CN1332765C - Process for preparing cracking catalyst for hydrocarbons containing molecular sieves - Google Patents
Process for preparing cracking catalyst for hydrocarbons containing molecular sieves Download PDFInfo
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- CN1332765C CN1332765C CNB2004100376815A CN200410037681A CN1332765C CN 1332765 C CN1332765 C CN 1332765C CN B2004100376815 A CNB2004100376815 A CN B2004100376815A CN 200410037681 A CN200410037681 A CN 200410037681A CN 1332765 C CN1332765 C CN 1332765C
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- hydrated alumina
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005336 cracking Methods 0.000 title claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title 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 abstract description 102
- 239000002002 slurry Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000004927 clay Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 229910021536 Zeolite Inorganic materials 0.000 claims 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 description 45
- 239000004411 aluminium Substances 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000010009 beating Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- -1 molecular sieve hydrocarbon Chemical class 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 57
- 239000000571 coke Substances 0.000 abstract description 11
- 239000008187 granular material Substances 0.000 abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004537 pulping Methods 0.000 abstract 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 25
- 229910001593 boehmite Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 15
- 239000005995 Aluminium silicate Substances 0.000 description 13
- 235000012211 aluminium silicate Nutrition 0.000 description 13
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 150000002910 rare earth metals Chemical class 0.000 description 13
- 238000005299 abrasion Methods 0.000 description 12
- 238000001694 spray drying Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 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 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052621 halloysite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 2
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002063 nanoring Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a preparation method of a hydrocarbon cracking catalyst containing a molecular sieve, which comprises: firstly, aluminum sol, hydrated alumina, clay, acid, a molecular sieve and water are pulped and uniformly mixed to obtain slurry, and the solid content of the slurry is made as 25 to 40 wt%; secondly, the obtained slurry is dried. Silica sol comprising granules with the average granule diameter of 5 to 100 nanometers is also added during pulping, and the granule diameters of more than 80% of the granules are 0.5 to 1.5 times larger than the average granule diameter. During pulping, inorganic acid is added after the aluminum sol and the hydrated alumina are added. The average pore diameter of the catalyst prepared with the method is large, and in addition, the pore volume of each mesopore with the pore diameter of 5 to 100 nanometers and the pore volume of each macropore with the pore diameter of 5 to 100 nanometers are larger. The catalyst prepared with the method has the advantages of high light oil selectivity and low coke selectivity.
Description
Technical field
The invention relates to a kind of preparation method of hydrocarbon cracking catalyzer, further say, is the preparation method who contains the molecular sieve hydrocarbon cracking catalyzer about a kind of.
Background technology
In recent years, the heaviness of catalytically cracked material tendency is serious day by day, and macromolecular substances such as the colloid in the raw material, asphalitine have bigger molecular diameter.During macropore, these macromolecular substances not only are difficult to be converted into light oil, and easily generate coke and thousand gas on the surface of catalyst in lacking in the catalyst, cause selection of catalysts bad, be that the STRENGTH ON COKE selectivity is higher, to light oil, promptly the selectivity of diesel oil and gasoline is lower.The aperture and the middle macropore pore volume that increase Cracking catalyst are to improve the important means of splitting catalyst selectivity.It is generally acknowledged that the hole size that catalyst is suitable should be 2-6 a times of macromolecular reaction thing diameter, the molecular diameter of decompression residuum is the 2.5-15 nanometer, and therefore, the increase bore dia is that the middle macropore pore volume of 5-100 nanometer helps improving selection of catalysts.
CN1098130A discloses a kind of preparation method of Cracking catalyst, this method comprises mixes making beating 25-35 minute with clay and deionized water, added hcl acidifying 0.5-1 hour, added the boehmite stirring to pulp 25-35 minute, wherein, the addition of water guarantees that the solid content of slurries is 20-55 weight %, and the addition of hydrochloric acid is the 15-50 weight % of aluminium oxide in the boehmite; At 50-80 ℃ of aging 0.5-2 hour; Adding aluminium colloidal sol stirred 10-20 minute; Add ground molecular sieve, continue making beating 25-35 minute, drying and moulding and washing, drying.This method adopts two aluminium base binding agents, and wherein, aluminium colloidal sol is used for improving the intensity of catalyst, and boehmite is used for improving the pore structure of catalyst, and heavy oil cracking activity obtains raising to a certain degree.But less than normal with the aperture of the Cracking catalyst of this method preparation and middle macropore pore volume that bore dia is the 5-100 nanometer, selection of catalysts is bad.
CN1247885A discloses a kind of preparation method of Cracking catalyst, this method comprises aluminium colloidal sol, boehmite, clay, inorganic acid and molecular sieve pulp making beating mixed makes catalyst slurry, the solid content that makes slurries is 20-45 weight %, spray-drying then, wherein, aluminium colloidal sol added before clay and inorganic acid, and molecular sieve pulp adds after inorganic acid.Less than normal with the aperture of the Cracking catalyst of this method preparation and middle macropore pore volume that bore dia is the 5-100 nanometer, selection of catalysts is bad.
CN1246515A discloses a kind of preparation method of Cracking catalyst, this method comprises aluminium colloidal sol, boehmite, clay, inorganic acid and molecular sieve pulp making beating mixed makes catalyst slurry, the solid content that makes slurries is 25-45 weight %, spray-drying then, wherein, molecular sieve pulp added before clay and inorganic acid, and inorganic acid adds after aluminium colloidal sol.This method can improve the solid content of catalyst slurry, improves the production efficiency of catalyst, and still, the pore structure of the Cracking catalyst that obtains is not obviously improved, and selectivity is also bad.
CN1388213A discloses a kind of preparation method of Cracking catalyst, this method comprise with clay slurry with acid treatment after, add boehmite, water glass solution, add or do not add aluminium colloidal sol, carry out spray-drying, washing after adding molecular sieve pulp again.This method can shorten the technological process of Preparation of Catalyst, and still, the pore structure of the Cracking catalyst that obtains is not obviously improved, and selectivity is bad equally.
Summary of the invention
It is less than normal to the objective of the invention is the middle macropore pore volume that the catalyst aperture of preparing at above-mentioned existing production of cracking catalyst and bore dia be the 5-100 nanometer, the shortcoming that selection of catalysts is bad, it is that the middle macropore pore volume of 5-100 nanometer is bigger that a kind of aperture and bore dia are provided, and selectivity contains the preparation method of molecular sieve hydrocarbon cracking catalyzer preferably.
Preparation of catalysts method provided by the invention comprises aluminium colloidal sol, hydrated alumina, clay, acid, molecular sieve and water making beating is mixed, make a kind of slurries, the solid content that makes slurries is 25-45 weight %, the dry then slurries that obtain, wherein, when making beating, also add a kind of Ludox, described Ludox is that average particulate diameter is the particle of 5-100 nanometer, and the particle diameter more than 80% is between 0.5-1.5 times of average particulate diameter, when making beating, inorganic acid adds after aluminium colloidal sol and hydrated alumina.
Because method provided by the invention has been used the narrower Ludox of a kind of particle diameter distribution, the catalyst of preparing has big average pore diameter, and bore dia is that the middle macropore pore volume of 5-100 nanometer is bigger, has higher light oil selectivity and lower coke selectivity.
In addition, method provided by the invention adopts acid adding aluminium colloidal sol and hydrated alumina after can keep the described method of CN1246515A can improve the solid content of slurries before the catalyst spray-drying, the advantage that reduces energy consumption and production costs.
The specific embodiment:
According to method provided by the invention, described Ludox is that average particulate diameter is the particle of 5-100 nanometer, and the 80% above Ludox of particle diameter between 0.5-1.5 times of average particulate diameter.Under the preferable case, the average particulate diameter of described Ludox is the 10-80 nanometer.Described Ludox with above-mentioned particle diameter distribution can be commercially available, and also can adopt ion-exchange to prepare.Described employing ion-exchange prepares the method for Ludox referring to Ralph K Iler, JohnWiley and Sons write " The Chemistry ofSilica:Polymerization, Colloid And SurfaceProperties, And Biochemistry " and US4304575.
Described hydrated alumina is selected from one or more in the normally used hydrated alumina of Cracking catalyst, as has in the hydrated alumina of boehmite (Pseudoboemite) structure, a diaspore (Boehmite) structure, gibbsite (GibbsRe) structure and bayerite (Bayerite) structure one or more.The hydrated alumina that is preferably hydrated alumina and/or has the gibbsite structure with structure of similar to thin diaspore.
The consumption of each component is the consumption of each material in the conventional production of cracking catalyst in the described slurries, and in general, by butt, the consumption of each component makes catalyst slurry contain 5-50 weight %, the clay of preferred 10-35 weight %; 5-50 weight %, the aluminium oxide that the hydrated alumina of preferred 15-45 weight % provides; 1-25 weight %, the aluminium oxide that the aluminium colloidal sol of preferred 5-20 weight % provides; 1-30 weight %, the silica that the Ludox of preferred 5-20 weight % provides; 15-60 weight %, the molecular sieve of preferred 20-50 weight %.
The consumption of acid is the conventional amount used of acid in the production of cracking catalyst, and in general, it is 0.18-0.30 that the consumption of acid makes the mol ratio sour and aluminium oxide that hydrated alumina provides, is preferably 0.20-0.25.Described acid is selected from one or more in the various acid used in the production of cracking catalyst, one or more in example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and the acetate, and preferred acid is hydrochloric acid, nitric acid and/or phosphoric acid.
According to method provided by the invention, when making beating, described acid adds after aluminium colloidal sol and hydrated alumina.Under the preferable case, described acid adds after aluminium colloidal sol and hydrated alumina, and aluminium colloidal sol added before clay, and Ludox adds after clay and hydrated alumina.The addition sequence of rest materials has no particular limits.
Described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.These zeolites and molecular sieve are conventionally known to one of skill in the art.
Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, Q zeolite, modenite, the ZSM.18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the disclosed phosphorous zeolite of CN119418iA) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more with MFI structure.
Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titan silicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of metal combination, silicoaluminophosphate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.
Under the preferable case, described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.These clays are conventionally known to one of skill in the art.
The drying means of slurries and condition are conventionally known to one of skill in the art.For example, dry method can be dry, oven dry, forced air drying, spray-drying, the method for preferably spray drying.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃
The solid that drying obtains can according to circumstances wash or not wash, and the washing back is dry.The purpose of washing is that the sodium oxide content of catalyst is reduced to below the 0.3 weight %.Drying means after the washing and condition are conventionally known to one of skill in the art, for example, dry method can be dry, oven dry, forced air drying.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃
According to method provided by the invention,, can also add one or more oxides or its precursor of rare-earth oxide, alkaline earth oxide, titanium oxide, phosphorous oxide, zirconia, manganese oxide at the arbitrary steps in when making beating.The precursor of described oxide refers in described Cracking catalyst preparation process, can form in the material of described oxide one or more.For example, one or more in the hydroxide of all cpds of rare earth metal, alkaline-earth metal, titanium, phosphorus, zirconium, manganese, particularly rare earth metal, alkaline-earth metal, titanium, zirconium, manganese, nitrate, chloride, phosphoric acid, the phosphate.
Following example will the present invention is described further.
The abrasion index of the catalyst that following example and Comparative Examples are prepared is measured according to the RIPP29-90 method in " petrochemical industry analytical method (RIPP test method) " (nineteen ninety publishes for volume such as Yang Cuiding, Science Press).Catalyst average pore diameter and bore dia are that the pore volume of 5-100 nano-pore adopts cryogenic nitrogen absorption BET method to measure.
Example 1
This example illustrates Preparation of catalysts method provided by the invention.
Under agitation, with 3.23 kilograms deionized waters and 1.6 kilograms of Ludox (Jiangyin Guobang Chemical Co., Ltd.'s product, average particulate diameter are 15 nanometers, 95% silica sol granule diameter between the 8-22 nanometer, SiO
2Content is 25 weight %) pulling an oar mixes, add 1.54 kilograms of kaolin (Suzhou kaolin company product successively, solid content 78 weight %), 0.95 kg aluminium colloidal sol (produce by the Shandong catalyst plant, alumina content 21 weight %), 1.29 (Shandong Aluminum Plant produces the kilogram boehmite, alumina content 62 weight %), 4.38 the industrial trade mark of kilogram is molecular sieve (the Shandong catalyst plant product of DM-4, lattice constant is 24.45 dusts, the ultra-steady Y molecular sieve that contains rare earth and magnesium, mixed rare-earth oxide content is 3.0 weight %, wherein, lanthana content is 1.1 weight %, cerium oxide content is 1.7 weight %, other rare earth oxide content is 0.2 weight %, content of magnesia is 1.5 weight %) content is that slurries and 313 ml concns of 32 weight % are the hydrochloric acid of 20 weight %, all pulling an oar after component of every adding mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst Cl.Table 1 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C1, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 2
This example illustrates Preparation of catalysts method provided by the invention.
Method by example 1 prepares catalyst, different is, the addition of deionized water is 1.36 kilograms, the addition of hydrochloric acid is 287 milliliters, the addition sequence of each component is aluminium colloidal sol, boehmite, kaolin, hydrochloric acid, Ludox and the slurries that contain the DM-4 molecular sieve during making beating, obtains catalyst C2.Table 1 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C2, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 3
This example illustrates Preparation of catalysts method provided by the invention.
Method by example 1 prepares catalyst, different is, the addition of deionized water is 1.36 kilograms, the addition of hydrochloric acid is 287 milliliters, the addition sequence of each component is boehmite, aluminium colloidal sol, kaolin, hydrochloric acid, the slurries that contain the DM-4 molecular sieve and Ludox during making beating, obtains catalyst C3.Table 1 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C3, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 4
This example illustrates Preparation of catalysts method provided by the invention.
Method by example 1 prepares catalyst, different is, the addition of deionized water is 1.36 kilograms, the addition of hydrochloric acid is 300 milliliters, the addition sequence of each component is boehmite, aluminium colloidal sol, the slurries that contain the DM.4 molecular sieve, kaolin, hydrochloric acid and Ludox during making beating, obtains catalyst C4.Table 1 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C4, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Comparative Examples 1
The preparation method of this Comparative Examples explanation reference catalyst.
Method according to CN1098130A prepares catalyst.6.7 kilograms deionized waters and 1.54 kilograms of kaolin (with example 1) making beating are mixed, add the hydrochloric acid that 450 ml concns are 20 weight %, stir, add 1.94 kilograms of example 1 described boehmites, be warmed up to after stirring 65 ℃ aging 2 hours, add 0.95 kg aluminium colloidal sol (with example 1) again and stir, the molecular sieve content that to add 4.38 kilograms of industrial trades mark then be DM-4 is the slurries of 32 weight %, making beating mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst CB1.Table 3 has provided the average pore diameter of catalyst CB1, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Comparative Examples 2
The preparation method of this Comparative Examples explanation reference catalyst.
Method according to CN1388213A prepares catalyst.3.51 kilograms deionized waters and 1.54 kilograms of kaolin (with example 1) making beating are mixed, add the hydrochloric acid that 300 ml concns are 20 weight %, stir, add 1.29 kilograms of example 1 described boehmites, being warmed up to 65 ℃ after stirring wore out 2 hours, adding 0.95 kg aluminium colloidal sol (with example 1) and 4.0 kg water glass (silica content is 10 weight %) again stirs, the molecular sieve content that to add 4.38 kilograms of industrial trades mark then be DM-4 is the slurries of 32 weight %, making beating mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst CB2.Table 1 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst CB2, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 5
This example illustrates Preparation of catalysts method provided by the invention.
Under agitation, 2.45 kilograms deionized waters and 1.90 kilograms of example 1 described aluminium colloidal sol making beating are mixed, add 1.61 kilograms of examples, 1 described boehmite successively, (solid content is 74 weight % to 0.54 kilogram of halloysite, Xuyong, Sichuan china clay company product), 342 ml concns are that the hydrochloric acid of 20 weight %, 2.4 kilograms of Ludox are (according to card chemicals Co., Ltd product, average particulate diameter is 40 nanometers, 90% silica sol granule diameter between the 20-60 nanometer, SiO
2Content is 25 weight %), 4.0 kilograms of industrial trades mark molecular sieve content that is DM-4 is that (silica alumina ratio is 70 for the slurries of 32 weight % and 1.0 kilograms of ZSM-5 zeolites, sodium oxide content is 0.1 weight %, Shandong catalyst plant product) content is the slurries of 32 weight %, all pulling an oar after a kind of component of every adding mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst C5.Table 2 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries thousand base compositions, slurries.Table 3 has provided the average pore diameter of catalyst C5, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 6
This example illustrates Preparation of catalysts method provided by the invention.
Under agitation, 1.73 kilograms deionized waters and 1.90 kilograms of example 1 described aluminium colloidal sol making beating are mixed, add 0.65 kilogram of example, 1 described boehmite successively, 0.31 (Shandong Aluminum Plant produces the kilogram gibbsite, alumina content is 64 weight %), 1.28 kilogram kaolin (with example 1), 0.51 (solid content is 78 weight % in the kilogram imvite, Zhong Xiang county, Hubei iron ore factory produces), 366 ml concns are the nitric acid of 20 weight %, 3.2 kilogram example 1 described Ludox and 2.5 kilograms of Y-shaped molecular sieve containing rare earth (Shandong catalyst plant products that the industrial trade mark is REHY, lattice constant is 24.62 dusts, the Y zeolite that contains rare earth, mixed rare-earth oxide content is 4.5 weight %, wherein, lanthana content is 1.7 weight %, cerium oxide content is 2.6 weight %, other rare earth oxide content is 0.2 weight %, sodium oxide content is 1.5 weight %) content is the slurries of 32 weight %, all pulling an oar after a kind of component of every adding mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst C6.Table 2 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C6, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Example 7
This example illustrates Preparation of catalysts method provided by the invention.
Under agitation, in 3.81 kilograms of examples, 1 described aluminium colloidal sol, adding 0.63 kilogram of example, 6 described gibbsites, 0.77 kilogram of kaolin (with example 1), 224 ml concns successively is that the nitric acid of 20 weight %, 0.5 kilogram of Ludox are (according to card chemicals Co., Ltd product, average particulate diameter is 60 nanometers, 90% silica sol granule diameter between the 30-90 nanometer, SiO
2Content is 40 weight %), 4.20 the industrial trade mark of kilogram is ultra-steady Y molecular sieve (the Shandong catalyst plant product of DASY, lattice constant is 24.46 dusts, sodium oxide content is 0.99 weight %,) content is that (the Shandong catalyst plant is produced for the slurries of 40 weight % and molecular sieve that 0.8 kilogram of industrial trade mark is ZRP-1, the zeolite that contains rare earth and phosphorus with MFI structure, silica alumina ratio is 20, mixed rare-earth oxide content is 1.5 weight %, wherein, lanthana content is 0.6 weight %, cerium oxide content is 0.8 weight %, other rare earth oxide content is 0.1 weight %, phosphorus pentoxide content is 1.4 weight %) content is the slurries of 40 weight %, all pulling an oar after a kind of component of every adding mixes, and obtains slurries.With the slurries spray drying forming that obtains, obtain the solid particle that diameter is the 20-120 micron under 250 ℃ temperature, spend deionised water and be not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst C7.Table 2 has provided the solid content and the mol ratio sour and aluminium oxide that hydrated alumina provides of described slurries butt composition, slurries.Table 3 has provided the average pore diameter of catalyst C7, pore volume and the abrasion index that bore dia is the 5-100 nano-pore.
Table 1
| Example number | 1 | 2 | 3 | 4 | Comparative Examples 1 | Comparative Examples 2 |
| Clay types | Kaolin | Kaolin | Kaolin | Kaolin | Kaolin | Kaolin |
| Clay content, weight % | 30 | 30 | 30 | 30 | 30 | 30 |
| The hydrated alumina kind | Boehmite | Boehmite | Boehmite | Boehmite | Boehmite | Boehmite |
| The alumina content that hydrated alumina provides, weight % | 20 | 20 | 20 | 20 | 30 | 20 |
| The alumina content that aluminium colloidal sol provides, weight % | 5 | 5 | 5 | 5 | 5 | 5 |
| The silica content that Ludox provides, weight % | 10 | 10 | 10 | 10 | 0 | 10 * |
| The molecular sieve kind | DM-4 | DM-4 | DM-4 | DM-4 | DM-4 | DM-4 |
| Molecular sieve content, weight % | 35 | 35 | 35 | 35 | 35 | 35 |
| The solid content of slurries, weight % | 30.0 | 35.0 | 35.0 | 35.0 | 25.0 | 25.0 |
| The mol ratio of the aluminium oxide that acid and hydrated alumina provide | 0.24 | 0.22 | 0.22 | 0.23 | 0.23 | 0.23 |
*The silica that waterglass provides
Table 2
| Example number | 5 | 6 | 7 |
| Clay types | Halloysite | Kaolin/imvite | Kaolin |
| Clay content, weight % | 10 | 25/10 | 15 |
| The hydrated alumina kind | Boehmite | Gibbsite/boehmite | Gibbsite |
| The alumina content that hydrated alumina provides, weight % | 25 | 5/10 | 10 |
| The alumina content that aluminium colloidal sol provides, weight % | 10 | 10 | 20 |
| The silica content that Ludox provides, weight % | 15 | 20 | 5 |
| The molecular sieve kind | DM-4/ZSM-5 | REHY | DASY/ZRP-1 |
| Molecular sieve content, weight % | 32/8 | 20 | 42/8 |
| The solid content of slurries, weight % | 28.0 | 32.0 | 36.5 |
| The mol ratio of the aluminium oxide that acid and hydrated alumina provide | 0.21 | 0.22 | 0.20 |
Table 3
| Example number | 1 | 2 | 3 | 4 | Comparative Examples 1 | Comparative Examples 2 | 5 | 6 | 7 |
| The catalyst numbering | C1 | C2 | C3 | C4 | CB1 | CB2 | C5 | C6 | C7 |
| The pore volume of bore dia 5-100 nano-pore, milliliter/gram | 0.10 | 0.11 | 0.12 | 0.11 | 0.06 | 0.08 | 0.11 | 0.10 | 0.11 |
| Average pore diameter, nanometer | 7.5 | 7.7 | 7.8 | 7.6 | 5.4 | 5.9 | 7.4 | 7.2 | 7.3 |
| Abrasion index, % | 1.5 | 1.5 | 1.7 | 1.6 | 2.5 | 3.0 | 1.9 | 1.3 | 2.1 |
From the result of table 3 as can be seen, with only add boehmite and compare with CB2 with the reference catalyst CB1 that the preparation method who adds waterglass prepares, adopt the described Ludox of adding provided by the invention the average pore diameter of catalyst C1-C7 of preparation method preparation and the pore volume that the aperture is the 5-100 nano-pore obviously increase, abrasion index is less, adopt the described acid of example 2-4 after aluminium colloidal sol and boehmite, to add, and aluminium colloidal sol added before kaolin, the catalyst of the method preparation that Ludox adds after kaolin and boehmite, average pore diameter and aperture are that the pore volume of 5-100 nano-pore increases more outstanding.
Example 8-14
This example illustrates the catalytic performance of the catalyst of method preparation provided by the invention.
With the catalyst C1-C7 of example 1-7 preparation at 800 ℃, with aging 4 hours of 100% steam, the small fixed flowing bed device of packing into (the ACE Model R of U.S. KTI company production
+Little anti-) reactor in, the catalyst loading amount is 10 grams, is 500 ℃ in reaction temperature, agent weight of oil ratio is 7.03, condition under, feed the miscella of vacuum gas oil (VGO) shown in the table 4 and reduced crude, this miscella is carried out catalytic cracking, the result is as showing shown in the 5-6.
Comparative Examples 3-4
The catalytic performance of the catalyst of this Comparative Examples explanation reference method preparation.
Method by example 8 is carried out catalytic cracking to same feedstock oil under similarity condition, different is that catalyst system therefor is respectively the catalyst CB1 and the CB2 of Comparative Examples 1 and Comparative Examples 2 preparations.The result is as shown in table 5.
Table 4
| The feedstock oil title | The miscella of vacuum gas oil (VGO) and reduced crude | |
| Density (20 ℃), gram-centimeter -3 | 0.9044 | |
| Index of refraction (20 ℃) | 1.5217 | |
| Viscosity (100 ℃), millimeter 2Second -1 | 9.96 | |
| Freezing point, ℃ | 40 | |
| Aniline point, ℃ | 95.8 | |
| C, weight % | 85.98 | |
| H, weight % | 12.86 | |
| S, weight % | 0.55 | |
| N, weight % | 0.18 | |
| Carbon residue, weight % | 3.0 | |
| Boiling range, ℃ | Initial boiling point | 243 |
| 5 weight % | 294 | |
| 10 weight % | 316 | |
| 30 weight % | 395 | |
| 50 weight % | 429 | |
| 70 weight % | 473 | |
Table 5
| Example number | 8 | 9 | 10 | 11 | Comparative Examples 3 | Comparative Examples 4 |
| Catalyst | C1 | C2 | C3 | C4 | CB1 | CB2 |
| Crackate is formed, weight % H 2-C 2Liquefied gas C 5 +Gasoline, diesel heavy oil coke amounts to | 1.75 17.79 53.05 14.77 5.32 7.32 100.00 | 1.72 17.62 53.16 14.87 5.35 7.28 100.00 | 1.73 17.61 53.03 15.07 5.36 7.2 100.00 | 1.7 17.71 53.17 14.95 5.29 7.18 100.00 | 1.91 18.08 52.56 14.57 4.87 8.01 100.00 | 1.85 17.92 52.72 14.74 5.03 7.74 100.00 |
| Conversion ratio, weight % | 79.91 | 79.78 | 79.57 | 79.76 | 80.56 | 80.23 |
| Gasoline+diesel oil | 67.82 | 68.03 | 68.1 | 68.12 | 67.13 | 67.46 |
| Product selectivity (gasoline+diesel oil)/conversion ratio coke/conversion ratio | 0.849 0.0916 | 0.853 0.0913 | 0.856 0.0905 | 0.854 0.0900 | 0.833 0.0994 | 0.841 0.0965 |
Table 6
| Example number | 12 | 13 | 14 |
| Catalyst | C5 | C6 | C7 |
| Crackate is formed, weight % H 2-C 2Liquefied gas C 5 +Gasoline, diesel heavy oil coke amounts to | 1.69 17.85 53.13 15.01 4.97 7.35 100 | 1.79 17.73 52.67 15.21 5.15 7.45 100 | 1.68 18.01 53.97 14.24 4.75 7.35 100 |
| Conversion ratio, weight % | 80.02 | 79.64 | 81.01 |
| Gasoline+diesel oil | 68.14 | 67.88 | 68.21 |
| Product selectivity (gasoline+diesel oil)/conversion ratio coke/conversion ratio | 0.852 0.0919 | 0.852 0.0935 | 0.842 0.0907 |
From the result of table 5 as can be seen, the reference catalyst CB1 identical or close with the composition that adopts existing method preparation compares with CB2, the catalyst C1-C4 of method preparation provided by the invention obviously improves the selectivity of light oil (gasoline and diesel oil), and coke selectivity obviously descends.C2-C4 to the selectivity of light oil improve more outstanding, it is more obvious that coke selectivity descends.C5-C7 also obviously improves the selectivity of light oil (gasoline and diesel oil), and coke selectivity also obviously descends.
Claims (8)
1. preparation method who contains the molecular sieve hydrocarbon cracking catalyzer, this method comprises aluminium colloidal sol, hydrated alumina, clay, acid, molecular sieve and water making beating is mixed, make a kind of slurries, the solid content that makes slurries is 25-45 weight %, the dry then slurries that obtain, it is characterized in that, when making beating, also add a kind of Ludox, described Ludox is that average particulate diameter is the particle of 5-100 nanometer, and the particle diameter more than 80% is between 0.5-1.5 times of average particulate diameter, when making beating, inorganic acid adds after aluminium colloidal sol and hydrated alumina.
2. method according to claim 1 is characterized in that, the average particulate diameter of described Ludox is the 10-80 nanometer.
3. method according to claim 1, it is characterized in that, by butt, the consumption of each component makes catalyst slurry contain the clay of 5-50 weight %, the aluminium oxide that the hydrated alumina of 5-50 weight % provides, the aluminium oxide that the aluminium colloidal sol of 1-25 weight % provides, the silica that the Ludox of 1-30 weight % provides, the molecular sieve of 15-60 weight %.
4. method according to claim 3, it is characterized in that, by butt, the consumption of each component makes catalyst slurry contain the clay of 10-35 weight %, the aluminium oxide that the hydrated alumina of 15-45 weight % provides, the aluminium oxide that the aluminium colloidal sol of 5-20 weight % provides, the silica that the Ludox of 5-20 weight % provides, the molecular sieve of 20-50 weight %.
5. according to claim 1,3 or 4 described methods, it is characterized in that, described molecular screening from y-type zeolite, Beta zeolite, have in the zeolite of MFI structure one or more.
6. method according to claim 1 is characterized in that, it is 0.18-0.30 that the consumption of acid makes the mol ratio sour and aluminium oxide that hydrated alumina provides.
7. according to claim 1 or 6 described methods, it is characterized in that described acid is selected from hydrochloric acid, nitric acid and/or phosphoric acid.
8. method according to claim 1 is characterized in that, in when making beating, described acid adds after aluminium colloidal sol and hydrated alumina, and aluminium colloidal sol added before clay, and Ludox adds after clay and hydrated alumina.
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| CN103447070A (en) * | 2012-06-01 | 2013-12-18 | 湖北赛因化工有限公司 | FCC (Fluid Cracking Catalyst) catalyst containing silicon binder and preparation method thereof |
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