CN1123383C - Amorphous silica-alumina and its preparing method - Google Patents
Amorphous silica-alumina and its preparing method Download PDFInfo
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- CN1123383C CN1123383C CN97116404A CN97116404A CN1123383C CN 1123383 C CN1123383 C CN 1123383C CN 97116404 A CN97116404 A CN 97116404A CN 97116404 A CN97116404 A CN 97116404A CN 1123383 C CN1123383 C CN 1123383C
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- amorphous aluminum
- aluminum silicide
- silicide
- pore volume
- amorphous
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- 238000000034 method Methods 0.000 title claims description 44
- 239000011959 amorphous silica alumina Substances 0.000 title 1
- 239000011148 porous material Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 34
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 28
- 230000032683 aging Effects 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 239000004411 aluminium Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- 239000012153 distilled water Substances 0.000 description 29
- 230000008569 process Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000012065 filter cake Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000007865 diluting Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 238000010009 beating Methods 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal aluminate Chemical class 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005280 amorphization Methods 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 230000002101 lytic effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 229910000989 Alclad Inorganic materials 0.000 description 1
- 101100004286 Caenorhabditis elegans best-5 gene Proteins 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to macroporous amorphous silaceous aluminium with high acidity and a high specific surface, which has the silicon oxide content of 10 to 50w%, has the specific surface of 350 to 600m<2>/g, has the pore volume of 0.8 to 1.5 ml/g, and has the infrared acidity of 0.25 to 0.55 mmol/g. The amorphous silaceous aluminium not only has an acidic function required by cracking reactions, but also has the physicochemical structure of a common carrier, so it is a favorable catalysis material.
Description
The present invention relates to a kind of high pore volume, acid amorphous aluminum silicide of high-ratio surface and preparation method thereof.
Amorphous aluminum silicide requires itself must have enough big specific surface and pore volume as one of important carrier component of catalyst, with carrying reactive metal component.On the other hand, effectively carry out in order to make reaction, amorphous aluminum silicide generally also needs the acidic cleavage function that provides certain.But it is this difunctional that present disclosed prior art all can not embody fully, as the amorphous aluminum silicide of acidic components need be dispersed in than on the matrixes such as the refractory oxide of high-ratio surface and pore volume such as amorphous alumina jointly as the carrier of catalyst, amorphous aluminum silicide with prior art for preparing, owing to be subjected to preparation method's restriction, if require its have can be directly as the pore structure of catalyst carrier, just can't introduce enough silica, make its acid site number low excessively; If, add enough silica, just certainly will cause pore structure to be destroyed for improving its acid site number.
GB2166971 discloses a kind of amorphous aluminum silicide preparation method, and it is earlier after under the high pH (12-12.5) alkali metal aluminate and silicate being mixed, make with reacting aluminum sulfate again, from the embodiment of this patent as can be known, the SiO of its product sial
2Content under situation less than 35w%, specific surface 277m
2/ g, pore volume 0.31ml/g.Though have lytic activity, its shortcoming remains pore volume and specific surface is not high, is not enough to separately as carrier component when carrying the metal component of higher amount.This patented method is that a kind of employing pump rapid mixing mode becomes glue, and equipment is required height, and the production difficulty is big, has certain production limitation.
US4758338 after pH value 2-10 swing obtains alumina sol, adding silicon compound formation amorphous aluminum silicide, but this process operation complexity is restive with the pH swing method, and the SiO of its product
2Not high, the highest only 8.7w%, main carrier, this product specific surface 308m as the Hydrobon catalyst that does not need the acidic cleavage function
2/ g, pore volume can reach 1.78ml/g, but the pore volume of 3-10nm 0.31ml/g only is main on the macropore of 10-100nm.EP0788270 a kind ofly handles aluminium oxide with waterglass or Ludox, improves the amorphous aluminum silicide product property through hydrothermal treatment consists again, and final amorphous aluminum silicide contains SiO
2At 6-12w%, what this product specific surface was the highest handles the 12w% hydrothermal treatment consists amorphous aluminum silicide that obtains with Ludox, and specific surface also only has 214m
2/ g, preparation method's condition harshness of this product, the hydrothermal treatment consists energy consumption is big.
The objective of the invention is to, a kind of amorphous aluminum silicide that is directly used in catalyst carrier is provided, both had suitable specific surface, pore volume, have enough silica contents again, guarantee the required acid function of chemical reaction.Another object of the present invention is to, a kind of preparation method of above-mentioned amorphous aluminum silicide is provided, simplify preparation process, reduce material consumption, energy consumption.
In order to improve the pore structure character of amorphous aluminum silicide, amorphous aluminum silicide of the present invention uses and stream Stationary pH method, and not only process is easy to control, and product has better character index, amorphous aluminum silicide pore volume of the present invention is 0.8-1.5ml/g at least, and specific surface is 350-600m at least
2/ g, aperture 40-150 * 10
-10The pore volume of m accounts for more than 50% of total pore volume.
The physico-chemical property characteristics of amorphous aluminum silicide of the present invention are silicon oxide-containing 10-50w%, specific surface 350-600m
2/ g, general 400-550m
2/ g, preferably 450-500m
2/ g, pore volume 0.8-1.5ml/g, general 0.9-1.4ml/g, preferably 1.0-1.3ml/g.Amorphous aluminum silicide 40-150 of the present invention * 10
-10The pore volume in m aperture accounts for more than 50% of total pore volume.Infrared acidity 0.3-0.55mmol/g, general 0.35-0.50mmol/g, preferably 0.40-0.45mmol/g.
Amorphous aluminum silicide preparation principle of the present invention is, form the preceding matrix of aluminium oxide earlier, and control the crystalline form that aforesaid neutrality condition obtains certain feature, make silicon atom replace the aluminium atom site again, this is different from prior art and adopts silicon source impregnated alumina, silicon atom just deposits simply, promptly can not significantly improve acidity, also can make the carrier duct impaired.The characteristics of amorphous aluminum silicide of the present invention are to make silicon attack aluminium atom and replacing under advantage concentration, thereby formed a large amount of original acid site frameworks, because the existence of free aluminum and amorphization subsequently make these original acid site frameworks mainly embody L acid characteristics, the meleic acid result of table 1. has shown this point.Substituted subsequently aluminium atom enters sol system once more, together with aluminium atom superfluous in the system, continue to form new micelle and with established Al
2O
3, SiO
2Reach the initial sial that forms and interact, deposition or gathering form bigger micelle; Under certain aging condition effect, the growth tendency that destroys crystalline form also promotes to unbodied conversion.Because the These characteristics of amorphous aluminum silicide of the present invention make this amorphous aluminum silicide not only have higher acidity, and the amorphization degree of amorphous aluminum silicide is very high, has very high specific surface, pore volume.Compared with prior art, amorphous aluminum silicide of the present invention not only has higher acidity, simultaneously because the crystalline form degree is low, and amorphization degree height, itself have very high specific surface and pore volume, thus amorphous aluminum silicide of the present invention must hydrothermal treatment consists or alternate manner come reaming.
Amorphous aluminum silicide of the present invention prepares by following process:
(a) a kind of acid aluminium salt solution and a kind of alkaline precipitating agent and stream are joined in the reaction vessel of small amount of deionized water, at pH value 7.0-9.0, temperature 50-70 ℃ forms colloidal sol, and the neutralization reaction time is 1-2 hour.
(b) material that step (a) is obtained was stablized under the condition of pH8-9 0-60 minute.
(c) in 5-10 minute, a kind of silicon compound joined in the material that step (b) obtains.
(d) at pH value 7.5-9.5, the material 10-60 that 50-70 ℃ following ℃ aging step (c) obtains minute.
(e) filter and material that washing step (d) obtains.
(f) dry materials that step (e) is obtained is pulverized and the acquisition product.
In the amorphous aluminum silicide preparation process of the present invention, (a) middle acid aluminium salt can be Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3In a kind of, alkaline precipitating agent can be NaOH, NH
4OH, NaAlO
2In a kind of.But in commercial Application, by Al
2(SO
4)
3Inexpensive and be commonly used; And different alkaline precipitating agents can make (a) middle alumina substrate that obtains difference to some extent, and the aluminium oxide micelle size order that general different precipitating reagent obtained is: NaOH＜NaAlO
2＜NH
4OH, (c) in related silicon compound can be waterglass, Ludox or organosilicon.Amorphous aluminum silicide preparation process of the present invention or method can use different precipitating reagents to make amorphous aluminum silicide within physico-chemical property scope of the present invention, and the difference of its aperture and pore size distribution can make it be applied to respectively on the different catalytic reaction things or on the reaction type.
In the process of the present invention, (a) the pH value in is generally at 7.0-9.0, preferably 7.5-8.5; Temperature 50-70 ℃, preferably 55-65 ℃; (b) the general 0-60 of the stabilizing take in minute, preferably 15-45 minute.Condition enactment in the invention described above condition and range, all can obtain the acid amorphous aluminum silicide of the high-ratio surface large pore volume within the physico-chemical property scope of the present invention, and, include within the present invention's restriction because of the variation of condition causes the difference of aperture and pore size distribution that it is applied to respectively on the different catalytic reaction things or on the reaction type.
Because the difference of application purpose, acidic cleavage function to amorphous aluminum silicide has different requirements, can come the acidity or the lytic activity of the amorphous aluminum silicide of appropriate change process preparation of the present invention by the addition of step (c) adjustment silicon compound, and amorphous aluminum silicide preparation process of the present invention can not resemble some prior art, the specific surface and the pore volume size that how much can have influence on final products strongly that the silicon amount is introduced, amorphous aluminum silicide of the present invention still can obtain high-ratio surface large pore volume amorphous aluminum silicide in a very wide silica content scope.Because aforementioned preparation characteristic of the present invention and mechanism, silicon compound adds the time that step (b) obtains product and should add in the short period of time, to guarantee in this reaction system the advantage concentration of silicon ion in a period of time, comes matrix before the aluminium oxide that attack forms.Certainly, owing to stir the efficient of mass transfer, the time can not be too short, and the joining day is generally at 5-10 minute, best 5 minutes.
After introducing the silicon source, the pH value of reaction system will have the process or the trend of a variation, be presented at the forming process that has begun amorphous aluminum silicide on the alumina substrate, this process is different from the silicon alclad method of prior art, but the primary oxidation silicon particle that the established alumina substrate of silicon ion attack and being accompanied by forms after silicon ion, free aluminum ion, the introducing system and the multiple reciprocation of elementary amorphous aluminum silicide micelle.After reaction reaches balance, continue the certain condition of control, finish (d) process, this process should be the ageing process of a broad sense, has comprised that promptly reaction forms the process of amorphous aluminum silicide, has also comprised product amorphization process subsequently.In this process, pH value, temperature, ageing time all are important control parameters, general pH value 7.5-9.5, preferably 8.0-9.0; Temperature 50-70 ℃, preferably 55-65 ℃; General 0-60 of time minute, preferably 15-45 minute.
Behind aging the end, process (e) and (d) can be according to the method for routine, with the amorphous aluminum silicide product washing that obtains removing impurity such as iron ion, sodium ion, sulfate radical, chlorion, and dry, pulverizing and obtain amorphous aluminum silicide of the present invention.The purpose that removes impurity is at amorphous aluminum silicide of the present invention during as the carrier of catalyst or acidic components, unlikely activity of such catalysts or the stability of having influence on of its impurity level.The drying of amorphous aluminum silicide of the present invention can be used oven drying or spray-drying, generally adopts oven drying, descends dry 6-10 hour at 110 ℃, makes the butt of final amorphous aluminum silicide product reach 60-80w%.Dried amorphous aluminum silicide product sieves, below particle diameter 150 orders, below best 200 orders.
Amorphous aluminum silicide of the present invention also can contain the phosphorus of 1-5w%, and purpose is to improve the distribution in aperture, also may produce delicate influence to later catalyst property.Method is that above-mentioned amorphous aluminum silicide is pulled an oar once more, adds the phosphoric acid of metering, makes the phosphorous 1-5w% of amorphous aluminum silicide of the present invention, refilters, dry and pulverize and obtain phosphorous amorphous aluminum silicide product.
The application characteristic of amorphous aluminum silicide of the present invention be can be simultaneously as the acidic components of the catalyst carrier component of holding concurrently, providing outside bearing area and the reaction compartment, also have certain acid cracked activity for the reactive metal component.Amorphous aluminum silicide of the present invention is specially adapted to the required catalyst of catalysis process of oil and derived product thereof, comprise hydrocracking and Hydrobon catalyst, catalytic cracking catalyst as hydrotreating catalyst, as carrier component and part or all of acidic components.Simultaneously, above-mentioned scope does not constitute the application of amorphous aluminum silicide of the present invention restriction, and in other words, amorphous aluminum silicide of the present invention can be applicable to any carrier specific surface and pore volume be had relatively high expectations, and needs the aspect of certain acid function simultaneously again.
Because amorphous aluminum silicide of the present invention is at SiO
2In the content 10-50w% scope, the general 400-550m of specific surface
2/ g, the general 0.9-1.4ml/g of pore volume, 40-150 * 10
-10The pore volume in m aperture accounts for more than 50% of total pore volume, has higher acidity simultaneously, the general 0.35-0.50mmol/g of infrared acidity.Thereby amorphous aluminum silicide of the present invention can have certain acidic cleavage function simultaneously directly as the carrier component of a kind of large pore volume and high-ratio surface.Amorphous aluminum silicide of the present invention adopts fractional precipitation rather than infusion process or pH value swing method, do not need other last handling processes such as hydrothermal treatment consists yet, but can make amorphous aluminum silicide have very high pore volume and specific surface, also can provide higher acidity during during separately as carrier component or as catalyst component, help the turnover of reactant and product and satisfy the better products selectivity.On the other hand, procedure of the present invention is simple, control easily, and energy consumption is low, does not need special installation.
Example 1
4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a), Al
2O
3The about 4g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (c).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a) flow so that the neutralization reaction time at one hour, and the flow of adjusting rapidly (b) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (c) 3.3 liters, adds in 10 minutes, and the ageing process of beginning system keeps the pH value 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-1.
Example 2
8000g solid sulphuric acid aluminium is joined in about 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a2), Al
2O
3Concentration 8g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a2) flow so that the neutralization reaction time at two hours, and the flow of adjusting rapidly (b) makes the pH value of system remain on 7.0, and the temperature of the hierarchy of control is at 70 ℃.After reacting aluminum sulfate is intact, stop to add ammoniacal liquor and by finally containing SiO
2Amount begins to add (c) 1.6 liters in the metering example 1, and after adding in 5 minutes, the ageing process of beginning system keeps the pH value about 7.5, temperature 65-70 ℃.Aging after 60 minutes, filter colloidal solution and obtain wet cake, with the filter cake washing, refilter and obtain filter cake (d).After (d) pulled an oar once more, add 17.6ml phosphoric acid, continue to stir filter after 30 minutes filter cake (e), will (e) 110 ℃ of dryings after 8 hours down, pulverize, sieve amorphous aluminum silicide product S-2.
Example 3
3.2 liters of a kind of technical grade aluminum sulfate concentrated solutions are joined in 4.2 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a3), Al
2O
3The about 6g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a3) flow so that the neutralization reaction time at 40 minutes, and the flow of adjusting rapidly (b) makes the pH value of system remain on 9.0, and the temperature of the hierarchy of control is at 50-55 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 30 minutes, by finally containing SiO
2Amount begins to add (c) 1.4 liters in the example 1 of metering, and after adding in 10 minutes, the ageing process of beginning system keeps the pH value about 9.0, temperature 55-60 ℃.Aging after 30 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-3.
Example 4
3.5 liters of a kind of technical grade aluminum sulfate concentrated solutions are joined in 4.0 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a4), Al
2O
3Concentration 8g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).5 liters of distilled water are joined in modulus 3.0 concentrated sodium silicates of 2.4 liters of technical grades, obtain rare water glass solution (c).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a4) flow so that the neutralization reaction time at 1.5 hours, and the flow of adjusting rapidly (b) makes the pH value of system remain on 8.5, and the temperature of the hierarchy of control is at 55 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add (c) 6.2 liters in the example 1 of metering, and after adding in 5 minutes, the ageing process of beginning system keeps the pH value 8.5, temperature 60-65 ℃.Aging after 15 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).After (d) pulled an oar once more, add 31.5ml phosphoric acid, continue to stir filter after 30 minutes filter cake (e), will (e) will (d) in drying under 110 ℃ after 8 hours, pulverize, sieve amorphous aluminum silicide product S-4.
Example 5
9800g solid sulphuric acid aluminium is joined in 6.2 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a5), Al
2O
3Concentration 10g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, set (a) flow so that the neutralization reaction time at one hour, and the flow of adjusting rapidly (b) makes the pH value of system remain on 8.0, and the temperature of the hierarchy of control is at 60 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 40 minutes, by finally containing SiO
2Amount begins to add (c) 2.0 liters in the metering example, and after adding in 10 minutes, the ageing process of beginning system keeps the pH value about 8.5, temperature 50-55 ℃.Aging after 40 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-5.
Example 6
4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a6), Al
2O
3Concentration 4g/100ml.Technical grade 40% dense NaOH is added an amount of distilled water diluting into about 15% weak solution (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and NaOH respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a6) flow so that the neutralization reaction time at 110 minutes, and the flow of adjusting rapidly (b) makes the pH value of system remain on 7.0, and the temperature of the hierarchy of control is at 70 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor and by finally containing SiO
2Amount begins to add (c) 4.2 liters in the metering example 1, and after adding in 5 minutes, the ageing process of beginning system keeps the pH value 7.5, temperature 65-70 ℃.Aging after 60 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-6.
Example 7
The dense sodium aluminate solution of technical grade is joined in 6 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain sodium aluminate solution (a7), Al
2O
3Concentration 18g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a7) flow so that the neutralization reaction time at one hour, and the flow of adjusting rapidly (b) makes the pH value of system remain on 8.0, and the temperature of the hierarchy of control is at 60 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 40 minutes, by finally containing SiO
2Amount begins to add (c) 3.3 liters in the metering example 1, and after adding in 10 minutes, the ageing process of beginning system keeps the pH value 8.5, temperature 50-55 ℃.Aging after 40 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-7.
Example 8
3.0 liters of dense liquor alumini chloridis are joined in 4 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a8), Al
2O
3Concentration 4g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a8) flow so that the neutralization reaction time at 40 minutes, and the flow of adjusting rapidly (b) makes the pH value of system remain on 9.0, and the temperature of the hierarchy of control is at 50-55 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 30 minutes, by finally containing SiO
2Amount begins to add (c) 2.0 liters in the metering example 1, and after adding in 10 minutes, the ageing process of beginning system keeps the pH value 9.0, temperature 55-60 ℃.Aging after 30 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-8.
Example 9
3.2 liters of solution of red fuming nitric acid (RFNA) aluminium are joined in 7 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain rare aluminum nitrate solution (a9), Al
2O
3Concentration 6g/100ml.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has aluminum sulfate and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a9) flow so that the neutralization reaction time at 1.5 hours, and the flow of adjusting rapidly (b) makes the pH value of system remain on 8.5, and the temperature of the hierarchy of control is at 55 ℃.After reacting aluminum sulfate is intact, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add (c) 1.0 liters in the metering example 1, and after adding in 5 minutes, the ageing process of beginning system keeps the pH value 8.5, temperature 60-65 ℃.Aging after 15 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide product S-9.
Table 1. amorphous aluminum silicide product property
| Amorphous aluminum silicide | SiO 2 (w％) | Specific surface (m2/g) | Pore volume (ml/g) | Aperture (* 10-10m) | Infrared acidity (mmol/g) | ||
| I acid | B acid | L acid | |||||
| S-1 | 30 | 530 | 1.44 | 111 | 0.48 | 0.08 | 0.40 |
| S-2 | 20 | 504 | 1.30 | 110 | 0.44 | 0.07 | 0.37 |
| S-3 | 15 | 390 | 0.91 | 94 | 0.36 | 0.05 | 0：31 |
| S-4 | 45 | 452 | 1.15 | 102 | 0.54 | 0.11 | 0.43 |
| S-5 | 25 | 433 | 1.12 | 98 | 0.45 | 0.07 | 0.38 |
| S-6 | 35 | 355 | 0.89 | 89 | 0.28 | 0.08 | 0.20 |
| S-7 | 30 | 403 | 1.01 | 97 | 0.31 | 0.06 | 0.25 |
| S-8 | 20 | 483 | 1.22 | 106 | 0.36 | 0.06 | 0.30 |
| S-9 | 10 | 471 | 1.19 | 102 | 0.26 | 0.06 | 0.20 |
| The reference aluminium oxide | 0 | 390 | 1.05 | 94 | 0.22 | 0.04 | 0.18 |
| The reference amorphous aluminum silicide | 60 | 280 | 0.65 | 71 | 0.55 | 0.12 | 0.43 |
Annotate: the reference aluminium oxide is the industrial products that Fushun No.3 Petroleum Factory produces in the table, the reference amorphous aluminum silicide Industrial products for Lanzhou Oil Refinery production.
Claims (18)
1. a macropore amorphous aluminum silicide is characterized in that silicon oxide-containing 10-50w%, the specific surface 350-600m of described amorphous aluminum silicide
2/ g, pore volume 0.8-1.5ml/g, infrared acidity 0.25-0.55mmol/g.
2. amorphous aluminum silicide as claimed in claim 1 is characterized in that silicon oxide-containing 20-40w%.
3. amorphous aluminum silicide as claimed in claim 1 is characterized in that specific surface 400-550m
2/ g.
4. amorphous aluminum silicide as claimed in claim 1 is characterized in that specific surface 450-500m
2/ g.
5. amorphous aluminum silicide as claimed in claim 1 is characterized in that pore volume 0.9-1.4ml/g.
6. amorphous aluminum silicide as claimed in claim 1 is characterized in that pore volume 1.0-1.3ml/g.
7. amorphous aluminum silicide as claimed in claim 1 is characterized in that infrared acidity 0.30-0.50mmol/g.
8. amorphous aluminum silicide as claimed in claim 1 is characterized in that infrared acidity 0.35-0.45mmol/g.
9. amorphous aluminum silicide as claimed in claim 1, it is characterized in that can phosphorous 1-5w%.
10. the preparation method of amorphous aluminum silicide as claimed in claim 1 is characterized in that preparing according to the following steps:
(a) a kind of acid aluminium salt solution and a kind of alkaline precipitating agent and stream are joined in the reaction vessel that fills low amounts of water, at pH value 7.0-9.0, form colloidal sol under the temperature 50-70 ℃ of condition, the neutralization reaction time is 0.5-2 hour;
(b) material that step (a) is obtained was stablized under the condition of pH8-9 0-60 minute;
(c) in 5-10 minute, a kind of silicon compound joined in the material that step (b) obtains;
(d) at pH value 7.5-9.5,50-70 ℃ of material 10-60 minute of descending aging step (c) to obtain;
(e) filter and material that washing step (d) obtains;
(f) dry materials that step (e) is obtained is pulverized and the acquisition product.
11. the method as claim 10, the acid aluminium salt that it is characterized in that (a) step are selected from a kind of in aluminum sulfate, aluminium chloride and the aluminum nitrate.
12. the method as claim 10 is characterized in that the acid aluminium salt concentration 4-12g/100ml of (a) step.
13. the method as claim 10, the alkaline precipitating agent that it is characterized in that (a) step are to be selected from a kind of in NaOH, sodium metaaluminate and the ammoniacal liquor.
14. the method as claim 10 is characterized in that the pH value of (a) step is 7.5-8.5.
15. the method as claim 10, the temperature that it is characterized in that (a) step is 55-65 ℃.
16. the method as claim 10, be 15-45 minute stabilization time that it is characterized in that (b) step.
17. the method as claim 10 is characterized in that the pH value of (d) step is 8.0-9.0, temperature is 55-65 ℃, and the time is 15-45 minute.
18. the method as claim 10 is characterized in that the silicon compound of (c) step is selected from a kind of of waterglass or Ludox.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116404A CN1123383C (en) | 1997-09-10 | 1997-09-10 | Amorphous silica-alumina and its preparing method |
| KR10-1998-0036804A KR100488815B1 (en) | 1997-09-10 | 1998-09-07 | Amorphous Silica Alumina and Its Manufacturing Method |
| JP25662998A JP3828293B2 (en) | 1997-09-10 | 1998-09-10 | Amorphous silica alumina and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116404A CN1123383C (en) | 1997-09-10 | 1997-09-10 | Amorphous silica-alumina and its preparing method |
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| CN1210755A CN1210755A (en) | 1999-03-17 |
| CN1123383C true CN1123383C (en) | 2003-10-08 |
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| JP (1) | JP3828293B2 (en) |
| KR (1) | KR100488815B1 (en) |
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| JP3881162B2 (en) * | 2000-07-12 | 2007-02-14 | 触媒化成工業株式会社 | Hydrotreating shaped catalyst and process |
| CN101239328B (en) * | 2007-02-09 | 2010-12-01 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
| RU2469789C2 (en) * | 2007-08-27 | 2012-12-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Catalyst of aromatic hydrocarbons hydration and method of such catalyst obtaining and application |
| JP2009267338A (en) * | 2007-09-28 | 2009-11-12 | Nippon Chemicon Corp | Electrode body, and electric double layer capacitor |
| CN103041804B (en) * | 2011-10-17 | 2014-12-31 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN102489335B (en) * | 2011-12-20 | 2013-07-17 | 淄博齐创化工科技开发有限公司 | Preparation method of high-solid-content amorphous silicon aluminium |
| CN102921439B (en) * | 2012-11-15 | 2014-12-17 | 山东星都石油化工科技股份有限公司 | Phosphorus-containing amorphous silica-alumina dry gel and preparation method thereof |
| CN102941126B (en) * | 2012-11-15 | 2014-10-22 | 山东星都石油化工科技股份有限公司 | Preparation method for microspheroidal catalyst carrier containing phosphor, fluorine and titanium |
| US20140187411A1 (en) * | 2012-12-27 | 2014-07-03 | Pq Corporation | Preparation of silica-alumina composition |
| CN104549538B (en) * | 2013-10-23 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of amorphous silicon alumina supporter |
| CN104549540B (en) * | 2013-10-23 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of macropore amorphous silicon alumina supporter |
| CN103877928B (en) * | 2014-02-14 | 2016-04-13 | 浙江工业大学 | A kind of SiO with macropore, bigger serface 2-Al 2o 3the synthetic method of material |
| CN105148984B (en) * | 2014-05-29 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN105056928B (en) * | 2015-09-10 | 2018-02-16 | 中国海洋石油总公司 | A kind of preparation method of controllable hole structure sial composite oxides |
| CN106587085B (en) * | 2015-10-15 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of large aperture Alusil |
| CA3036333A1 (en) * | 2016-09-08 | 2018-03-15 | Reliance Industries Limited | A hydrothermally stable catalyst composition and a process for preparation thereof |
| JP6815843B2 (en) * | 2016-11-21 | 2021-01-20 | 日揮触媒化成株式会社 | Silica alumina and its manufacturing method |
| JP7426258B2 (en) * | 2020-03-03 | 2024-02-01 | テイカ株式会社 | Silica-containing alumina powder and its manufacturing method |
| CN112110660A (en) * | 2020-09-22 | 2020-12-22 | 广西大学 | Geopolymer powder and preparation method thereof |
| CN114506867B (en) * | 2020-10-29 | 2023-07-28 | 中国石油化工股份有限公司 | Silicon-containing pseudo-boehmite and preparation method and application thereof |
| WO2022196025A1 (en) | 2021-03-19 | 2022-09-22 | 日揮触媒化成株式会社 | Silica-alumina powder, method for producing silica-alumina powder, fluid catalytic cracking catalyst and method for producing same |
| CN115920961B (en) * | 2021-08-10 | 2024-05-28 | 中国石油天然气股份有限公司 | Preparation method of silicon-containing pseudo-boehmite slurry |
| CN113881121B (en) * | 2021-09-16 | 2023-01-31 | 宁波色母粒股份有限公司 | High-coloring high-aging-resistance polyethylene color master batch and preparation method thereof |
| CN113926488A (en) * | 2021-11-14 | 2022-01-14 | 福州大学 | Preparation method of Fe-Si suspension bed hydrocracking catalyst |
| CN114700030B (en) * | 2022-05-19 | 2024-05-28 | 青岛惠城环保科技集团股份有限公司 | Preparation method of fire-resistant oil adsorption regenerant |
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| CN1053636A (en) * | 1990-01-19 | 1991-08-07 | 中国石油化工总公司石油化工科学研究院 | Distillate oil hydrogenation catalyst |
| CN1060977A (en) * | 1990-11-02 | 1992-05-13 | 中国石油化工总公司石油化工科学研究院 | The preparation method who contains the ultrastable of amorphous aluminum silicide |
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| FR2398540A1 (en) * | 1977-07-29 | 1979-02-23 | Raffinage Cie Francaise | PROCESS FOR THE PREPARATION OF ALUMINA WITH CONTROLLED POROSITY AND APPLICATIONS OF ALUMINA THUS PREPARED |
| US4758330A (en) * | 1987-03-11 | 1988-07-19 | Phillips Petroleum Company | Hydrotreating employing silica-modified alumina |
| US5879539A (en) * | 1994-04-01 | 1999-03-09 | Institut Francais Du Petrole | Precious metal and silica-alumina based catalyst and hydroisomerisation treatment process for heavy feeds |
-
1997
- 1997-09-10 CN CN97116404A patent/CN1123383C/en not_active Expired - Lifetime
-
1998
- 1998-09-07 KR KR10-1998-0036804A patent/KR100488815B1/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053636A (en) * | 1990-01-19 | 1991-08-07 | 中国石油化工总公司石油化工科学研究院 | Distillate oil hydrogenation catalyst |
| CN1060977A (en) * | 1990-11-02 | 1992-05-13 | 中国石油化工总公司石油化工科学研究院 | The preparation method who contains the ultrastable of amorphous aluminum silicide |
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| CN1210755A (en) | 1999-03-17 |
| KR19990029603A (en) | 1999-04-26 |
| JPH11157828A (en) | 1999-06-15 |
| JP3828293B2 (en) | 2006-10-04 |
| KR100488815B1 (en) | 2005-09-02 |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031008 |