CN1488440A - Phosphor and silicon-containing alumina supporter and preparing method thereof - Google Patents
Phosphor and silicon-containing alumina supporter and preparing method thereof Download PDFInfo
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- CN1488440A CN1488440A CNA021331189A CN02133118A CN1488440A CN 1488440 A CN1488440 A CN 1488440A CN A021331189 A CNA021331189 A CN A021331189A CN 02133118 A CN02133118 A CN 02133118A CN 1488440 A CN1488440 A CN 1488440A
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- Prior art keywords
- silicon
- aluminium hydroxide
- phosphorous
- preparation
- alumina supporter
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Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 28
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 50
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 29
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 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 description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000010009 beating Methods 0.000 claims description 8
- 238000001935 peptisation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012778 molding material Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 238000009827 uniform distribution Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003292 glue Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 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 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- UHAQRCJYQAKQEE-UHFFFAOYSA-M [O-2].[OH-].O.[Al+3].P Chemical compound [O-2].[OH-].O.[Al+3].P UHAQRCJYQAKQEE-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention refers to a kind of aluminium oxide carrier containing phosphorus and silicon and the manufacturing method, the silicon disperses evenly on the surface of the carrier, the 3~15nm hole capacity accounts for over 90% of the whole hole capacity. The adding mode of assistant is: adds in assistant phosphorus in the sediment and aging process, adds in assistant silicon in the forming period, the assistant silicon is nano silicon dioxide. The craft is easy, the cost is low; and it has a good performance.
Description
1, technical field
The present invention relates to a kind of alumina supporter and preparation method thereof, the macropore of particularly phosphorous and silicon, bigger serface alumina supporter and preparation method thereof.
2, background technology
In general, heavy distillate hydrocracking pretreatment catalyst is all with aluminum oxide or contain one or more other elements such as the aluminum oxide of Si, Ti, P, B, F etc. is a carrier.In catalyst preparation process, can in system, introduce above-mentioned element in different steps, its objective is basically identical, i.e. regulating catalyst acid and/or improve interaction between active ingredient and carrier.In the support material building-up process as prepare aluminium hydroxide with the precipitator method, add multiple above-mentioned element simultaneously, because each material addition sequence changes, cause very big-difference at the residing position of alumina surface and with the effect degree of catalyst surface can for certain element, thereby catalyst property is produced bigger influence, simultaneously because process promptly adds silicon twice reaming influence that phosphorates again, the deficiency that can bring alumina pore to distribute and be difficult for removing than disperse, aperture in system; Add preparation catalyzer needed certain or multiple auxiliary agent in the support material building-up process and in the carrier moulding process respectively, as long as the interpolation auxiliary agent technical measures of taking are reasonable and/or interpolation auxiliary agent mode is proper, not only can eliminate problems such as catalyst preparation process complexity, difficult forming; Also more effectively physico-chemical property such as the acidity of modulation carrier, porous and then more effectively regulating catalyst acid and/or improve interaction between active ingredient and carrier, thus the physico-chemical property of preparing and use properties can both satisfy the carrier of catalyzer requirement.
US4,629,716 have described with in the P contained compound bialuminate aqueous solution (adding phosphoric acid as aluminum chloride) and alkali aluminate soln (as sodium metaaluminate) preparation alumina supporter preparation process, and this carrier aperture＜5nm accounts for more than 80%, specific surface area＞300m
2/ g, aluminum oxide phosphorus content are 0.1m%～4.5m%.Because phosphorus is to add in the alumina supporter with the precipitator method, therefore, not only has part phosphorus to enter the alumina body phase, has reduced the utilization ratio of phosphorus, the structure to aluminum oxide has adverse influence simultaneously.
Chinese patent CN1048037C has described and has adopted the production process for preparing alumina supporter in the liquor alumini chloridi with ammoniacal liquor, behind neutralization precipitation, add sodium silicate solution, filtration washing then, with filter cake making beating and adding phosphoric acid or primary ammonium phosphate etc., filtration at last, drying prepare phosphorous and silicon aluminium hydroxide again.Its weak point is that the silicon source of the system of introducing is a sodium silicate solution, and this solution belongs to the colloidal type material, and this silicon source and adding method exist the influence of process to the character and/or the microtexture of aluminum oxide.The colloidalmaterial that exists with the micelle form contacts the inhomogeneous state that is in the system aluminum oxide, especially when alumina concentration in the reaction system increases, the ununiformity of system is more obvious, cause the unhomogeneity of product aluminum oxide physico-chemical property easily, thereby influence the surface properties and the use properties of siliceous alumina supporter.In addition, because the adding of auxiliary agents of silicon, the pore distribution that makes aluminum oxide is than disperse.
3, summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of auxiliary agent at the alumina surface homodisperse, pore distribution concentration, the alumina supporter and the preparation method of the phosphorous and silicon that surface acidity is stronger.
Alumina supporter of the present invention contains auxiliary agent phosphorus and silicon, silicon is at the alumina surface homodisperse, the hole of carrier 3～15nm accounts for more than 85% of total pore volume, be preferably in more than 90%, contain Vanadium Pentoxide in FLAKES 0.3～3.0%, silicon-dioxide 0.5～10.0% in the carrier by weight, the carrier pore volume is 0.55～0.70ml/g, and average pore diameter is 6.5～9.5nm, and specific surface area is 290～350m
2/ g, tap density is 0.6～0.7g/ml.
The present invention is phosphorous with the preparation process silicon oxidation alumina supporter to be:
(1) contains aluminum salt solution and under agitation condition, mix, obtain aluminum hydroxide precipitation, wear out then, filter, wash, filter with precipitation agent;
(2) the filter cake making beating that above-mentioned filtration is obtained adds P contained compound, and the control slurry temperature is 30～90 ℃, filters also dry then;
(3), and in moulding process, add siliceous Nano compound with the above-mentioned phosphorous aluminium hydroxide that obtains and other aperture aluminium hydroxide moulding;
(4) dry, the above-mentioned molding materials of roasting makes phosphorous and the silicon oxidation alumina supporter.
The addition sequence (earlier add phosphorus after add silicon) of the inventive method by changing auxiliary agent, and after aluminum oxide precursor Stability Analysis of Structures, add auxiliary agents of silicon, help keeping the textural property of aluminum oxide, make the pore distribution concentration of carrier, solved with alumina supporter in the prior art and added the shortcoming that phosphorus and silicon make the pore distribution disperse simultaneously, the peptization of material is good simultaneously, is easy to moulding, the support strength height.In addition, it is the source of auxiliary agents of silicon that the inventive method is taked with the nanometer silicon-containing compound, has improved the dispersity of auxiliary agents of silicon on alumina carrier surface greatly, and has improved the surface acidity of carrier, helps improving the reactivity worth of catalyzer.The inventive method adds the needed auxiliary agent of preparation catalyzer respectively in the support material building-up process and in the carrier moulding process, neither increase additional step, can improve the physico-chemical property such as acid matter, porous of carrier again effectively, and then regulating catalyst acid and/or improve interaction between active ingredient and carrier more effectively, help improving levels of catalysts.
4, embodiment
The present invention is phosphorous, the preparation process of silicon oxidation alumina supporter is:
(1) contains aluminum salt solution and under agitation condition, mix, obtain aluminum hydroxide precipitation, wear out then, wash, filter with precipitation agent.Containing aluminum salt solution and precipitation agent can be aluminum chloride and ammoniacal liquor, Tai-Ace S 150 and ammoniacal liquor, aluminum nitrate and ammoniacal liquor, Tai-Ace S 150 and sodium metaaluminate, sodium metaaluminate and nitric acid, sodium metaaluminate and carbonic acid gas etc., does not preferably have the Tai-Ace S 150 and the sodium metaaluminate method of ammonia and nitrogen pollution and produces.Precipitation and condition such as aging can suitably be adjusted according to required aluminum oxide character.
(2) the filter cake making beating that above-mentioned filtration is obtained adds P contained compound, and the control slurry temperature is 30～90 ℃, filters also dry then.P contained compound is selected from the ammonium salt of phosphoric acid or phosphoric acid.
(3), and in moulding process, add siliceous Nano compound with the above-mentioned phosphorous aluminium hydroxide that obtains and other aperture aluminium hydroxide moulding.The weight ratio of mixture of phosphorous aluminium hydroxide and aperture aluminium hydroxide is 1: 1～1: 4.Siliceous Nano compound is a nano silicon, and particle diameter is 6～100nm.Aperture aluminium hydroxide pore volume is 0.2～0.6ml/g, and average pore diameter is 2.0～10.0nm, and specific surface area is 200～300m
2/ g.The adding method of siliceous Nano compound can be in the following way: 1. the nanometer silicon-containing compound with contain aluminium source material (aluminium hydroxide or aluminum oxide) and mix, 2. the nanometer silicon-containing compound contains in the material of aluminium source with deionized water wetting back adding, 3. add after the nanometer silicon-containing compound mixes with the peptization acid solution and contain in the material of aluminium source, 4. add the nanometer silicon-containing compound again after adding the peptization acid solution, 5. mix (making peptizing agent) with all or part of aperture aluminium hydroxide with peptization acid solution and nanometer silicon-containing compound, mix with macropore aluminium hydroxide then, 6. substep adds, 1. above-mentioned, 2., 3., 4. and, in 5. wantonly two steps or two steps above in adding respectively.Preferably with after phosphorous aluminium hydroxide and the mixing of part aperture aluminium hydroxide, add the peptizing agent made from another part aperture aluminium hydroxide and nano silicon, peptization acid solution, wherein the part of sneaking into of aperture aluminium hydroxide is 1: 1～25: 1 with the weight ratio of doing the peptizing agent part.
(4) dry, the above-mentioned molding materials of roasting obtains phosphorous and the silicon oxidation alumina supporter.
The present invention is phosphorous to can be used for preparing the mink cell focus hydrogenation pretreatment catalyst with the silicon oxidation alumina supporter, in particular for preparation heavy distillate hydrogenation pretreatment catalyst.
Be example with Tai-Ace S 150 and sodium metaaluminate method below, specify the preparation method of the phosphorous and silicon oxidation alumina supporter of the present invention.
(1) preparation aluminum sulfate aqueous solution, alumina content is 30～70gAl
2O
3/ l.
(2) the preparation sodium metaaluminate aqueous solution, alumina content is 120～260gAl
2O
3/ l, causticity compares NaOH/Al
2O
3(mass ratio) is 1.25～1.6.
(3) preparation aqueous sodium carbonate, concentration is 100g/l～300g/l.
(4) under agitation condition, aluminum sulfate aqueous solution is become glue in the certain water gaging of adding simultaneously continuously with the sodium metaaluminate aqueous solution, become the glue temperature to be controlled at 40～90 ℃ according to the porous of needed phosphorous aluminium hydroxide, being preferably the glue temperature is 50～70 ℃, become glue pH value to be adjusted to 7～9, be preferably 7.5～8.5, material solution adds in the colloid system simultaneously continuously, making the slurries alumina content is 30～80g/l, suitable alumina content is 40～60g/l, charging time is 30～180 minutes, is preferably 60～120 minutes.
(5) above-mentioned system slurries were aging after one-tenth glue was finished, and aging temperature is 40～90 ℃, and optimum temperature is 50～70 ℃, and aging pH is 6.0～9, is preferably 7.5～8.5, and digestion time is no more than 120 minutes at most, wears out and also carries out under agitation condition.
(6) the liquid-solid mixture of (5) step gained is filtered, filter cake adds the deionized water making beating to liquid-solid mixing states of matter, add (3) step gained aqueous sodium carbonate washing aluminium hydroxide hydrogel, the sodium carbonate solution add-on is that benchmark yellow soda ash accounts for 15～30m% to become glue to drop into alumina amount, regulating washing pH is 9.0～10.5, preferred pH is 9.5～10.0, wash temperature is 40～90 ℃, preferred temperature is 55～75 ℃, washing time is preferably 30～60 minutes, and the suitable alumina content of slurries is 20～40g Al in the system
2O
3/ l.Successively decrease along with washing times increases pH, can regulate slurries pH with ammonia soln or the ammonium bicarbonate aqueous solution of 2～10m% in the washing process.Dope filtration washing 4～5 times, Na in the aluminium hydroxide of preparation
+Content＜0.05m%, SO
4=content＜1.2m%, Fe
+++Till content＜0.08m%.Also can use ammoniacal liquor to wash.
(7) the qualified aluminum hydroxide filter cake of (6) step gained impurity is added the deionized water making beating to liquid-solid mixing states of matter, the control slurry temperature is 30～90 ℃ and adds P contained compound such as phosphoric acid or ammonium phosphate salt that making phosphorus content is 0.5～6.0m%.Churning time is preferably 30～40 minutes more than 15 minutes.
(8) the liquid-solid mixture of (7) step gained is filtered, the filtration cakes torrefaction temperature is 90～150 ℃, makes alumina content＞70m% in the aluminum hydroxide solid elastomer.
(9) with the phosphorous aluminum hydroxide solid elastomer of (8) step gained and a kind of aperture aluminium hydroxide, extrusion aid, mix, add the peptizing agent that contains nano silicon and mix, fully mix and pinch (mix and pinch the time) more preferably greater than 20 minutes, mixing to pinch becomes plastic, is extruded into bar on banded extruder.
(10) with the bar of (9) step gained 90～150 ℃ of dryings 8～16 hours, then 450～650 ℃ of roastings 1～6 hour, promptly get the phosphorous and silicon oxidation alumina supporter of the present invention.
Further specify technical solution of the present invention below by embodiment.
Embodiment 1
Step 1 adds the 1200ml deionized water in a clean container, be warming up to 65 ℃, be 1.35 the sodium metaaluminate aqueous solution with proportion and be 1.15 aluminum sulfate aqueous solution with 65ml/ minute flow velocity with 30ml/ minute flow velocity proportion, join simultaneously in the deionized water of stirring, keep 65 ℃ of temperature, pH is 8.5, and the reinforced time is 90 minutes.
Step 2 stop reinforced after, system under above-mentioned pH value and temperature condition aging 90 minutes, the filter cake after the filtration adds the deionized water pulp, and the adding sodium carbonate solution washs 5 times, washs Na to the aluminum oxide
+Content＜0.05m%, SO
4=content＜1.2m%, Fe
+++Till content＜0.08m%.
Step 3 joins aluminum hydroxide filter cake in the solution of 2.5L deionized water and 42g85m% phosphoric acid making beating evenly, and the control slurry temperature is 65 ℃, 40 minutes after-filtration of pulp.
Step 4 filter cake is directly stand-by after 8 hours 120 ℃ of dryings.
The above-mentioned phosphorous aluminium hydroxide 142g of step 5 weighing, aperture aluminium hydroxide 252g, nano silicon 7.5g, extrusion aid sesbania powder 10g and 90g deionized water, mix, the solution that adding is mixed with by 24g40% salpeter solution and 340g water purification mixes and pinches into plastic, is extruded into the trifolium bar of φ 1.5mm with banded extruder, drying is 8 hours under 120 ℃ of temperature condition, then 500 ℃ of following roastings 4 hours, i.e. cost example, character sees Table 1 (1).
Embodiment 2
Step 1 is with embodiment 1 step 1, step 2.
Step 2 changes the 42.0g85m% phosphoric acid in embodiment 1 step 3 into 56g85m% phosphoric acid by embodiment 2, i.e. cost example, and character sees Table 1 (2).
Step 3 is with embodiment 1 step 4, step 5.
Embodiment 3
Step 1 is with embodiment 1 step 1, step 2.
Step 2 changes the 42.0g85m% phosphoric acid in embodiment 1 step 3 into 75g85m% phosphoric acid by embodiment 3, i.e. cost example, and character sees Table 1 (2).
Step 3 is with embodiment 1 step 4, step 5.
Embodiment 4
Step 1 is with embodiment 1 step 1, step 2, step 3, step 4.
Step 2 changes the maturing temperature in embodiment 1 step 5 into 550 ℃ by embodiment 4, roasting 3 hours, i.e. and cost example, character sees Table 1 (5).
Embodiment 5
Step 1 is with embodiment 1 step 1, step 2, step 3, step 4.
Step 2 changes the maturing temperature in embodiment 1 step 5 into 600 ℃ by embodiment 5, roasting 4 hours, i.e. and cost example, character sees Table 1 (5).
Embodiment 6
In embodiment 1, change nano silicon into 13g, nano silicon mixes with salpeter solution, adds then in macropore aluminium hydroxide and the aperture aluminium hydroxide, and other is with embodiment 1, i.e. cost example, character sees Table 1 (6).
Embodiment 7
In embodiment 1, change nano silicon into 20g, 10% and salpeter solution of nano silicon and aperture aluminium hydroxide are made peptizing agent, mix with macropore aluminium hydroxide and residue aperture aluminium hydroxide then, other is with embodiment 1, i.e. cost example, and character sees Table 1 (7).
Embodiment 8
In embodiment 1, change nano silicon into 25g, wherein nano silicon is divided into two equal portions, a with add the wetting back of deionized water and add in the aluminium hydroxide material, another part adds in the aluminium hydroxide material after making peptizing agent with 5% and salpeter solution of aperture aluminium hydroxide, other step is with embodiment 1, i.e. cost example, and character sees Table 1 (8).
Comparative example 1
Nano silicon in embodiment 1 step 5 is used instead the silica sol liquid of 95g20% in embodiment 1, deionized water 430g changes 390g into,, i.e. cost example, character sees Table 1 (9).
Comparative example 2
In embodiment 1, used phosphorous aluminium hydroxide changes Chinese Chang Ling oil-refining chemical limited-liability company catalyst plant into in the Tai-Ace S 150 and the prepared phosphorous and silicon aluminium hydroxide of sodium metaaluminate, without nano silicon, i.e. and cost example, character sees Table 1 (10).
Embodiment 7
Catalyst A is the phosphorous and silicon oxidation alumina supporter of the technology of the present invention embodiment 1 described process preparation among the embodiment 7, adopts molybdenum-nickel-phosphorus solution to flood 75 minutes by general pickling process, the elimination excess solution, and drying, catalyzer is made in roasting.Catalyst B is the production of Fushun Petrochemical Company catalyst plant, extensively 3936 heavy distillate Hydrobon catalysts of industry use.Two kinds of catalyzer physico-chemical properties and at reaction stagnation pressure 15.7MPa, volume space velocity 1.0h
-1, hydrogen to oil volume ratio 1000: 1 and 376 ℃ processing condition under, the hydrodenitrification performance of hydrotreatment triumph VGO oil sees Table 2, stock oil character sees Table 3.
Table 1
TPD-NH
3Pile up crushing than table average pore distribution, (v%) real P
2O
5SiO
2Pore volume
(total acid content) density intensity area aperture example % % ml/g＜3nm 3-15nm＞15nm
Mmol/g g/ml N/cm m
2/g nm(1) 1.00 2.19 0.67 0.67 151 0.597 320 7.9 2.3 95.6 2.1(2) 1.32 2.17 0.65 0.65 152 0.613 325 8.0 1.9 95.7 2.4(3) 1.74 2.19 0.62 0.64 156 0.625 318 8.1 2.6 94.9 2.5(4) 1.10 2.18 0.64 0.63 157 0.637 315 8.2 2.0 95.0 3.0(5) 1.07 2.20 0.66 0.64 154 0.645 305 8.4 2.1 94.0 3.9(6) 1.09 4.08 0.70 0.66 153 0.611 339 7.8 2.2 95.8 2.0(7) 1.08 5.88 0.73 0.65 150 0.619 337 7.9 2.5 95.4 2.1(8) 1.11 7.21 0.75 0.64 155 0.624 334 8.0 2.4 94.9 2.7(9) 1.09 5.90 0.52 0.56 159 0.650 290 8.6 2.6 88.1 9.3(10) 1.61 2.20 0.50 0.58 153 0.660 300 8.3 8.5 85.7 5.8
Table 2
Catalyst agent A catalyst B
MoO
3，w％ 25.0 25.5
NiO，w％ 3.60 3.98
Specific surface area, m
2/ g 171 165
Pore volume, ml/g 0.341 0.332
Mean pore size, nm 7.8 7.9
Generate oily nitrogen content, g/g 6.0 22.0
Relative denitrification activity, % 125 100
Runtime, h 500 500
Table 3
Stock oil triumph VGO
Density (20 ℃), g/cm
30.9066
Boiling range, ℃
IBP 346
50％ 435
EBP 525
Carbon residue, % 0.05
S，m％ 0.59
N，μg/g 1640
By table 1 data as can be seen, in comparative example 1, adopt the phosphorous aluminium hydroxide of the inventive method preparation to add the prepared alumina supporter of silica sol liquid, the pore distribution of mean pore size between 3-15nm accounts for 88.1% of total hole, pore distribution greater than 15nm accounts for 9.3% of total hole, tap density 0.56g/ml.Phosphorous and the prepared alumina supporter of silicon aluminium hydroxide that adopts the Tai-Ace S 150 method to produce in comparative example 2, the pore distribution of mean pore size between 3-15nm accounts for 86.7% of total hole, accounts for 10.0% of total hole, tap density 0.58g/ml less than the pore distribution of 3nm.With the carrier of the inventive method preparation, pore distribution concentration, mean pore size accounts for more than 94% of total hole, tap density＞0.63g/ml, crushing strength＞150N/cm, pore volume＞0.59ml/g, specific surface area＞300m in the pore distribution between the 3-15nm
2/ g, and have suitable surface acidity, be suitable for use as the particularly carrier of heavy distillate hydrogenation pretreatment catalyst of mink cell focus.
By table 2 data as can be seen, the carrier with the inventive method preparation supports the catalyst A that nickel-the molybdenum active metal component is made, and its relative denitrification activity is 125% of the extensive industrial heavy distillate hydrogenation pretreatment catalyst B that uses.
Claims (10)
1, a kind of alumina supporter, contain auxiliary agent phosphorus and silicon, it is characterized in that containing by weight Vanadium Pentoxide in FLAKES 0.3%～3.0%, silicon-dioxide 0.5%～10.0%, auxiliary agents of silicon is at the alumina surface uniform distribution, and the hole of carrier 3～15nm accounts for more than 90% of total pore volume.
2, according to the described alumina supporter of claim 1, it is characterized in that described carrier pore volume is 0.55～0.70ml/g, average pore diameter is 6.5～9.5nm, specific surface area is 290～350m
2/ g, tap density is 0.6～0.7g/ml.
3, the preparation method of the described alumina supporter of a kind of claim 1 may further comprise the steps:
(1) contains aluminum salt solution and under agitation condition, mix, obtain aluminum hydroxide precipitation, wear out then, wash, filter with precipitation agent;
(2) the filter cake making beating that above-mentioned filtration is obtained adds P contained compound, filters then and drying;
(3), and in moulding process, add siliceous Nano compound with above-mentioned phosphorous aluminium hydroxide that obtains and the moulding of aperture aluminium hydroxide;
(4) dry, the above-mentioned molding materials of roasting makes phosphorous and the silicon oxidation alumina supporter.
4,, it is characterized in that step (1) is described and contain aluminum salt solution and precipitation agent is Tai-Ace S 150 and sodium metaaluminate according to the described preparation method of claim 3.
5,, it is characterized in that the described making beating of step (2) back control slurry temperature is 30～90 ℃ according to the described preparation method of claim 3.
6, according to the described preparation method of claim 3, its spy is characterised in that the described siliceous Nano compound of step (3) is a nano silicon, and particle diameter is 6～100nm.
7, according to the described preparation method of claim 3, it is characterized in that the character of the described aperture aluminium hydroxide of step (3) is: pore volume is 0.2ml/g～0.6ml/g, and average pore diameter is 2.0nm～10.0nm, and specific surface area is 200m
2/ g～300m
2/ g; The weight ratio of mixture of phosphorous aluminium hydroxide and aperture aluminium hydroxide is 1: 1～1: 5.
8, according to the described preparation method of claim 3, the adding method that it is characterized in that described siliceous Nano compound is: 1. the nanometer silicon-containing compound with contain aluminium source mixing of materials, 2. the nanometer silicon-containing compound contains in the material of aluminium source with deionized water wetting back adding, 3. add after the nanometer silicon-containing compound mixes with the peptization acid solution and contain in the material of aluminium source, 4. add the nanometer silicon-containing compound again after adding the peptization acid solution, 5. mix with peptization acid solution and nanometer silicon-containing compound with all or part of aperture aluminium hydroxide, mix with macropore aluminium hydroxide then, 6. substep adds, 1. above-mentioned, 2., 3., 4. and, in 5. wantonly two steps or two steps above in adding respectively.
9, according to the described preparation method of claim 8, during the adding method of the siliceous Nano compound described in it is characterized in that adopting 3., the part that aperture aluminium hydroxide is sneaked into phosphorous aluminium hydroxide is 1: 1～25: 1 with the weight ratio that is used as the peptizing agent part.
10,, it is characterized in that the washing process of described step (1) uses sodium carbonate solution or ammoniacal liquor according to the described preparation method of claim 3.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133118 CN1201865C (en) | 2002-10-10 | 2002-10-10 | Phosphor and silicon-containing alumina supporter and preparing method thereof |
| EP03753239.7A EP1552880B1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| JP2004545680A JP5006516B2 (en) | 2002-10-10 | 2003-09-29 | Silicon-containing alumina support, method for preparing the same, and catalyst containing the alumina support |
| KR1020057006163A KR100884595B1 (en) | 2002-10-10 | 2003-09-29 | Silicon-containing alumina carrier, preparation method thereof, and catalyst comprising the carrier |
| PCT/CN2003/000839 WO2004037408A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| CA2501973A CA2501973C (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| AU2003272858A AU2003272858A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| US10/682,221 US6875722B2 (en) | 2002-10-10 | 2003-10-09 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
| US11/069,034 US7253135B2 (en) | 2002-10-10 | 2005-02-28 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
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|---|---|---|---|
| CN 02133118 CN1201865C (en) | 2002-10-10 | 2002-10-10 | Phosphor and silicon-containing alumina supporter and preparing method thereof |
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| CN1201865C CN1201865C (en) | 2005-05-18 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431964C (en) * | 2006-10-27 | 2008-11-12 | 北京化工大学 | Alumina in high hydrothermal stability, and preparation method |
| CN101491767B (en) * | 2008-01-23 | 2011-04-20 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| CN101890374B (en) * | 2009-05-19 | 2012-11-21 | 中国石油化工股份有限公司 | Modified aluminum oxide carrier and preparation method thereof |
| CN101890375B (en) * | 2009-05-19 | 2013-04-10 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and preparation method thereof |
| CN103721732A (en) * | 2014-01-23 | 2014-04-16 | 山东允能催化技术有限公司 | Catalyst carrier material made of phosphorated and modified pseudo-boehmite and preparation method |
| CN109529899A (en) * | 2018-12-04 | 2019-03-29 | 宁波中科远东催化工程技术有限公司 | Heavy-oil hydrogenation composite catalyst and preparation method thereof and application method |
| CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst and application for preparing m-xylylenediamine |
-
2002
- 2002-10-10 CN CN 02133118 patent/CN1201865C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431964C (en) * | 2006-10-27 | 2008-11-12 | 北京化工大学 | Alumina in high hydrothermal stability, and preparation method |
| CN101491767B (en) * | 2008-01-23 | 2011-04-20 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| CN101890374B (en) * | 2009-05-19 | 2012-11-21 | 中国石油化工股份有限公司 | Modified aluminum oxide carrier and preparation method thereof |
| CN101890375B (en) * | 2009-05-19 | 2013-04-10 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and preparation method thereof |
| CN103721732A (en) * | 2014-01-23 | 2014-04-16 | 山东允能催化技术有限公司 | Catalyst carrier material made of phosphorated and modified pseudo-boehmite and preparation method |
| CN109529899A (en) * | 2018-12-04 | 2019-03-29 | 宁波中科远东催化工程技术有限公司 | Heavy-oil hydrogenation composite catalyst and preparation method thereof and application method |
| CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst and application for preparing m-xylylenediamine |
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| CN1201865C (en) | 2005-05-18 |
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