CN103769230A - Preparation method of alumina dry glue containing silicon - Google Patents
Preparation method of alumina dry glue containing silicon Download PDFInfo
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- CN103769230A CN103769230A CN201210409223.4A CN201210409223A CN103769230A CN 103769230 A CN103769230 A CN 103769230A CN 201210409223 A CN201210409223 A CN 201210409223A CN 103769230 A CN103769230 A CN 103769230A
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- Prior art keywords
- aluminium
- accordance
- silicon
- solution
- flyash
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- 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 94
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003292 glue Substances 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 239000010881 fly ash Substances 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012670 alkaline solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000004645 aluminates Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 55
- 230000032683 aging Effects 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000004033 plastic Substances 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 159000000013 aluminium salts Chemical class 0.000 claims description 11
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 11
- 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 9
- 238000001879 gelation Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 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 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000003921 oil Substances 0.000 abstract description 11
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RNUBFUJXCFSMQP-UHFFFAOYSA-N borol-2-one Chemical compound O=C1B=CC=C1 RNUBFUJXCFSMQP-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of an alumina dry glue containing silicon. The preparation method comprises the following steps: adding fly ash into a strong alkaline solution to carry out a treatment, filtering so as to obtain an alkaline solution containing silicon and aluminum, then carrying out a parallel-flow glue-forming reaction by using the alkaline solution containing silicon and aluminum and an acidic aluminate solution, then filtering, washing, and drying the glue-forming reaction product so as to obtain alumina dry glue containing silicon, and finally burning the alumina dry glue containing silicon so as to obtain the alumina containing silicon. The method fully utilizes fly ash, thus greatly reduces the cost, and raises the additional value of fly ash at the same time. The obtained alumina containing silicon has the advantages of large pore volume and large pore diameter, and is especially suitable for being used as a carrier component of catalyst for heavy oil or residual oil hydro-treatment.
Description
Technical field
The present invention relates to the preparation method of the dry glue of a kind of silicon-containing alumina, particularly a kind of preparation method of the dry glue of silicon-containing alumina that is applicable to heavy oil or catalyst for hydrotreatment of residual oil carrier material.
Background technology
The carrier matrix of common heavy oil, residual oil hydrocatalyst is aluminium oxide.Due to heavy oil, residual oil character is severe, so heavy oil, the kind of residual oil hydrocatalyst is many, consumption is large and catalyst life cycle is short, therefore, heavy oil is prepared in requirement, the raw alumina of residual oil hydrocatalyst carrier must be cheap, simultaneously, because the relative molecular weight of petroleum is increasing, the diffusional resistance running in order to reduce macromolecular reaction, to hold more carbon deposit and metal deposit etc., also require heavy oil, residual oil hydrocatalyst carrier has larger aperture and pore volume and suitable acidity, duct, large aperture can be played passage and be held the effect of metal deposit, make the more efficiently utilization of catalyst inner surface, larger pore volume can hold more impurity, to guarantee catalyst service life, suitable acidity can guarantee that catalyst has certain hydrogenation activity, and the activity of catalyst and stability just can be improved like this.
First, prepare cheap aluminium oxide, must guarantee that the cost of material of Borolon is cheap.At present, aluminium oxide generally has three kinds of preparation methods industrial:
(1) neutralization reaction of aluminium salt and alkali, as Alchlor process:
AlCl
3+3NH
4OH→Al（OH）
3+3NH
4Cl
(2) metathesis reaction of aluminium salt and aluminate, as aluminum sulfate method:
Al
2（SO
4）
3+6NaAlO
2+12H
2O→8Al（OH）
3+3Na
2SO
4
(3) aluminate and sour neutralization reaction, as carbonizatin method:
2NaAlO
2+CO
2+3H
2O→2Al（OH）
3+Na
2CO
3
All necessary assurances without any impurity of raw material of conventionally preparing aluminium oxide, therefore, the price of the raw material of Borolon will be higher than the low like product of grade, so synthetic price of aluminium oxide is also relatively costly.
Secondly, a little less than the simple support acidity with alumina preparation, and be mainly L acid, B acid is extremely weak or containing B acid, easily and active metal component generation strong interaction and form the species of non-activity, thereby affects the performance of catalyst.Therefore,, for regulating the acidity of catalyst carrier, in aluminium oxide building-up process, can add appropriate auxiliary agent according to different requirements, as Si, Ti and P etc.Typical Si source adopts waterglass, Ludox and molecular sieve etc. to improve the acidity of carrier more.
USP4721696 has described a kind of preparation method of silicon-containing alumina, take aluminum nitrate and sodium aluminate as raw material, adopts pH in 2 ~ 10 swing methods, in the false colloidal sol of the aluminium hydroxide obtaining, adds sodium metasilicate, after washing, dry, roasting, obtains silicon-containing alumina.The method preparation process is too complicated.
CN01118437.X has described a kind of preparation method of cracking catalyst for petroleum hydrocarbon, it be by clay slurry with after acid treatment, add boehmite, water glass solution, add aluminium colloidal sol, then add molecular sieve pulp, spraying is dry, washing.The method is applicable to the preparation of the molecular sieve catalyst of silicon-aluminum containing matrix.The small-bore proportion of the catalyst <5nm of preparation is larger, is not suitable for as heavy oil or residual oil hydrocatalyst material.
CN92112511.9 discloses a kind of heavy-oil hydrogenation denitrification catalyst, and the feature of this catalyst is in carrier extruded moulding process, to add low sodium Ludox to increase the pore volume of carrier, makes pore size distribution more concentrated simultaneously, and has increased the acid amount of carrier.SiO on carrier
2content 14～19wt%, pore volume 0.55 ~ 0.65ml/g, average pore size is less.Although this patent adds low sodium Ludox, has improved support acidity, aperture is still less, is not suitable for heavy oil, residual oil compared with the hydrogenation process of macromolecular reaction thing.
CN02109422.5 discloses a kind of mink cell focus and hydrotransforming catalyst for residual oil and preparation method thereof, it is support material that catalyst adopts a kind of silicon-containing alumina, the preparation process of silicon-containing alumina adopts and in plastic process, adds a small amount of silicon, adds the silicon of surplus after plastic or in ageing process.This catalyst aperture distributes and mainly concentrates on 5-10nm.Be silicon source owing to selecting sodium metasilicate, guarantee to have compared with low sodium content in product, washing process can produce a large amount of waste water, to environment.
Flyash is a kind of industrial residue that coal-fired boiler in thermal power plant is discharged, and is one of industrial solid castoff of current discharge capacity maximum in the world, not only serious environment pollution, and harm humans health, but also take a large amount of soils.The main component of flyash is aluminium oxide and silica.Flyash is mainly used in the aspects such as construction material, hydraulic engineering, road engineering, and added value is low.Becoming more meticulous of flyash utilized in the extraction and application that mainly concentrates on silicon, aluminium.Such as: CN200810115355.X discloses a kind of method of preparing metallurgical-grade aluminum oxide.The autograph delivered of " silicate circular " the 26th the 1st phase of volume (2007) is " flyash step-leached sial is prepared the research of pure zeolite molecular sieve ", is to utilize sial in flyash for the synthesis of X-type, A type, the pure zeolite product of P type.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the dry glue of a kind of silicon-containing alumina.The method makes full use of flyash, not only cheap, and improves the added value of flyash, and the silicon-containing alumina pore volume of gained is large, and aperture is large, is particularly suitable for as carrier component heavy, slag hydrotreating catalyst.
The preparation method of the dry glue of silicon-containing alumina of the present invention, comprising:
(1) flyash is joined to strong alkali solution and process, then remove by filter residue, obtain siliceous and alkaline solution aluminium;
(2) prepare acid aluminum salt solution;
(3) adopt and flow plastic method, acid aluminium salt solution stream that the alkaline solution of the siliceous and aluminium that step (1) is obtained and step (2) obtain carry out plastic reaction, control at least 50 ℃ of plastic temperature, preferably 50 ~ 95 ℃, more preferably 60 ~ 90 ℃, controlling plastic pH value is 7.0 ~ 10.5, preferably 7.5 ~ 9.5;
(4) slurries of step (4) gained are filtered, washing, obtains the dry glue of silicon-containing alumina after drying.
More than the granularity of the flyash described in step (1) is preferably 200 orders.Alumina content 15wt%～50wt% in described flyash, silica content 30 wt%～60 wt%.
Step (1) joins strong alkali solution by flyash and processes, and treatment temperature is for being at least 100 ℃, and preferably 100 ~ 180 ℃, more preferably 120 ~ 150 ℃, the processing time is 2 ~ 8 hours, preferably 4 ~ 6 hours.
The described strong alkali solution of step (1) is one or both mixed solutions in NaOH, potassium hydroxide, preferably sodium hydroxide solution.The liquid-solid ratio of described flyash and strong alkali solution is 1 ~ 6mL/g, preferably 2 ~ 4mL/g.The molal quantity that adds highly basic in described strong alkali solution is 2.6 ~ 5.0 times of aluminium molal quantity in flyash, preferably 2.8 ~ 4.0, more preferably 3.0 ~ 3.4.
In the alkaline solution of the siliceous and aluminium described in step (1), the total concentration of silicon and aluminium is counted 120 ~ 220g/L with aluminium oxide and silica gross mass, preferably 160 ~ 200g/L.
One or more of the described acid aluminium salt preferably sulfuric acid of step (2) aluminium, aluminum nitrate, aluminium chloride etc., more preferably sulfuric acid aluminium.The concentration of described acid aluminium salt solution is 40 ~ 100g Al
2o
3/ L, preferably 50 ~ 80g Al
2o
3/ L.
It is 30 ~ 80 minutes that step (3) is controlled gelation time.
After the reaction of step (3) plastic finishes, can be preferably through overaging.Described aging condition is as follows: at least 50 ℃ of aging temperatures, and preferably 50 ~ 95 ℃, more preferably 65 ~ 90 ℃, ageing time is below 90 minutes, preferably 10 ~ 90 minutes, more preferably 10 ~ 60 minutes.
The drying condition that step (4) is described: 100 ~ 150 ℃ are dried 2 ~ 6 hours, preferably 110 ~ 130 ℃, dry 4 ~ 6 hours.
The preparation method of silicon-containing alumina of the present invention, comprising: the dry glue of the silicon-containing alumina of step (4) gained, through roasting, obtains silicon-containing alumina, wherein roasting condition: 500 ~ 950 ℃ of roastings 2 ~ 6 hours, preferably 600 ~ 900 ℃ of roastings 3 ~ 5 hours.
In the inventive method, can be as required in the alkaline solution of the siliceous and aluminium of step (1), add basic aluminate.Described basic aluminate is one or more in sodium metaaluminate, potassium metaaluminate, preferably sodium metaaluminate.Add the total concentration of silicon and aluminium in the alkaline solution of the siliceous and aluminium of gained after basic aluminate to count 120 ~ 220g/L with aluminium oxide and silica gross mass, preferably 160 ~ 200g/L.
In silicon-containing alumina of the present invention, the content of silica is 1wt% ~ 50wt%, preferably 2wt% ~ 40wt%.Silicon-containing alumina character of the present invention is as follows: pore volume is 0.75-1.10mL/g, and specific area is 280-350m
2/ g, pore size distribution is as follows: the pore volume in the hole of bore dia < 6nm accounts for below 20% of total pore volume, and the pore volume in the hole of bore dia > 15nm accounts for the more than 30% of total pore volume.
In the present invention, porous and specific area are to adopt the analysis of low temperature liquid nitrogen absorption method, and silica content is to adopt metric measurement.
The inventive method is take flyash as silicon source and part aluminium source, widen the He Gui source, aluminium source of synthetic silicon-containing alumina, synthetic silicon-containing alumina price is significantly reduced, improve the added value of flyash, also solved the serious problem of environmental pollution that flyash brings.
The main component of the inventive method flyash used is Al
2o
3and SiO
2, wherein also contain Fe
3+, Ca
2+, Mg
2+, Ti
4+deng material, first make flyash react with strong alkali solution, generate soluble aluminum hydrochlorate and silicate, and Fe
3+, Ca
2+, Mg
2+, Ti
4+stay in residue with alkali reaction generation precipitation Deng material, make siliceous and alkaline solution aluminium, more also flow with acid aluminium salt solution, prepare large pore volume, wide-aperture silicon-containing alumina.Pore structure and the surface acidity of this silicon-containing alumina are suitable, are applicable to as weight, carrier component, the especially hydrodesulfurization of catalyst for hydrotreatment of residual oil and the carrier component of de-carbon residue catalyst.
The invention has the advantages that, in the dry glue of prepared silicon-containing alumina, the content of silica regulates simple, prepare the silicon-containing alumina that silicone content is higher, can not produce a large amount of waste water yet, because alkaline He Gui source, aluminium source exists with ionic species, under acid solution effect, precipitate simultaneously, silicon can be dispersed in aluminium oxide better, and combine with the aluminium oxide skeleton generating, so, the silica that siliceous aluminium hydroxide prepared by the present invention adds can play the object of modification, modified aluminas well, increases the acidity of catalyst.
The specific embodiment
Below by further statement technical characterictic of the present invention of embodiment, but be not limited to embodiment.Wt% is mass fraction.
Embodiment 1
Take and consist of SiO
244.28wt%, Al
2o
348.80wt%, Fe
2o
3the flyash 500g that 3.29wt%, CaO 2.56wt% and granularity 200 order all-pass are crossed, joins 2500mL containing in the solution of NaOH 287g, stirs, and under 130 ℃ of conditions, processes 4 hours, and reaction finishes rear filtering residue, obtains siliceous and alkaline solution aluminium.Adjust above-mentioned mixed solution with sodium aluminate solution, make Al in solution
2o
3, SiO
2concentration summation is 160g/L, stand-by.
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 50g/L, stand-by.
In plastic retort, add 1.0L deionized water, be heated with stirring to 70 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 7.5, keeps retort temperature at 70 ℃ in course of reaction, and gelation time is 50 minutes.Then carry out aging, 70 ℃ of aging temperatures, ageing time 30min.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 120 ℃ are dried 3 hours, obtain the dry glue of silicon-containing alumina, through 600 ℃ of roastings 3 hours, obtain silicon-containing alumina A.
Embodiment 2
Other condition, with embodiment 1, just makes Al in solution
2o
3, SiO
2concentration summation is 130g/L, prepares silicon-containing alumina B.
Embodiment 3
Take and consist of SiO
244.28wt%, Al
2o
348.80wt%, Fe
2o
3the flyash 500g that 3.29wt%, CaO2.56wt% and granularity 200 order all-pass are crossed, joins 2000mL containing in the solution of NaOH 500g, stirs, and under 150 ℃ of conditions, processes 3 hours, and reaction finishes rear filtering residue, obtains siliceous and alkaline solution aluminium.Adjust above-mentioned mixed solution with sodium aluminate solution, make Al in solution
2o
3, SiO
2concentration summation is 160g/L, stand-by.
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 60g/L, stand-by.
In plastic retort, add 1.0L deionized water, be heated with stirring to 80 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 8.5, keeps retort temperature at 80 ℃ in course of reaction, and gelation time is 60 minutes.Then through aging, 80 ℃ of ageing time 40min of aging temperature.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 110 ℃ are dried 5 hours, obtain the dry glue of silicon-containing alumina, through 700 ℃ of roastings 4 hours, obtain silicon-containing alumina C.
Embodiment 4
Take and consist of SiO
248.0 wt %, Al
2o
338.0 wt %, Fe
2o
3the flyash 500g that 5.0 wt %, CaO3.5 wt % and granularity 200 order all-pass are crossed, joins 2500mL containing in the solution of NaOH 287g, stirs, and under 130 ℃ of conditions, processes 4 hours, and reaction finishes rear filtering residue, obtains siliceous and alkaline solution aluminium.Adjust above-mentioned mixed solution with sodium aluminate solution, make Al in solution
2o
3, SiO
2concentration summation is 200g/L, stand-by.
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 50g/L, stand-by.
In plastic retort, add 1.2L deionized water, be heated with stirring to 85 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 9.5, keeps retort temperature at 85 ℃ in course of reaction, and gelation time is 35 minutes.Then through aging, 85 ℃ of aging temperatures, ageing time 20min.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 120 ℃ are dried 4 hours, obtain the dry glue of silicon-containing alumina, through 750 ℃ of roastings 3 hours, obtain silicon-containing alumina D.
Embodiment 5
Take and consist of SiO
248.0 wt %, Al
2o
338.0 wt %, Fe
2o
3the flyash 500g that 5.0 wt %, CaO3.5 wt % and granularity 200 order all-pass are crossed, joins 2500mL containing in the solution of NaOH 500g, stirs, under 150 ℃ of conditions, process 6 hours, reaction finishes rear filtering residue, obtains siliceous and alkaline solution aluminium, Al in solution
2o
3, SiO
2concentration summation is 130g/L, stand-by.
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 50g/L, stand-by.
In plastic retort, add 1.2L deionized water, be heated with stirring to 85 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 9.5, keeps retort temperature at 85 ℃ in course of reaction, and gelation time is 70 minutes.Then through aging, 85 ℃ of aging temperatures, ageing time 20min.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 120 ℃ are dried 4 hours, obtain the dry glue of silicon-containing alumina, through 600 ℃ of roastings 3 hours, obtain silicon-containing alumina E.
Comparative example 1
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 50g/L, preparation is containing Al
2o
3for the sodium aluminate solution 3000mL of 160g/L, stand-by.
In plastic retort, add 1.0L deionized water, be heated with stirring to 70 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 7.5, keeps retort temperature at 70 ℃ in course of reaction, and gelation time is 50 minutes.Acid-base solution all adds rear reaction to finish, and adds waterglass 31.25g(containing SiO
226wt%) enter the ageing step, 70 ℃ of aging temperatures, ageing time 30min.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 120 ℃ are dried 3 hours, obtain the dry glue of silicon-containing alumina, through 600 ℃ of roastings 3 hours, obtain silicon-containing alumina F.
Comparative example 2
Preparation is containing Al
2o
3for the aluminum sulfate solution 5000mL of 50g/L, preparation 3000mL sodium metaaluminate and waterglass mixed solution, make Al in mixed solution
2o
3, SiO
2concentration summation is 160g/L, stand-by.
In plastic retort, add 1.0L deionized water, be heated with stirring to 70 ℃.Measure respectively above-mentioned alkaline solution 1250mL and acid solution 2500mL, and flow to and in retort, add above-mentioned two kinds of solution, keeping retort pH value is 7.5, keeps retort temperature at 70 ℃ in course of reaction, and gelation time is 50 minutes.Acid-base solution all adds rear reaction to finish, and enters the ageing step, 70 ℃ of aging temperatures, ageing time 30min.Slurries after aging are washed till neutrality by the deionized water of 70 ℃, and 120 ℃ are dried 3 hours, obtain the dry glue of silicon-containing alumina, through 600 ℃ of roastings 3 hours, obtain silicon-containing alumina G.
The physicochemical property of the silicon-containing alumina that obtained is above listed in to table 1.
Table 1 silicon-containing alumina physicochemical property
| Numbering | A | B | C | D | E | Comparative Example F | Comparative example G |
| Pore volume, mL/g | 0.981 | 1.06 | 0.923 | 0.836 | 0.802 | 0.825 | 0.971 |
| Specific area, m 2/g | 317 | 344 | 294 | 288 | 286 | 282 | 336 |
| Pore-size distribution, % | |||||||
| <6nm | 7.5 | 9.3 | 12.4 | 16.7 | 19.1 | 25.3 | 29.6 |
| 6~15nm | 47.3 | 50.9 | 50.5 | 46.8 | 49.7 | 43.0 | 32.6 |
| >15nm | 45.2 | 39.8 | 37.1 | 36.5 | 31.2 | 31.7 | 37.8 |
| SiO 2，wt% | 2.5 | 6.1 | 21.8 | 35.2 | 40.7 | 2.41 | 2.43 |
| Total acid, mmol/g | 0.482 | 0.473 | 0.453 | 0.436 | 0.428 | 0.397 | 0.402 |
As can be seen from Table 1, in the time containing close silica in aluminium oxide, the silicon source that employing flyash prepares is compared with adding sodium metasilicate, and pore size distribution is more concentrated, has also increased the acidity of silicon-containing alumina simultaneously.Therefore be applicable to being used as the carrier component of the catalyst such as residuum hydrogenating and metal-eliminating, hydrodesulfurization and hydro-conversion.
Claims (19)
1. a preparation method for the dry glue of silicon-containing alumina, comprising:
(1) flyash is joined to strong alkali solution and process, then remove by filter residue, obtain siliceous and alkaline solution aluminium;
(2) prepare acid aluminum salt solution;
(3) adopt and flow plastic method, the acid aluminium salt solution that the alkaline solution of the siliceous and aluminium that step (1) is obtained and step (2) obtain carries out and flows plastic reaction, and controlling plastic temperature is 50 ℃ ~ 95 ℃, and plastic pH value is 7.0 ~ 10.5;
(4) slurries of step (4) gained are filtered, washing, obtains the dry glue of silicon-containing alumina after drying.
2. the granularity that in accordance with the method for claim 1, it is characterized in that the described flyash of step (1) is more than 200 orders.
3. in accordance with the method for claim 1, it is characterized in that in the described flyash of step (1) alumina content 15wt%～50wt%, silica content 30 wt%～60 wt%.
4. in accordance with the method for claim 1, it is characterized in that step (1) joins strong alkali solution by flyash and processes, treatment temperature is 100 ~ 180 ℃, and the processing time is 2 ~ 8 hours.
5. in accordance with the method for claim 1, it is characterized in that step (1) joins strong alkali solution by flyash and processes, treatment temperature is 120 ~ 150 ℃, and the processing time is 4 ~ 6 hours.
6. in accordance with the method for claim 1, it is characterized in that the described strong alkali solution of step (1) is one or both mixed solutions in NaOH, potassium hydroxide.
7. in accordance with the method for claim 1, the liquid-solid ratio that it is characterized in that described flyash and strong alkali solution is 1 ~ 6mL/g, and the molal quantity that adds highly basic in described strong alkali solution is 2.6 ~ 5.0 times of aluminium molal quantity in flyash.
8. in accordance with the method for claim 1, it is characterized in that adding in described strong alkali solution the molal quantity of highly basic be in flyash aluminium molal quantity 2.8 ~ 4.0.
9. in accordance with the method for claim 1, it is characterized in that in the alkaline solution of the described siliceous and aluminium of step (1), the total concentration of silicon and aluminium is counted 120 ~ 220g/L with aluminium oxide and silica gross mass.
10. in accordance with the method for claim 1, it is characterized in that the described acid aluminium salt of step (2) is one or more in aluminum sulfate, aluminum nitrate, aluminium chloride, the concentration of described acid aluminium salt solution is 40 ~ 100g Al
2o
3/ L.
11. in accordance with the method for claim 1, it is characterized in that the described acid aluminium salt of step (2) is aluminum sulfate, and the concentration of described acid aluminium salt solution is 50 ~ 80g Al
2o
3/ L.
12. in accordance with the method for claim 1, it is characterized in that 60 ~ 90 ℃ of step (3) control plastic temperature, and plastic pH value is 7.5 ~ 9.5.
13. in accordance with the method for claim 1, it is characterized in that it is 30 ~ 80 minutes that step (3) is controlled gelation time.
14. in accordance with the method for claim 1, and after it is characterized in that the reaction of step (3) plastic finishes, through overaging, described aging condition is as follows: aging temperature is 50 ℃ ~ 95 ℃, and ageing time is 10 ~ 90 minutes.
15. in accordance with the method for claim 1, it is characterized in that the drying condition that step (4) is described: 100 ~ 150 ℃ are dried 2 ~ 6 hours.
16. in accordance with the method for claim 1, it is characterized in that the dry glue of silicon-containing alumina of gained was through 500 ~ 950 ℃ of roastings 2 ~ 6 hours, and in gained silicon-containing alumina, the content of silica is 1wt% ~ 50wt%.
17. in accordance with the method for claim 1, it is characterized in that: in the alkaline solution of the siliceous and aluminium of step (1), add basic aluminate; Described basic aluminate is one or more in sodium metaaluminate, potassium metaaluminate, adds the total concentration of silicon and aluminium in the alkaline solution of the siliceous and aluminium of gained after basic aluminate to count 120 ~ 220g/L with aluminium oxide and silica gross mass.
The preparation method of 18. 1 kinds of silicon-containing aluminas, comprising: the dry glue of silicon-containing alumina prepared by claim 1 ~ 17 either method, through roasting, obtains silicon-containing alumina.
19. in accordance with the method for claim 18, it is characterized in that described roasting condition: 500 ~ 950 ℃ of roastings 2 ~ 6 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283815A1 (en) * | 1987-03-11 | 1988-09-28 | Phillips Petroleum Company | Silica-modified alumina |
| CN102029192A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283815A1 (en) * | 1987-03-11 | 1988-09-28 | Phillips Petroleum Company | Silica-modified alumina |
| CN102029192A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邬国栋等: ""低温碱溶粉煤灰中硅和铝的溶出规律研究"", 《环境科学研究》 * |
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