CN100496707C - Process of preparing alumina carrier - Google Patents
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- CN100496707C CN100496707C CNB2006100469221A CN200610046922A CN100496707C CN 100496707 C CN100496707 C CN 100496707C CN B2006100469221 A CNB2006100469221 A CN B2006100469221A CN 200610046922 A CN200610046922 A CN 200610046922A CN 100496707 C CN100496707 C CN 100496707C
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 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 34
- 230000032683 aging Effects 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 150000004645 aluminates Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000000243 solution Substances 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- -1 alkali metal aluminate Chemical class 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 2
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims 1
- 238000001879 gelation Methods 0.000 claims 1
- 235000010339 sodium tetraborate Nutrition 0.000 claims 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 24
- 239000003921 oil Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000000295 fuel oil Substances 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 11
- 159000000013 aluminium salts Chemical class 0.000 description 11
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 11
- 239000002002 slurry Substances 0.000 description 6
- 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 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明涉及一种氧化铝载体的制备方法，包括酸性铝盐与碱性铝酸盐并流中和和摆动中和过程，中和物料老化，然后过滤、洗涤、成型、干燥和焙烧，得到氧化铝载体。制备过程中老化在高于中和温度和高于中和pH值的条件下进行的。本发明方法不需改变现有氧化铝载体制备流程，只需调整中和及老化过程的工艺条件，制备过程简单。本发明方法制备的氧化铝载体孔径大，孔容大，可以用于重、渣油加氢处理催化剂，特别适用于渣油加氢脱金属催化剂和脱硫催化剂。The invention relates to a preparation method of an alumina carrier, which comprises the co-current neutralization and swing neutralization process of an acidic aluminum salt and an alkaline aluminate, aging of the neutralized material, and then filtering, washing, molding, drying and roasting to obtain an oxidized Aluminum carrier. The aging in the preparation process is carried out under the conditions higher than the neutralization temperature and higher than the neutralization pH value. The method of the invention does not need to change the existing preparation process of the alumina carrier, only needs to adjust the technological conditions of the neutralization and aging process, and the preparation process is simple. The aluminum oxide carrier prepared by the method of the invention has large pore diameter and large pore volume, and can be used as a catalyst for hydrogenation of heavy oil and residual oil, and is especially suitable for a catalyst for hydrodemetallization and desulfurization of residual oil.
Description
Technical field
The present invention relates to a kind of alumina support or contain the preparation method of small amounts silicon (diboron trioxide or phosphorus pentoxide) alumina support.
Background technology
Catalyst carrier character such as surface area, aperture play an important role to activity of such catalysts stability.Concerning heavy distillate especially residual oil, metal impurities (as Ni, V etc.) content height.If the aperture of catalyst carrier little (less than 15nm) just causes the aperture of catalyst little, cause heavy distillate especially the metal impurities in the residual oil be deposited near the catalyst aperture, the blocking catalyst aperture reduces catalyst activity reduction, stability.If the average pore size of catalyst carrier is excessive, then Zhi Bei catalyst strength is low, and abrasion are high.Therefore, the heavy distillate especially suitable average pore size of residual oil catalyst for demetalation carrier is 15～30nm, and the most probable aperture is 15～30nm.Pore volume wants big in addition, and because of pore volume is big, the metal of deposition is many, and the catalyst activity good stability generally requires the carrier specific surface to be not more than 200m
2G
-1
Physics expanding agents such as usefulness such as US4448896, US4102822 carbon black, starch enlarge the aperture of alumina support, but pore size distribution is concentrated, and intensity is relatively poor.CN 1209355A proposes a kind of macropore alumina supporter and preparation method thereof, be higher than under the condition of room temperature, the boehmite raw material is carried out peptization or slaking, material after the moulding is handled with the compound that contains ammonium ion, the pore volume that makes the carrier hole diameter and be 10～20nm accounts for 70～85% of total pore volume, and its processing procedure is complicated.
CN1164563A, US4562059 etc. disclose the preparation method that a kind of swing method prepares catalyst carrier for hydrgenating.This method needs swing repeatedly in preparation carrier process, comparatively loaded down with trivial details, in industrial very difficult realization.
CN1141821A discloses a kind of preparation method of catalyst carrier for hydrgenating.Its neutralization is carried out under the same conditions with aging, and the catalyst carrier hole of preparation mainly concentrates in 7～12nm scope, and particularly the catalyst for hydrotreatment of residual oil carrier is not too suitable as heavy distillate.
CN1184078A discloses a kind of preparation method of catalyst carrier for hydrgenating.This method and stream become the pH value of glue identical with the swing endpoint pH, and aging condition is identical with one-tenth adhesive tape part, is unfavorable for growing up of aluminum hydroxide grain.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method for preparing large aperture and large pore volume alumina support simply, efficiently.
The preparation method of alumina support of the present invention is:
(1) adds end water in and in the still and be heated to 50～95 ℃, add the acid aluminium salt aqueous solution simultaneously, make the pH value be controlled at 2～4, stablize a period of time;
(2) in and add simultaneously continuously the acid aluminium salt aqueous solution and alkali metal aluminate (or alkaline precipitating agent) solution in the still, adjust pH is 6～8, stablizes a period of time;
(3) feed alkali metal aluminate solution (or alkaline sedimentation agent solution), a period of time is stablized in adjust pH to 8.5～12;
(4) feed the acid aluminium salt aqueous solution, a period of time is stablized in adjust pH to 2～4;
(5) feed the alkali aluminate soln or the alkaline precipitating agent aqueous solution, a period of time is stablized in adjust pH to 8.5～12;
(6) repeat 1～4 time step (4) and (5);
(7) after the cemented into bundles, in being higher than neutral temperature and being higher than and under the condition of pH value, wear out, after filtration, washing, drying, moulding and roasting obtain alumina support; Wherein aging temperature is higher than 10 ℃～100 ℃ of neutral temperatures, during aging pH value is higher than with pH value 0.2～4.0.
Add silicate, borate, phosphate solution or their mixed solution when needing in (1) the acid aluminium salt aqueous solution in step, addition is with SiO
2, P
2O
5Or B
2O
3Content account for carrier 0.1～5.0wt% and be as the criterion.Described silicate solutions is the suitableeest to be sodium silicate solution, and borate solution is the suitableeest to be dobell's solution, and phosphate solution is the suitableeest to be ammonium phosphate solution.
The described acid aluminium salt aqueous solution is meant AlCl
3, Al
2(SO
4)
3Or Al (NO
3)
3Solution, the suitableeest is Al
2(SO
4)
3Solution; Described alkali metal aluminate refers to NaAlO
2Or KAlO
2Solution; Described alkaline precipitating agent is meant NaOH, (NH
4)
2CO
3Or NH
4OH solution, the suitableeest is NH
4OH or (NH
4)
2CO
3Solution.
The described temperature range of step (1) is 50～95 ℃, and suitable is 55～75 ℃, and the suitableeest is 60～70 ℃; Described pH value is 2.0～4.0, and suitable is 3～4, and the suitableeest is 3.0～3.5; Be 3～10 minutes described stabilization time.The described pH value of step (2) scope is 6.0～8.0, and suitable is 6.5～7.5, and the suitableeest is 7.0～7.5; Described time range is 10～60 minutes, and suitable is 10～30 minutes, and the suitableeest is 10～25 minutes.The described pH value of step (3) scope is 8.5～12, and suitable is 9～10, and the suitableeest is 9.0～9.7; Described time range is 5～20 minutes, and suitable is 5～15 minutes, and the suitableeest is 5～10 minutes.The described pH value of step (4) scope is 2.0～4.0, and suitable is 3～4, and the suitableeest is 3.0～3.5; Described time range is 3～30 minutes, and suitable is 5～15 minutes, and the suitableeest is 5～10 minutes.The described pH value of step (5) scope is 8.5～12, and suitable is 9～10, and the suitableeest is 9.0～9.7; Described time range is 3～30 minutes, and suitable is 5～15 minutes, and the suitableeest is 5～10 minutes.
The described repetition number of oscillations of step (6) is 1～4 time, and suitable is 2～4 times, and the suitableeest is 2～3 times.
The described aging temperature scope of step (7) is 85～150 ℃, and suitable is 90～140 ℃, and the suitableeest is 100～120 ℃; Aging pH value scope is 8.0～10.0, and suitable is 8.5～9.7, and the suitableeest is 9.0～9.6.Ageing time is 0.1～2 hour, and suitable 0.1～1 hour, the suitableeest was 0.1～0.5 hour.Described drying condition is: drying is 3～10 hours under 50～140 ℃; Described roasting condition was: 700～950 ℃ of following constant temperature 1～4 hour.Aging temperature generally is higher than 10 ℃～100 ℃ of neutral temperatures, preferred 20 ℃～80 ℃, during aging pH value is higher than with pH value 0.2～4.0, preferred 1.5～2.5.Neutral temperature described here and in and pH value refer at stream also and be neutralized into the temperature and the pH value of glue process.
Zhi Bei alumina support has bigger aperture, suitable specific surface and bigger pore volume as stated above, and the most probable aperture is 18～25nm; Surface area is 80～180m
2/ g is preferably 120～170m
2/ g; Pore volume is 0.80～1.1ml/g, and preferably pore volume is 0.90～1.0ml/g.
Preparation of aluminium hydroxide process of the present invention is actual to be the process of cocurrent process and swing method combination.This method combines cocurrent process and swing method advantage separately, and its swing alkali side pH value is higher than and flows the pH value that neutralizes, and aging temperature and pH value are higher than and are neutralized into glue temperature and pH value, and help crystal grain and develop to augment direction, thus hole diameter enlargement.
Carrying alumina preparation of the present invention adopts earlier and the swing neutralization of stream neutralization back, carries out burin-in process simultaneously under higher temperature and pH value, and the material that obtains can obtain the alumina support of larger aperture after moulding, roasting.Preparation process of the present invention is simple, only needs to adjust operating condition, need not change existing preparation process, can make large aperture large pore volume alumina support.Alumina support of the present invention (or contains a small amount of SiO
2, P
2O
5Or B
2O
3) carrier, can be used as carrier of hydrogenating catalyst, be specially adapted to the carrier of catalyst for hydrotreatment of residual oil.
The specific embodiment
Preparing the alumina support detailed process by the present invention may further comprise the steps:
A) the preparation acid aluminium salt aqueous solution, Al
2O
3Concentration is 2～10g/100ml;
B) the preparation basic aluminate aqueous solution, Al
2O
3Concentration is 8～30g/100ml, or the preparation dilute ammonia solution, NH
3Content is 8～16g/100ml;
C) add a certain amount of acid aluminium salt aqueous solution in neutralization end water, make its pH value reduce to 2.0～4.0, suitable is 3～4, and the suitableeest is 3.0～3.5, and solution temperature is 50～95 ℃, and suitable is 55～75 ℃, and the suitableeest is 60～70 ℃; Stop to add acid aluminium salt solution, stablized 3～10 minutes;
D) the acid aluminium salt aqueous solution and the basic aluminate aqueous solution join continuously in the step (b) simultaneously and neutralize, in and pH be 6.0～8.0, suitable is 6.5～7.5, the suitableeest is 7.0～7.5; In and time range be 10～30 minutes, suitable is 15～30 minutes, the suitableeest is 15～25 minutes; In and slurries Al
2O
3Content 5～10wt%;
E) stop to add the acid aluminium salt aqueous solution, continue again to feed basic aluminate (or alkaline precipitating agent) solution, make the pH value rise to 8.5～12, suitable is 9～10, and the suitableeest is 9.0～9.7, and stabilization time, scope was 5～20 minutes, suitable is 5～15 minutes, and the suitableeest is 5～10 minutes;
F) feed the acid aluminium salt aqueous solution, make the pH value reduce to 2.0～4.0, suitable is 3～4, and the suitableeest is 3.0～3.5, and stabilization time, scope was 3～10 minutes;
G) feed basic aluminate (or alkaline precipitating agent) solution, make the pH value rise to 8.5～12, suitable is 9～10, and the suitableeest is 9.0～9.7.Stabilization time, scope was 5～20 minutes, and suitable is 5～15 minutes, and the suitableeest is 5～10 minutes;
H) at 85～150 ℃, suitable 90～140 ℃, the suitableeest is 100～120 ℃; PH is 8.0～10.0, fits 8.5～9.7, and the suitableeest is 9.0～9.6; 0.1～2 hour time, suitable 0.1～1 hour, the suitableeest was to wear out under the condition in 0.1～0.5 hour;
In a), add silicate, borate, phosphate or its mixture solution when i) needing;
J) filter, wash;
K) under 50～140 ℃ of temperature dry 3～10 hours;
L) moulding.
M) rise to 700～950 ℃ with 200～300 ℃ of/hour programming rates, preferred 800～900 ℃ of following constant temperature calcinings 1～4 hour promptly make alumina support of the present invention.
Large aperture of the present invention, large pore volume aluminium oxide (or contain a small amount of SiO
2, B
2O
3Or P
2O
5) preparation method of carrier, further specify with following embodiment, but these embodiment can not limit the present invention.
Embodiment 1
With the 2L sodium metaaluminate aqueous solution (Al
2O
3Concentration is 15g/100ml) and 3L aluminum sulfate aqueous solution (Al
2O
3Concentration is 4g/100ml) be respectively charged in the container of high level, connect down in the rustless steel container that flowmeter flows into belt stirrer that the 6L water purification is housed and heating jacket, be heated to 70 ℃; Under stirring state, add aluminum sulfate solution, make slurry pH value reduce to 3.5, stablize 5 minutes after, two kinds of materials are added in the stainless cylinder of steel simultaneously by certain speed, keeping pH is 7.2, in and 15 minutes.In and a period of time after, stop to add aluminum sulfate solution, make the pH value rise to 9, stop to add sodium aluminate solution, stablize a period of time; Feed aluminum sulfate solution, make the pH value reduce to 3, stablize a period of time; Feed sodium aluminate solution, make the pH value rise to 9.Repeat to swing 3 times.Swing is used NH after finishing
4OH adjusting slurry pH value is 9.6, in closed container slurry temperature is risen to 110 ℃, and is aging after 0.1 hour, isolated by filtration mother liquor, washing.Drying is 3 hours under 140 ℃ of temperature, and moulding is warming up to 800 ℃ with 200 ℃/speed at one hour rating again, and constant temperature calcining 4 hours gets sample 1.
Embodiment 2
Compare with embodiment 1, swing pH value of solution value becomes 3 by 9 and becomes 9 process again and repeat 2 times, and the unclassified stores consumption is identical with embodiment 1 with operating condition, must sample 2.
Embodiment 3
Compare with embodiment 1, aging temperature rises to 120 ℃, and the unclassified stores consumption is identical with embodiment 1 with operating condition, gets sample 3.
Embodiment 4
Compare with embodiment 1, use NaAlO
2Regulating slurry pH value is 10.0, and aging temperature is 150 ℃, and ageing time is 0.3 hour, obtains sample 4.
Embodiment 5
Compare with embodiment 1, swing pH value of solution value becomes 3 by 9 and becomes 9 process again and repeat 3 times, uses NH
4It is 10.5 that OH solution is regulated slurry pH value, and aging temperature is 90 ℃, and ageing time is 1.0 hours.Get sample 5.
Embodiment 6
Prepare alumina support according to embodiment 1 described method, institute's 200ml sodium silicate aqueous solution that is not both adds in the aluminum sulfate aqueous solution, gets sample 6.
Comparative Examples 1
Prepare catalyst carrier according to the CN1184078A disclosed method, swing process control pH value is 10 and 11.5, swings 5 times, gets sample 7.
Comparative Examples 2
Prepare catalyst carrier according to the CN1184078A disclosed method, swing process control pH value is 2.5 and 10, swings 5 times, gets sample 8.
The physico-chemical property data of above-mentioned sample are listed in table 1.
The physico-chemical property of table 1 alumina support
By above result as can be seen, greater than comparative example, carrier aperture and pore volume are all greater than the carrier of comparative example preparation by the grain size of the aluminium oxide of the inventive method preparation.Explanation can be satisfied the especially requirement of residuum hydrogenating and metal-eliminating catalyst and desulphurization catalyst of mink cell focus well by the aluminium oxide of the inventive method preparation or the alumina support that contains small amounts silicon.
Claims (8)
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|---|---|---|---|
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|---|---|---|---|
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| CN100496707C true CN100496707C (en) | 2009-06-10 |
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|---|---|---|---|---|
| CN101468322B (en) * | 2007-12-27 | 2010-12-01 | 中国石油化工股份有限公司 | A kind of alumina carrier and preparation method thereof |
| CN101492612B (en) * | 2008-01-23 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst and its producing process |
| CN101745400B (en) * | 2008-12-17 | 2012-07-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| SG174897A1 (en) | 2009-03-23 | 2011-11-28 | Jx Nippon Oil & Energy Corp | Hydrotreating catalyst, process for producing same, and process for hydrotreating hydrocarbon oil |
| CN102029192B (en) * | 2009-09-28 | 2013-01-09 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
| CN102259033B (en) * | 2010-05-24 | 2013-11-06 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
| CN102309994B (en) * | 2010-07-07 | 2013-04-10 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102910656B (en) * | 2011-08-01 | 2014-07-23 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite and porous alumina |
| CN103043694B (en) * | 2011-10-17 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of hydrated alumina |
| CN103769126B (en) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| TWI666310B (en) * | 2013-03-15 | 2019-07-21 | Advanced Refining Technologies Llc | Catalyst compositions, process for hydrotreating heavy hydrocarbon fractions, and process of preparing precipitated alumina compositions |
| EP3050624B1 (en) | 2013-09-27 | 2019-05-01 | Cosmo Oil Co., Ltd. | Hydrogenation treatment catalyst for heavy hydrocarbon oil, and method for hydrogenation treatment of heavy hydrocarbon oil |
| CN111099646B (en) * | 2018-10-26 | 2022-11-22 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
| CN111001424A (en) * | 2019-11-27 | 2020-04-14 | 浙江石油化工有限公司 | Phosphorus-containing residual oil hydrotreating catalyst and preparation method thereof |
| CN114057213B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN116440886B (en) * | 2022-01-06 | 2024-10-15 | 中国石油化工股份有限公司 | Macroporous modified alumina and its production process |
| CN116474840B (en) * | 2022-01-13 | 2025-04-08 | 中国石油化工股份有限公司 | Spherical silicon-aluminum carrier and preparation method thereof |
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