CN114425405B - Catalytic cracking auxiliary agent for improving propylene concentration and preparation method and application thereof - Google Patents
Catalytic cracking auxiliary agent for improving propylene concentration and preparation method and application thereof Download PDFInfo
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- CN114425405B CN114425405B CN202010998211.4A CN202010998211A CN114425405B CN 114425405 B CN114425405 B CN 114425405B CN 202010998211 A CN202010998211 A CN 202010998211A CN 114425405 B CN114425405 B CN 114425405B
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- catalytic cracking
- modified
- acid
- zeolite
- sol
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 88
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010457 zeolite Substances 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 23
- 239000004927 clay Substances 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims description 89
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- 239000002002 slurry Substances 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 45
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 40
- 235000011007 phosphoric acid Nutrition 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 25
- 238000004537 pulping Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000004568 cement Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- 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 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- -1 rectorite Chemical compound 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000001694 spray drying Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 238000005336 cracking Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000009718 spray deposition Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007970 homogeneous dispersion Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium 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
- 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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a catalytic cracking auxiliary agent for improving propylene concentration and a preparation method and application thereof, wherein the catalytic cracking auxiliary agent contains 10-50 wt% of ZSM-5 zeolite, 5-40 wt% of modified sol, 2-30 wt% of modified gumming residue and 20-70 wt% of clay based on the total weight of the catalytic cracking auxiliary agent; based on the total weight of the modified adhesive residue, the modified adhesive residue contains 0 to 2.0 weight percent of Na 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified adhesive slag is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm.
Description
Technical Field
The invention relates to a catalytic cracking auxiliary agent for improving propylene concentration, a preparation method and application thereof.
Background
Catalytic cracking is one of the important processes for producing light olefins, and for most catalytic cracker units, it is an effective method to employ a catalyst or promoter containing a zeolite having an MFI structure, a typical representative of which is ZSM-5 zeolite, in order to increase propylene. Basic reaction of MFI structure zeoliteThe mechanism is to selectively crack C in the gasoline fraction 6 ～C 12 Alkanes and alkenes, to C 3 ～C 5 Olefin, thus improving the yield of low-carbon olefin and simultaneously improving the octane number of gasoline.
US3758403 discloses a catalyst with ZSM-5 and a large pore zeolite (mainly Y-type zeolite) as active components, which increases the octane number of gasoline and increases the yield of C3 and C4 olefins at the same time, wherein the large pore zeolite cracks the raw material to produce gasoline and diesel, and the ZSM-5 shape selective molecular sieve further cracks the raw material to lower olefins. CN 1049406C discloses a zeolite containing phosphorus and rare earth and having MFI structure, which has excellent hydrothermal activity stability and good low-carbon olefin selectivity when used for high-temperature hydrocarbon conversion. CN 1176020C discloses a phosphorus-and transition metal-modified MFI structure zeolite having an anhydrous chemical expression of (0.about.0.3) Na2O (0.5.about.5) Al on the basis of the mass of the oxide 2 O 3 ·(1.3～10)P 2 O 5 ·(0.7～15)M 2 O 3 ·(70～99)SiO 2 . Wherein M is selected from one of transition metal elements Fe, co and Ni. Compared with the zeolite provided by the prior art, the zeolite can improve the yield and selectivity of C2-C4 olefins, has higher liquefied gas yield, but has higher dry gas yield.
The catalytic cracking catalyst or the auxiliary agent for increasing the yield of propylene disclosed in the prior art pays attention to the modification of the ZSM-5 molecular sieve. The active component of the catalyst is of fundamental importance, but the role of the binder is not neglected. The catalyst can be synergistic with active components of a molecular sieve while guaranteeing the wear resistance of the catalyst, and the activity and hydrothermal stability of the catalyst are improved. The most commonly used binder in the catalyst preparation process is aluminum sol, and because of the high chlorine content in the aluminum sol, hydrochloric acid is generated in the catalyst spray drying forming process, equipment is corroded, the environment is influenced, and meanwhile, the formed hydrochloric acid gas also damages the structure of a molecular sieve in the catalyst, so that the activity of the catalyst is reduced. There are a number of patents and literature reports on the replacement of aluminum sol by phosphorus-containing aluminum sol during catalyst preparation. USP 3544476 discloses a preparation of a phosphorus and aluminum containing water treatment agentThe preparation method comprises the following steps: metal aluminum powder was added to the hydrochloric acid solution, reacted at 90 ℃ for 2 hours, then phosphoric acid was added, and then aged at 80 ℃ for 30 minutes. The preparation method provided by CN1417296A is as follows: pulping and dispersing acid-peptized aluminum hydroxide or aluminum oxide and deionized water into slurry with solid content of 15-35 wt%, adding concentrated phosphoric acid into the slurry according to the weight ratio of P/Al=1.2-6 under stirring, heating to 65-95 ℃, and reacting at the temperature for 15-90 min until the slurry becomes transparent colloid. The preparation method of the aluminum phosphate sol provided by CN102050434A comprises the following steps: pulping an acid-soluble aluminum precursor with deionized water to obtain a slurry with a solid content of 10-35 wt%, adding phosphoric acid with a concentration of 60-98% and HNO according to a weight ratio of P/Al=1.0-2.5 to the slurry under stirring 3 /Al 2 O 3 Nitric acid with the concentration of 40-98% is added in the weight ratio of 0.2-2.0, and the aluminum phosphate sol is obtained after the reaction.
The wear resistance of the cracking catalyst prepared by adopting the phosphorus-containing aluminum sol as a binder is improved, and the chlorine content of the catalyst is slightly reduced. However, the phosphorus-containing aluminum sol is used as a binder and has the problems of poor stability and fluidity, and the P/Al ratio of the commonly used phosphorus-containing aluminum sol is relatively high, so that the pH value of the sol is relatively low, the structure of a molecular sieve is damaged, and the activity of a catalyst is influenced.
The role of the matrix of the catalyst is also not negligible. It is generally believed that the catalyst matrix should have a relatively large pore size, suitable activity and good hydrothermal stability so that the catalyst can withstand the harsh hydrothermal operating conditions and pre-crack the heavy feedstock. The gum residue is produced by the operations of sedimentation, filtration, residue cutting and the like of waste water generated in the production of the catalytic cracking catalyst, and Al is used 2 O 3 And SiO 2 The waste residue as main component also contains 2 to 15 percent of Na 2 O and 1-15% RE 2 O 3 . At present, a plurality of catalyst manufacturers generally discard the glue residues directly and do not reuse the glue residues, so that a large amount of resources such as Si, al and the like are lost and wasted. Meanwhile, the waste and landfill of the gumming residue occupies a large amount of land resources, and the gumming residue entersSoil enters water along with natural circulation, so that pollution of soil and water resources is caused, and serious environmental problems are caused.
Disclosure of Invention
The invention aims to provide a catalytic cracking auxiliary agent for improving the concentration of propylene, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a catalytic cracking aid for increasing propylene concentration, the catalytic cracking aid comprising, based on the total weight of the catalytic cracking aid:
(1) 10 to 50 wt% of a ZSM-5 zeolite;
(2) 5 to 40 wt% of a modified sol;
(3) 2 to 30 weight percent of modified gumming slag, wherein the modified gumming slag contains 0 to 2.0 weight percent of Na based on the total weight of the modified gumming slag 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified glue residue is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm; and, a step of, in the first embodiment,
(4) 20 to 70% by weight of clay.
Alternatively, the modified sol contains 50 to 80 wt% of P based on the total weight of the modified sol 2 O 5 And 20 to 50 wt.% of Al 2 O 3 The molar ratio of P to Al is 1.5-2.5, the diameter of colloidal particles is 10-50 nm, and the pH value of the modified sol is 1.5-3.5.
Optionally, the catalytic cracking aid contains 20 to 45 wt% of the ZSM-5 zeolite, 10 to 35 wt% of the modified sol, 5 to 25 wt% of the modified cement and 25 to 65 wt% of the clay.
In a second aspect, the present invention provides a method for preparing the catalytic cracking aid provided in the first aspect, the method comprising: mixing ZSM-5 zeolite, modified sol, modified glue residue, a first solvent and clay, and then carrying out first drying and roasting;
wherein, the modified rubber residue is prepared by the following steps: mixing the solid gum residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5.
Optionally, the method for preparing the catalytic cracking catalyst comprises the following steps: mixing and pulping the clay, the modified gumming residue and the first solvent to obtain first slurry; and mixing the first slurry, the ZSM-5 zeolite and the modified sol, and then performing first drying and roasting on the obtained second slurry.
Optionally, the method for preparing the solid gum residue comprises the following steps: performing secondary drying on the glue residue to obtain the solid glue residue;
the solid content of the solid gum slag is 70-95 wt%; the solid gum residue contains 10-50 wt% of Al based on the dry weight of the solid gum residue 2 O 3 30 to 70 weight percent of SiO 2 2 to 15 weight percent of Na 2 O and 1 to 15 wt% of RE 2 O 3 。
Optionally, the modified sol is prepared by a method comprising the following steps:
mixing an aluminum source, water and an organic solvent to obtain a first mixture, mixing the first mixture with phosphoric acid to obtain a second mixture, and reacting the second mixture at 40-65 ℃ for 30-180 min.
Optionally, mixing the first mixture with phosphoric acid comprises:
mixing and stirring the first mixture and the first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; mixing the third mixture with a second portion of the phosphoric acid to obtain the second mixture.
Optionally, the weight of the first portion of phosphoric acid is 30 to 70% based on the total weight of the first and second portions of phosphoric acid.
Optionally, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated as aluminum oxide.
Optionally, the ZSM-5 zeolite is selected from HZSM-5 zeolite and/or modified ZSM-5 zeolite, wherein the modified ZSM-5 zeolite contains one or more of phosphorus, iron and rare earth metals;
the clay is one or more selected from kaolin, rectorite, diatomite, montmorillonite, bentonite and sepiolite;
the acid solution contains organic acid and/or inorganic acid, wherein the organic acid is one or more selected from oxalic acid, acetic acid and citric acid, and the inorganic acid is one or more selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride;
the first solvent and the second solvent are each independently selected from one or more of deionized water, decationized water and distilled water.
The third aspect of the invention provides an application of the catalytic cracking auxiliary agent provided by the first aspect of the invention in catalytic cracking of crude oil.
Optionally, the conditions for catalytic cracking of the crude oil include: the temperature is 490-530 ℃, and the agent-oil ratio is 3-8;
the content of the catalytic cracking auxiliary agent is 1-50 wt% based on the total weight of the catalytic cracking auxiliary agent and the catalytic cracking catalyst.
Through the technical scheme, the catalytic cracking auxiliary agent contains the modified gumming slag, so that the catalytic cracking auxiliary agent has better cracking activity while recycling gumming slag, and the concentration of propylene in liquefied gas can be effectively increased.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a catalytic cracking auxiliary, which comprises, based on the total weight of the catalytic cracking auxiliary:
(1) 10 to 50 wt% of a ZSM-5 zeolite;
(2) 5 to 40 wt% of a modified sol;
(3) 2 to 30 weight percent of modified adhesive residue, wherein the modified adhesive residue contains 0 to 2.0 weight percent of Na based on the total weight of the modified adhesive residue 2 O, 10-40 wt% of Al 2 O 3 20 to 70 weight percent of SiO 2 And 1 to 15 wt.% RE 2 O 3 The specific surface area of the modified adhesive slag is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm; and, a step of, in the first embodiment,
(4) 20 to 70% by weight of clay.
Wherein RE 2 O 3 Refers to rare earth metal oxides, which are well known to those skilled in the art and are not described in detail herein. The catalytic cracking additive contains modified gumming slag, realizes effective recycling of silicon, aluminum, rare earth and other resources in the production process of the catalyst, has higher cracking activity, and can obviously increase the concentration of propylene in liquefied gas.
According to the invention, the modified sol may contain 50 to 80% by weight of P, based on the total weight of the modified sol 2 O 5 And 20 to 50 wt.% of Al 2 O 3 The molar ratio of P to Al is 1.5-2.5, the pH value of the modified sol is 1.5-3.5, the diameter of colloidal particles is 10-50 nm, and the preferred diameter is 20-30 nm. The catalytic cracking auxiliary agent adopts the modified sol as the binder, has proper colloidal particle diameter range, forms a handle ring system among colloidal particles, and can reduce aggregation among colloidal particles to form large particles with the diameter of 50-100 nm. Compared with the conventional aluminum phosphate sol, the aluminum phosphate colloid system is more stable, ensures that the catalytic cracking auxiliary has good abrasion resistance, and also has higher specific surface area, crystallinity and cracking activity, and can show when the catalytic cracking auxiliary is used for catalytic cracking reactionThe concentration of propylene in the liquefied gas is significantly increased.
According to the present invention, the catalytic cracking aid may contain 20 to 45 wt% of ZSM-5 zeolite, 10 to 35 wt% of modified sol, 5 to 25 wt% of modified cement and 25 to 65 wt% of clay.
According to the invention, the specific surface area of the catalytic cracking auxiliary can be 200-300 m 2 The water drop pore volume per gram can be 0.33-0.45 mL/g, the abrasion index can be 0.5-3.5%, and the micro-inverse activity index can be 40-60.
In a second aspect, the present invention provides a method for preparing the catalytic cracking aid provided in the first aspect, the method comprising: mixing ZSM-5 zeolite, modified sol, modified glue residue, a first solvent and clay, and then carrying out first drying and roasting;
wherein, the modified glue residue is prepared by the following steps: mixing the solid gum residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5, preferably 2-4.
The method can realize recycling of the gumming residues, and can prepare the catalytic cracking auxiliary agent with good cracking activity.
In one embodiment, the modified cement is prepared by the following steps: the solid gum residue and the second solvent are mixed according to the weight ratio of 1: (5-20), mixing the obtained mixture with an acid solution to obtain slurry, reacting the obtained slurry at 20-90 ℃ for 30-120 min, taking out solid, and drying the solid at 60-150 ℃ for 6-24 hours.
According to the present invention, the first drying mode is not particularly limited, and may be, for example, spray drying, constant temperature drying, air flow drying, and the tail gas temperature of spray drying may be 130 to 200 ℃, preferably 140 to 180 ℃. The calcination is well known to those skilled in the art, and may be performed in, for example, a muffle furnace or a tube furnace, the temperature of the calcination may be varied within a wide range, preferably 300 to 650 ℃, and the time may be 1 to 5 hours, and the calcination atmosphere is not particularly limited, and may be an air atmosphere or an inert atmosphere, and inert gases may include helium, argon, and the like.
In one embodiment of the present invention, a method of preparing a catalytic cracking catalyst comprises: mixing clay, modified glue residue and a first solvent, and pulping to obtain a first slurry; after the first slurry, ZSM-5 zeolite and modified sol are mixed, the obtained second slurry is subjected to first drying and calcination. The time of mixing and beating is not particularly limited, and may be, for example, 30 to 120 minutes. More preferably, the ZSM-5 zeolite is added after the first slurry and the modified sol are mixed and stirred for 10 to 90 minutes, and then mixed and stirred for 10 to 60 minutes.
According to the invention, na of the modified gum residue 2 The O content may be 0 to 1.8 wt.%.
In one embodiment of the present invention, a method of preparing solid gum residue may include: performing secondary drying on the glue residue to obtain solid glue residue; the second drying method is not particularly limited, and may be spray drying, air drying, constant temperature drying, preferably spray drying, and the spray drying tail gas temperature is 130 to 200 ℃, more preferably 140 to 180 ℃. The method of the invention uses the glue residue after drying and molding, and can solve the problems of high viscosity and Na of the glue residue 2 The problems of difficult O washing and difficult filtration are beneficial to preparing the catalytic cracking auxiliary agent with good cracking activity.
According to the invention, the solid content of the solid cement is 70-95 wt%, and the solid cement contains 10-50 wt% of Al based on the dry weight of the solid cement 2 O 3 30 to 70 weight percent of SiO 2 2 to 15 weight percent of Na 2 O and 1 to 20 wt%, for example 1 to 15 wt%, RE 2 O 3 。
According to the invention, the modified sol can be prepared by a method comprising the following steps: mixing an aluminum source, water and an organic solvent to obtain a first mixture, mixing the first mixture with phosphoric acid to obtain a second mixture, reacting the second mixture at 40-65 ℃ for 30-180 min, and carrying out third drying on the reaction product. The temperature of the mixing is not particularly limited, and may be 0 to 40 ℃. The concentration of phosphoric acid may vary widely and is preferably 60 to 98% by weight. According to the method, the organic solvent is added before the peptization aluminum phosphate source is added, so that the stability and fluidity of sol-gel groups can be improved, and the preparation of the catalytic cracking auxiliary agent with better cracking activity is facilitated.
In one embodiment of the invention, mixing the first mixture with phosphoric acid comprises: mixing and stirring the first mixture and the first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; the third mixture is mixed with a second portion of the phosphoric acid to yield a second mixture.
According to the invention, the weight of the first part of phosphoric acid may be 30 to 70%, preferably 30 to 60%, based on the total weight of the first and second parts of phosphoric acid.
The solids content of the modified sol according to the invention may vary within wide limits, preferably from 25 to 50% by weight, more preferably from 25 to 45% by weight.
According to the present invention, the organic solvent may be one or more selected from methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated by alumina.
According to the invention, the ZSM-5 zeolite may be selected from HZSM-5 zeolite and/or modified ZSM-5 zeolite, the modified ZSM-5 zeolite containing one or more of phosphorus, iron and rare earth metals; the rare earth metal may be Sc, Y, la, ce, pr or the like. Clays are well known to those skilled in the art and may be selected from one or more of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite and sepiolite. The acid solution may contain an organic acid selected from one or more of citric acid, acetic acid and oxalic acid, and/or an inorganic acid selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride. The first solvent and the second solvent may each be independently selected from one or more of deionized water, distilled water, and decationized water.
The third aspect of the invention provides an application of the catalytic cracking auxiliary agent provided by the first aspect of the invention in catalytic cracking of crude oil.
According to the present invention, the conditions for catalytic cracking of crude oil may include: the temperature is 490-530 ℃, and the agent-oil ratio is 3-8.
According to the present invention, when the catalytic cracking aid of the present invention is used in the catalytic cracking process, the catalytic cracking aid may be added to the catalytic cracking reactor alone or may be used in combination with a catalytic cracking catalyst. In one embodiment, the catalytic cracking aid is provided in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the total amount of catalytic cracking aid and cracking catalyst.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The gum residue is obtained from waste water generated in the production of the catalytic cracking catalyst through operations such as sedimentation, filtration, residue cutting and the like, the solid content of the gum residue is 25%, and the gum residue contains 9.0% by weight of Na based on the dry weight of the gum residue 2 O, 23.0 wt% Al 2 O 3 48.0 wt% SiO 2 9.2 wt% RE 2 O 3 。
Kaolin is produced by the company su zhou kaolin with a solids content of 76% by weight;
pseudo-boehmite produced by Shandong Albazaar with a solids content of 62.0 wt%;
the alumina content in the alumina sol was 21.5 wt%; the solid content of the aluminum phosphate sol is 28.0 weight percent and contains P 2 O 5 75%;
hydrochloric acid is produced by Beijing chemical plant, the specification is analytically pure, and the mass concentration is 36%;
phosphoric acid is produced by Beijing chemical plant, the specification is analytically pure, and the mass concentration is 85%;
HZSM-5 zeolite solid content 75 wt%, siO 2 /Al 2 O 3 ＝25，Na 2 The O content was 0.15 wt%;
HZSM-5 zeolite is produced by China petrochemical catalyst Co., ltd, and the rest of the reagents are produced by China medicine group chemical reagent Co., ltd, and the specifications are all analytically pure;
the sample was 1.33X10 by using ASAP 2405N V1.01 automatic adsorbent, low temperature static nitrogen adsorption capacity method of Micromerics company -2 Vacuum degassing at 300 deg.C under Pa for 4 hr, and mixing with N 2 The adsorption-desorption isotherms of the samples were determined at 77.4K for the adsorption media. Calculating the specific surface area of the sample according to the BET formula (S BET ) Determination of the relative pressure p/p 0 Sample adsorption N when=0.98 2 Converting the volume of the liquid nitrogen into a liquid nitrogen volume, namely a pore volume;
determining the average pore diameter of the sample by adopting a Q/SH 3360-206 method;
determining the colloidal particle diameter of the sample by adopting a TEM method;
the sample composition was determined using X-ray fluorescence spectroscopy (XRF).
Example 1
S1, preparing modified rubber residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 25 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 180 ℃ to obtain solid gumming slag (the solid content is 92 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:10, adding hydrochloric acid with the concentration of 36 weight percent to adjust the pH value of the slurry to 3.0, stirring for 90min at 60 ℃, filtering to obtain solid, and then drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:10, adding hydrochloric acid with the concentration of 36 weight percent to adjust the pH value of the slurry to 3.0, stirring for 90min at 60 ℃, filtering to obtain solid, and then drying again at 120 ℃, wherein the obtained modified glue residue is JZ-1. Analyzed, na of 2 The content of O was 1.15 wt%, A1 2 O 3 The content of (C) was 27.7 wt%, siO 2 The content of (C) was 59.9 wt%, RE 2 O 3 The content of (C) was 8.3% by weight and the specific surface area was 220m 2 Per g, pore volume 0.65mL/g, average pore diameter 35nm.
S2, preparing modified sol: mixing 52.2g of pseudo-boehmite, 0.65g of ethanol and 149g of deionized water, pulping for 30min, and uniformly dispersing to obtain a first mixture; then pouring 60g of 85 wt% phosphoric acid solution, stirring for 30min at 18 ℃, and adding the rest 50gA second mixture is obtained as a phosphoric acid solution with 85 weight percent, the second mixture is heated to 45 ℃ and stirred for 180min; a modified sol PA-1 having a solids content of 32% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 32.3%, P 2 O 5 The mass content is 67.2%, the P/Al molar ratio is 1.5, the pH value of the sol is 3.3, and the average colloidal particle diameter is 30nm.
S3, preparing a catalytic cracking auxiliary agent: 20g of the modified gumming residue (JZ-1), 79g of kaolin and 451g of deionized water are added into a pulping tank for pulping for 60min, 93g of HZSM-5 zeolite is added, stirring is carried out for 30min, 156g of the modified sol (PA-1) is finally added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 30min, the solid content of the obtained slurry is 25 wt%, then the obtained slurry is subjected to spray drying and forming, and roasting is carried out at 500 ℃ for 2 h, so that the catalytic cracking auxiliary CZ-1 provided by the invention is obtained, and the composition and characteristic parameters are shown in Table 1 and are the same in the following examples.
Example 2
S1, preparing modified rubber residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 20 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 150 ℃ to obtain solid gumming slag (the solid content is 88 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:8, adding 30 weight percent nitric acid to adjust the pH value of the slurry to 3.5, stirring for 60min at 90 ℃, filtering to obtain solid, and then drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:8 mixing, adding 30 wt% nitric acid to adjust pH to 3.5, stirring at 90deg.C for 60min, filtering to obtain solid, drying again at 120deg.C to obtain modified gelatin residue (JZ-2), analyzing, and Na 2 O content was 0.56 wt%, A1 2 O 3 The content of (C) was 22.6 wt%, siO 2 The content of (C) was 69.7 wt%, RE 2 O 3 The content of (C) was 8.2% by weight, and the specific surface area was 210m 2 Per g, pore volume was 0.72mL/g and average pore diameter was 30nm.
S2, preparing modified sol: 41g of pseudo-boehmite, 2.55g of normal hexane and 168g of deionized water are mixed and pulped for 60min, and the mixture is uniformly dispersed to obtain a first mixture; then pour into60g of 85 wt% phosphoric acid solution, continuously stirring for 20min at 18 ℃, adding the rest 60g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 65 ℃, and stirring for 60min; a modified sol PA-2 having a solids content of 30% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 25.5%, P 2 O 5 The mass content is 74.5%, the P/Al molar ratio is 2.1, the pH value of the sol is 2.8, and the average colloidal particle diameter is 30nm.
S3, preparing a catalytic cracking auxiliary agent: 79g of kaolin, 30g of the modified cement (JZ-2) and 444g of decationized water are added into a pulping tank for pulping for 60min, then 80g of HZSM-5 zeolite is added, stirring is carried out for 30min, finally 166g of the modified sol (PA-2) is added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 60min, the solid content of the obtained slurry is 25%, then the obtained slurry is subjected to spray drying and shaping, and roasting is carried out at 450 ℃ for 1.5 h, so that the catalytic cracking additive CZ-2 provided by the invention is obtained.
Example 3
S1, preparing modified rubber residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 30 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 150 ℃ to obtain solid gumming slag (the solid content is 87.8 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:20, adding ammonium sulfate, wherein the ammonium sulfate is 20 weight percent of the mass of the gum residue, adjusting the pH value of the slurry to 3.5 by using dilute hydrochloric acid with a concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering to obtain a solid, and drying at 150 ℃; mixing the dried solid with deionized water according to a mass ratio of 1:20, adding ammonium sulfate, wherein the ammonium sulfate is 20% by weight of the mass of the gumming residue, adjusting the pH value of the slurry to 3.5 by using dilute hydrochloric acid with a concentration of 5% by weight, stirring for 120min at 60 ℃, filtering to obtain the solid, and drying again at 150 ℃ to obtain modified gumming residue JZ-3, wherein Na of the modified gumming residue JZ-3 is analyzed 2 O content was 0.74 wt%, A1 2 O 3 The content of (C) was 26.5 wt%, siO 2 The content of (C) was 54.9 wt%, RE 2 O 3 The content of (C) was 9.2% by weight, and the specific surface area was 240m 2 Per g, pore volume was 0.8mL/g and average pore diameter was 38nm.
S2, modified solventPreparation of the glue: mixing and pulping 36g of pseudo-boehmite, 1.12g of isopropanol and 194g of deionized water for 50min, and uniformly dispersing to obtain a first mixture; then pouring 66g of 85 wt% phosphoric acid solution, continuously stirring at 18 ℃ for 60min, adding the rest 60g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 50 ℃ and stirring for 90min; a modified sol PA-3 having a solids content of 28% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 22.2%, P 2 O 5 The mass content is 77.6%, the P/Al molar ratio is 2.5, the pH value of the sol is 2.6, and the average colloidal particle diameter is 25nm.
S3, preparing a catalytic cracking auxiliary agent: 66g of kaolin, 40g of the modified cement (JZ-3) and 390g of decationized water are added into a pulping tank for pulping for 60min, then 107g of HZSM-5 zeolite is added, stirring is carried out for 30min, finally 200g of the modified sol (PA-3) is added, the obtained slurry is homogeneously dispersed (stirred) for 60min, the solid content of the obtained slurry is 25 wt%, then the obtained slurry is spray-dried and molded, and roasting is carried out at 550 ℃ for 1 h, thus obtaining the catalytic cracking additive CZ-3 provided by the invention.
Example 4
S1, preparing modified rubber residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 20 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 200 ℃, so as to obtain solid gumming slag (the solid content is 92.8 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:15, adding phosphoric acid with a concentration of 20 wt% to adjust the pH value of the slurry to 3.1, stirring for 120min at 25 ℃, filtering to obtain a solid, and drying at 120 ℃; mixing the dried solid with deionized water according to a mass ratio of 1:15, adding phosphoric acid with a concentration of 20 wt% to adjust the pH value of the slurry to 3.1, stirring for 120min at 25 ℃, filtering to obtain the solid, drying again at 120 ℃, marking the obtained modified glue residue as JZ-4, and analyzing the Na of the modified glue residue 2 The content of O was 1.23 wt%, A1 2 O 3 The content of (C) was 23.1 wt%, siO 2 The content of (C) was 52.1 wt%, RE 2 O 3 The content of (C) was 9.5% by weight and the specific surface area was 210m 2 Per g, pore volume was 0.66mL/g and average pore diameter was 28nm.
S2, preparing modified sol: mixing 39g of pseudo-boehmite, 1.97g of acetic acid and 194g of deionized water, pulping for 60min, and uniformly dispersing to obtain a first mixture; then pouring 70g of 85 wt% phosphoric acid solution, continuously stirring at 18 ℃ for 60min, adding the rest 50g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 55 ℃ and stirring for 90min; a modified sol PA-4 having a solids content of 35% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 24.5%, P 2 O 5 The mass content is 75.5%, the P/Al molar ratio is 2.2, the pH value of the sol is 2.4, and the average colloidal particle diameter is 20nm.
S3, preparing a catalytic cracking auxiliary agent: 60g of kaolin, 4g of the modified cement (JZ-4) and 428g of decationized water are added into a pulping tank for pulping for 60min, then 107g of HZSM-5 zeolite is added, stirring is carried out for 60min, finally 200g of the modified sol (PA-4) is added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 40 min, the solid content of the obtained slurry is 25 wt%, then the obtained slurry is subjected to spray drying and molding, and roasting is carried out at 500 ℃ for 1 h, so that the catalytic cracking additive CZ-4 provided by the invention is obtained.
Example 5
S1, preparing modified rubber residues: uniformly stirring the gumming slag, wherein the solid content of the slurry is 25 weight percent, spray drying and forming, and the temperature of spray drying tail gas is 200 ℃, so as to obtain solid gumming slag (the solid content is 92.5 weight percent); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:8, adding ammonium sulfate, wherein the ammonium sulfate is 30 weight percent of the mass of the gum residue, adjusting the pH value of the slurry to 3.0 by using dilute hydrochloric acid with a concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering, and drying at 150 ℃; mixing the solid obtained by drying with deionized water according to the mass ratio of 1:8, adding ammonium sulfate, wherein the ammonium sulfate is 30 weight percent of the mass of the gumming residue, adjusting the pH value of the slurry to 3.0 by using dilute hydrochloric acid with the concentration of 5 weight percent, stirring for 120min at 60 ℃, filtering, and drying again at 150 ℃ to obtain gumming residue JZ-5, wherein the Na of the gumming residue JZ-5 is obtained 2 O content was 0.75 wt%, A1 2 O 3 The content of (C) was 26.4 wt%, siO 2 The content of (C) was 55.0 wt%, RE 2 O 3 Is 9.1 weight percentPercent, specific surface area of 260m 2 Per g, pore volume 0.85mL/g, average pore diameter 40nm.
S2, preparing modified sol: mixing and pulping 37g of pseudo-boehmite, 0.69g of oxalic acid and 194g of deionized water for 30min, and uniformly dispersing to obtain a first mixture; then pouring 80g of 85 wt% phosphoric acid solution, continuously stirring for 30min at 18 ℃, adding the rest 45g of 85 wt% phosphoric acid solution to obtain a second mixture, heating the second mixture to 60 ℃, and stirring for 120min; a modified sol PA-5 having a solids content of 35% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 23.1%, P 2 O 5 The mass content is 76.9%, the P/Al molar ratio is 2.4, the pH value of the sol is 2.0, and the average colloidal particle diameter is 20nm.
S3, preparing a catalytic cracking auxiliary agent: 126g of kaolin, 10g of the modified cement (JZ-5) and 471g of decationized water are added into a pulping tank for pulping for 60min, 67g of HZSM-5 zeolite is added, stirring is carried out for 60min, 125g of the modified sol (PA-5) is finally added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 30min, the solid content of the obtained slurry is 25 wt%, then the obtained slurry is subjected to spray drying and molding, and roasting is carried out at 500 ℃ for 2 h, so that the catalytic cracking additive CZ-5 provided by the invention is obtained.
Example 6
Catalytic cracking promoter CZ-6 was prepared in the same manner as in example 1, except that the preparation method of the modified sol in step S2 was different, and the modified sol was prepared as follows:
mixing 52.2g of pseudo-boehmite, 0.65g of ethanol and 149g of deionized water, pulping for 30min, and uniformly dispersing to obtain a first mixture; pouring 110g of 85 wt% phosphoric acid solution into the mixture to obtain a second mixture, heating the second mixture to 45 ℃ and stirring for 180min; a modified sol PA-6 having a solids content of 32% by weight was obtained. By analysis, al in the modified sol 2 O 3 The mass content is 32.3%, P 2 O 5 The mass content is 67.2%, the P/Al molar ratio is 1.5, the pH value of the sol is 1.5, and the average colloidal particle diameter is 50nm.
Example 7
The catalytic cracking promoter CZ-7 was prepared in the same manner as in example 1, except that the preparation method of the modified cement in step S1 was different, and the modified cement was prepared as follows:
uniformly stirring the glue slag of the catalytic cracking catalyst, wherein the solid content of slurry is 20 wt%, spray drying and forming, and the temperature of spray drying tail gas is 180 ℃ to obtain solid glue slag (the solid content is 89.5 wt%); mixing the obtained solid gum residue with deionized water according to a mass ratio of 1:15, adding 85 wt% phosphoric acid to adjust the pH value of the slurry to 4.1, stirring at 25 ℃ for 120min, filtering to obtain solid, and drying at 120 ℃; and mixing the solid obtained by drying with deionized water according to a mass ratio of 1:15, adding 85 wt% phosphoric acid to adjust the pH of the slurry to 4.1, stirring at 25deg.C for 120min, filtering to obtain solid, drying again at 120deg.C to obtain modified gum residue, designated JZ-6, and analyzing to obtain Na 2 The content of O was 1.23 wt%, A1 2 O 3 The content of (C) was 22.4 wt%, siO 2 The content of (C) was 48.1 wt%, RE 2 O 3 The content of (C) was 8.7% by weight and the specific surface area was 200m 2 Per g, pore volume was 0.71mL/g and average pore diameter was 22nm.
Example 8
A catalytic cracking promoter CZ-8 was prepared in the same manner as in example 1 except that the preparation method of the catalytic cracking promoter in step S3 was different, and the catalytic cracking promoter was prepared as follows:
26g of kaolin, 50g of the modified cement (JZ-1) and 451g of deionized water are added into a pulping tank for pulping for 60min, 72g of HZSM-5 zeolite is added, stirring is carried out for 30min, 238g of the modified sol (PA-1) is finally added, the obtained slurry is subjected to homogeneous dispersion (stirring) for 30min, the solid content of the obtained slurry is 25 wt%, the obtained slurry is subjected to spray drying and shaping, and the obtained slurry is roasted at 500 ℃ for 2 h, so that the catalytic cracking additive CZ-8 provided by the invention is obtained.
Comparative example 1
This comparative example illustrates a cracking aid prepared using a conventional phosphorus modified alumina sol and unmodified gum residue.
The phosphorus-modified alumina sol DA3 was prepared according to the method of example 1 in CN1417296A, as follows:
5.8 kg of pseudo-boehmite (containing Al) 2 O 3 1.8 kg) and 4.0 kg of deionized water for 30 minutes, adding 9.6 kg of concentrated phosphoric acid into the slurry under stirring, heating to 70 ℃, and then reacting for 45 minutes at 20 ℃ to obtain colorless and transparent phosphorus-containing aluminum sol. The phosphorus-aluminum sol contains P through analysis 2 O 5 The mass content is 83.3%, al 2 O 3 The mass content is 16.7%, the P/Al molar ratio is 2.7, and the pH value is 1.7.
According to the method of example 1 of the present invention, 79g of kaolin, 20g of unmodified cement and 451g of decationized water were added into a pulping tank to be pulped for 60 minutes, then 93g of HZSM-5 zeolite was added, stirring was performed for 30 minutes, finally 156g of the above modified sol (DA 3) was added, and the resultant slurry was homogeneously dispersed (stirred) for 30 minutes, the solid content of the slurry was 25%, and then the resultant slurry was spray-dried and molded, and calcined at 500℃for 2 hours, to obtain comparative catalytic cracking promoter CZ-D1, the composition and characteristic parameters of which are shown in Table 2, and the following comparative examples were the same.
Comparative example 2
This comparative example illustrates the use of a conventional phosphorus modified alumina sol and a cracking aid prepared without gum residue.
Phosphorus-modified alumina sol DA3 was prepared in the same manner as in comparative example 1.
According to the method of example 1 of the present invention, 105g of kaolin and 451g of decationized water were added to a pulping tank to pulp for 60 minutes, then 93g of HZSM-5 zeolite was added, stirred for 30 minutes, finally 156g of the above-mentioned modified sol (DA 3) was added, dispersed (stirred) for 30 minutes, the resulting slurry had a solid content of 25%, and then the resulting slurry was spray-dried to be molded, and calcined at 500 ℃ for 2 hours, to obtain a comparative catalytic cracking aid CZ-D2.
TABLE 1 composition and physicochemical Properties of catalytic cracking aid
TABLE 2 composition and physicochemical Properties of catalytic cracking aid
Test case
Catalytic cracking assistants CB1 to CB8 prepared in examples 1 to 8 and CZ-D1 to CZ-D2 prepared in comparative examples 1 to 2 of the present invention were mixed with a brand SGC-1 industrial catalyst (provided by Qilu division Co., ltd., main properties are shown in Table 3) in proportion to form a catalyst mixture, and the catalyst mixture was subjected to 100% water vapor aging at 800℃for 17 hours on a fixed bed aging device. The raw oil used was then evaluated on an ACE unit and the properties are shown in table 4. The reaction temperature, the catalyst-to-oil ratio, the weight hourly space velocity and the evaluation results are shown in Table 5.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield;
propylene concentration in liquefied gas = propylene yield/liquefied gas yield.
TABLE 3 Properties of commercial catalysts
| Name of the name | SGC-1 |
| Chemical composition/% | |
| RE 2 O 3 | 3.4 |
| Al 2 O 3 | 52.3 |
| Na 2 O | 0.16 |
| Physical Properties | |
| Specific surface area/(m) 2 ×g -1 ) | 269 |
| Pore volume/(mL. Times.g) -1 ) | 0.38 |
| Bulk density/(g.times.cm) -3 ) | 0.75 |
| Sieving mass composition/% | |
| 0～20mm | 1.5 |
| 0～40mm | 12.8 |
| 0～149mm | 90.1 |
| APSmm | 76.8 |
| Wear index/(%) | 1.2 |
| MA(800℃/4h) | 78 |
TABLE 4 Properties of raw oil
Table 5 evaluation results
Table 6 evaluation results
As can be seen from tables 5 and 6, the catalytic cracking auxiliary agent prepared by the method of the invention has excellent propylene yield, can obviously improve the concentration of propylene in liquefied gas, and has high cracking activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (7)
1. A catalytic cracking aid for increasing the concentration of propylene, the catalytic cracking aid comprising, based on the total weight of the catalytic cracking aid:
(1) 10 to 50 wt% of a ZSM-5 zeolite;
(2) 5-40 wt% of a modified sol; the modified sol contains 50-80 wt% of P based on the total weight of the modified sol 2 O 5 And 20 to 50 wt% of Al 2 O 3 The molar ratio of P to Al is 1.5-2.5, the diameter of colloidal particles is 10-50 nm, and the pH value of the modified sol is 1.5-3.5;
(3) 2-30 wt% of modified cement, wherein the modified cement contains 0-2.0 wt% of Na based on the total weight of the modified cement 2 O, 10-40 wt% of Al 2 O 3 20 to 70 wt% of SiO 2 And 1 to 15 wt% RE 2 O 3 The specific surface area of the modified glue residue is 180-350 m 2 Per gram, the pore volume is 0.6-1.0 mL/g, and the average pore diameter is 10-50 nm; and, a step of, in the first embodiment,
(4) 20-70 wt% clay;
the method for preparing the catalytic cracking auxiliary comprises the following steps: mixing ZSM-5 zeolite, modified sol, modified glue residue, a first solvent and clay, and then carrying out first drying and roasting;
the modified glue residue is prepared by the following steps: mixing the solid glue residue, the second solvent and the acid solution, reacting the obtained slurry at 20-90 ℃ for 30-120 min, and taking out the solid, wherein the pH value of the slurry is 1-5;
the modified sol is prepared by adopting a method comprising the following steps: mixing an aluminum source, water and an organic solvent to obtain a first mixture; mixing and stirring the first mixture and the first part of phosphoric acid at 40-65 ℃ for 10-60 min to obtain a third mixture; mixing the third mixture with a second part of the phosphoric acid to obtain a second mixture, and reacting the second mixture at 40-65 ℃ for 30-180 min;
taking the total weight of the first part and the second part of the phosphoric acid as a reference, wherein the weight of the first part of the phosphoric acid is 30-70%; the organic solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, isobutanol, heptane, n-hexane, cyclohexane, n-octane, acetone, butanone, formic acid, oxalic acid, acetic acid and propionic acid; the weight of the organic solvent is 2-10% of the weight of the aluminum source, and the weight of the aluminum source is calculated by alumina.
2. The catalytic cracking aid according to claim 1, wherein the catalytic cracking aid comprises 20-45 wt% of the ZSM-5 zeolite, 10-35 wt% of the modified sol, 5-25 wt% of the modified cement and 25-65 wt% of the clay.
3. The catalytic cracking aid of claim 1, wherein the process for preparing the catalytic cracking catalyst comprises: mixing and pulping the clay, the modified gumming residue and the first solvent to obtain first slurry; and mixing the first slurry, the ZSM-5 zeolite and the modified sol, and then performing first drying and roasting on the obtained second slurry.
4. The catalytic cracking aid of claim 1, wherein the process for preparing the solid gum residue comprises: performing secondary drying on the glue residue to obtain the solid glue residue;
the solid content of the solid gum residue is 70-95 wt%; based on the dry weight of the solid gum slag, the solid gum slag contains 10-50 wt% of Al 2 O 3 30-70 wt% of SiO 2 2 to 15 wt% of Na 2 O and 1 to 15 wt% of RE 2 O 3 。
5. The catalytic cracking aid according to claim 1, wherein the ZSM-5 zeolite is selected from HZSM-5 zeolite and/or modified ZSM-5 zeolite, the modified ZSM-5 zeolite containing one or more of phosphorus, iron and rare earth metals;
the clay is one or more selected from kaolin, rectorite, diatomite, montmorillonite, bentonite and sepiolite;
the acid solution contains organic acid and/or inorganic acid, wherein the organic acid is one or more selected from oxalic acid, acetic acid and citric acid, and the inorganic acid is one or more selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate and ammonium chloride;
the first solvent and the second solvent are each independently selected from one or more of deionized water, decationized water and distilled water.
6. The catalytic cracking aid according to any one of claims 1 to 5, for use in catalytic cracking of crude oil.
7. The use of claim 6, wherein the conditions for catalytic cracking of crude oil comprise: the temperature is 490-530 ℃, and the agent-oil ratio is 3-8;
the content of the catalytic cracking auxiliary agent is 1-50 wt% based on the total weight of the catalytic cracking auxiliary agent and the catalytic cracking catalyst.
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