CN1031029A - Cracking catalyst of clay molecular sieve with layer structure - Google Patents
Cracking catalyst of clay molecular sieve with layer structure Download PDFInfo
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- CN1031029A CN1031029A CN 87104718 CN87104718A CN1031029A CN 1031029 A CN1031029 A CN 1031029A CN 87104718 CN87104718 CN 87104718 CN 87104718 A CN87104718 A CN 87104718A CN 1031029 A CN1031029 A CN 1031029A
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- clay
- molecular sieve
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- layer structure
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000004927 clay Substances 0.000 title claims abstract description 81
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 238000005336 cracking Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 33
- 239000011707 mineral Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 22
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- 239000004411 aluminium Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 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 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 238000007796 conventional method Methods 0.000 claims description 9
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- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910000632 Alusil Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims 1
- 235000017491 Bambusa tulda Nutrition 0.000 claims 1
- 241001330002 Bambuseae Species 0.000 claims 1
- 229910052781 Neptunium Inorganic materials 0.000 claims 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims 1
- 239000011425 bamboo Substances 0.000 claims 1
- 239000002734 clay mineral Substances 0.000 claims 1
- LFNLGNPSGWYGGD-UHFFFAOYSA-N neptunium atom Chemical compound [Np] LFNLGNPSGWYGGD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- -1 carbonium ion Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 229910021647 smectite Inorganic materials 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 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 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000010009 beating Methods 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 7
- 238000005243 fluidization Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000002101 lytic effect Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
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- 229910052618 mica group Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 101100004280 Caenorhabditis elegans best-2 gene Proteins 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- ORQBXQOJMQIAOY-UHFFFAOYSA-N nobelium Chemical compound [No] ORQBXQOJMQIAOY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
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- 235000013339 cereals Nutrition 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 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 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 244000144980 herd Species 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of clay molecular sieve with layer structure catalytic cracking catalyst, be to be the raw material of active component with natural or artificial synthetic clay with regular interbed mineral structure, can be aided with other molecular sieve, be equipped with the carrier component and the binding agent of proper proportion, by carrying out cross-linking reaction, and make through steps such as burin-in process, roastings with the inorganic metal hydroxy polymer.Its basal spacing (d001) is 17.0～50.0 * 10
-10Rice, interlamellar spacing is 0～33.0 * 10
-10Rice.This catalyst not only has the layer pole structure of macropore opening, good heat and hydrothermal stability, and have activity and selectivity preferably, be applicable to the catalytic process of the carbonium ion reaction that comprises residual oil cracking.
Description
The present invention relates to Hydrocarban coversion catalysts and preparation method thereof.Exactly, the present invention relates to a kind of cracking catalyst of clay molecular sieve with layer structure made from the crosslinked regular interbed mineral substance clay of inorganic metal hydroxy polymer and preparation method thereof.
Since 1976, crosslinked smectite class clay molecular sieve with layer structure occurred, it is to react with crosslinking agent (as the inorganic metal hydroxy polymer etc.) and natural or synthetic smectite class clay to make.Smectite class clay is a single-storeyed mineral structure, and its general structure is:
｛Ca，Na｝
x（Al，Mg）
Ⅵ 4〔Si，Al，Fe〕
Ⅳ 8O
20（OH）
4
Exchangeable cations hexa-coordinate ion four-coordination ion
Its basal spacing (d
001) be 9.0～15.0 * 10
-10Rice.The crosslinked smectite class clay molecular sieve with layer structure of making through cross-linking reaction has certain hole, specific surface and catalytic activity, and the aperture can be 6.0～30.0 * 10
-10Adjust in the rice scope, help the catalytic reaction of macromolecule hydrocarbon.But its heat endurance and hydrothermal stability are poor, and after 4 hours, its specific surface will lose 90% through 730 ℃ of steam treatment, and pore volume will lose 80%, the light diesel fuel lytic activity are dropped to 30%(Occelli by 80% of initial activity, M.L., I﹠amp; EC, Prod.Res.﹠amp; Dev., 22,553,1983).The crosslinked smectite class clay molecular sieve with layer structure catalyst abrasion intensity difference of preparing with common technology of preparing, molecular sieve itself is caking, easily layering easily, and very easily coking in hydrocarbon conversion reactions, for example in catalytic cracking reaction, it is higher 2～3 times than the coking yield of conventional REY type molecular sieve catalyst.Because above-mentioned major defect, crosslinked smectite class clay molecular sieve with layer structure is failed so far to be developed to and is industrial catalyst.
For overcoming existing crosslinked smectite class clay molecular sieve with layer structure heat endurance and this disadvantage of hydrothermal stability difference, we develop another kind of clay catalysis material-regular interbed mineral clay beyond the smectite class clay, and develop a class with this and have the good novel clay molecular sieve with layer structure of macropore and high-temperature hydrothermal stability-the have clay molecular sieve with layer structure (EP197012A of regular interbed mineral structure
2).This novel clay molecular sieve with layer structure is to react with crosslinking agent (inorganic metal hydroxy polymer) and the natural or synthetic clay with regular interbed mineral structure to make.The clay of rule interbed mineral structure is according to the mode interleaved of public adjacent 2: 1 argillic horizons, an orderly class crystalline mineral clay that forms, its basal spacing (d of arranging by expandable and nondistensible two kinds of individual layer mineral clays
001) be 17.0～50.0 * 10
-10Rice.Adjustable through the clay molecular sieve with layer structure that cross-linking reaction is made except that aperture with crosslinked smectite class clay molecular sieve with layer structure with regular interbed mineral structure, have certain catalytic activity, help also having good heat and hydrothermal stability the advantages such as catalytic reaction of macromolecule hydrocarbon.For example after 17 hours, its specific surface only loses 26% to the aluminum cross-linked rectorite clay molecular sieve with layer structure through 800 ℃, normal pressure, 100% steam treatment, and pore volume only changes 15%, can keep 90% of initial activity to the lytic activity of light diesel fuel.
The object of the present invention is to provide a kind of clay molecular sieve with layer structure catalytic cracking catalyst product, it is had in the catalytic cracking reaction of hydro carbons conform with various physical and chemical performances and the catalytic performance that catalytic cracking requires with regular interbed mineral structure.
Another object of the present invention is to provide the method for this catalytic cracking catalyst of preparation.
Catalytic cracking catalyst product provided by the present invention is made of active component, carrier component and binder component.Active component is for accounting for catalyst weight 1～100%(by bright base, down together), best 40～60% the clay molecular sieve with layer structure that comprises the regular interbed mineral structure of having of cross-linked rectorite or this clay molecules sieve and other molecular sieve are as faujasite, the mixture of faujasite, ZSM series molecular sieve etc. after various chemistry and/or stabilization processes.The carrier component is for accounting for catalyst weight 0～99%, best 30～40% the various natural claies that comprise kaolin, rectorite, or various artificial synthetic refractory oxide carriers, comprise amorphous aluminum silicide, aluminium oxide, silica or contain among them one or more mixture, be preferably halloysite.Binder component is for accounting for catalyst weight 0～99%, and best 10～30% aluminium colloidal sol, Ludox, silicon-aluminum sol or contain among them one or more mixture is preferably aluminium colloidal sol or Alusil.
Catalytic cracking catalyst provided by the present invention is owing to contain the clay molecular sieve with layer structure with regular interbed mineral structure, thereby has the pore structure feature of macropore opening: the basal spacing (d of its fresh sample and natural wind dry sample
001) be respectively 17.0～50.0 * 10
-10Rice and 27.0～33.0 * 10
-10Rice, interlamellar spacing is respectively 0～33.0 * 10
-10Rice and 8.0～16.0 * 10
-10Rice.
The apparent density of the microspheres product of catalytic cracking catalyst provided by the present invention is 0.6～0.9 grams per milliliter; The fluidisation abrasion index is less than 4 heavy %; Average grain diameter is 50～60 * 10
-6Rice, wherein particle diameter is 40～80 * 10
-6The microballoon of rice accounts for more than the 80 heavy %.
Catalytic cracking catalyst provided by the present invention is to be the raw material of active component with the natural or artificial synthetic clay with regular interbed mineral structure, can be aided with other molecular sieve, be equipped with the natural of proper proportion or artificial synthetic carrier component and binding agent, by carrying out cross-linking reaction, and make through steps such as burin-in process, roastings with the inorganic metal hydroxy polymer.Its preparation technology's flow process can be divided into " back is crosslinked " and " earlier crosslinked " two kinds.
According to preparation method provided by the invention, " back is crosslinked " preparation flow of this catalytic cracking catalyst is as follows:
1. moulding: will be: 0～99: 0～99 as the mixture of having of active component raw material regular interbed mineral structure clay or this clay and other molecular sieve and carrier component, binder component according to 1～100, preferably 40～60: 30～40: 10～30 weight ratio is mixed, moulding, as to want product be microspheroidal, and the slurry solid content that then is used to spray is that 20～40 heavy % are advisable;
2. the preparation of crosslinked fluid: with commercially available or be mixed with dilute aqueous solution by the inorganic metal hydroxy polymer that prior art is prepared, for example aluminum crosslinker be diluted to 100 mM aluminium/liter below (other metal standard is according to this pressed equivalents conversion), and use NH
4OH transfers to 4～6 with its pH value, and best 5～6;
3. cross-linking reaction: with the regular interbed mineral clay in every gram active component with 1.5～5.0, the amount ratio of best 3.0～4.0 mM aluminum crosslinkers (other crosslinking agent standard is according to this pressed the equivalents conversion), the catalysis material of moulding is added in the crosslinked fluid, under agitation carry out cross-linking reaction 5 minutes more than the kind, use NH during reaction in room temperature
4The pH value of OH control slurries maintains 4～6, best 5～6;
4. aging: keep slurries PH4～6 after the cross-linking reaction, best 5～6, stir down at 70～75 ℃ aging 1～5, best 2～4 hours;
5. filtration washing according to a conventional method;
6. room temperature to 300 ℃ drying;
7.550～750 ℃ of roastings 0.5～4 hour best 2～3 hours, promptly get catalytic cracking catalyst provided by the present invention.
According to preparation method provided by the invention, this catalytic cracking catalyst " earlier crosslinked " preparation flow promptly: will carry out cross-linking reaction and the flow process of aftershaping with the inorganic metal hydroxy polymer earlier as the clay of the regular interbed mineral structure of having of active component raw material.Have the operation that the clay of regular interbed mineral structure mixes with other molecular sieve, carrier component, binder component and both can also can carry out after cross-linking reaction before the cross-linking reaction, operating parameters all in other operation and the preparation process is all identical with " back is crosslinked " preparation flow.
The clay that is used as the regular interbed mineral structure of having of active component raw material in the preparation process be meant comprise rectorite interior, natural or artificial synthetic, by expandable and nondistensible two kinds of individual layer mineral clays according to the mode interleaved of public adjacent 2: 1 argillic horizons, arrange a class crystalline mineral clay that forms in order.As other molecular sieve of active component, can be faujasite, the faujasite after various chemistry and/or stabilization processes, ZSM series molecular sieve etc.The carrier component can be the various natural claies that comprise kaolin, rectorite, also can be various artificial synthetic refractory oxide carriers, comprise amorphous aluminum silicide, aluminium oxide, silica or contain among them one or more mixture, be preferably halloysite.Binder component can be aluminium colloidal sol, Ludox, silicon-aluminum sol or the mixture that contains among them one or more, is preferably aluminium colloidal sol or Alusil.When use contained the binding agent of aluminium colloidal sol, the aluminium colloidal sol in this binding agent can play the effect of crosslinking agent simultaneously and need not to re-use inorganic metal hydroxy polymer crosslinking agent.As the both common commercial goods of the inorganic metal hydroxy polymer of crosslinking agent (as: " the aluminium colloidal sol " that Zhou village, Shandong catalyst plant is produced, its aluminium content is 11～13 heavy %, the Al/Cl weight ratio is 1.1～1.2), also can adopt USP4,176, the various known technologies of being quoted in 090 or USP4,248,739 are prepared into.
For further improving the hydrothermal stability of catalytic cracking catalyst provided by the present invention, aging step can repeatedly repeat before and after each step thereafter.When the sample after the roasting carried out burin-in process once more, method of operating was: 20 times of deionized waters to example weight are added in the sample, stir, use NH
4OH adjusts and also to keep solution PH 4～7, and is best 5～7, stirs best 2～4 hours down aging 1～5 hour at 70～75 ℃.
Be coking yield that is reduced in catalytic cracking catalyst provided by the present invention in the catalytic cracking of hydrocarbon process and the stability of improving product, component that can some is suitable in preparation process is drawn the fair pretty ⑴ Zhen ⒐ ancient piece of jade, round, flat and with a hole in its centre curtain rank nobelium oyster surname rooms at the sides of or facing the principal rooms ┰ Dao tool of the sincere tip of the real barium mire beech of Yun reef looks branch school rooms at the sides of or facing the principal rooms ┦ by the mode of dipping, and to herd that a street mqb street loyalty falls from the sky or outer space be that a sodium clear rank nobelium a red-spotted lizard ancient type of banner hoisted on a featherdecked mast is held in the mouth polished the region between the heart and the diaphragm and entreated the dizzy ⑴ Zhen ⒐ ancient piece of jade, round, flat and with a hole in its centre Qi that makes a noise and examine Pu furan woods QiKang～5%, be preferably 0.5～3%, dipping terminal point PH is advisable with 5～7, and dipping can carry out after calcination steps.
Catalytic cracking catalyst provided by the present invention has the layer pole structure of macropore opening, good heat and hydrothermal stability, and activity and selectivity preferably are applicable to the catalytic process of the carbonium ion reaction that comprises RFCC.Its microspheres product has the screening similar with the semi-synthetic carrier microballoon of the conventional REY type of industry molecular sieve Cracking catalyst, heap ratio, pore volume, specific surface and good abrasion resistance.
Catalytic cracking catalyst preparation method provided by the present invention is applicable to the catalyst prod of other shape beyond preparation microballoon and the microballoon.
Be example with the lamellar clay-rectorite that belongs to regular interbed mineral structure below, product provided by the present invention and preparation method are further specified.
The rectorite mineral clay is by nondistensible mica layer and shared 2: the 1 adjacent argillic horizon of expandable smectite layer, alternately arranges a kind of crystalline mineral clay that forms in order.Fig. 1 is the rectorite structural representation, and wherein A is nondistensible mica layer, and B is expandable smectite layer, and C is 2: 1 argillic horizons, and D is the exchangeable cations in the smectite layer, and E is the fixedly cation in the mica layer.Fig. 2 is the X-ray diffraction pattern of rectorite mineral clay, and test is carried out CuK on Japan D/max-III of science A type X-ray diffractometer
αRadiation, Ni filtering, scintillation counter, slit are 1 °, 0.3 °, 1 °.Basal spacing (the d of the air-dry sample of this rectorite mineral clay
001) be 19.0～29.0 * 10
-10Rice.In homemade paragonite and the calcium montmorillonite chemical composition expression formula of alternately arranging in order after the rectorite dehydration that forms by 1: 1 rule be:
｛（Na
0.72K
0.02Ca
0.05）（Ca
0.24Na
0.07）｝（Al
4.00Mg
0.02）
In the mica layer fixedly in the cation smectite layer in the commutative positive argillic horizon six
The ion coordination ion
〔Si
6.58Al
1.62〕O
22
Four-coordination ion in the argillic horizon
Example 1
Preparing with the cross-linked rectorite with the preparation flow of " back is crosslinked " is active component, is carrier with the halloysite, is the clay molecular sieve with layer structure microspherical catalyst of binding agent with the aluminium colloidal sol that makes from boehmite.
1. contain the preparation of rectorite clay microphere:
The NaCl aqueous solution with 0.5～0.6 mole, with the amount ratio of every gram rectorite with 0.005～0.01 gram equivalent of NaCl, the ion-exchange of natural calcium type rectorite concentrate is become sodium type rectorite, exchange was at room temperature carried out 1 hour, use the NaCl aqueous solution drip washing of same quantity after the filtration again, promptly get sodium type rectorite.It is 30% clay slurry that gained sodium type rectorite filter cake is made solid content with deionized water making beating.
Get 37.5 parts (by bright base, down together) commercially available Suzhou machine selects the 2# halloysite, make the clay slurry of solid content about 24% with the deionized water making beating, add commercially available 37% hydrochloric acid, the addition of hydrochloric acid stirs Shandong Aluminum Plant's commercially available prod boehmite that adds 12.5 parts after 0.5 hour again for 0.22% of the basic boehmite weight of burning, and continues to stir 0.5 hour, be warming up to 60 ℃ then, the under agitation aging carrier component that promptly obtained containing binding agent in 1 hour.
The clay slurry of getting 50 parts of sodium type rectorites joins in the above-mentioned carrier component, and gained mixed serum solid content is about 30%, according to a conventional method spray drying forming.
2. the preparation of crosslinked fluid: get 1 moles of NaOH and 1 mole of AlCl
3React the concentration of (Z.Anorg.Allgem.Chem, 248,319,1941) making and be 325 mM aluminium/liter more than the polymerization polymeric aluminum chloride, with deionized water be diluted to 80 mM aluminium/liter, and use NH
4OH transfers its PH to 5.0～6.0.
3. cross-linking reaction: with the amount ratio of every gram rectorite clay with 3.29 mM aluminium, the above-mentioned microballoon that contains rectorite is added in the above-mentioned crosslinked fluid, under agitation room temperature reaction is 10 minutes, uses NH during reaction
4The pH value of OH control slurries maintains 5.0～6.0.
4. aging: as to keep slurries PH5.0～6.0 after the cross-linking reaction, stirred aging 3 hours down at 70 ℃.
5. filter and be washed till no Cl with deionized water
-
6. the interior 110 ℃ of dryings of baking oven are 2 hours.
7.650 roasting promptly got and consists of 50% cross-linked rectorite-37.5% kaolin-12.5%Al in 2 hours in ℃ air
2O
3The clay molecular sieve with layer structure microspherical catalyst.
The microspherical catalyst that makes thus records its chemical composition with the conventional chemical method and sees Table 1, screening, apparent density, the fluidisation abrasion index that records with conventional method and use low temperature N
2The specific surface that absorption method records, pore volume data see Table 2.By table 2 data as can be known: microspherical catalyst provided by the present invention is the product that has qualified screening, raft ratio, the excellent wear energy is arranged.
Table 3 has been listed this microspherical catalyst fresh sample and through 800 ℃, the basal spacing (d001) and the micro-activity of normal pressure, 100% steam treatment 17 hours (being called for short, as follows) back sample at 800 ℃/17 o'clock.Basal spacing records with conventional x-ray powder diffraction.Micro-activity is estimated out on conventional light oil micro-reactor, and reaction raw materials is huge port light diesel fuel (235～337 ℃ of fraction), and reaction temperature is 460 ℃, and weight space velocity is 16 o'clock
-1, oil ratio is 3.2.By table 3 data as can be known: microspherical catalyst provided by the present invention has activity stability and hydrothermal stability preferably.
Table 4 has been listed the lytic activity of 800 ℃/10 o'clock sample counterweight matter of this microspherical catalyst oil.Activity assessment carries out on small fixed flowing bed, and reaction raw materials is 330～520 ℃ of fraction oil, and reaction temperature is 500 ℃, and oil ratio is 3.0, and weight space velocity is 20 o'clock
-1By table 4 data as can be known: microspherical catalyst provided by the present invention is applicable to the cracking of heavy fraction of oil.Conversion ratio in the listed data is: (gasoline+diesel oil+gas+coke)/(raw material) * 100%(weight by weight) product selectivity is the productive rate percentage (following example together) of this product under the unit conversion rate.
*Zhou village, Shandong catalyst plant product.
*Consist of 25% super steady Y-55% kaolin-20%Al
2O
3
Example 2
Make binding agent with Ludox, help improving the coke selectivity of cracking catalyst of clay molecular sieve with layer structure.
By example 1 described method the ion-exchange of natural calcium type rectorite concentrate is become sodium type rectorite.Get 35 parts of halloysites, pull an oar with deionized water and make the clay slurry of solid content about 31%, (chemical plant, Jiangyin, Jiangsu Province produces, wherein SiO to add 15 parts of Ludox again
2Content 25 heavy %, PH8～9), stirred 0.5 hour, be warming up to 60 ℃ then, under agitation aging 1 hour.Contain at this and to add 50 parts of sodium type rectorite filter cakes in carrier component of binding agent, with the deionized water making beating, gained mixed serum solid content is about 25%, uses the conventional method spray drying forming then.The gained clay microphere is carried out cross-linking reaction, aging, filtration washing, drying, roasting according to example 1 described method promptly to be got and consists of 50% cross-linked rectorite-35% kaolin-15%SiO
2The clay molecular sieve with layer structure microspherical catalyst.
This microspherical catalyst is carried out the micro-activity evaluation by the condition of example 1, and the initial activity of its fresh sample is that the stabilizing active of 56%, 800 ℃/17 o'clock samples is 40%, and giving birth to the charcoal factor only is 4/5ths of example 1 sample.This shows that the clay molecular sieve with layer structure microspherical catalyst of making as binding agent with Ludox not only has activity stability preferably equally, and coke selectivity has obvious improvement.
Example 3
When containing the adhesive preparation clay molecular sieve with layer structure catalyst of aluminium colloidal sol, aluminium colloidal sol wherein can play the effect of crosslinking agent.
It is 30% clay slurry I that 50 parts of calcium type rectorites and 15 parts of Ludox are made solid content with the deionized water making beating.
With 25 parts of halloysites and 10 parts of aluminium colloidal sols (Zhou village, Shandong catalyst plant product, wherein Al
2O
3Content is 12.3 heavy %, and Al/Cl=1.18) making solid content with the deionized water making beating is 30% clay slurry II.
Clay slurry I and II are mixed, pulled an oar 1 hour, gained mixed serum solid content is 30%, according to a conventional method spray drying forming.With 40 times of deionized waters the gained clay microphere is pulled an oar then, use 3%NH to example weight
4The OH aqueous solution is kept slurries PH5～7, stirs down aging 2 hours at 75 ℃, carries out filtration washing, drying, roasting according to example 1 described method again and promptly gets and consist of 50% cross-linked rectorite-25% kaolin-15%SiO
2-10%Al
2O
3The clay molecular sieve with layer structure microspherical catalyst.
Recording its apparent density with the method described in the example 1 is 0.77 grams per milliliter, and the fluidisation abrasion index is 4.1, drinks Jie Zhu Bo ╠ 001) be 27.0～29.0 * 10
-10Rice, the little anti-initial activity of light oil is 46%.
Example 4
Boron can improve the coke selectivity of cracking catalyst of clay molecular sieve with layer structure significantly.
Preparing with the cross-linked rectorite with the preparation flow of " earlier crosslinked " is active component, is the clay molecular sieve with layer structure microspherical catalyst of carrier with the halloysite:
50 parts of sodium type rectorites and 50 parts of halloysites are made solid content less than 5% clay slurry with the deionized water making beating; With 0.2 moles of NaOH and 0.2 mole of AlCl
3The reaction after aged at room temperature 6 days and dilute one times make concentration be 33.3 mM aluminium/liter polymerization polymeric aluminum chloride crosslinked fluid; According to the amount ratio of every gram rectorite with 3.29 mM aluminium, clay slurry is added in the crosslinked fluid, cross-linking reaction is 30 minutes under stirring at normal temperature, uses 3%NH during reaction
4The pH value of OH control slurries makes it to remain on 4～6, continues to keep slurries PH4～6 at room temperature to leave standstill then aging 24 hours, more after filtration, washing is to there not being Cl
-, roasting 2 hours in the 110 ℃ of dryings, 650 ℃ of air, promptly get and consist of the kaolinic clay molecular sieve with layer structure catalyst of 50% cross-linked rectorite-50%.
Recording its basal spacing (d001) with the method described in the example 1 is 27.0～29.0 * 10
-10The little anti-initial activity of rice light oil is that the stabilizing active of 60%, 800 ℃/17 o'clock samples is 47%.
With commercially available boric acid (gold small cup chemical plant, Beijing product, chemical pure) dissolves with deionized water, according to catalyst: boron: water=amount ratio of 1: 0.005: 1 floods 800 ℃/10 o'clock samples of above-mentioned molecular sieve catalyst, and the roasting in 110 ℃ of dryings, 450 ℃ of air of the sample behind the dipping promptly got the sample of this molecular sieve catalyst boracic 0.5% in 2 hours.
To above-mentionedly soak boron, not soak the boron sample, and industrial REY type molecular sieve cracking catalyst handles the back through hydrothermal deactivation respectively carry out lytic activity evaluation on the small stationary bed apparatus, and reactant is 330～520 ℃ of fraction oil, and reaction temperature is 500 ℃, oil ratio is 1.6, and weight space velocity is 10 o'clock
-1, evaluation result sees Table 5.
Table 5
*Zhou village, Shandong catalyst plant product.
Example 5
Dipping tin can improve the activity stability of its catalytic cracking on the clay molecular sieve with layer structure catalyst.
The clay molecular sieve with layer structure microspherical catalyst that example 1 is prepared is with the SnCl of PH1.5
2Aqueous hydrochloric acid solution carries out the saturated dipping in hole, SnCl
2It is 1% of catalyst weight that the consumption of solution makes the tin content on the catalyst, uses 10 times of deionized water rinsings twice to example weight then, uses 20 times of deionized water pulps to example weight again, uses 3%NH
4OH adjusts slurries PH to 5～7, stirs down aging 2 hours at 75 ℃, more after filtration, washing is to there not being Cl
-, roasting 2 hours in the 110 ℃ of dryings, 550 ℃ of air, promptly get the wicking sample of this molecular sieve catalyst.
Carry out the micro-activity evaluation with the method described in the example 1, the results are shown in Table 6.
Table 6
Example 6
Contain ZSM-5 molecular sieve cracking catalyst of clay molecular sieve with layer structure and have the advantages that to improve octane number.
With sodium type rectorite: ZSM-5 molecular sieve: halloysite: amount ratio boehmite=47: 3: 35: the 15(basic weight ratio of burning), prepare according to example 1 described method and to consist of 47% cross-linked rectorite-3%ZSM-5-35% kaolin-15%Al
2The clay molecular sieve with layer structure microspherical catalyst of O3.Recording its basal spacing (d001) with the method described in the example 1 is 27.0～29.0 * 10
-10Rice, apparent density is 0.88 grams per milliliter, the fluidisation abrasion index is 2.6, the little anti-initial activity of light oil is 63%, the stabilizing active of 800 ℃/17 o'clock samples is 40%, and is higher by about 2.0 than the motor octane number of using general industry REY type molecular sieve cracking catalyst gained gasoline with this clay molecular sieve with layer structure catalyst during according to 330～520 ℃ of fraction oil of example 1 described condition cracking.
Example 7
The cracking catalyst of clay molecular sieve with layer structure that contains super-stable Y molecular sieves has better initial activity and selectivity.
With sodium type rectorite: super-stable Y molecular sieves (SiO
2/ Al
2O
3=8.5): halloysite: amount ratio boehmite=41: 9: 35: the 15(basic weight ratio of burning), prepare according to example 1 described method and to consist of 41% cross-linked rectorite-9% super-stable Y molecular sieves-35% kaolin-15%Al
2O
3The clay molecular sieve with layer structure microspherical catalyst.
The basal spacing of this microspherical catalyst (d001) is 27.0～29.0 * 10
-10Rice.Table 7 has been listed the light oil microactivity of this catalyst fresh sample estimated out by example 1 described method and 800 ℃/17 o'clock samples and 800 ℃/10 o'clock samples cracking selectivity to 330～520 ℃ of fraction oil.
Table 7
Example 8
The cracking catalyst of clay molecular sieve with layer structure that contains super-stable Y molecular sieves and boron has raft ratio, high abrasion, activity stability and characteristics optionally preferably, is applicable to the catalytic cracking of mink cell focus.
With sodium type rectorite: super-stable Y molecular sieves: halloysite: amount ratio boehmite=47: 3: 35: the 15(basic weight ratio of burning), prepare according to example 1 described method and to consist of 47% cross-linked rectorite-3% super-stable Y molecular sieves-35% kaolin-15%Al
2O
3The clay molecular sieve with layer structure microspherical catalyst.
800 ℃/10 o'clock samples of this microspherical catalyst are made the sample of boracic 0.5 heavy % according to example 4 described methods.According to example 1 described method record its chemical composition, physico-chemical parameter is listed in table 8 and the table 9 respectively.Table 10 has been listed this microspherical catalyst and has been soaked the light oil microactivity that assesses according to example 1 described method before the boron and soak after the boron cracking selectivity to 306～555 ℃ of fraction oil (through the hydrodesulfurization preliminary treatment).Cracking performance evaluation to mink cell focus is carried out on small fixed flowing bed, and reaction temperature is 500 ℃, and weight space velocity is 15 o'clock
-1, oil ratio is 3.0.
Table 8
| Main chemical composition | Na 2O | CaO | Fe 2O 3 | Al 2O 3 | SiO 2 | B |
| Content, heavy % | 0.95 | 2.17 | 1.39 | 50.9 | 43.0 | 0.5 |
Table 9
| Basal spacing (d001), * 10 －10Rice | Apparent density, grams per milliliter | The fluidisation abrasion index |
| 25.0～28.0 | 0.7～0.9 | 2.6 |
Table 10
Preparation flow with " earlier crosslinked " also can be prepared cracking catalyst of clay molecular sieve with layer structure provided by the present invention.
With natural calcium type rectorite, deionized water, sodium type cationic ion-exchange resin (strongly acidic styrene system, exchange capacity is 4 milliequivalent/grams) mix according to 1: 20: 3 weight ratio, stirred 8 hours, standing over night, the soil particle diameter that takes out the upper strata suspension is less than 2 * 10
-6The clay slurry of rice, its solid content are 2.29 heavy %.With 0.2 moles of NaOH and 0.2 mole of AlCl
3Reaction is after aged at room temperature 6 days and dilute one times of polymerization polymeric aluminum chloride that makes (its concentration be 33.3 mM aluminium/liter) and be crosslinking agent, with the rate of charge of every gram soil clay slurry is added in the crosslinking agent by 3.29 mM aluminium, cross-linking reaction is 30 minutes under stirring at normal temperature, uses 3%NH during reaction
4The pH value of OH control solution makes it to remain on 4～6, continues to keep solution PH 4～6 at room temperature to leave standstill then aging 24 hours, more after filtration, washing is to there not being Cl
-, roasting 2 hours in the 110 ℃ of dryings, 650 ℃ of air, promptly get the cross-linked rectorite clay molecular sieve with layer structure.
35 parts of halloysites and 20 parts of aluminium colloidal sols are made clay slurry with 58 parts of deionized water making beating, under agitation add 25 parts of super-stable Y molecular sieves and 20 parts of cross-linked rectorite clay molecular sieve with layer structure, continue to stir 50 minutes, the gained slurry solid content is about 38%, spray drying forming washs to there not being Cl with deionized water then according to a conventional method
-, the interior 110 ℃ of dryings of baking oven 2 hours, roasting is 2 hours in 550 ℃ of air, promptly gets to consist of 20% cross-linked rectorite-25% super-stable Y molecular sieves-35% kaolin-20%Al
2O
3Clay molecular sieve with layer structure microspherical catalyst A.
25 parts of halloysites and 30 parts of Ludox are made clay slurry with 42 parts of deionized water making beating, under agitation add 25 parts of super-stable Y molecular sieves and 20 parts of cross-linked rectorite clay molecular sieve with layer structure, continue to stir 50 minutes, the gained slurry solid content is about 28%, spray drying forming is used the most of Na of deionized water flush away then according to a conventional method
+, the interior 110 ℃ of dryings of baking oven 2 hours, roasting is 2 hours in 550 ℃ of air, promptly gets to consist of 20% cross-linked rectorite-25% super-stable Y molecular sieves-25% kaolin-30%SiO
2Clay molecular sieve with layer structure microspherical catalyst B.
Catalyst A that makes thus and B record its chemical composition with the conventional chemical method and see Table 11, and apparent density, fluidisation abrasion index and the specific surface that records with low temperature N2 absorption method, the pore volume data that record with conventional method see Table 12.
Table 11
Table 12
| Catalyst | Apparent density, grams per milliliter | The fluidisation abrasion index | Pore volume, milliliter/gram | Specific surface, rice 2/ gram |
| A B | 0.72 0.63 | 1.3 / | 0.16 0.19 | 170 259 |
Example 11
The cracking catalyst of clay molecular sieve with layer structure of preparing with the preparation flow of " earlier crosslinked " that contains super-stable Y molecular sieves has activity, selectivity and octane number preferably equally, is applicable to the catalytic cracking of mink cell focus.
Sample after the fresh sample of the catalyst A prepared in the example 9～10 and B and hydrothermal deactivation handled carries out the micro-activity evaluation by condition described in the example 1 respectively, and evaluation result sees Table 13.
800 ℃/10 o'clock samples of catalyst A and B are carried out the lytic activity evaluation with 310～510 ℃ and 306～555 ℃ of fraction oil respectively on small fixed flowing bed.Reaction temperature is 500 ℃, and weight space velocity is 15 o'clock
-1, oil ratio is 3.0, evaluation result sees Table 14.
Table 13
| Catalyst | Initial activity, heavy % | Stabilizing active, heavy % | |
| 800 ℃/4 o'clock samples | 800 ℃/17 o'clock samples | ||
| A B | >80 >80 | 62 56 | 42 35 |
Table 14
| Catalyst | The heavy % of conversion ratio | Selectivity, heavy % | Gasoline RON | |||
| Gasoline | Diesel oil | Gas | Coke | |||
| Raw material: 310～510 ℃ of fraction oil | ||||||
| A B | 56.25 51.98 | 34.31 34.82 | 40.71 42.71 | 21.69 19.82 | 3.29 2.65 | / |
| / | ||||||
| Raw material: 306～555 ℃ of fraction oil (through the hydrodesulfurization preliminary treatment) | ||||||
| The external octane number catalyst of A B | 53.7 47.1 52.5 | 24.8 22.3 25.0 | 39.3 40.8 40.0 | 25.9 28.2 24.8 | 10.1 8.7 10.3 | 88.0 85.7 87.3 |
Claims (9)
1, a kind of clay molecular sieve with layer structure catalytic cracking catalyst is characterized in that:
(1) it contains the architectural feature of rule space layer clay mineral, basal spacing (d
001) be 17.0～50.0 * 10
-10Rice, interlamellar spacing is 0～33.0 * 10
-10Rice;
(2) it is by 1～100: 0～99: active component, carrier component and the binder component of 0～99 (the basic weight ratio of burning) constitute;
(3) its active component is the mixture that comprises clay molecular sieve with layer structure or this clay molecules sieve of the regular interbed mineral structure of having of cross-linked rectorite and comprise other molecular sieve of faujasite, the faujasite after various chemistry and/or stabilization processes, ZSM series molecular sieve;
(4) its carrier component is the various natural claies that comprise kaolin, rectorite, or comprises amorphous aluminum silicide, Al
2O
3, SiO
2Or the mixture that contains among them one or more is at interior various artificial synthetic refractory oxide carriers;
(5) its binder component is aluminium colloidal sol, Alusil, silicon-aluminum sol or the mixture that contains among them one or more;
(6) it is prepared as follows:
I) will be as the mixture with planning interbed mineral structure clay or this clay and other molecular sieve of active component raw material and carrier component, binder component according to 1～100: 0～99: 0～99 bright basic weight ratio be mixed, moulding, as to want product be microspheroidal, and the slurry solid content that then is used to spray is 20～40 heavy %;
II) the inorganic metal hydroxy polymer is mixed with concentration be 100 mM aluminium/liter below dilute aqueous solution (other metal standard is according to this pressed equivalents conversion), and use NH
4OH transfers to 4～6 with its pH value;
III) with the amount ratio (other crosslinking agent according to this standard press equivalents conversion) of the regular interbed mineral clay in every gram active component with 1.5～5.0 mM aluminum crosslinkers, the catalysis material of moulding is added in the crosslinked fluid, at room temperature carry out cross-linking reaction, use NH during reaction
4The pH value of OH control slurries maintains 4～6;
IV) keeps slurries PH4～6 after the cross-linking reaction, stirred aging 1～5 hour down at 70～75 ℃;
V) filtration washing according to a conventional method;
VI) room temperature to 300 ℃ drying;
VII) 550～750 ℃ of roastings are 0.5～4 hour.
2, according to the described catalyst of claim 1, it is characterized in that said clay as the regular interbed mineral structure of having of active component raw material be meant comprise rectorite, natural or artificial synthetic, punishing ripples by expandable and nondistensible two kinds of ゲ rough bamboo mat neptunium moving to and fro, to gather exhibition angry the Meng: the mode interleaved of 1 argillic horizon, arrange a class crystalline mineral clay that forms in order.
3,, it is characterized in that preferably halloysite of said carrier component according to the described catalyst of claim 1.
4,, it is characterized in that said binder component preferably aluminium colloidal sol or Alusil according to the described catalyst of claim 1.
5, according to the described catalyst of claim 1, the bright basic weight ratio that it is characterized in that said active component, carrier component and binder component preferably 40～60: 30～40: 10～30.
6, according to the described catalyst of claim 1, it is characterized in that the pH value of used crosslinked fluid is preferably 5～6 in the preparation process, preferably 3.0～4.0 mMs aluminium/gram is native for the consumption of crosslinking agent during cross-linking reaction, the pH value of slurries preferably maintains 5～6 during reaction, the pH value of slurries preferably maintained 5～6 when the reaction back was aging, and ageing time is preferably 2～4 hours.
7, according to the described catalyst of claim 1, it is characterized in that the aging step after the cross-linking reaction can repeatedly repeat before and after each step thereafter, should be earlier when wearing out after the roasting with 20 times of deionized waters to example weight with the sample pulp, use NH
4OH adjusts and keeps slurries PH4～7 best 5～7 and wear out.
8, according to the described catalyst of claim 1, the mode that it is characterized in that available dipping after the calcination steps is introduced catalyst with the compound of tin, boron, silicon or two or more other compound or the mixture that contain in these elements, the introducing amount is counted 0～5% of catalyst weight with the weight of tin, boron, silicon, be preferably 0.5～3%, dipping terminal point PH is advisable with 5～7.
9, according to the described catalyst of claim 1, it is characterized in that this catalyst also can adopt will carry out cross-linking reaction with the inorganic metal hydroxy polymer earlier and the flow process of aftershaping prepares as the clay of the regular interbed mineral structure of having of active component raw material, have the operation that the clay of regular interbed mineral structure mixes with other molecular sieve, carrier component, binder component and both can also can carry out after cross-linking reaction before the cross-linking reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104718 CN1007879B (en) | 1987-07-13 | 1987-07-13 | Cracking catalyst of clay molecular sieve with layer structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104718 CN1007879B (en) | 1987-07-13 | 1987-07-13 | Cracking catalyst of clay molecular sieve with layer structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031029A true CN1031029A (en) | 1989-02-15 |
| CN1007879B CN1007879B (en) | 1990-05-09 |
Family
ID=4814976
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|---|---|---|---|
| CN 87104718 Expired CN1007879B (en) | 1987-07-13 | 1987-07-13 | Cracking catalyst of clay molecular sieve with layer structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007879B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048427C (en) * | 1994-02-18 | 2000-01-19 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| CN1062006C (en) * | 1997-09-02 | 2001-02-14 | 彭清生 | Process for preparing heavy oil cracking catalyst |
| CN1069682C (en) * | 1997-12-23 | 2001-08-15 | 中国石油化工总公司 | Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation |
| US6670490B1 (en) | 2002-12-23 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Platinum-rhenium-tin catalyst for hydrogenation in aqueous solution |
| US6908544B2 (en) * | 2001-12-25 | 2005-06-21 | China Petroleum & Chemical Corporation | Cracking catalyst comprising layered clays and a process for cracking hydrocarbon oils using the same |
| CN101205070B (en) * | 2006-12-22 | 2010-12-22 | 中国石油化工股份有限公司 | Rectorite comprising adjuvant component and method for making same |
| CN101745417B (en) * | 2008-11-28 | 2011-12-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| 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 |
| CN116924426A (en) * | 2023-06-06 | 2023-10-24 | 中国石油大学(华东) | Method for regulating and controlling silicon-aluminum distribution of molecular sieve framework and product thereof |
-
1987
- 1987-07-13 CN CN 87104718 patent/CN1007879B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048427C (en) * | 1994-02-18 | 2000-01-19 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| CN1062006C (en) * | 1997-09-02 | 2001-02-14 | 彭清生 | Process for preparing heavy oil cracking catalyst |
| CN1069682C (en) * | 1997-12-23 | 2001-08-15 | 中国石油化工总公司 | Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation |
| US6908544B2 (en) * | 2001-12-25 | 2005-06-21 | China Petroleum & Chemical Corporation | Cracking catalyst comprising layered clays and a process for cracking hydrocarbon oils using the same |
| US6670490B1 (en) | 2002-12-23 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Platinum-rhenium-tin catalyst for hydrogenation in aqueous solution |
| CN101205070B (en) * | 2006-12-22 | 2010-12-22 | 中国石油化工股份有限公司 | Rectorite comprising adjuvant component and method for making same |
| CN101745417B (en) * | 2008-11-28 | 2011-12-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| 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 |
| CN116924426A (en) * | 2023-06-06 | 2023-10-24 | 中国石油大学(华东) | Method for regulating and controlling silicon-aluminum distribution of molecular sieve framework and product thereof |
| CN116924426B (en) * | 2023-06-06 | 2025-11-21 | 中国石油大学(华东) | Method for regulating and controlling silicon-aluminum distribution of molecular sieve framework and product thereof |
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| Publication number | Publication date |
|---|---|
| CN1007879B (en) | 1990-05-09 |
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