CN105642334A - Catalytic cracking catalyst for blending tight oil and preparing method thereof - Google Patents
Catalytic cracking catalyst for blending tight oil and preparing method thereof Download PDFInfo
- Publication number
- CN105642334A CN105642334A CN201610063454.2A CN201610063454A CN105642334A CN 105642334 A CN105642334 A CN 105642334A CN 201610063454 A CN201610063454 A CN 201610063454A CN 105642334 A CN105642334 A CN 105642334A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalytic cracking
- boehmite
- solution
- cracking catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 63
- 238000002156 mixing Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 85
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 15
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 56
- 229910001593 boehmite Inorganic materials 0.000 claims description 38
- 238000007670 refining Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 28
- 239000004005 microsphere Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 13
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 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 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001935 peptisation Methods 0.000 claims description 7
- -1 wherein in oxide Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000000758 substrate Substances 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000002775 capsule Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 229910000632 Alusil Inorganic materials 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052570 clay Inorganic materials 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
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003502 gasoline Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical class [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 2
- 239000011159 matrix material Substances 0.000 abstract 1
- 150000002830 nitrogen compounds Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 239000003079 shale oil Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 102100036568 Cell cycle and apoptosis regulator protein 2 Human genes 0.000 description 2
- 101000715194 Homo sapiens Cell cycle and apoptosis regulator protein 2 Proteins 0.000 description 2
- 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 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B01J35/615—
-
- B01J35/633—
-
- 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
-
- 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
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a catalytic cracking catalyst for blending tight oil and a preparing method thereof. The catalyst is prepared from a first molecular sieve component, a second molecular sieve component, modified pseudo-boehmite, pseudo-boehmite, clay and a binding agent. The catalytic cracking catalyst has the advantage of having a large matrix specific area, shows up high catalytic cracking activity in the process of conducting a catalytic cracking reaction on raw oil used for blending the tight oil and has a high conversion rate in the process of conducting catalytic cracking treatment on the tight oil (the basic nitrogen content of mixed oil is about 1200-2000 micrograms/g) with high blending basic nitrogen compound content, a high gasoline and diesel oil yield can be obtained, and particularly the yield of light oil like gasoline is high.
Description
Technical field
The present invention relates to catalyst technical field, particularly to a kind of catalytic cracking catalyst mixing the fine and close oil of refining, and the preparation method of this catalytic cracking catalyst.
Background technology
Fluidized catalytic cracking is turned to the important means of crude oil secondary operations, occupies very important status in petroleum refining industry, and its each small progress all will bring huge economic benefit for enterprise. Fluidized catalytic cracking catalyst is one of technological core of catalytic cracking process, and its technological progress is also the important means that fluid catalytic cracking process obtains greatest benefit.
In catalytic cracking process, the residual oil of heavy end such as vacuum distillate or more heavy constituent reacts in the presence of a catalyst, is converted into the high value added products such as liquefied gas, gasoline, diesel oil. Along with exhaustion, the heaviness day by day of catalytically cracked stock, the in poor quality day by day of petroleum resources, mixing other inferior raw material of refining has become the important channel of expansion catalytically cracked material source, refinery and enhancing efficiency by relying on tapping internal latent power. Therefore, increasingly pay attention to other oil sources beyond crude oil is processed in PETROLEUM PROCESSING industry.
Fine and close oil is a kind of non-conventional oil resource, and along with U.S.'s shale gas development technique successful Application in fine and close oil exploitation, the World's Oil and Gas Resources center of production caused moves westwards so that U.S. status in global Oil Gas supply system promotes further. Therefore, the raw material causing oil refining also just occurs to change.
In order to make full use of the crude oil having cost advantage from shale formation, U.S. refiner must solve and process the lot of challenges that fine and close oil phase closes.
Fine and close oil is light crude oil, and API severe on average higher than conventional crude, has low sulfur content, relatively low arene content and higher paraffinicity. Nickel and content of vanadium in fine and close oil are general not high, and other metals, the content such as ferrum, sodium, potassium and calcium is high, also higher according to the basic n content of some fine and close oil of the place of production.
It is that the iron content in oil is high that a key challenge of the fine and close oil of refining is mixed in catalytic cracking process processing, and catalyst is had significant impact by deposition of iron, and this impact can be further exacerbated by together with calcium, sodium, potassium. In catalytic cracking process, thin and scattered iron oxide particle can cause the node forming " glassy " at catalyst surface.Calcium, in conjunction with Silicon stone, calcium, alkali metal and other pollutant, can form the mixture of low melting point, thus destroying the pore structure of catalyst. Another challenge is the impact overcoming the high alkalinity nitrogen content of some fine and close oil to cause catalyst temporarily to inactivate.
Fine and close oil is emerging a kind of energy recent years, less about its applied research in catalytic cracking. Research in the past is mainly based upon the part work that the refining of shale oil is done, the problem that majority is curved about how refining the quality of shale oil and how processing. Such as: US4218309 proposes the method how reducing sulfur content in shale oil recovery process. US4142961 proposes to process shale oil first with heat treatment, coking, then to the processing method that its liquid hydrocarbon product withdrawn carries out hydrotreatment. US4238320 introduces and utilizes method of hydrotreating first to reduce nitrogen content then the method that shale oil is carried out further denitrogenation by spent ion exchange resin. US4344840 proposes the method that shale oil carries out hydrogenation cracking and hydrofinishing production boat coal and diesel oil in multistage reactor. CN101067089A proposes a kind of shale oil first hydrogenated process and obtains hydrogenated oil, hydrogenated oil is separated into hydrogenation heavy oil and light-end products, obtaining dry gas, liquefied gas, gasoline, diesel oil and catalytic heavy after the hydrogenation catalyzed conversion of heavy oil, diesel oil can return to the processing scheme of hydrotreating step. These patents are not directed to catalytic cracking catalyst refining this shale oil and preparation method thereof.
Traditional micro porous molecular sieve is less due to its duct, bigger raw molecule is demonstrated and significantly limits diffusion, particularly when cell channels is blocked by heavy metal, simple micro porous molecular sieve is made to be difficult in adapt in the catalytic cracking mixing the higher fine and close oil of ironmaking content, so that use aperture relatively big, reactant molecule be there is no the molecular screen material of diffusion-restricted.
Summary of the invention
It is difficult in adapt in the catalytic cracking demand mixing the higher fine and close oil of ironmaking content to meet current molecular sieve, the embodiment of the present invention provides a kind of catalytic cracking catalyst mixing the fine and close oil of refining and preparation method thereof, this catalytic cracking catalyst has higher conversion ratio to mixing the higher fine and close oil (if miscella basic n content is about 1200-2000 �� g/g) of smelting soda nitrogen compound content and carry out in the process of catalytic cracking process, and can obtain higher gasoline and diesel yield. By modifiying boehmite so that it is while inheriting original material property, also give its special catalytic performance. Therefore, its catalysis activity can be made compared with prior art to be greatly improved.
In order to realize foregoing invention purpose, the invention provides a kind of catalytic cracking catalyst mixing the fine and close oil of refining, described catalyst includes following components: the first molecular sieve component, the second molecular sieve component, modified boehmite, boehmite, clay and binding agent.
Described first molecular sieve component is one or more the mixture in rare earth Y type molecular sieve REY, rare earth superstable Y-type molecular sieve REUSY or ultra-steady Y molecular sieve USY; And/or described modified boehmite is doping TiO2Boehmite, wherein in oxide, TiO2Doping is the 1-10wt% of quality of alumina.
With the butt weight of described catalytic cracking catalyst for benchmark, in described catalyst, the mass percent of each component is: the first molecular sieve component 10-35%, the second molecular sieve component 5-30%, modified boehmite 5-20%, boehmite 2-20%, clay 20-50% and binding agent 6-20%.
The preparation method of described modified boehmite is as follows:
(1), by technical grade aluminium hydroxide at 300��400 DEG C, after dry 15��20 seconds, it is crushed to the aluminium hydrate powder that granularity is less than 5 ��m, the aluminium hydrate powder that granularity is less than 5 ��m is placed in 600��800 DEG C, after 2��6 seconds, prepare alumina powder standby;
(2), in JZPD capsule groove, add 50��60 DEG C of pure water, boehmite is added in pure water and make serosity, aluminum nitrate solution is added in serosity, it is subsequently adding sodium hydroxide and pH value is adjusted to 6-9, pass into water vapour and carry out hydration reaction 2 hours, prepare crystal seed standby; Described pure water: the mass ratio of boehmite butt is 2:2-3, described aluminum nitrate solution concentration is the 6-10wt% that in 100g/l, described aluminum nitrate solution, aluminum nitrate butt quality accounts for boehmite butt quality;
(3), in hydration reaction groove, being added in the pure water that temperature is 70��80 DEG C by the alumina powder obtained, stir and make alumina slurry in 2 hours in step (1), alumina powder mass ratio in alumina slurry is 20-70%;
(4), the crystal seed that step (2) is prepared, join in the alumina slurry that step (3) prepares, described crystal seed quality accounts for the 40wt% of the alumina dry substrate amount in alumina slurry, being subsequently adding organic titanium stirring to heat up, rise to 60-90 DEG C in 2 hours, mixing speed is 145 revs/min, mixing time is 2-4 hour, obtain activated alumina mixed liquor, wherein in oxide, TiO2The 1-10wt% that doping is quality of alumina;
(5) the activated alumina mixed liquor of step (4) gained washed, filter and be pressed into filter cake;
(6) at 80-100 DEG C, filter cake is carried out ripening; Then placing 3-5h, dry obtaining modifiies boehmite.
Organic titanium in described step (4) is butyl titanate or isopropyl titanate.
The preparation method of described second molecular sieve component is as follows:
2.55 kilograms of sodium silicate and 2.60 kg of water are mixed to get solution one by the first step,
0.035 kilogram of sodium hydroxide, 0.164 kilogram of sodium aluminate and 1.60 kg of water are mixed to get solution two, solution one is at the uniform velocity added in solution two, the feed time of solution one controls at 0.5-1.0 hour, stir 3 hours after adding, then heat to 100 DEG C and continue stirring 8 hours, obtain Y zeolite nanometer presoma;
Second step, 6.949 kilograms of 1-cetyl-3-methy limidazolium and 24 kg of water are mixed to get solution three, take under agitation the Y zeolite nanometer presoma that 6.949 kilograms of first steps obtain at the uniform velocity be added in solution three solution four, the feed time of Y zeolite nanometer presoma controls at 0.5-1.0 hour, then with the pH to 11.5 of 25% sulfuric acid regulation solution four, solution five is obtained;
3rd step, solution five, 100 DEG C of static crystallizations 20 hours, filters to obtain pressed powder, and pressed powder is washed, and dries, then 500-700 DEG C of roasting 5 hours, obtains Na type meso-porous molecular sieve material.
4th step, the Na type meso-porous molecular sieve material 0.48 kilogram obtained is mixed by the mass ratio of 1:4-20 with water, add ammonium salt, 20 DEG C-100 DEG C exchanges, swap time >=0.30h, the mass ratio of described Na type meso-porous molecular sieve material and ammonium salt is 1:0.05-1.0, solid is obtained after filtration, washing, is washed to the sodium oxide content��1.5wt% in solid, obtains the second molecular sieve component.
Described ammonium salt is ammonium chloride or ammonium sulfate.
Described clay is one or more the mixture in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, meerschaum, attapulgite and bentonite.
Described binding agent is one or more in Alumina gel, Ludox or Alusil.
Described modified boehmite: specific surface area is more than 400m2/ g, pore volume 0.4-0.8mL/g.
In order to better realize goal of the invention, the preparation method that the present invention also provides for a kind of catalytic cracking catalyst mixing the fine and close oil of refining, said method comprising the steps of:
Each component is taken in described ratio, under agitation, Xiang Shuizhong adds the first molecular sieve component, second molecular sieve component, modified boehmite, boehmite is mixed to get serosity, in gained serosity, water accounts for the 50-80% of serosity gross mass, in the serosity obtained, add hydrochloric acid carry out peptization, acid aluminum mass ratio is 1:10, after stirring 30 minutes, sequentially add clay, binding agent, pull an oar 2 hours after mixing, then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, wash to sodium oxide content less than 0.20wt% with ammonium salt solution at 20-80 DEG C, finally with deionized water drip washing catalyst microspheres, filter rear catalyst microsphere to dry at 100-150 DEG C, the catalytic cracking catalyst of the fine and close oil of refining must be mixed.
When washing with ammonium salt solution at 20-80 DEG C, ammonium sulfate in washing every time: water: catalyst microspheres mass ratio is 0.05: 5: 1.
Described ammonium salt is ammonium chloride or ammonium sulfate.
The technical scheme that the embodiment of the present invention provides has the benefit that the meso-porous molecular sieve material prepared by Y zeolite nanometer presoma that the present invention selects, not only there is bigger duct, and there is the unexistent more acid site of conventional mesopore molecular sieve, while solving the problem of iron pollution plug-hole impact diffusion, moreover it is possible to overcome the difficult problem that fine and close oil basic n content is too high; The another kind of material that the present invention selects is modified boehmite material, not only have a bigger duct, and at modulation after modified the quantity in its acid site and intensity, there is iron-resistant equally and pollute the function of plug-hole and high alkalinity nitrogen content.
The catalytic cracking catalyst of the present invention has bigger substrate specific surface area, the process that the raw oil mixing the fine and close oil of refining is carried out catalytic cracking reaction shows of a relatively high catalytic cracking activity, to mixing the higher fine and close oil (if miscella basic n content is about 1200-2000 �� g/g) of smelting soda nitrogen compound content and carry out in the process of catalytic cracking process, there is higher conversion ratio, and higher gasoline and diesel yield can be obtained, particularly higher light oil such as yield of gasoline.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of the second molecular sieve component meso-porous molecular sieve material adopted in the described catalytic cracking catalyst of the present invention.
Fig. 2 is the transmission electron microscope photo (TEM) of the modified boehmite adopted in the described catalytic cracking catalyst of the present invention.
Detailed description of the invention
For problem of the prior art, the present invention provides and the invention provides a kind of catalytic cracking catalyst mixing the fine and close oil of refining, and catalyst includes following components: the first molecular sieve component, the second molecular sieve component, modified boehmite, boehmite, clay and binding agent.
Below by specific embodiment, the present invention will be further described, but the present invention is not restricted to following embodiment.
REY molecular sieve, REUSY molecular sieve, USY molecular sieve produce by Shandong Duo You Science and Technology Ltd.;
Alumina gel is produced by Shandong Duo You Science and Technology Ltd.;
Kaolin is purchased from Suzhou China Kaolin Co., Ltd;
Boehmite is purchased from Shandong Aluminum Plant.
1-cetyl-3-methy limidazolium: play bio tech ltd also known as the upper lake of bromination-1-cetyl-3-Methylimidazole. No. CAS: 132361-22-9
Table 1 is meso-porous molecular sieve material and the specific surface area of modified boehmite, the pore volume data of the second molecular sieve component adopted in the described catalytic cracking catalyst of the present invention.
Table 1
| Project | Specific surface area (m2/ g) | Pore volume (mL/g) |
| Second molecular sieve component | 1021 | 1.112 |
| Modified boehmite | 426 | 0.581 |
Embodiment 1
With the butt weight of described catalytic cracking catalyst for benchmark, in described catalyst, the mass percent of each component is: first molecular sieve component the 15%, second molecular sieve component 15%, modified boehmite 15%, boehmite 5%, clay 40% and binding agent 10%.
One, preparing the second molecular sieve component, preparation method is as follows:
2.55 kilograms of sodium silicate and 2.60 kg of water are mixed to get solution one by the first step,
0.035 kilogram of sodium hydroxide, 0.164 kilogram of sodium aluminate and 1.60 kg of water are mixed to get solution two, solution one is at the uniform velocity added in solution two, the feed time of solution one controls at 1.0 hours, stir 3 hours after adding, then heat to 100 DEG C and continue stirring 8 hours, obtain Y zeolite nanometer presoma;
Second step, 6.949 kilograms of 1-cetyl-3-methy limidazolium and 24 kg of water are mixed to get solution three, take under agitation the Y zeolite nanometer presoma 6.949 kilograms that the first step obtains at the uniform velocity be added in solution three solution four, the feed time of Y zeolite nanometer presoma controls at 0.5 hour, then with the PH to 11.5 of 25% sulfuric acid regulation solution four, solution five is obtained;
3rd step, solution five, 100 DEG C of hydro-thermal static crystallizations 20 hours, filters to obtain pressed powder, and pressed powder is washed, and dries, then 500 DEG C of roastings 5 hours, obtains Na type meso-porous molecular sieve material.
4th step, obtain the Na type meso-porous molecular sieve material 0.48 kilogram arrived to mix by the mass ratio of 1:4 with water, the mass ratio adding ammonium salt, described Na type meso-porous molecular sieve material and ammonium salt is 1:0.05,100 DEG C of exchanges, swap time 0.5h, obtain solid, washing after filtration, be washed to the sodium oxide content��1.5wt% in solid, obtaining described second molecular sieve component, recording the sodium oxide content in the second molecular sieve component is 1.34wt%.
Two, the modified boehmite of preparation, preparation method is as follows:
(1), by technical grade aluminium hydroxide at 400 DEG C, after dry 15 seconds, it is crushed to the aluminium hydrate powder that granularity is less than 5 ��m, the aluminium hydrate powder that granularity is less than 5 ��m is placed in 800 DEG C, after 2 seconds, prepare alumina powder standby;
(2), in JZPD capsule groove, add 50 DEG C of pure water, boehmite is added in pure water and make serosity, in serosity, add aluminum nitrate solution, be subsequently adding sodium hydroxide and pH value is adjusted to 6, pass into water vapour and carry out hydration reaction 2 hours, prepare crystal seed standby; Described pure water: boehmite mass ratio is 2:3, described aluminum nitrate solution concentration is the 6wt% that in 100g/l, described aluminum nitrate solution, aluminum nitrate butt quality accounts for boehmite butt quality;
(3), in hydration reaction groove, the alumina powder obtained is added in the pure water that temperature is 70��80 DEG C, stir and make alumina slurry in 2 hours in step (1);Alumina powder mass ratio in alumina slurry is 70%;
(4), the crystal seed that step (2) is prepared, join in the alumina slurry that step (3) prepares, described crystal seed quality accounts for the 40wt% of the alumina dry substrate amount in alumina slurry, being subsequently adding organic titanium stirring to heat up, rise to 60-90 DEG C in 2 hours, mixing speed is 145 revs/min, mixing time is 2 hours, obtain activated alumina mixed liquor, wherein in oxide, TiO2The 6.3wt% that doping is quality of alumina;
(5) the activated alumina mixed liquor of step (4) gained washed, filter and be pressed into filter cake;
(6) at 100 DEG C, filter cake is carried out ripening; Then placing 3h, dry obtaining modifiies boehmite.
Organic titanium in described step (4) is butyl titanate.
The transition metal titanium atom with feature of appraising at the current rate is introduced in macropore activity boehmite skeleton.
The modified boehmite obtained: specific surface area is more than 400m2/ g, pore volume 0.8mL/g.
Three, the catalytic cracking catalyst of the fine and close oil of refining is mixed in preparation, and preparation method comprises the following steps:
Each component is taken in described ratio, under agitation, Xiang Shuizhong adds the first molecular sieve component, the second molecular sieve component, modified boehmite, boehmite (i.e. common boehmite, refer to the thin water aluminum of plan of non-modified) it is mixed to get serosity, in gained serosity, water accounts for the 50% of serosity gross mass, in the serosity obtained, add hydrochloric acid carry out peptization, acid aluminum mass ratio is 0.10, after stirring 30 minutes, sequentially add Kaolin, Alumina gel, pull an oar 2 hours after mixing, then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, exchange with ammonium sulfate at 80 DEG C, wash to sodium oxide content less than 0.20wt%, ammonium sulfate described in exchange washing every time: water: catalyst microspheres mass ratio is 0.05: 5: 1, finally with deionized water drip washing catalyst microspheres, dry at 100 DEG C in catalyst microspheres after filtration, the catalytic cracking catalyst of the fine and close oil of refining must be mixed. by butt quality, first molecular sieve component REY molecular sieve the 15%, second molecular sieve component 15% in catalyst, modified boehmite 15%, boehmite 5%, clay are Kaolin 40%, binding agent is Alumina gel 10%.
Embodiment 2
With the butt weight of described catalytic cracking catalyst for benchmark, in described catalyst, the mass percent of each component is: first molecular sieve component the 35%, second molecular sieve component 25%, modified boehmite 10%, boehmite 9%, clay 11% and binding agent 10%.
One, preparing the second molecular sieve component, preparation method is as follows:
2.55 kilograms of sodium silicate and 2.60 kg of water are mixed to get solution one by the first step,
0.035 kilogram of sodium hydroxide, 0.164 kilogram of sodium aluminate and 1.60 kg of water are mixed to get solution two, solution one is at the uniform velocity added in solution two, the feed time of solution one controls at 0.5 hour, stir 3 hours after adding, then heat to 100 DEG C and continue stirring 8 hours, obtain Y zeolite nanometer presoma;
Second step, 6.949 kilograms of 1-cetyl-3-methy limidazolium and 24 kg of water are mixed to get solution three, the Y zeolite nanometer presoma first step obtained under agitation 6.949 kilograms is at the uniform velocity added in solution three and obtains solution four, the feed time of Y zeolite nanometer presoma controls at 1.0 hours, then with the PH to 11.5 of 25% sulfuric acid regulation solution four, solution five is obtained;
3rd step, solution five, 100 DEG C of static crystallizations 20 hours, filters to obtain pressed powder, and pressed powder is washed, and dries, then 700 DEG C of roastings 5 hours, obtains Na type meso-porous molecular sieve material.
4th step, obtain the Na type meso-porous molecular sieve material 0.48 kilogram arrived to mix by the mass ratio of 1:20 with water, add ammonium salt, the mass ratio of described Na type meso-porous molecular sieve material and ammonium salt is 1:1.0,20 DEG C of exchanges, swap time 1h, solid washing is obtained after filtration, being washed to the sodium oxide content��1.5wt% in solid, obtain described second molecular sieve component, recording the sodium oxide content in the second molecular sieve component is 1.21wt%.
Two, the modified boehmite of preparation, preparation method is as follows:
(1), by technical grade aluminium hydroxide at 300 DEG C, after dry 20 seconds, it is crushed to the aluminium hydrate powder that granularity is less than 5 ��m, the aluminium hydrate powder that granularity is less than 5 ��m is placed in 600 DEG C, after 6 seconds, prepare alumina powder standby;
(2), in JZPD capsule groove, add 60 DEG C of pure water, boehmite is added in pure water and make serosity, in serosity, add aluminum nitrate solution, be subsequently adding sodium hydroxide and pH value is adjusted to 9, pass into water vapour and carry out hydration reaction 2 hours, prepare crystal seed standby; Described pure water: boehmite mass ratio is 1:1, described aluminum nitrate solution concentration is the 10wt% that in 100g/l, described aluminum nitrate solution, aluminum nitrate butt quality accounts for boehmite butt quality;
(3), in hydration reaction groove, the alumina powder obtained is added in the pure water that temperature is 70 DEG C, stir and make alumina slurry in 2 hours in step (1); Alumina powder mass ratio in alumina slurry is 20%;
(4), the crystal seed that step (2) is prepared, join in the alumina slurry that step (3) prepares, described crystal seed quality accounts for the 40wt% of the alumina dry substrate amount in alumina slurry, being subsequently adding organic titanium stirring to heat up, rise to 60-90 DEG C in 2 hours, mixing speed is 145 revs/min, mixing time is 4 hours, obtain activated alumina mixed liquor, wherein in oxide, TiO2The 4.8wt% that doping is quality of alumina,
(5) the activated alumina mixed liquor of step (4) gained washed, filter and be pressed into filter cake;
(6) at 80 DEG C, filter cake is carried out ripening; Then placing 5h, dry obtaining modifiies boehmite.
Organic titanium in described step (4) is isopropyl titanate.
The modified boehmite obtained: specific surface area is more than 400m2/ g, pore volume 0.6mL/g.
Three, the catalytic cracking catalyst of the fine and close oil of refining is mixed in preparation, and preparation method comprises the following steps:
Each component is taken in described ratio, under agitation, Xiang Shuizhong adds the first molecular sieve component, the second molecular sieve component, modified boehmite, boehmite (i.e. common boehmite, refer to the thin water aluminum of plan of non-modified) it is mixed to get serosity, in gained serosity, water accounts for the 80% of serosity gross mass, in the serosity obtained, add hydrochloric acid carry out peptization, acid aluminum mass ratio is 0.10, after stirring 30 minutes, sequentially add Kaolin, Alumina gel, pull an oar 2 hours after mixing, then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, exchange with ammonium sulfate at 50 DEG C, wash to sodium oxide content less than 0.20wt%, ammonium sulfate described in exchange washing every time: water: catalyst microspheres mass ratio is 0.05: 5: 1, finally with deionized water drip washing catalyst microspheres, dry at 150 DEG C in catalyst microspheres after filtration, the catalytic cracking catalyst of the fine and close oil of refining must be mixed.By butt quality, in catalyst, first molecular sieve component REUSY molecular sieve the 15%, second molecular sieve component 15%, modified boehmite 15%, boehmite 5%, clay kaolin 42% and binding agent are Alumina gel 8%.
Embodiment 3-5
Method according to embodiment 1 prepares catalytic cracking catalyst respectively, institute is as shown in table 2 below respectively the difference is that inventory, carrying out spray drying again after mixing making beating uniformly, the inventory of each component is all with parts by weight, thus preparing catalytic cracking catalyst C-3��C-5 respectively. In embodiment 1-5, catalytic component is in Table 2.
Component (in butt) in catalytic cracking catalyst in table 2 embodiment 1-5
Tests prove that clay can be one or more the mixture in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, meerschaum, attapulgite and bentonite; Binding agent can be one or more in Alumina gel, Ludox or Alusil. First molecular sieve component is one or more the mixture in rare earth Y type molecular sieve REY, rare earth superstable Y-type molecular sieve REUSY, ultra-steady Y molecular sieve USY. Ammonium salt is ammonium chloride or ammonium sulfate
Following comparative example can illustrate the synergism of each component in catalyst:
Comparative example 1
Under agitation, by butt quality, Xiang Shuizhong is by the first molecular sieve component REY molecular sieve 30%, modified boehmite 15%, common boehmite 5%, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, acid aluminum ratio (weight) is 0.10, after stirring 30 minutes, sequentially add Kaolin 40%, Alumina gel 10%, pull an oar 2 hours after mixing. Then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, exchange with ammonium sulfate, wash at 20-80 DEG C, (ammonium sulfate: water: microspherical catalyst=0.05: 5: 1), to sodium oxide content less than 0.20wt%, finally use deionized water drip washing, dry at 100-150 DEG C after filtration, thus preparing catalytic cracking catalyst DBC-1.
Comparative example 2
Under agitation, by butt quality, Xiang Shuizhong is by first molecular sieve component REY molecular sieve the 15%, second molecular sieve component (meso-porous molecular sieve material that Y zeolite nanometer presoma prepares) 15%, common boehmite 20%, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, acid aluminum ratio (weight) is 0.10, after stirring 30 minutes, sequentially add Kaolin 40%, Alumina gel 10%, pull an oar 2 hours after mixing. Then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, exchange with ammonium sulfate, wash at 20-80 DEG C, (ammonium sulfate: water: microspherical catalyst=0.05: 5: 1), to sodium oxide content less than 0.20wt%, finally use deionized water drip washing, dry at 100-150 DEG C after filtration, thus preparing catalytic cracking catalyst DBC-2.
Comparative example 3
Under agitation, by butt quality, Xiang Shuizhong is by the first molecular sieve component REY molecular sieve 30%, common boehmite 20%, and in the serosity obtained, add the hydrochloric acid peptization that concentration is 36 weight %, acid aluminum ratio (weight) is 0.10, after stirring 30 minutes, sequentially add Kaolin 40%, Alumina gel 10%, pull an oar 2 hours after mixing. Then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, exchange with ammonium sulfate, wash at 20-80 DEG C, (ammonium sulfate: water: microspherical catalyst=0.05: 5: 1), to sodium oxide content less than 0.20wt%, finally use deionized water drip washing, dry at 100-150 DEG C after filtration, thus preparing catalytic cracking catalyst DBC-3.
The physicochemical data of embodiment 1-5 and comparative example 1-3 catalyst is in Table 3.
Table 3
Test case
By above-mentioned catalytic cracking catalyst C1-C5 and DC1-DC3 through metallic pollution, so that each of which contains nickel 3000ppm, vanadium 2000ppm, ferrum 5000ppm, then 800 DEG C, 100% water vapour when aging 17 hours, be seated in the reactivity worth evaluating catalytic cracking catalyst in fixed fluidized bed ACE device afterwards.
Appreciation condition: the amount of fill of catalyst is 9.0g, reaction temperature is 510 DEG C, air speed is 16h-1, oil ratio (weight) be 4.
What list in table 4 is the fcc raw material oil mixing refining 20wt% densification oil, and table 5 is evaluation result.
Table 4
Table 5ACE evaluation result
| Catalyst | C-1 | C-2 | C-3 | C-4 | C-5 | DBC-1 | DBC-2 | DBC-3 |
| Reaction temperature/DEG C | 530 | 530 | 530 | 530 | 530 | 530 | 530 | 530 |
| Air speed/h-1 | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 |
| Oil ratio | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 |
| Product slates/wt% | ||||||||
| Dry gas | 1.64 | 1.62 | 1.58 | 1.71 | 1.55 | 1.99 | 2.02 | 2.15 |
| Liquefied gas | 15.59 | 15.31 | 15.95 | 16.85 | 13.62 | 12.01 | 12.35 | 11.19 |
| Gasoline | 44.50 | 44.83 | 45.91 | 45.21 | 43.85 | 39.21 | 38.88 | 34.50 |
| Diesel oil | 20.56 | 20.43 | 20.42 | 18.21 | 22.77 | 23.25 | 23.61 | 22.66 |
| Heavy oil | 9.77 | 9.99 | 9.13 | 9.51 | 10.35 | 14.65 | 14.38 | 19.59 |
| Coke | 7.95 | 7.82 | 7.01 | 8.51 | 7.86 | 8.89 | 8.76 | 9.91 |
| Amount to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| Conversion ratio/wt% | 69.67 | 69.58 | 70.45 | 72.28 | 66.88 | 62.1 | 62.01 | 57.75 |
| Liquid+vapour+bavin | 80.65 | 80.57 | 82.28 | 80.27 | 80.24 | 74.47 | 74.84 | 68.35 |
| Vapour+bavin | 65.06 | 65.26 | 66.33 | 63.42 | 66.62 | 62.46 | 62.49 | 57.16 |
| The green coke factor | 3.46 | 3.42 | 2.94 | 3.26 | 3.89 | 5.43 | 5.37 | 7.25 |
* fresh catalyst was through 800 DEG C, under 100% water vapor conditions aging 17 hours
Can be seen that by embodiment 1-5 and comparative example 1-3 is compared respectively, each component of the catalyst of the present invention has good synergism, under the synergism of each component, the catalytic cracking catalyst of the present invention carries out showing of a relatively high catalytic cracking activity in the process of catalytic cracking process at refining 20% raw oil of mixing that heavy metal ferrum and basic n content are higher, it is obtained in that higher conversion ratio, is particularly obtained in that higher yield of gasoline.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. the catalytic cracking catalyst mixing the fine and close oil of refining, it is characterised in that described catalyst includes following components: the first molecular sieve component, the second molecular sieve component, modified boehmite, boehmite, clay and binding agent.
2. the catalytic cracking catalyst mixing the fine and close oil of refining according to claim 1, it is characterized in that, described first molecular sieve component is one or more the mixture in rare earth Y type molecular sieve REY, rare earth superstable Y-type molecular sieve REUSY or ultra-steady Y molecular sieve USY;
And/or described modified boehmite is doping TiO2Boehmite, wherein in oxide, TiO2Doping is the 1-10wt% of quality of alumina.
3. the catalytic cracking catalyst mixing the fine and close oil of refining according to claim 1 and 2, it is characterized in that, with the butt weight of described catalytic cracking catalyst for benchmark, in described catalyst, the mass percent of each component is: the first molecular sieve component 10-35%, the second molecular sieve component 5-30%, modified boehmite 5-20%, boehmite 2-20%, clay 20-50% and binding agent 6-20%.
4. according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-3, it is characterised in that the preparation method of described modified boehmite is as follows:
(1), by technical grade aluminium hydroxide at 300��400 DEG C, after dry 15��20 seconds, it is crushed to the aluminium hydrate powder that granularity is less than 5 ��m, the aluminium hydrate powder that granularity is less than 5 ��m is placed in 600��800 DEG C, after 2��6 seconds, prepare alumina powder standby;
(2), in JZPD capsule groove, add 50��60 DEG C of pure water, boehmite is added in pure water and make serosity, aluminum nitrate solution is added in serosity, it is subsequently adding sodium hydroxide and pH value is adjusted to 6-9, pass into water vapour and carry out hydration reaction 2 hours, prepare crystal seed standby;Described pure water: the mass ratio of boehmite butt is 2:2-3, described aluminum nitrate solution concentration is the 6-10wt% that in 100g/l, described aluminum nitrate solution, aluminum nitrate butt quality accounts for boehmite butt quality;
(3), in hydration reaction groove, being added in the pure water that temperature is 70��80 DEG C by the alumina powder obtained, stir and make alumina slurry in 2 hours in step (1), alumina powder mass ratio in alumina slurry is 20-70%;
(4), the crystal seed that step (2) is prepared, join in the alumina slurry that step (3) prepares, described crystal seed quality accounts for the 40wt% of the alumina dry substrate amount in alumina slurry, being subsequently adding organic titanium stirring to heat up, rise to 60-90 DEG C in 2 hours, mixing speed is 145 revs/min, mixing time is 2-4 hour, obtain activated alumina mixed liquor, wherein in oxide, TiO2The 1-10wt% that doping is quality of alumina;
(5) the activated alumina mixed liquor of step (4) gained washed, filter and be pressed into filter cake;
(6) at 80-100 DEG C, filter cake is carried out ripening; Then placing 3-5h, dry obtaining modifiies boehmite.
5. the catalytic cracking catalyst mixing the fine and close oil of refining according to claim 4, it is characterised in that the organic titanium in described step (4) is butyl titanate or isopropyl titanate.
6. according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-5, it is characterised in that the preparation method of described second molecular sieve component is as follows:
2.55 kilograms of sodium silicate and 2.60 kg of water are mixed to get solution one by the first step,
0.035 kilogram of sodium hydroxide, 0.164 kilogram of sodium aluminate and 1.60 kg of water are mixed to get solution two, solution one is at the uniform velocity added in solution two, the feed time of solution one controls at 0.5-1.0 hour, stir 3 hours after adding, then heat to 100 DEG C and continue stirring 8 hours, obtain Y zeolite nanometer presoma;
Second step, 6.949 kilograms of 1-cetyl-3-methy limidazolium and 24 kg of water are mixed to get solution three, take under agitation the Y zeolite nanometer presoma that 6.949 kilograms of first steps obtain at the uniform velocity be added in solution three solution four, the feed time of Y zeolite nanometer presoma controls at 0.5-1.0 hour, then with the pH to 11.5 of 25% sulfuric acid regulation solution four, solution five is obtained;
3rd step, solution five, 100 DEG C of static crystallizations 20 hours, filters to obtain pressed powder, and pressed powder is washed, and dries, then 500-700 DEG C of roasting 5 hours, obtains Na type meso-porous molecular sieve material;
4th step, obtain the Na type meso-porous molecular sieve material 0.48 kilogram arrived to mix by the mass ratio of 1:4-20 with water, add ammonium salt, 20 DEG C-100 DEG C exchanges, swap time >=0.30h, the mass ratio of described Na type meso-porous molecular sieve material and ammonium salt is 1:0.05-1.0, solid is obtained after filtration, washing, is washed to the sodium oxide content��1.5wt% in solid, obtains the second molecular sieve component.
7. according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-6, it is characterised in that described ammonium salt is ammonium chloride or ammonium sulfate.
8. according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-7, it is characterized in that, described clay is one or more the mixture in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, meerschaum, attapulgite and bentonite.
9. according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-8, it is characterised in that described binding agent is one or more in Alumina gel, Ludox or Alusil.
10. the preparation method according to the arbitrary described catalytic cracking catalyst mixing the fine and close oil of refining of claim 1-9, it is characterised in that said method comprising the steps of:
Each component is taken in described ratio, under agitation, Xiang Shuizhong adds the first molecular sieve component, second molecular sieve component, modified boehmite, boehmite is mixed to get serosity, in gained serosity, water accounts for the 50-80% of serosity gross mass, in the serosity obtained, add hydrochloric acid carry out peptization, acid aluminum mass ratio is 1:10, after stirring 30 minutes, sequentially add clay, binding agent, pull an oar 2 hours after mixing, then carry out spray drying and obtain catalyst microspheres, thus obtained microsphere was through 550 DEG C of roastings 30 minutes, wash to sodium oxide content less than 0.20wt% with ammonium salt solution at 20-80 DEG C, finally with deionized water drip washing catalyst microspheres, filter rear catalyst microsphere to dry at 100-150 DEG C, the catalytic cracking catalyst of the fine and close oil of refining must be mixed.
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