CN102836747A - Preparation method for alumina oxide carrier - Google Patents

Preparation method for alumina oxide carrier Download PDF

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Publication number
CN102836747A
CN102836747A CN2011101702845A CN201110170284A CN102836747A CN 102836747 A CN102836747 A CN 102836747A CN 2011101702845 A CN2011101702845 A CN 2011101702845A CN 201110170284 A CN201110170284 A CN 201110170284A CN 102836747 A CN102836747 A CN 102836747A
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pore volume
described method
drying
alumina
bore dia
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CN102836747B (en
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隋宝宽
王刚
刘文杰
吴国林
安�晟
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The present invention discloses a preparation method for an alumina carrier. The method comprises: concurrently and continuously adding an acidic aluminum salt aqueous solution and an alkaline aluminate solution; stabilizing; adding the resulting mixed solution to an ultrasonic reactor to carry out a treatment; carrying out filtering, washing and drying to obtain an alumina dry gel; and carrying out molding, drying and calcination to obtain the alumina carrier. According to the method of the present invention, the acidic aluminum salt and the alkaline aluminate are selected, co-current neutralization gel forming is adopted, and a suitable ultrasonic treatment is performed, such that molecule resonance can be generated when the frequency is close to the natural frequency of the aluminum hydroxide particles, the amplitude of molecule vibration is greatly increased, agglomeration of the aluminum hydroxide particles in a growth process due to slow mechanical stirring is avoided, heat generated by mutual vibration of the aluminum hydroxide particles is more uniform than external heating so as to easily achieve a uniform particle size of the particles, and pore distribution of the resulting alumina carrier is centralized in 6-10 nm. In addition, the alumina carrier prepared by the method of the present invention can be used for preparation of distillate oil hydrotreating catalysts.

Description

A kind of preparation method of alumina support
Technical field
The present invention relates to a kind of preparation method of alumina support, specifically about a kind of preparation method of catalyst for hydrorefining distillate oil carrier.
Background technology
Catalyst for hydrorefining distillate oil generally has the metal or the metal oxide of hydrogenating function and forms with the carrier with certain acid function.Metal component commonly used is cobalt-molybdenum, nickel-molybdenum or nickel-tungsten, and carrier is generally aluminium oxide.In order to make alumina support be fit to the fraction oil hydrogenation refining reaction better, need carry out the character that modification comes the modulation carrier to alumina support, it is concentrated relatively especially to require carrier hole to distribute.
CN97112397.7 relates to a kind of catalyst for hydrorefining distillate oil; Consist of nickel oxide 1～5 heavy %; Tungsten oxide 12～35 heavy %; All the other are aluminium oxide; This aluminium oxide is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75:25～50:50, and to be bore dia account for the aluminium oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60～600 dust holes accounts for the aluminium oxide of total pore volume more than 70%.CN01123765.1 relates to a kind of catalyst for hydrogenation treatment of diesel oil and loads on molybdenum and/or tungsten and nickel and/or the cobalt on this carrier; Said carrier is made up of aluminium oxide and zeolite; The weight ratio of aluminium oxide and zeolite is 90:10～50:50, and said aluminium oxide is to adopt the CN97112397.7 disclosed method to be composited by little porous aluminum oxide and the macroporous aluminium oxide weight ratio according to 75:25～50:50.The alumina support that CN97112397.7 and CN01123765.1 adopted is to be composited by macroporous aluminium oxide and little porous aluminum oxide, so just makes the preparation process complicated, and causes the relatively disperse of pore size distribution of carrier, has increased the factor that influences catalyst performance.
CN03133554.3 discloses a kind of preparation method of aluminium oxide, and wherein to become the glue temperature be 10 ~ 45 ℃ and under the ultrasonic wave effect, carry out.This method is in becoming the glue process, to adopt ultrasonic Treatment; Formed aluminum hydroxide particles aggravates vibration under the ultrasonic wave effect; Consequent heat can't be taken away from the slurries system fast; It is bigger to cause into the glue temperature fluctuation, cause the alumina grain change of size bigger, thereby the pore size distribution scope is more wide in range.
Summary of the invention
To the deficiency of prior art, the invention provides the preparation method that a kind of crystal grain was evenly distributed, avoided the alumina support of particle aggregation.The alumina support pore structure of this method gained is reasonable, is applicable to the fraction oil hydrogenation refining process.
The preparation method of alumina support of the present invention comprises:
(1) in add 20～60 ℃ water purification with still;
(2) in still in add simultaneously continuously the acid aluminium salt aqueous solution and alkali aluminate soln, control pH value is 7.5～9.0, stablizes 10～60 minutes;
(3) system that step (2) is obtained places ultrasound reactor, handles 0.5～6.0 hour;
(4) filtration, washing, drying obtain alumina dry glue;
(5),, obtain alumina support through drying and roasting with the alumina dry glue kneading and compacting.
In the inventive method, as required, can in the acid aluminium salt aqueous solution, add in silicate, borate and the phosphate one or more, its addition is with SiO 2, P 2O 5And/or B 2O 3Content 0.1wt%～10.0wt% of accounting for the carrying alumina body weight be as the criterion.Said silicate is preferably sodium metasilicate, and borate is preferably Boratex, and phosphate is preferably ammonium phosphate.
Described acid aluminium salt is AlCl 3, Al 2(SO 4) 3And Al (NO 3) 3In one or more, be preferably Al 2(SO 4) 3Described basic aluminate is NaAlO 2And/or KAlO 2
The described temperature range of step (1) is 20～60 ℃, is preferably 45～55 ℃;
Step (2) is described to be stablized 10～60 minutes, was preferably 30～60 minutes;
The said pH value of step (2) scope is 7.5～9.0, is preferably 8.0～9.0;
The described ultrasonic frequency of step (3) is 200～300kHZ, is preferably 220 ~ 280 kHZ, and ultrasonic power 0.05～5.0W/ml is preferably 0.1 ~ 3.0W/ml.
The described processing time of step (3) is 0.5～6.0 hour, is preferably 2.0～4.0 hours;
The described drying condition of step (4) is: drying is 3～6 hours under 50～140 ℃.
The described drying condition of step (5) is: drying is 3～6 hours under 50～140 ℃; Described roasting condition was: 450～600 ℃ of following constant temperature 1～4 hour.Described moulding can be undertaken by conventional method, such as extruded moulding, roller forming, rotational forming etc., can also process suitable shape as required, such as clover, bunge bedstraw herb, four impellers etc.In forming process, can add shaping assistant, such as in peptizing agent, extrusion aid, the adhesive etc. one or more, those skilled in the art can adjust addition as required.Extrusion aid can be the sesbania powder, and the addition of extrusion aid is Al 2O 30.5% ~ 10.0% of the weight that feeds intake.Peptizing agent can be inorganic acid and/or organic acid, and inorganic acid is preferably nitric acid, and organic acid is preferably acetic acid, and the addition of peptizing agent is Al 2O 30.5% ~ 12.0% of the weight that feeds intake.Adhesive can be the aperture aluminium oxide, and the addition of adhesive is Al 2O 30.5% ~ 12.0% of the weight that feeds intake.
The specific area of the alumina support of gained of the present invention is 180～260m 2/ g, pore volume are 0.4～0.60ml/g, most probable aperture 8～12nm, and pore size distribution is following: the ratio that the pore volume in bore dia 2～4nm hole accounts for total pore volume is less than 5%, preferably less than 4%; The ratio that the pore volume in bore dia 4～6nm hole accounts for total pore volume is 10%～20%; The ratio that the pore volume in bore dia 6～10nm hole accounts for total pore volume is 60%～75%, preferred 65%～75%; The ratio that the pore volume in the hole that bore dia 10nm is above accounts for total pore volume is 10%～20%.
The advantage of the inventive method is: in the slurries of the method preparation that acid aluminium salt and basic aluminate adopt and stream neutralizes; Aluminum hydroxide particles is among the random motion; When selecting suitable ultrasonic wave, make itself and aluminum hydroxide particles intrinsic frequency near the time can cause and the resonance of molecule the Oscillation Amplitude of molecule is increased greatly; Avoiding crossing slowly because of mechanical agitation speed makes aluminum hydroxide particles that agglomeration take place in growth process; And the heat that aluminum hydroxide particles vibrates generation each other is more even than outer heating, and it is even to help particle size, and the pore distribution concentration that makes alumina support is at 6-10nm.
It is simple that the present invention prepares process, only needs the adjustment operating condition, need not adopt two kinds of aluminium oxide allotments can make the catalyst for hydrorefining distillate oil carrier.
The prepared alumina support of the inventive method can be used for the Hydrobon catalyst that boiling range is 80～550 ℃ a fraction oil of petroleum.
The specific embodiment
In the preparation process of alumina support of the present invention, in the described acid aluminium salt aqueous solution, Al 2O 3Concentration is 2～10g/100ml; In the described basic aluminate aqueous solution, Al 2O 3Concentration is 8～30g/100ml.
Among the present invention, specific area and pore structure adopt the low temperature liquid nitrogen absorption method to test.
The preparation method of catalyst carrier of the present invention further specifies 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 the aqueous solution (Al of 3L aluminum sulfate 2O 3Concentration is 2g/100mL) be respectively charged in the container of high level, connect the flowmeter inflow down and be equipped with in the rustless steel container of 6L water purification belt stirrer and heating jacket, be heated to 50 ℃; And continuous aluminum sulfate solution and the sodium aluminate solution of adding of stream, make the pH value rise to 8.5, stablized 50 minutes; And after the stream end, it is inserted in the ultrasound reactor, ultrasonic frequency is 240kHZ, ultrasonic power 0.13W/ml handled after 2.0 hours, isolated by filtration mother liquor, washing.Drying is 3 hours under 100 ℃ of temperature, and moulding is warming up to 500 ℃ with 180 ℃/speed at one hour rating again, and constant temperature 3 hours gets sample A, and its physical property data is seen table 1.
Embodiment 2
With the 2L sodium metaaluminate aqueous solution (Al 2O 3Concentration is 15g/100mL) and the aqueous solution (Al of 3L aluminum sulfate 2O 3Concentration is 2g/100mL) be respectively charged in the container of high level, connect the flowmeter inflow down and be equipped with in the rustless steel container of 6L water purification belt stirrer and heating jacket, be heated to 40 ℃; And continuous aluminum sulfate solution and the sodium aluminate solution of adding of stream, make the pH value rise to 8.0, stablized 60 minutes; And after the stream end, it is inserted in the ultrasound reactor, ultrasonic frequency is 270kHZ, ultrasonic power 0.20W/ml handled after 4 hours, isolated by filtration mother liquor, washing.Drying is 3 hours under 120 ℃ of temperature, and moulding is warming up to 480 ℃ with 180 ℃/speed at one hour rating again, and constant temperature 4 hours gets sample B, and its physical property data is seen table 1.
Comparative example 1
Become sonicated in the glue process according to the CN03133554.3 method, specific as follows: with the 2L sodium metaaluminate aqueous solution (Al 2O 3Concentration is 15g/100mL) and the aqueous solution (Al of 3L aluminum sulfate 2O 3Concentration is 2g/100mL) be respectively charged in the container of high level, connect the flowmeter inflow down and be equipped with in the rustless steel container of 6L water purification belt stirrer and heating jacket, be heated to 40 ℃; And continuous aluminum sulfate solution and the sodium aluminate solution of adding of stream, make the pH value rise to 8.5, stablized 50 minutes; Become in the glue process, adopt ultrasonic Treatment, ultrasonic frequency is 25kHZ, and ultrasonic power 0.03W/ml handled after 2.0 hours, isolated by filtration mother liquor, washing.Drying is 3 hours under 100 ℃ of temperature, and moulding is warming up to 500 ℃ with 180 ℃/speed at one hour rating again, and constant temperature 3 hours gets catalyst carrier C, and its physical property data is seen table 1.
Table 1 catalyst carrier physical property
Catalyst carrier A B C
Specific area, m 2/g 250 230 270
Pore volume, mL/g 0.52 0.50 0.48
Pore size distribution, % ? ? ?
2～4nm 3.4 3.0 13.6
4～6nm 15.0 10.0 25.6
6～10nm 69.0 72.0 40.2
＞10nm 12.6 15.0 20.6
By finding out in the table 1; Carrier hole distribution 6 ~ 10nm according to the present invention's preparation accounts for about 70% of total pore volume; And prepare relatively disperse of carrier hole distribution according to the CN03133554.3 method; 6 ~ 10nm only accounts for 40.2% of total pore volume, so according to the catalyst carrier pore distribution concentration of this method preparation.

Claims (13)

1. the preparation method of an alumina support comprises:
(1) in add 20～60 ℃ water purification with still;
(2) in still in add simultaneously continuously the acid aluminium salt aqueous solution and alkali aluminate soln, control pH value is 7.5～9.0, stablizes 10～60 minutes;
(3) system that step (2) is obtained places ultrasound reactor, handles 0.5～6.0 hour;
(4) filtration, washing, drying obtain alumina dry glue;
(5),, obtain alumina support through drying and roasting with the alumina dry glue kneading and compacting.
2. according to the described method of claim 1, it is characterized in that in the acid aluminium salt aqueous solution, adding in silicate, borate and the phosphate one or more, its addition is with SiO 2, P 2O 5And/or B 2O 3Content 0.1wt%～10.0wt% of accounting for the carrying alumina body weight be as the criterion.
3. according to the described method of claim 2, it is characterized in that said silicate is sodium metasilicate, borate is a Boratex, and phosphate is ammonium phosphate.
4. according to the described method of claim 1, it is characterized in that described acid aluminium salt is AlCl 3, Al 2(SO 4) 3And Al (NO 3) 3In one or more; Described basic aluminate is NaAlO 2And/or KAlO 2
5. according to the described method of claim 1, it is characterized in that the described temperature of step (1) is 45～55 ℃.
6. according to the described method of claim 1, it is characterized in that the described pH value of step (2) is 8.0～9.0, be 30～60 minutes stabilization time.
7. according to the described method of claim 1, it is characterized in that the described frequency of ultrasonic of step (3) is 200～300kHZ, hyperacoustic power 0.05～5.0W/ml.
8. according to the described method of claim 1, it is characterized in that the described frequency of ultrasonic of step (3) is 220 ~ 280 kHZ, hyperacoustic power 0.1 ~ 3.0W/ml.
9. according to the described method of claim 1, it is characterized in that the described ultrasonic treatment time of step (3) is 2.0～4.0 hours.
10. according to the described method of claim 1, it is characterized in that the described drying condition of step (4) is: drying is 3～6 hours under 50～140 ℃.
11. according to the described method of claim 1, it is characterized in that the described drying condition of step (5) is: drying is 3～6 hours under 50～140 ℃; Described roasting condition was: 450～600 ℃ of following constant temperature 1～4 hour.
12. according to the described method of claim 1, it is characterized in that step (5) in forming process, add shaping assistant.
13. the alumina support of the arbitrary method gained of claim 1 ~ 12, its character is following: specific area is 180～260m 2/ g, pore volume are 0.4～0.60ml/g, most probable bore dia 8～12nm, and pore size distribution is following: the ratio that the pore volume in bore dia 2～4nm hole accounts for total pore volume is less than 5%; The ratio that the pore volume in bore dia 4～6nm hole accounts for total pore volume is 10%～20%; The ratio that the pore volume in bore dia 6～10nm hole accounts for total pore volume is 60%～75%; The ratio that the pore volume in the hole that bore dia 10nm is above accounts for total pore volume is 10%～20%.
CN201110170284.5A 2011-06-23 2011-06-23 Preparation method for alumina oxide carrier Active CN102836747B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549537A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Preparation method for heavy oil hydrogenation catalyst carrier
CN104549538A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Method for preparing amorphous silica-alumina supporter
CN104549540A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Preparation method of macroporous amorphous silica-alumina carrier
CN106946279A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 A kind of aluminium hydroxide and preparation method thereof
CN114057211A (en) * 2020-07-27 2022-02-18 中国石油化工股份有限公司 Preparation method of aluminum oxide material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765748A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Gama-Al2O3 preparation method
CN1768948A (en) * 2004-10-29 2006-05-10 中国石油化工股份有限公司 Method for preparing alumina supporter

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1765748A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Gama-Al2O3 preparation method
CN1768948A (en) * 2004-10-29 2006-05-10 中国石油化工股份有限公司 Method for preparing alumina supporter

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549537A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Preparation method for heavy oil hydrogenation catalyst carrier
CN104549538A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Method for preparing amorphous silica-alumina supporter
CN104549540A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Preparation method of macroporous amorphous silica-alumina carrier
CN104549537B (en) * 2013-10-23 2017-01-18 中国石油化工股份有限公司 Preparation method for heavy oil hydrogenation catalyst carrier
CN104549540B (en) * 2013-10-23 2017-07-14 中国石油化工股份有限公司 A kind of preparation method of macropore amorphous silicon alumina supporter
CN104549538B (en) * 2013-10-23 2017-07-14 中国石油化工股份有限公司 A kind of preparation method of amorphous silicon alumina supporter
CN106946279A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 A kind of aluminium hydroxide and preparation method thereof
CN114057211A (en) * 2020-07-27 2022-02-18 中国石油化工股份有限公司 Preparation method of aluminum oxide material
CN114057211B (en) * 2020-07-27 2023-07-28 中国石油化工股份有限公司 Preparation method of alumina material

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