | S1 | SD1 | SD2 | S2 | S3 | S4 |
| Degree of crystallization/%) | 75 | 85 | 87 | 58 | 72 | 70 |
| SiO2/Al2O3Molar ratio of | 25 | 22 | 35 | 24 | 23 | 24 |
| SBET/(m2/g) | 289 | 256 | 420 | 224 | 267 | 255 |
| (VMesoporous structure/VGeneral hole)/％ | 49 | 32 | 58 | 36 | 40 | 38 |
| (V5nm-20nm/VMesoporous structure)/％ | 96 | 90 | 90 | 90 | 90 | 91 |
| (amount of strong acid/total acid)/% | 41 | 45 | 60 | 44 | 45 | 45 |
| Acid amount of B acid/acid amount of L acid | 10 | 36 | 15 | 25 | 25 | 22 |
| Na2O content/weight% | 0.08 | 0.09 | 0.13 | 0.10 | 0.08 | 0.09 |
| MgO content/weight% | 18.9 | - | - | 14.7 | 17.6 | 17.2 |
| CaO content/weight% | - | - | - | - | - | - |
| ZrO2Content/weight% | 3.56 | 3.78 | - | 3.42 | 9.1 | - |
| CeO2Content/weight% | 3.78 | 3.91 | - | 3.69 | - | 8.9 |
| TiO2Content/weight% | - | - | - | - | - | - |
| P2O5Content/weight% | 1.89 | 1.92 | 7.5 | 1.88 | - | - |
| B2O3Content/weight% | - | - | - | - | - | - |
TABLE 4
| Modified ZSM-5 molecular sieve | S5 | S6 | S7 | S8 | S9 | S10 | S11 |
| Degree of crystallization/%) | 68 | 65 | 71 | 78 | 70 | 88 | 70 |
| SiO2/Al2O3Molar ratio of | 23 | 22 | 39 | 25 | 25 | 27 | 24 |
| SBET/(m2/g) | 252 | 240 | 278 | 312 | 278 | 315 | 277 |
| (VMesoporous structure/VGeneral hole)/％ | 41 | 44 | 46 | 27 | 42 | 46 | 38 |
| (V5nm-20nm/VMesoporous structure)/％ | 90 | 91 | 93 | 68 | 89 | 92 | 89 |
| (amount of strong acid/total acid)/% | 48 | 44 | 50 | 55 | 46 | 55 | 46 |
| Acid amount of B acid/acid amount of L acid | 28 | 26 | 15 | 18 | 17 | 18 | 15 |
| Na2O content/weight% | 0.09 | 0.08 | 0.10 | 0.14 | 0.10 | 0.11 | 0.09 |
| MgO content/weight% | 17.9 | 17.1 | 18.7 | 19.3 | - | 10.86 | 18.32 |
| CaO content/weight% | - | - | - | - | 17.8 | - | - |
| ZrO2Content/weight% | - | 1.89 | 3.32 | - | 3.52 | 3.53 | 3.59 |
| CeO2Content/weight% | - | 1.86 | 3.45 | - | 3.68 | 3.75 | 3.65 |
| TiO2Content/weight% | - | 1.77 | - | - | - | - | - |
| P2O5Content/weight% | 9.6 | 1.24 | 1.78 | - | 1.91 | 1.85 | 1.86 |
| B2O3Content/weight% | - | 1.09 | - | - | - | - | - |
Note: vMesoporous structure/VGeneral holeModified ZSM-5 molecular sieve representing mesopore volumeThe proportion of total pore volume;
V5nm-20nm/Vmesoporous structureRepresents the proportion of the mesoporous volume with the aperture of 5nm to 20nm in the total mesoporous volume;
the strong acid amount/total acid amount represents the ratio of the strong acid amount to the total acid amount;
The amount of B acid/L acid represents the ratio of the amount of B acid to the amount of L acid.
TABLE 5
TABLE 5 continuation
TABLE 6
The data in table 4 show that the modified ZSM-5 molecular sieve containing the alkaline earth metal element obtained by the method of the present invention has richer mesopores, higher mesopore content between 5nm and 20nm in pore diameter, lower proportion of strong acid to total acid, and lower proportion of acid amount of B acid to acid amount of L acid, and is beneficial to generation and diffusion of intermediates and products of isomerization reaction and aromatization reaction under the synergistic effect with the alkaline earth metal element, thereby reducing coking deactivation, and inhibiting hydrogen transfer reaction of generated olefin, and increasing the yield of low carbon olefin.
From the data in tables 5 and 6, it can be seen that when the catalyst prepared by using the modified ZSM-5 molecular sieve of the present invention is used for catalytic cracking, the cracking ability of the catalyst is stronger, the liquefied gas yield, the ethylene yield, the propylene yield are higher, and the propylene selectivity is higher.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A catalytic cracking catalyst, the catalyst comprising: modified ZSM-5 molecular sieve and binder and optionally clay; based on the dry weight of the catalyst, the content of the modified ZSM-5 molecular sieve is 20-60 wt% in terms of dry basis, the content of the clay is 0-50 wt% in terms of dry basis, and the content of the binder is 10-40 wt% in terms of oxide;
the modified ZSM-5 molecular sieve comprises a ZSM-5 molecular sieve and an alkaline earth metal element; on the basis of the dry weight of the modified ZSM-5 molecular sieve, the content of the alkaline earth metal element is 10-30 wt% calculated by oxide;
SiO of the modified ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50;
the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 25-60% of the total pore volume of the modified ZSM-5 molecular sieve;
the ratio of the B acid amount to the L acid amount of the modified ZSM-5 molecular sieve is 8-45.
2. The catalyst of claim 1, wherein the modified ZSM-5 molecular sieve is present in an amount of 25 to 50 wt% on a dry basis, the clay is present in an amount of 12 to 45 wt% on a dry basis, and the binder is present in an amount of 12 to 38 wt% on an oxide basis, based on the weight of the catalyst on a dry basis;
preferably, the modified ZSM-5 molecular sieve is present in an amount of 25 to 40 wt% on a dry basis, the clay is present in an amount of 25 to 40 wt% on a dry basis, and the binder is present in an amount of 20 to 35 wt% on an oxide basis, based on the dry weight of the catalyst;
Preferably, the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, preferably kaolin and/or halloysite;
preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, preferably at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphoalumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
3. The catalyst according to claim 1 or 2, wherein the modified ZSM-5 molecular sieve has a mesopore volume of 5nm to 20nm in a proportion of 85% or more, preferably 90% or more, of the total mesopore volume;
preferably, the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 30-50% of the total pore volume of the modified ZSM-5 molecular sieve;
preferably, the modified ZSM-5 molecular sieve has SiO2/Al2O3The molar ratio is 20-40;
Preferably, the content of the alkaline earth metal element is 12 to 20% by weight in terms of oxide.
4. The catalyst of any one of claims 1 to 3, wherein the modified ZSM-5 molecular sieve has a strong acid content of 35-55%, preferably 40-50%, based on the total acid content;
preferably, the modified ZSM-5 molecular sieve has a ratio of the amount of the B acid to the amount of the L acid of 8 to 30, preferably 10 to 28.
5. The catalyst according to any one of claims 1 to 4, wherein the modified ZSM-5 molecular sieve further comprises an auxiliary element, wherein the auxiliary element is present in an amount of 1 to 15 wt%, preferably 6 to 12 wt%, and more preferably 7 to 10 wt%, calculated as an oxide, based on the dry weight of the modified ZSM-5 molecular sieve;
the auxiliary element comprises a first auxiliary element and/or a second auxiliary element;
the first auxiliary element is selected from at least one of IB group, IIB group, IVB group, VIIB group, VIII group and rare earth elements, preferably the first auxiliary element is selected from at least one of Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn element, preferably at least one of Ti, Zr and Ce element;
the second auxiliary element is at least one element selected from B, P and N, preferably, the second auxiliary element is B element and/or P element;
Preferably, the content of the first auxiliary element is 1-10 wt%, preferably 5-10 wt%, and more preferably 5-9 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve; the content of the second auxiliary element is 0.1-10, preferably 0.1-5 wt%, and more preferably 1-3 wt%;
preferably, the alkaline earth metal element is at least one element selected from Mg, Ca, Sr and Ba elements, and more preferably Mg element.
6. A method of preparing a catalytic cracking catalyst, the method comprising:
(1) in the presence of a first solvent, contacting a ZSM-5 molecular sieve with compounds of alkali and alkaline earth metals, and then sequentially filtering and drying to obtain a solid product;
(2) carrying out acid treatment on the solid product obtained in the step (1) by adopting an acid solution;
(3) roasting the product after acid treatment to obtain a modified ZSM-5 molecular sieve;
(4) pulping the modified ZSM-5 molecular sieve, the binder and the optional clay to obtain slurry, and performing spray drying and optional roasting on the slurry;
the modified ZSM-5 molecular sieve, the binder and the optional clay are used in amounts such that the prepared catalyst has a modified ZSM-5 molecular sieve content of 20-60 wt% on a dry basis, a clay content of 0-50 wt% on a dry basis and a binder content of 10-40 wt% on an oxide basis, based on the dry weight of the catalyst;
The ZSM-5 molecular sieve and the alkaline earth metal compound are used in an amount such that the modified ZSM-5 molecular sieve contains 10-30 wt% of the alkaline earth metal element in terms of oxide based on the dry weight of the modified ZSM-5 molecular sieve;
SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 15-50.
7. The process of claim 6, wherein the ZSM-5 molecular sieve and the compound of an alkaline earth metal are used in an amount such that the modified ZSM-5 molecular sieve is produced with an alkaline earth metal element content of 12 to 20 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve;
preferably, the SiO of the ZSM-5 molecular sieve2/Al2O3The molar ratio is 20-40;
preferably, the ZSM-5 molecular sieve is selected from at least one of an ammonium type ZSM-5 molecular sieve, a Na type ZSM-5 molecular sieve and a hydrogen type ZSM-5 molecular sieve, and is preferably a Na type ZSM-5 molecular sieve.
8. The method of claim 6, wherein the base is selected from at least one of sodium hydroxide, potassium carbonate, and sodium carbonate;
preferably, the base is introduced in the form of an alkaline solution having a molar concentration of 0.1 to 2mol/L, preferably 0.3 to 0.9 mol/L;
Preferably, the alkali solution is used in an amount of 1 to 100 parts by weight, preferably 5 to 20 parts by weight, relative to 100 parts by weight of the ZSM-5 molecular sieve;
preferably, the alkaline earth metal is selected from at least one of Mg, Ca, Sr and Ba elements, more preferably Mg element;
preferably, the compound of the alkaline earth metal is selected from at least one of an oxide, a chloride, a nitrate and a sulfate of the alkaline earth metal, more preferably at least one of magnesium oxide, magnesium chloride, magnesium sulfate and magnesium nitrate;
preferably, the first solvent is used in an amount of 100-1000 parts by weight with respect to 100 parts by weight of the ZSM-5 molecular sieve.
9. The method of any one of claims 6-8, wherein the contacting conditions of step (1) comprise: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
10. The method according to any one of claims 6 to 9, wherein the acid of step (2) is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid and acetic acid, preferably sulfuric acid and/or oxalic acid, and further preferably sulfuric acid and oxalic acid;
preferably, the weight ratio of the sulfuric acid to the oxalic acid is 1: 1-4;
Preferably, the acid solution has a weight content of 5-98 wt.%, preferably 10-30 wt.%;
preferably, the weight ratio of the acid to the solid product obtained in step (1) on a dry basis is from 0.5 to 2;
preferably, the reaction conditions of the acid treatment of step (2) include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
11. The method according to any one of claims 6 to 10, wherein the method further comprises modifying the product obtained by the acid treatment in step (2) after step (2) and before step (3), wherein the modification comprises: carrying out modification reaction on the product obtained by acid treatment in the step (2) and a soluble compound of an auxiliary agent in the presence of a second solvent;
preferably, the soluble compound of the auxiliary agent is used in an amount such that the content of the auxiliary agent element in the prepared modified ZSM-5 molecular sieve is 1-15 wt%, preferably 6-12 wt%, and more preferably 7-10 wt%, calculated as oxide, based on the dry weight of the modified ZSM-5 molecular sieve;
the auxiliary element comprises a first auxiliary element and/or a second auxiliary element;
the first auxiliary element is selected from at least one of IB group, IIB group, IVB group, VIIB group, VIII group and rare earth elements, preferably the first auxiliary element is selected from at least one of Zr, Ti, Ag, La, Ce, Fe, Cu, Zn and Mn element, preferably at least one of Ti, Zr and Ce element;
The second auxiliary element is at least one element selected from B, P and N, preferably, the second auxiliary element is B element and/or P element;
preferably, the soluble compound of the auxiliary agent is used in an amount such that the content of the first auxiliary agent element in the prepared modified ZSM-5 molecular sieve is 1 to 10 wt%, preferably 5 to 10 wt%, and more preferably 5 to 9 wt%, calculated as an oxide; the content of the second auxiliary element is 0.1-10, preferably 0.1-5 wt%, and more preferably 1-3 wt%;
preferably, the conditions of the modification reaction include: the temperature is 50-90 ℃ and the time is 1-5 h; preferably, the temperature is 60-80 ℃ and the time is 2-3 h.
12. The method of any one of claims 6-11, wherein the firing conditions of step (3) comprise: the temperature is 500-800 ℃, preferably 550-650 ℃; the time is 1-10h, preferably 2-3 h.
13. The process of any of claims 6-12, wherein the modified ZSM-5 molecular sieve, binder, and optionally clay are used in amounts such that the resulting catalyst has a modified ZSM-5 molecular sieve content of 25 to 50 wt% on a dry basis, a clay content of 12 to 45 wt% on a dry basis, and a binder content of 12 to 38 wt% on an oxide basis, based on the dry weight of the catalyst;
Preferably, the modified ZSM-5 molecular sieve is present in an amount of 25 to 40 wt% on a dry basis, the clay is present in an amount of 25 to 40 wt% on a dry basis and the binder is present in an amount of 20 to 35 wt% on an oxide basis, based on the dry weight of the catalyst.
14. The process according to any one of claims 6 to 13, wherein the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, preferably kaolin and/or halloysite;
preferably, the binder is a refractory inorganic oxide, preferably one or more of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, and/or a refractory inorganic oxide precursor, which is at least one of acidified pseudo-boehmite, alumina sol, silica sol, phosphor-alumina sol, silica-alumina sol, magnesium-alumina sol, zirconium sol and titanium sol, preferably acidified pseudo-boehmite and alumina sol.
15. The method of any one of claims 6-14, wherein step (4) comprises slurrying the filtrate filtered in step (1), the modified ZSM-5 molecular sieve, the binder, and optionally the clay;
Preferably, the filtrate obtained by filtration in step (1) has a total weight content of aluminium in terms of oxides and silicon in terms of oxides of from 1 to 20% by weight, preferably from 5 to 10% by weight;
preferably, the filtrate obtained by filtering in the step (1) is used in an amount such that Al introduced into the obtained catalyst from the filtrate obtained by filtering in the step (1) is used based on the dry weight of the catalyst2O3And SiO2The total content of (A) is 5-10 wt%;
preferably, the slurry of step (4) has a solids content of 15 to 45 wt%, preferably 30 to 40 wt%.
16. A catalyst prepared by the process of any one of claims 6 to 15.
17. Use of a catalyst as claimed in any one of claims 1 to 5 and 16 in catalytic cracking.
18. A method of catalytic cracking, the method comprising: under the condition of catalytic cracking, the hydrocarbon oil is in contact reaction with a catalyst; the catalyst is as claimed in any one of claims 1 to 5 and 16.
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| CN116060095A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of modified ZSM-5 molecular sieve |
| CN114192184A (en) * | 2021-12-31 | 2022-03-18 | 新疆理工学院 | Cracking catalyst and preparation method and application thereof |
| CN114192184B (en) * | 2021-12-31 | 2023-08-11 | 新疆理工学院 | Cracking catalyst and preparation method and application thereof |
| CN115805098A (en) * | 2023-02-07 | 2023-03-17 | 河北鑫鹏新材料科技有限公司 | Catalytic cracking catalyst containing phosphorus-silicon composite binder and preparation method thereof |
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