CN111744541A - Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve and preparation method thereof - Google Patents
Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 62
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000005342 ion exchange Methods 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000011156 evaluation Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000008279 sol Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000009718 spray deposition Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 omits the roasting Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
Abstract
The invention provides a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve and a preparation method thereof. The method comprises the following steps: mixing and molding the sodium type high-silicon ZSM-5 molecular sieve and other raw materials for preparing the catalytic cracking catalyst; roasting, ammonium ion exchange, washing and drying the formed product to prepare the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve; wherein the sodium type high-silicon ZSM-5 molecular sieve is a sodium type high-silicon ZSM-5 molecular sieve which is not demoulded and/or is not subjected to ion exchange treatment. The technical scheme of the invention simplifies the roasting, demoulding and/or ion exchange processes of the high-silicon sodium type molecular sieve at the early stage of catalyst preparation, shortens the process flow of catalyst preparation, reduces a large amount of energy consumption and reduces the synthesis cost. The catalytic cracking reaction evaluation result shows that compared with the catalyst obtained by the traditional method, the catalyst prepared by the method has equivalent gasoline and diesel yield and propylene yield.
Description
Technical Field
The invention relates to a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve and a preparation method thereof, belonging to the technical field of catalytic cracking catalysts.
Background
The petroleum is praised as industrial blood, and the black gold in economic development is used as an important fossil energy and has profound significance in the economic development of Chinese people. The catalytic cracking technology is an important production technology for secondary processing of crude oil, and has the characteristics of low investment, flexible product scheme, low operation pressure, high yield of light oil, high conversion rate of heavy oil, wide adaptability of raw materials and the like. The produced commercial gasoline accounts for over 80 percent in China, the commercial diesel oil accounts for about 33 percent, and partial olefin resources are provided. Since the development of 1942, the catalytic cracking technology has been greatly developed and innovated. The main growth point of the global catalytic cracking development is in China, and the processing capacity of 210Mt/a is achieved at present.
It is worth noting that such a huge processing capacity is followed by a large consumption of the associated catalytic cracking catalyst. The ZSM-5 molecular sieve has a unique MFI framework pore channel structure and good shape-selective catalytic performance, so that the ZSM-5 molecular sieve becomes a very important active component in a catalytic cracking catalyst. At present, the preparation process of the catalytic cracking catalyst with ZSM-5 added in the industry is complicated, and generally comprises the following steps: the synthesis of the molecular sieve, roasting and demoulding, ion exchange, spray forming of the catalyst, ion exchange and a subsequent series of drying and roasting processes are difficult to realize in all operation processes, particularly the roasting and demoulding process, which is accompanied with larger energy consumption and environmental problems, and in addition, the roasting process can influence the acidity of the molecular sieve to a certain extent.
In order to solve the problem, related researchers develop a template-free method for synthesizing the ZSM-5 molecular sieve. In 1981, Grose et al (Novel zeolite composition and process for preparation and use: US,4257885[ P ].1981-03-24) first successfully synthesized ZSM-5 molecular sieve at 200 ℃ for 68-72h without template, which proves that the template-free method is feasible and effective. Later, Itabashi K et al (A Working hydrolysis for purifying Framework Types of Zeolite in Seed-synthesized Synthesis with organic Structure-Directing Agent [ J ]. J Am Chem Soc,2012,134: 11542 and 11549) found that a molecular sieve having similar primary structural units to ZSM-5 could also be used as a Seed to induce the Synthesis of ZSM-5. Chinese patent CN105836756A discloses a method for preparing monodisperse regular-crystal-morphology ZSM-5 molecular sieve without a template agent by adding a small amount of MFI molecular sieve micronucleus sol solution into mother liquor. Chinese patent CN102502696A discloses a method for rapidly synthesizing nano ZSM-5 zeolite with good crystallinity under the condition of no template agent and low-price template agent dosage, which is characterized in that acid and alkali are added to respectively adjust the polymerization degrees of a silicon source and an aluminum source to obtain high-activity reactants, and a large amount of rapid nucleation can be performed in a system to obtain the nano zeolite.
In catalytic cracking catalysts, high silicon ZSM-5 is often used as the co-active component, because when the silica-alumina ratio of ZSM-5 is low, ZSM-5 has more strong acid centers, and carbon deposition is easy to deactivate in the catalytic reaction, which is not beneficial to exerting the shape selectivity, in contrast, high silicon ZSM-5 has higher stability.
The ZSM-5 shape-selective molecular sieve with high silica-alumina ratio can be successfully synthesized and prepared by using an organic template, and in order to dredge a pore channel and remove sodium to generate an acid center after preparation, the organic template is removed by a high-temperature roasting method, and then ion exchange is carried out. Therefore, in the production of the related industrial shape-selective ZSM-5 molecular sieve, after the high-silicon ZSM-5 is synthesized, roasting, demolding and ion exchange processes are often carried out, and the process is long, and the energy consumption and the material consumption are high.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a catalytic cracking catalyst and a preparation method thereof, the preparation method combines the preparation processes of a sodium type high-silicon ZSM-5 molecular sieve and the catalytic cracking catalyst, omits the roasting, membrane removal and/or ion exchange process of the molecular sieve at the early stage of preparation, simplifies the process production flow of the catalyst, greatly reduces the preparation cost, and the prepared catalyst can still keep good catalytic cracking activity.
In order to achieve the above purpose, the invention provides a preparation method of a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve, which comprises the following steps:
mixing and molding the sodium type high-silicon ZSM-5 molecular sieve and other raw materials of the catalytic cracking catalyst;
roasting, ammonium ion exchange, washing and drying the formed product to prepare the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve;
wherein the sodium type high-silicon ZSM-5 molecular sieve is a sodium type high-silicon ZSM-5 molecular sieve which is not demoulded and/or is not subjected to ion exchange treatment.
In the preparation process of the catalyst, the roasting, demoulding and/or ion exchange processes in the high-silicon ZSM-5 molecular sieve synthesis process are omitted, and the sodium content in the catalyst is reduced by means of the high-temperature roasting process in the forming stage of the catalyst and the formed ion exchange process, so that the preparation process flow of the catalyst is greatly shortened, the manufacturing cost is reduced, and the environment-friendly emission of the roasting template agent and the ion exchange is reduced.
In the preparation method, preferably, the sodium type high-silicon ZSM-5 molecular sieveSilicon to aluminum ratio (SiO) of2/Al2O3Molar ratio, the following is the same) of not less than 50; more preferably 120-300.
In the preparation method, preferably, the content of the sodium-type high-silicon ZSM-5 molecular sieve is 5-40% of the total mass of the raw material of the catalytic cracking catalyst; more preferably 15% to 35%.
In the above preparation method, the other raw materials may further include Y-type zeolite. The silica-alumina ratio of the Y-type zeolite is preferably not less than 7. The content of the Y-type zeolite may be controlled to be 0 to 35% (35% or less) based on the total mass of the raw material of the catalytic cracking catalyst. The Y-type zeolite may contain a rare earth element.
In the above production method, preferably, the other raw material includes a carrier. The content of the carrier may be 60% to 95%, preferably 65% to 85%, based on the total mass of the raw material of the catalytic cracking catalyst. The carrier may include one or a combination of two or more of kaolin, alumina sol, silica sol, and the like.
According to a specific embodiment of the present invention, the feedstock of the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve comprises, based on the total mass of the feedstock: 5-40% of sodium type high silicon ZSM-5 molecular sieve, 0-35% of Y type zeolite and 60-95% of carrier, wherein the sum of the percentages of the components is 100%.
In the above preparation method, preferably, the forming is performed by beating spray forming; more preferably, the slurry prepared by pulping has a solid content of 20% to 50% by weight. When preparing the slurry, a proper amount of water is required to be added according to the solid content requirement.
In the above preparation method, preferably, the temperature of the calcination is 350 ℃ or more (for example, controlled to 350 ℃ C. and 650 ℃ C.), and the time is 5 minutes or more (for example, controlled to 5 to 90 minutes).
In the above preparation method, the ammonium ion exchange may be carried out by a conventional ion exchange method, for example, the solid-liquid mass ratio of the molecular sieve to the deionized water is controlled to 1: 5-20. Preferably, the ammonium ion exchange conditions are 65-95 ℃ water bath heating for 3-12 h. The ammonium source used for ammonium ion exchange may be at least one selected from ammonium sulfate, ammonium nitrate, ammonium chloride, and ammonium phosphate. According to the embodiment of the invention, hydrochloric acid, sulfuric acid and phosphoric acid can be used for adjusting the pH value of the ammonium exchange solution.
In the above preparation method, preferably, the drying condition is drying at 60-120 ℃ for 12-36 h.
According to a specific embodiment of the present invention, the above preparation method can be performed according to the following specific steps:
mixing the sodium type high-silicon ZSM-5 molecular sieve which is not demoulded and/or is not subjected to ion exchange treatment with other raw materials of the catalytic cracking catalyst, pulping, and spray-forming;
roasting the spray-formed product at 350-650 ℃ for 5-90 minutes, then carrying out ammonium ion exchange for 3-12 hours under the water bath heating of 65-95 ℃, washing, and drying at 60-120 ℃ for 12-36 hours to prepare the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve.
The invention also provides a catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve, which is prepared by the preparation method.
The invention also provides the application of the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve in catalytic cracking, and preferably, the catalytic cracking catalyst is used as a catalyst or an auxiliary agent. The catalyst provided by the invention (or used as an auxiliary agent) can be used for improving the content of propylene and/or the octane number of gasoline.
It is noted that in the field of petrochemical processing, the large throughput base is a significant feature, for example, a catalytic cracker often reaches a throughput of one hundred or even several million tons/year, so that the overall yield of propylene is a little bit higher, even a few tenths of a percent, and is quite large. Because the market price of propylene is higher than that of gasoline and diesel oil, and the propylene belongs to a high-value product, people are always searching for a method capable of improving the yield of propylene. It is also obvious that the product gain is brought by increasing the octane number, and generally, the per ton selling price of the gasoline can be increased by more than one hundred yuan for every unit increase of the octane number.
The technical scheme of the invention simplifies the roasting, demoulding and/or ion exchange processes of the high-silicon sodium type molecular sieve at the early stage of catalyst preparation, shortens the process flow of catalyst preparation, reduces a large amount of energy consumption and reduces the synthesis cost. And the catalytic cracking reaction evaluation result shows that compared with the catalyst obtained by the traditional (including the previous roasting stripping and ion exchange process), the catalyst prepared by the method has the equivalent yield of gasoline, diesel and propylene.
Detailed Description
The following detailed description of the present invention/embodiments will be provided for the purpose of better understanding the technical features, objects and advantages of the present invention, but should not be construed as limiting the operable scope of the present invention.
Example 1
The embodiment provides a preparation method of a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve, which comprises the following steps (1-2):
(1) sodium type high silicon ZSM-5 molecular sieve with a silica-alumina ratio of 200 (without demoulding and ion exchange) is mixed with kaolin and alumina sol according to the following ratio: aluminum sol: molecular sieve 5: 1.5: 3.5, then carrying out spray forming on the mixture at high temperature and roasting for 60 minutes at 600 ℃;
(2) weighing 160g of deionized water and 40g of the spray-roasted sample, pouring the weighed sample into a 1000ml beaker, and stirring the sample in a 90 ℃ water bath; weighing 10.5g of ammonium sulfate (5 wt%), adding into the mixed solution, stirring and exchanging for 0.5h in water bath at 90 ℃; carrying out suction filtration on the mixed solution, adding no water, and carrying out suction drying, wherein the same steps are exchanged once again; carrying out suction filtration on the mixed solution again, adding deionized water, carrying out suction filtration to neutrality, and drying at 80-120 ℃ for 12-24h to obtain a sample labeled A1;
before the catalyst is evaluated for catalytic cracking reaction, the prepared fresh catalyst is aged in order to examine the equilibrium activity of the catalyst. The method specifically comprises the following steps: carrying out hydrothermal treatment on the sample A1 for 4 hours at 800 ℃ by using 100% of water vapor, and finally screening by using an electric screening machine to obtain a 40-60 mesh sample; then, mixing the screened catalyst sample with a catalytic cracking balancing agent (obtained from catalytic cracking unit of Qingyang petrochemical company of China) according to a mass ratio of 1: 9 and the resulting catalyst is labeled CK-1.
Example 2
The embodiment provides a preparation method of a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve, which comprises the following steps (1-3):
(1) weighing 400g of deionized water and 40g of sodium type high-silicon ZSM-5 molecular sieve (without demoulding and ion exchange) with the silicon-aluminum ratio of 200, pouring into a 1000ml beaker, and stirring in a water bath at 80 ℃; weighing 21.4g of ammonium chloride (1mol/L), adding the mixed solution, stirring in a water bath at 80 ℃, and exchanging for 3 h; carrying out suction filtration on the mixed solution without adding water, and carrying out suction drying; weighing 400g of deionized water and 21.4g of ammonium chloride with the same mass, mixing the deionized water and the ammonium chloride with the obtained filter cake, stirring in a water bath at 80 ℃, and exchanging for 3 hours; performing suction filtration on the mixed solution, adding deionized water, performing suction filtration to neutrality, and drying at 80-120 ℃ for 12-24 h;
(2) mixing the ammonium exchanged molecular sieve with kaolin and alumina sol according to the mass ratio of kaolin: aluminum sol: molecular sieve 5: 1.5: 3.5 mixing and pulping: then spray-forming the mixture at high temperature and roasting at 600 ℃ for 60 minutes;
(3) weighing 160g of deionized water and 40g of spray-molded and roasted sample, pouring into a 1000ml beaker, and stirring in a 90 ℃ water bath; weighing 10.5g of ammonium sulfate (5 wt%), adding the mixed solution, stirring in a water bath at 90 ℃, and exchanging for 0.5 h; carrying out suction filtration on the mixed solution, adding no water, and carrying out suction drying, wherein the same steps are exchanged once again; carrying out suction filtration on the mixed solution again, adding deionized water, carrying out suction filtration to neutrality, and drying at 80-120 ℃ for 12-24h to obtain a sample labeled A2;
before the catalyst is evaluated for catalytic cracking reaction, the prepared fresh catalyst is aged in order to examine the equilibrium activity of the catalyst. The method specifically comprises the following steps: carrying out hydrothermal treatment on the sample A2 for 4 hours at 800 ℃ by using 100% of water vapor, and finally screening by using an electric screening machine to obtain a 40-60 mesh sample; and (3) mixing the screened catalyst sample with the catalytic cracking balancing agent same as the catalytic cracking balancing agent in the example 1 according to the mass ratio of 1: 9 and the resulting catalyst is labeled CK-2.
Comparative example 1
The comparative example provides a preparation method of a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve, which comprises the following steps (1-4):
(1) roasting a sodium type high-silicon ZSM-5 molecular sieve with a silicon-aluminum ratio of 200 at 550 ℃ for 6 hours;
(2) weighing 400g of deionized water and 40g of roasted high-silicon ZSM-5 molecular sieve, pouring into a 1000ml beaker, and stirring in a water bath at 80 ℃; weighing 21.4g of ammonium chloride (1mol/L), adding the mixed solution, stirring in a water bath at 80 ℃, and exchanging for 3 h; carrying out suction filtration on the mixed solution without adding water, and carrying out suction drying; weighing 400g of deionized water and 21.4g of ammonium chloride with the same mass, mixing the deionized water and the ammonium chloride with the obtained filter cake, stirring in a water bath at 80 ℃, and exchanging for 3 hours; performing suction filtration on the mixed solution, adding deionized water, performing suction filtration to neutrality, and drying at 80-120 ℃ for 12-24 h;
(3) mixing the ammonium exchanged molecular sieve with kaolin and alumina sol according to the mass ratio of kaolin: aluminum sol: molecular sieve 5: 1.5: 3.5 mixing and pulping: then spray-forming the mixture at high temperature and roasting at 600 ℃ for 60 minutes;
(4) weighing 160g of deionized water and 40g of spray-molded and roasted sample, pouring into a 1000ml beaker, and stirring in a 90 ℃ water bath; weighing 10.5g of ammonium sulfate (5 wt%), adding the mixed solution, stirring in a water bath at 90 ℃, and exchanging for 0.5 h; carrying out suction filtration on the mixed solution, adding no water, and carrying out suction drying, wherein the same steps are exchanged once again; carrying out suction filtration on the mixed solution again, adding deionized water, carrying out suction filtration to neutrality, and drying at 80-120 ℃ for 12-24h to obtain a sample labeled A3;
before the catalyst is evaluated for catalytic cracking reaction, the prepared fresh catalyst is aged in order to examine the equilibrium activity of the catalyst. The method specifically comprises the following steps: carrying out hydrothermal treatment on the sample A3 for 4 hours at 800 ℃ by using 100% of water vapor, and finally screening by using an electric screening machine to obtain a 40-60 mesh sample; and (3) mixing the screened catalyst sample with the catalytic cracking balancing agent same as the catalytic cracking balancing agent in the example 1 according to the mass ratio of 1: 9 and the resulting catalyst is labeled CK-3.
Comparative example 2
In the comparative example, 100% of a catalytic cracking balancing agent (obtained from catalytic cracking unit of Qingyang petrochemical company of China) is used as a catalytic cracking catalyst, and the catalyst is marked as CK-4.
Test example 1
XRF (X-ray fluorescence) test analysis was performed on the elemental contents of catalyst samples a1, a2 prepared in examples 1, 2 and catalyst sample A3 prepared in comparative example 1, and the results are shown in table 1.
As can be seen from the results of the elemental analyses, samples A1 and A2 obtained by subjecting the molecular sieves of examples 1 and 2 to treatments such as spraying and ion exchange, and Na2The O content is reduced to 0.362 wt.% and 0.318 wt.%, which is slightly higher than sample A3, but which has reached the general requirements of industrial production (< 1 wt.%).
TABLE 1 elemental content of catalyst samples
Note: all elements are not listed here because they are present in minor amounts and do not contribute to the end result
Test example 2
This test example provides a catalytic cracking performance test experiment of the above catalyst.
The evaluation unit ACE was a stationary fluidized bed. The ACE fixed fluidized bed apparatus was designed and manufactured by Kayser corporation of america. The experimental conditions were: 9 g of catalyst loading, 1.5 g of oil inlet amount, 75 seconds of oil inlet time, 6.0 of agent-oil ratio (m/m) and 530 ℃ of reaction temperature. The gas phase product generated in the experimental process is analyzed by on-line refinery gas analysis chromatography, and the liquid phase product is analyzed by simulated distillation chromatography to obtain the content of gasoline and diesel fractions. After the carbon deposition of the catalyst is regenerated on line, CO is used2The analyzer obtains the carbon deposit content. The feed stock used was a real catalyst feed and its properties are given in table 2. The evaluation results of the catalysts prepared according to the invention are shown in Table 3.
TABLE 2 evaluation of Properties of feed oil (VGO) by catalytic cracking
| Properties of | Parameter(s) |
| Density (25 ℃ C.), g.cm-3 | 0.92 |
| Carbon residue, wt. -%) | 6.47 |
| C，wt.％ | 86.25 |
| H，wt.％ | 12.35 |
| N，wt.％ | 0.38 |
| Saturation fraction, wt. -%) | 56.17 |
| Is based on the weight percent of | 17.00 |
| Gum, wt. -%) | 16.14 |
| Asphaltenes, wt. -%) | 2.84 |
| Ni，μg·g-1 | 25.5 |
| V，μg·g-1 | 4.3 |
TABLE 3 cracked product distribution of the four catalysts
In the catalytic cracking catalyst, a proper amount of ZSM-5 shape-selective molecular sieve is added, which is helpful to improve the selectivity of the catalytic cracking reaction on low-carbon olefin (such as propylene). As can be seen from the data in Table 3, in the distribution of the cracked products of the catalyst sample CK-1 (simplified roasting demoulding and ion exchange process) and CK-2 (simplified roasting process), the yield of gasoline and diesel oil and the yield of propylene are basically equivalent to those of the catalyst sample CK-3 obtained by the traditional method, which indicates that the catalyst prepared by the method of the invention still maintains better catalytic cracking activity and propylene selectivity after the related operation (roasting demoulding and/or ion exchange) process is simplified.
Claims (10)
1. A preparation method of a catalytic cracking catalyst containing a high-silicon shape-selective molecular sieve comprises the following steps:
mixing and molding the sodium type high-silicon ZSM-5 molecular sieve and other raw materials for preparing the catalytic cracking catalyst;
roasting, ammonium ion exchange, washing and drying the formed product to prepare the catalytic cracking catalyst containing the high-silicon shape-selective molecular sieve;
wherein the sodium type high-silicon ZSM-5 molecular sieve is a sodium type high-silicon ZSM-5 molecular sieve which is not demoulded and/or is not subjected to ion exchange treatment.
2. The preparation method of claim 1, wherein the sodium-type high-silicon ZSM-5 molecular sieve has a silica-alumina ratio of not less than 50; preferably 120-300.
3. The preparation method according to claim 1 or 2, wherein the content of the sodium-type high-silicon ZSM-5 molecular sieve is 5% to 40% by mass of the total mass of the feedstock of the catalytic cracking catalyst; preferably 15 to 35 percent.
4. The production method according to any one of claims 1 to 3, wherein the other raw material comprises Y-type zeolite; preferably, the silicon-aluminum ratio of the Y-type zeolite is not less than 7;
preferably, the content of the Y-type zeolite is 0-35% by mass of the total mass of the raw material of the catalytic cracking catalyst;
more preferably, the Y-type zeolite contains a rare earth element.
5. The preparation method according to any one of claims 1 to 4, wherein the other raw material comprises a carrier, preferably the carrier is contained in an amount of 60 to 95% by mass based on the total mass of the raw material of the catalytic cracking catalyst; preferably 65% to 85%.
6. The production method according to claim 5, wherein the carrier comprises one or a combination of two or more of kaolin, alumina sol, and silica sol.
7. The production method according to any one of claims 1 to 6, wherein the molding is performed by beating spray molding; preferably, the slurry prepared by pulping has a solid content of 20% to 50% by weight.
8. The production method according to any one of claims 1 to 7, wherein the calcination is carried out at a temperature of 350 ℃ or more for a time of 5 minutes or more.
9. A catalytic cracking catalyst containing a high silicon shape-selective molecular sieve, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the catalytic cracking catalyst containing the high silicon shape selective molecular sieve according to claim 9 in catalytic cracking, preferably, the catalytic cracking catalyst is used as a catalyst or an auxiliary agent.
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| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
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| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
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