CN1393288A - Process for preparing alumina carrier - Google Patents
Process for preparing alumina carrier Download PDFInfo
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- CN1393288A CN1393288A CN 01114159 CN01114159A CN1393288A CN 1393288 A CN1393288 A CN 1393288A CN 01114159 CN01114159 CN 01114159 CN 01114159 A CN01114159 A CN 01114159A CN 1393288 A CN1393288 A CN 1393288A
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- alumina support
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- aluminium oxide
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Abstract
An alumina carrier for hydrocatalyst is prepared from the weakly acidic peptizing agent through adding monohydrated alumina in several times while adding alcohol compounds for increasing pore volume of the carrier. It features theta-Al2O3 structure, high pore volume (0.925-0.955 ml/g) and high specific surface area (100-240 sq.m/g) and (150-240 sq.m/g preferably).
Description
The present invention relates to the preparation method of alumina support, in particular for the carrying alumina preparation of hydrotreating catalyst.
Now, it is heavy that world's crude oil becomes gradually, and market increases comparatively fast the light-end products demand, and the deep processing of mink cell focus and utilization are worldwide especially paid attention to.One of key of heavy Oil Hydrotreating Processes is to develop the catalyst of excellent performance.Its performance not only depends on the chemical state of kind, content and the active specy of reactive metal, and it is closely related with the pore structure of catalyst base, for heavy oil hydrogenation demetal, desulfurization, having large pore volume is that catalyst keeps long-life important assurance.
U.S. Pat 5215955 discloses a kind of preparation method of alumina support, and the key step of preparation alumina support is: mix a water aluminium oxide (1) with water miscible acid, the pH value is in the 3.0-4.5 scope; (2) with sour with part in the nitrogenous aqueous slkali, the alkali number of adding is 0.6-1.0 a times of acid equivalent; (3) moulding; (4) 120 ℃ of dryings 2 hours, 200 ℃ of dryings 4 hours; (5) under being 800 ℃ condition, temperature carries out roasting.
The problem that the alumina support for preparing by above-mentioned open method exists is that the acid strength of inorganic acids such as (1) nitric acid is very strong, is easy to the pore structure of aluminium oxide sulfuric monohydrate is constituted destruction; (2) Zhi Bei carrier because alumina carrier surface crust phenomenon causes a part of duct to subside, thereby reduces the carrier pore volume in dry and roasting process.
The preparation method and the prepared product thereof that the purpose of this invention is to provide a kind of alumina support of pore volume increase.
The main points of the inventive method are: (1) will be contained water-soluble aqueous acid earlier and mix with volatile ammonium salt alkaline aqueous solution fully, the pH value of solution is reached between 5.0～6.5, then with account for whole aluminium oxide sulfuric monohydrate weight 30%-70%, preferably the partial oxidation aluminium sulfuric monohydrate of 40%-60% mixes, the pH value is reached more than 7.0, better be more than 8.0, preferably 8.1～8.5.Constant temperature is 0.5～1.5 hour after being heated to 100 ℃～150 ℃.And then add remainder aluminium oxide sulfuric monohydrate, mix and pinch into plastic; (2) moulding; (3) drying; (4) be at least calcination process under 800 ℃ the condition in temperature.
In described (1) step, also to add feed intake 0.5%～3.0% alcohol compound of weight of whole butt aluminium oxide, adding when described alcohol compound can be at partial oxidation aluminium and the water-soluble acid aqueous solution and the volatile ammonium salt alkaline aqueous solution mixes fully, but preferably add simultaneously when remaining aluminium oxide.
It is described that to contain water-soluble aqueous acid generally be nitric acid, formic acid etc., and described can complete volatile ammonium salt alkaline aqueous solution generally be ammonium carbonate, the alkaline aqueous solution of carbonic hydroammonium etc., described alcohol compound generally are ethanol, propyl alcohol, butanols etc.
Described aqueous acid consumption is generally 200-1400ml/kg aluminium oxide sulfuric monohydrate total amount, 550ml～800ml/kg aluminium oxide sulfuric monohydrate total amount preferably, acid concentration is generally 2.0g/100ml-15.0g/100ml, preferably 5.0g/100ml～9.0g/100ml.
The concentration of described ammonium salt aqueous solution generally is 2.0g/100ml-15.0g/100ml, preferably 4.0-10.0g/100ml%.
Described drying condition generally is: drying is 1～10 hour under 50～140 ℃ of temperature;
Described method of roasting is: rise to 800 ℃～1000 ℃ with 200～300 ℃/hour, constant temperature carried out roasting in 1～6 hour;
By the large pore volume alumina support of the inventive method preparation, it is characterized in that: phase structure is θ-AL
20
3Pore volume is at least 0.90ml/g, generally at 0.925～0.955ml/g; Surface area is 100～240m
2/ g is preferably 150～200m
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 boron, silicon, phosphorus, titanium etc. in the carrier of the present invention; Also can roasting in different temperature ranges, to obtain different pore size distributions and to contain the macropore alumina supporter of different adding ingredients.
Alumina support of the present invention can be used as carrier of hydrogenating catalyst, and being specially adapted to nickel removal, vanadium and desulfurization is the HDM of main purpose, the carrier of Hydrobon catalyst.
Compare with prior art (U.S. Pat 5215955), the advantage of the inventive method is:
1) do not use strong acid such as nitric acid to make peptizing agent merely.Therefore eliminated thus that the class material directly acts on the aluminium oxide sulfuric monohydrate and to the carrier hole structural damage.
2) earlier with a part of aluminium oxide sulfuric monohydrate and peptizing agent effect, make its effect complete, add remainder aluminium oxide sulfuric monohydrate again, can make like this aluminium oxide sulfuric monohydrate when mixed pinching peptizing agent structural damage is reduced to minimum degree to carrier hole;
3) owing to add alcohol compound, reduced aluminium oxide sulfuric monohydrate interfacial tension, in carrier drying and roasting process, carrier inside moisture been has in time has been scattered and disappeared, avoided interfacial tension excessive and cause a part of duct to subside, the pore volume of carrier is reduced.
Below further specify the preparation method of alumina support of the present invention with example.
Example 1
The acidic aqueous solution that 600ml is contained 50g nitric acid join 700ml contain mix in the alkaline solution of 30g ammonium carbonate after, join together in the aluminium oxide sulfuric monohydrate dry glue powder of 500g.Mixed 25 minutes, and heated to 100 ℃, constant temperature time is after 1.5 hours, mixed 30 minutes, and then, mix to pinch making material become plastic to aluminium oxide sulfuric monohydrate dry glue powder that wherein adds 600g and 15g butanols, be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter.After extrusion finished, 130 ℃ of dryings 5 hours, the speed with 280 ℃/hour rose to 800 ℃ under air atmosphere then, and constant temperature calcining 6 hours obtains alumina support A.
Example 2
The acidic aqueous solution that 620ml is contained 45g acetate joins 670ml and contains in the alkaline solution of 35g ammonium acetate, joins to take by weighing in the 400g aluminium oxide sulfuric monohydrate dry glue powder, mixes 20 minutes, heats to 120 ℃, and constant temperature time is 1.0 hours.Mixed 30 minutes, and added aluminium oxide sulfuric monohydrate dry glue powder and the 20g isopropyl alcohol of 600g again, make material blend together plastic.Be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter then.After extrusion finishes, 75 ℃ of dryings 3 hours, 105 ℃ of dryings 6 hours.Speed with 230 ℃/hour rises to 900 ℃ under air atmosphere then, and constant temperature calcining 1.5 hours obtains alumina support B.
Example 3
The acidic aqueous solution that 550ml is contained 49g formic acid joins 600ml and contains in the alkaline solution of 40g ammonium carbonate and mix, and joins in the aluminium oxide sulfuric monohydrate dry glue powder that takes by weighing 300g.Mixed 20 minutes, and heated to 150 ℃, the time is 0.5 hour.Mixed 30 minutes, and added aluminium oxide sulfuric monohydrate dry glue powder and the 20g ethanol of 700g again, mix to pinch making material become plastic.Be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter then.After extrusion finishes, 60 ℃ of dryings 4 hours, 90 ℃ of dryings 5 hours.Speed with 200 ℃/hour rises to 1000 ℃ under air atmosphere then, and constant temperature calcining 1 hour obtains alumina support C.
Comparative example 1
Preparation method according to catalyst carrier among the U.S. Pat 5215955 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 |
| The thing phase | ????θ-AL 2O 3 | ????θ-AL 2O 3 | ????θ-AL 2O 3 | ????θ-AL 2O 3 |
| Pore volume, ml/g | ????0.950 | ????0.930 | ????0.932 | ????0.830 |
| Specific surface, m 2/g | ????170 | ????168 | ????175 | ????173 |
By above result as can be seen, by the present invention preparation alumina support, pore volume is apparently higher than the 0.830ml/g of comparative example carrier.This shows the pore volume that adopts the inventive method can effectively improve alumina support.
Claims (9)
1, a kind of preparation method of alumina support, comprise that (1) will contain water-soluble aqueous acid earlier and mix with volatile ammonium salt alkaline aqueous solution fully, the pH value of solution is reached between 5.0～6.5, mix with the partial oxidation aluminium sulfuric monohydrate that accounts for required whole aluminium oxide sulfuric monohydrate weight 30%-70% then, the pH value is reached more than 7.0, be heated to 100 ℃～150 ℃ after, constant temperature 0.5～1.5 hour, add remainder aluminium oxide sulfuric monohydrate again, mix and pinch into plastic; (2) moulding; (3) drying; (4) roasting; The described amount of aqueous solution used that contains water soluble acid is the total amount of the required aluminium oxide sulfuric monohydrate of 200-1400ml/kg, and acid concentration is 2.0g/100ml-15.0g/100ml, and the concentration of described ammonium salt aqueous solution is 2.0g/100ml-15.0g/100ml.
2,, it is characterized in that in described (1) step, also will adding the feed intake alcohol compound of weight 0.5%～3.0% of whole butt aluminium oxide according to the preparation method of the described alumina support of claim 1.
3, according to the preparation method of the described alumina support of claim 1, it is characterized in that described drying condition is: drying is 1～10 hour under 50～140 ℃ of temperature.
4, according to the preparation method of the described alumina support of claim 1, it is characterized in that described method of roasting is: rise to 800 ℃～1000 ℃ with 200～300 ℃/hour, constant temperature carried out roasting in 1～6 hour.
5, according to the preparation method of the described alumina support of claim 1, it is characterized in that described aqueous acid consumption is the required aluminium oxide sulfuric monohydrate of a 550ml～800ml/kg total amount, acid concentration is 5.0g/100ml～9.0g/100ml.
6, according to the preparation method of the described alumina support of claim 1, the concentration that it is characterized in that described ammonium salt aqueous solution is 4.0-10.0g/100ml.
7,, it is characterized in that described alcohol compound adds with the residue aluminium oxide according to the preparation method of the described alumina support of claim 2.
8, the prepared carrier of preparation method of the described alumina support of a kind of claim 1, it is characterized in that: phase structure is θ-AL
2O
3Pore volume is at least 0.90ml/g, and surface area is 100～240m
2/ g.
9,, it is characterized in that described pore volume is 0.925～0.955ml/g according to the described carrier of claim 6; Surface area is 150～200m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01114159 CN1123391C (en) | 2001-07-02 | 2001-07-02 | Process for preparing alumina carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01114159 CN1123391C (en) | 2001-07-02 | 2001-07-02 | Process for preparing alumina carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393288A true CN1393288A (en) | 2003-01-29 |
| CN1123391C CN1123391C (en) | 2003-10-08 |
Family
ID=4660831
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01114159 Expired - Lifetime CN1123391C (en) | 2001-07-02 | 2001-07-02 | Process for preparing alumina carrier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431668C (en) * | 2004-05-28 | 2008-11-12 | 长春东狮科贸实业有限公司 | Hydrolyst for COS and CS2 and application thereof |
| CN100434177C (en) * | 2005-10-31 | 2008-11-19 | 中国石油化工股份有限公司 | Method for preparing carrier of alumina |
| 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 |
| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina carrier and preparation method thereof |
-
2001
- 2001-07-02 CN CN 01114159 patent/CN1123391C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431668C (en) * | 2004-05-28 | 2008-11-12 | 长春东狮科贸实业有限公司 | Hydrolyst for COS and CS2 and application thereof |
| 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 |
| CN100434177C (en) * | 2005-10-31 | 2008-11-19 | 中国石油化工股份有限公司 | Method for preparing carrier of alumina |
| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina carrier and preparation method thereof |
| CN106914279B (en) * | 2015-12-24 | 2019-07-05 | 中国石油天然气股份有限公司 | Alumina carrier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1123391C (en) | 2003-10-08 |
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Granted publication date: 20031008 |