CN1289645A - Process for preparing alumina carrier with centralized pores distribution - Google Patents
Process for preparing alumina carrier with centralized pores distribution Download PDFInfo
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- CN1289645A CN1289645A CN 99113271 CN99113271A CN1289645A CN 1289645 A CN1289645 A CN 1289645A CN 99113271 CN99113271 CN 99113271 CN 99113271 A CN99113271 A CN 99113271A CN 1289645 A CN1289645 A CN 1289645A
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Abstract
An alumina carrier with centralized pores distribution is prepared through dissolving the monohydrated alumina in weakly acidic aqueous solution of at least one organic acid, treating the acidified particular solid in alkaline aqueous solution to make pH value up to 7.5 or higher, and extruding bar at above 70 deg.C using heat generated by kneading and squeezing. Its advantages include no damage to pore structures, and no environmental pollution from nitrides and chlorides.
Description
The present invention relates to have the preparation method of the large pore volume alumina support of concentrated pore size distribution.
As everyone knows, the catalyst carrier that character is good is to obtain the key of high-performance supported type hydrotreating catalyst.For residuum hydrogenating and metal-eliminating catalyst, having large pore volume, suitable aperture and pore size distribution is that catalyst keeps high activity and long-life important assurance.
Chinese patent application 95194329.4 discloses a kind of preparation method of alumina support.The key step of preparation alumina support is the solid alumina monohydrate to be mixed to pH value with nitric acid or its equivalent example hydrochloric acid, hydrofluoric acid and hydrobromic acidic aqueous solution to reach about 3.0-4.5; Then, the ammonia alkali aqueous solution is sneaked into the granular solids of acid treatment, the granular solids alumina monohydrate handled of neutralizing acid at least in part, the common every angelic acid of ammonia alkali aqueous solution alkalinity is the about 1.1 equivalent ammonia alkalis of about 0.9-; It is also dry to be shaped through the solid of neutralization or part neutralization; The solid that has been shaped at least 871 ℃ of following calcinings of temperature.
The problem that the alumina support for preparing by above-mentioned open method exists is that the acid strength of inorganic salts such as nitric acid, hydrochloric acid is very strong, is easy to the pore structure of aluminium oxide sulfuric monohydrate is constituted destruction, causes bore dia to increase less than the aperture of 14nm thus.Another problem of this method is that nitride, chloride, fluoride or the bromide etc. that carrier produces in roasting process will produce serious pollution to environment.
The carrying alumina preparation that the purpose of this invention is to provide the non-environmental-pollution of a kind of effectively accelerating oxidation alumina supporter pore distribution concentration and pore volume increase.
The main points of the inventive method are, with alumina monohydrate with containing at least a organic acid slightly acidic water solution peptization, handle the granular solids of acidifying with containing ammoniacal liquor and at least a alkaline aqueous solution that contains complete volatile ammonium salt again, pH value is reached more than 7.5.The alkali equivalents of ammonia is more than 1.05 times of organic acid equivalents in the acidic aqueous solution in the alkaline aqueous solution, and ammonium salt weight is the feed intake 0.2-2.2m% of weight of butt aluminium oxide.Then, utilize the heat that produces in kneading and the extrusion process, extrusion under the temperature more than 70 ℃.After drying, at least 930 ℃ of following calcination process of temperature.
The concrete preparation process of the inventive method is:
1) with the alumina monohydrate dry glue powder, and contain at least a organic acid acidic aqueous solution and mix, peptization 5-15 minute, organic acid was formic acid, acetate, propionic acid preferably, also citric acid, tartaric acid, salicylic acid etc.Then, continue to mediate 0.3-1.5 hour, pH value is reached more than 7.5 with the granular solids after the alkaline aqueous solution processing acidifying that contains ammoniacal liquor and at least a volatile ammonium salt fully (as ammonium carbonate, carbonic hydroammonium, ammonium acetate etc.), best more than 8.0.Wherein the ammonia equivalents is more than 1.05 times of organic acid equivalents in the alkaline aqueous solution, and it is the feed intake 0.2-2.2m% of weight of butt aluminium oxide that ammonium salt adds weight;
2) utilize the heat of kneading process generation at 70-95 ℃ of extruded moulding;
3) at 50-100 ℃ of dry 1-10 hour, then at 105-145 ℃ of dry 1-8 hour;
4) rise to 930-1150 ℃ with 200-300 ℃/hour, constant temperature 1-6 hour.
A kind of large pore volume alumina support by the inventive method preparation, it is characterized in that: phase structure is θ-AL
2O
3Pore volume is at least 0.80-0.95ml/g; Bore dia is less than the pore volume 1-3% of 10nm, bore dia is 80-85% at the pore volume of 10-20nm, and particularly the pore volume between the 14-20nm reaches 70-80%, is preferably 75-80%, bore dia is less than 1% greater than the pore volume of 100nm, and all the other are the hole of 20-100nm; Surface area is 100-200m
2/ g.
The shape of alumina support of the present invention can change by changing mould according to different requirements.
The inorganic compound that can add elements such as boron, silicon, phosphorus, titanium, magnesium, zirconium in the carrier of the present invention; Also can roasting in different temperature ranges, to obtain pore distribution concentration in zones of different and contain the large pore volume alumina support of different adding ingredients.
Alumina support of the present invention can be used as carrier of hydrogenating catalyst, is specially adapted to the carrier that nickel removal, vanadium and desulfurization are main purpose HDM, Hydrobon catalyst.
Compare with prior art (Chinese patent application 95194329.4), the advantage of the inventive method is:
1) do not use the strong acid of nitric acid, hydrochloric acid and so on to make peptizing agent.Eliminated thus because of using this type of material the carrier hole structural damage;
2) eliminated the pollution to atmospheric environment such as the nitride that produced in the carrier roasting process, chloride.
Below further specify alumina support of the present invention and preparation method thereof with example.
Embodiment 1
Take by weighing 1470g and contain AL
2O
3The alumina monohydrate dry glue powder of 68m% is put in the kneading machine.Add 650ml while mixing and contain the acidic aqueous solution of 4g acetate, 15g citric acid, mixed ten minutes, add 670ml again and contain 20g ammoniacal liquor and (contain NH
335m%) and the alkaline solution of 6g ammonium carbonate.Because the kneading effect, temperature of charge rises to 60 ℃ gradually by room temperature, and material becomes plastic after about 40 minutes, and using F-26 (III) type twin-screw banded extruder and diameter then is 1.0mm cylindrical die extrusion.In the extrusion process, temperature of charge rises to 75 ℃ naturally by about 60 ℃ in the tube.After extrusion finishes, 60 ℃ of dryings 5 hours, 105 ℃ of dryings 6 hours.Speed with 200 ℃/hour rises to 935 ℃ under air atmosphere then, and constant temperature calcining 5 hours obtains alumina support A.
Embodiment 2
Take by weighing 1538g and contain AL
2O
3The alumina monohydrate dry glue powder of 65m% is put in the kneading machine.Add 600ml while mixing and contain the acidic aqueous solution of 45g acetate, mixed 5 minutes, add 600ml again and contain 45g ammoniacal liquor and (contain NH
335m%) and the alkaline solution of 15g ammonium acetate.Mix and pinch, in kneading process, temperature of charge rises to 62 ℃ by room temperature, and material becomes plastic after about 30 minutes, and using F-26 (III) type twin-screw banded extruder and diameter then is 1.0mm cylindrical die extrusion.In the extrusion process, temperature rises to 80 ℃ naturally by room temperature in the tube.The bar of extruding was 90 ℃ of dryings 3 hours, 105 ℃ of dryings 8 hours.In the presence of air, rise to 1080 ℃ with 260 ℃/hour speed then, constant temperature calcining 2 hours obtains alumina support B.
Embodiment 3
Take by weighing 14kg and contain AL
2O
3The alumina monohydrate dry glue powder of 71m% is put in the kneading machine.Add 7.0L while mixing and contain 50g formic acid, 50g propionic acid, 50g tartaric acid, the salicylic acidic aqueous solution of 50g, mixed 15 minutes, add 7.0L again and contain 210g ammoniacal liquor and (contain NH
335m%) and the alkaline solution of 190g ammonium carbonate.Mix and pinch, in this process, material rises to 65 ℃ naturally, and material becomes plastic after about 50 minutes, and using F-26 (III) type twin-screw banded extruder and diameter then is 1.0mm cylindrical die extrusion.In the extrusion process, temperature rises to 90 ℃ naturally by about 65 ℃ in the tube.The strip of extruding was 80 ℃ of dryings 7 hours, 105-120 ℃ of drying 4 hours.Speed with 280 ℃/hour rises to 980 ℃ in the presence of air then, and constant temperature calcining 3 hours obtains alumina support C.
Comparative example 1
Preparation method according to catalyst carrier among the Chinese patent application 95194329.4 example A makes alumina support D.
Comparative example 2
This example is the physico-chemical property contrast of embodiment alumina support and comparative example 1 carrier.
| Carrier | ????A | ????B | ????C | ????D |
| Thing phase pore volume, the ml/g pore size distribution, %＜10nm 10-14nm 14-20nm 20-100nm＞100nm most probable aperture, the nm specific area, m 2／g | ?θ-AL 2O 3?0．850 ?1．9 ?7．3 ?76．9 ?13．4 ?0．5 ?17．8 ?161 | ?θ-AL 2O 3?0．833 ?2．9 ?6．5 ?77．3 ?12．8 ?0．5 ?17．8 ?166 | ?θ-AL 2O 3?0．862 ?1．9 ?7．6 ?75．9 ?14．0 ?0．6 ?17．0 ?177 | ?θ-AL 2O 3?0．861 ?5．3 ?13．7 ?63．7 ?17．2 ?0．1 ?19．0 ?151 |
By above result as can be seen, by the alumina support of the inventive method preparation, bore dia reaches more than 80% at the pore volume between the 10-20nm, and particularly the pore volume between the 14-20nm reaches 75.9-77.3%, apparently higher than 63.7% of comparative example carrier.This shows, use strong inorganic acid as peptizing agent with the duct of heavy damage diameter as 14-20nm, and the inventive method is very effective to addressing this problem.
Claims (6)
1. the preparation method with alumina support of concentrated pore size distribution the steps include:
1) with alumina monohydrate with containing one or more organic acid slightly acidic water solution peptizations;
2) again with containing ammoniacal liquor and one or more granular solids of the alkaline aqueous solution processing acidifying of volatile ammonium salt fully, pH value is reached more than 7.5; The alkali equivalents of ammonia is more than 1.05 times of organic acid equivalents in the acidic aqueous solution in the alkaline aqueous solution, and ammonium salt weight is the feed intake 0.2-2.2m% of weight of butt aluminium oxide;
3) utilize the heat that produces in kneading and the extrusion process, extrusion under the temperature more than 70 ℃;
4) after drying, after 930 ℃ of following calcination process of temperature, get alumina support at least.
2. according to the described preparation method of claim 1, wherein said organic acid is formic acid, acetate, propionic acid, citric acid, tartaric acid or salicylic acid in the step 1).
3. according to the described preparation method of claim 1, wherein step 2) in said ammonium salt be ammonium carbonate, carbonic hydroammonium or ammonium acetate.
4. according to the described preparation method of claim 1, wherein step 2) in said Ph value be more than 8.0.
5. large pore volume alumina support according to the preparation of the described method of claim 1, it is characterized in that: phase structure is θ-AL
2O
3Pore volume is 0.80-0.95ml/g; Bore dia is 1-3% less than the pore volume of 10nm, and bore dia is 80-85% at the pore volume of 10-20nm, and particularly the pore volume between the 14-20nm reaches 70-80%, and bore dia is less than 1% greater than the pore volume of 100nm, and all the other are the hole of 20-100nm; Surface area is 100-200m
2/ g.
6. according to the described alumina support of claim 5, wherein the pore volume of 14-20nm is 75～80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113271A CN1102443C (en) | 1999-09-29 | 1999-09-29 | Process for preparing alumina carrier with centralized pores distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113271A CN1102443C (en) | 1999-09-29 | 1999-09-29 | Process for preparing alumina carrier with centralized pores distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289645A true CN1289645A (en) | 2001-04-04 |
| CN1102443C CN1102443C (en) | 2003-03-05 |
Family
ID=5276478
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113271A Expired - Lifetime CN1102443C (en) | 1999-09-29 | 1999-09-29 | Process for preparing alumina carrier with centralized pores distribution |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100496738C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
| CN100591415C (en) * | 2008-03-14 | 2010-02-24 | 厦门大学 | Preparation of active aluminum oxide carrier |
| CN104445309A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | High-purity aluminium oxide and preparation method thereof |
| CN104624247A (en) * | 2014-11-04 | 2015-05-20 | 华文蔚 | Preparation method for modified gamma-Al2O3 carrier for mechanical industry |
| CN105983400A (en) * | 2015-01-28 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of mesoporous alumina binder and application of mesoporous alumina binder in heavy oil catalytic cracking catalyst |
| CN107155324A (en) * | 2014-06-13 | 2017-09-12 | Ifp 新能源公司 | Amorphous mesoporous aluminas of distribution of pores with optimization and preparation method thereof |
| CN108262075A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Residual oil hydrotreating catalyst carrier and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2884622B2 (en) * | 1989-09-29 | 1999-04-19 | エヌオーケー株式会社 | Manufacturing method of structured catalyst support |
| CN1055877C (en) * | 1996-03-26 | 2000-08-30 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
| CN1060096C (en) * | 1996-10-15 | 2001-01-03 | 中国石油化工总公司 | Catalyst carrier and its preparing process |
| FR2764208B1 (en) * | 1997-06-10 | 1999-07-16 | Rhodia Chimie Sa | ALUMINA EXTRUDES, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS CATALYSTS OR CATALYST SUPPORTS |
-
1999
- 1999-09-29 CN CN99113271A patent/CN1102443C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100496738C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
| CN100591415C (en) * | 2008-03-14 | 2010-02-24 | 厦门大学 | Preparation of active aluminum oxide carrier |
| CN104445309A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | High-purity aluminium oxide and preparation method thereof |
| CN104445309B (en) * | 2013-09-17 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of high purity aluminium oxide and preparation method thereof |
| CN107155324A (en) * | 2014-06-13 | 2017-09-12 | Ifp 新能源公司 | Amorphous mesoporous aluminas of distribution of pores with optimization and preparation method thereof |
| CN104624247A (en) * | 2014-11-04 | 2015-05-20 | 华文蔚 | Preparation method for modified gamma-Al2O3 carrier for mechanical industry |
| CN105983400A (en) * | 2015-01-28 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of mesoporous alumina binder and application of mesoporous alumina binder in heavy oil catalytic cracking catalyst |
| CN105983400B (en) * | 2015-01-28 | 2018-07-13 | 中国石油天然气股份有限公司 | Preparation method of mesoporous alumina binder and application of mesoporous alumina binder in heavy oil catalytic cracking catalyst |
| CN108262075A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Residual oil hydrotreating catalyst carrier and preparation method thereof |
| CN108262075B (en) * | 2016-12-30 | 2020-12-01 | 中国石油天然气股份有限公司 | Residual oil hydrotreating catalyst carrier and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1102443C (en) | 2003-03-05 |
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