CN100378001C - Process for producing gama-alumina microsphere - Google Patents
Process for producing gama-alumina microsphere Download PDFInfo
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- CN100378001C CN100378001C CNB2004101554792A CN200410155479A CN100378001C CN 100378001 C CN100378001 C CN 100378001C CN B2004101554792 A CNB2004101554792 A CN B2004101554792A CN 200410155479 A CN200410155479 A CN 200410155479A CN 100378001 C CN100378001 C CN 100378001C
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- Prior art keywords
- pseudo
- boehmite
- nitric acid
- glue
- gama
- Prior art date
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- 239000004005 microsphere Substances 0.000 title claims abstract description 28
- 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 23
- 238000000034 method Methods 0.000 title description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims description 34
- 238000001879 gelation Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for producing gamma-alumina microspheres. The gamma-alumina microsphere is prepared by that pseudo-boehmite and nitric acid have a peptizing reaction to obtain colloid solution, the colloid solution is treated by centrifugal type spray-drying for forming, and then, the formed colloid solution is roasted. The method for producing gamma-alumina microspheres with pseudo-boehmite of the present invention is simple and feasible, can increase the production efficiency and the productivity, can meet the production requirements of gamma-Al2O3 microspheres of different granule sizes, and the production cost is low; the pore volume, the bulk density and the abrasion resistance of the gamma-Al2O3 microspheres can be changed by regulating the added amount of the pseudo-boehmite and the added amount of the nitric acid, the product quality is high, and the present invention is favorable for industrialized popularization and application.
Description
Technical field
The present invention relates to a kind of production method of gama-alumina microsphere, belong to the synthetic technology of preparing of compound.
Background technology
γ-Al
2O
3Microballoon is widely used in sorbent material and catalyzer industry, particularly catalyzer industry with the advantage of himself, mainly is to be applied in the fluidized-bed, so for γ-Al
2O
3Microballoon has more strict requirement, and the general aluminum oxide micro-sphere of producing is difficult to reach service requirements.
The earliest, γ-Al
2O
3Microballoon generally adopts the method for broken big ball to prepare, also there is equipment such as adopting coater to be prepared, adopt the method for broken big ball to prepare microballoon, because it is not enough that several aspects such as granularity and ball-type degree exist, caused abrasion higher, directly influenced result of use, and the rate of recovery of finished product is relatively low, present this production method has not been used basically; Though the microballoon ball-type degree of molding device preparations such as employing coater is good, but granularity is difficult to control, the general microballoon granularity of using in fluidized-bed is all below 500 μ m, and equipment such as coater are difficult to the following microballoon of prepared sizes 1mm, so this method is also less feasible.
Preparation γ-Al
2O
3Having that the method for microballoon is advanced is several, as Japanese Patent 63-17220, has introduced a kind of γ-Al
2O
3The preparation method of microballoon at first adopts sour peptization pseudo-boehmite (being false boehmite again), uses the alkali neutralizing acid then, last spray-dried moulding, roasting.Reported that in United States Patent (USP) 4301033 a kind of high heap is than low abrasion γ-Al
2O
3The preparation method of microballoon, it is two kinds of different aluminium colloidal sols of Al/Cl to be mixed prepare γ-Al
2O
3Microballoon.Chinese patent 93108631.0 has been introduced a kind of processing method for preparing aluminum oxide micro-sphere with pseudo-boehmite, its major technique feature is to utilize pseudo-boehmite in the alumina producing as raw material, employing adds the method that acid becomes glue and adds aluminium colloidal sol, utilizes spray-dired method to come the suitable aluminum oxide micro-sphere of prepared sizes again.This production technique needs to add the intensity that aluminium colloidal sol strengthens microballoon in changing the slurry process, and it is also bigger to add the acid amount, and these have all increased production cost greatly, and the microballoon pore volume of preparation is lower, influence the catalytic effect of microballoon.
Summary of the invention
The object of the present invention is to provide a kind of production method of utilizing pseudo-boehmite to produce gama-alumina microsphere, simple possible, production cost is low, can produce the γ-Al of different grain size size
2O
3Microballoon, and can improve the quality of products.
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again.
Mainly be to utilize the single raw material of pseudo-boehmite to add acid to become glue, simple possible, production cost is low, and spray drying forming can conveniently be controlled the granularity of microballoon, and particle diameter can be 10～120 microns, satisfies the specification of quality of product.
In the production method of the present invention:
The concentration of used nitric acid preferably is controlled to be 60～70%, and the add-on of nitric acid is 2～8% of a pseudo-boehmite weight, is preferably 3～5%.The nitric acid of other concentration also can,, can use to dense 98%, from 10% as rare if the volume of the rare partially adding nitric acid of concentration is just bigger, to guarantee to add enough nitric acid amounts; Need add towards rare back if concentration is higher.
The solvent and solute weight ratio that becomes glue to react is controlled to be 2～5 and suits, and is preferably 3～4.
Becoming the glue temperature is 30～100 ℃, is preferably 70～85 ℃; Gelation time is 1～8 hour, is preferably 4～6 hours.
By regulating the operational circumstances of centrifugal spray drying forming,, can satisfy γ-Al as concentration of slurry, spraying gun frequency, spray velocity, spraying size or the like
2O
3The moulding requirement of microballoon different-grain diameter size.
Maturing temperature is 500～1000 ℃, and roasting time is 1.5～3 hours, is preferably 2～3 hours.
The same routine operation of other processing condition repeats no more.
Production method gained γ-Al of the present invention
2O
3The microspheres product particle diameter is little, and pore volume is big, wears away for a short time, and heap is than high, is concrete technical indicator a pore volume 0.2? .6ml/g, particle diameter 10? 20 microns, abrasion≤3%, is the pine heap than 0.6? .85g/ml.
The present invention utilizes pseudo-boehmite to produce the production method of gama-alumina microsphere, simple possible, and production cost is low, can enhance productivity and production capacity, can satisfy different grain size size γ-Al again
2O
3The production requirement of microballoon, the addition by regulating pseudo-boehmite and add the acid amount and change γ-Al
2O
3The pore volume of microballoon, heap ratio and wear resisting property, the quality product height of production is beneficial to industrialization promotion and uses.
Description of drawings
Fig. 1, embodiment of the invention Production Flow Chart block diagram.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 65%, and the add-on of nitric acid accounts for 5% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 3;
Becoming the glue temperature is 50 ± 1 ℃, and gelation time is 4 hours;
Maturing temperature is 800 ± 10 ℃, and roasting time is 2 hours.
Embodiment 2
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 60%, and the add-on of nitric acid accounts for 8% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 4;
Becoming the glue temperature is 50 ± 1 ℃, and gelation time is 3 hours;
Maturing temperature is 600 ± 10 ℃, and roasting time is 3 hours.
Embodiment 3
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 70%, and the add-on of nitric acid accounts for 2% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 5;
Becoming the glue temperature is 60 ± 2 ℃, and gelation time is 2 hours;
Maturing temperature is 800 ± 15 ℃, and roasting time is 1.8 hours.
Embodiment 4
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 65%, and the add-on of nitric acid accounts for 6% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 3;
Becoming the glue temperature is 90 ± 1 ℃, and gelation time is 5 hours;
Maturing temperature is 900 ± 10 ℃, and roasting time is 2.5 hours.
Embodiment 5
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 62%, and the add-on of nitric acid accounts for 4.5% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 4;
Becoming the glue temperature is 60 ± 1 ℃, and gelation time is 6 hours;
Maturing temperature is 950 ± 15 ℃, and roasting time is 2.6 hours.
Embodiment 6
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 68%, and the add-on of nitric acid accounts for 5% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 3.5;
Becoming the glue temperature is 45 ± 1 ℃, and gelation time is 3 hours;
Maturing temperature is 750 ± 10 ℃, and roasting time is 1.6 hours.
Embodiment 7
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 64%, and the add-on of nitric acid accounts for 7% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 4.5;
Becoming the glue temperature is 80 ± 1 ℃, and gelation time is 8 hours;
Maturing temperature is 850 ± 10 ℃, and roasting time is 3 hours.
Embodiment 8
The production method of gama-alumina microsphere of the present invention becomes glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again, wherein:
The concentration of used nitric acid is controlled to be 66%, and the add-on of nitric acid accounts for 4% of pseudo-boehmite weight, becomes the solvent and solute weight ratio of glue reaction to be controlled to be 4;
Becoming the glue temperature is 65 ± 1 ℃, and gelation time is 5.5 hours;
Maturing temperature is 750 ± 10 ℃, and roasting time is 2 hours.
Claims (5)
1. the production method of a gama-alumina microsphere is characterized in that becoming glue by pseudo-boehmite with nitric acid reaction, by centrifugal spray drying forming, makes through roasting again; Wherein:
The concentration of used nitric acid is controlled to be 60～70%; The nitric acid add-on of reaction is 2～8% of a pseudo-boehmite weight;
Becoming the solvent and solute weight ratio of glue reaction is 2～5; Becoming the glue temperature is 30～85 ℃, and gelation time is 1～8 hour;
Maturing temperature is 500～1000 ℃, and roasting time is 1.5～3 hours.
2. the production method of gama-alumina microsphere according to claim 1 is characterized in that the nitric acid add-on of reacting is 3～5% of a pseudo-boehmite weight.
3. the production method of gama-alumina microsphere according to claim 1, the solvent and solute weight ratio that it is characterized in that into the glue reaction is 3～4.
4. the production method of gama-alumina microsphere according to claim 1, it is characterized in that into the glue temperature is 70～85 ℃, gelation time is 4～6 hours.
5. the production method of gama-alumina microsphere according to claim 1 is characterized in that maturing temperature is 500～1000 ℃, and roasting time is 2～3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101554792A CN100378001C (en) | 2004-11-26 | 2004-11-26 | Process for producing gama-alumina microsphere |
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|---|---|---|---|
| CNB2004101554792A CN100378001C (en) | 2004-11-26 | 2004-11-26 | Process for producing gama-alumina microsphere |
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|---|---|
| CN1631787A CN1631787A (en) | 2005-06-29 |
| CN100378001C true CN100378001C (en) | 2008-04-02 |
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| CNB2004101554792A Active CN100378001C (en) | 2004-11-26 | 2004-11-26 | Process for producing gama-alumina microsphere |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183501B (en) * | 2013-03-13 | 2015-01-07 | 湖南大学 | Micro-nano spherical SG corundum abrasive and preparation method thereof |
| CN105731506B (en) * | 2014-12-11 | 2017-09-29 | 中国石油天然气股份有限公司 | Preparation method of alumina colloid and alumina carrier, and alumina colloid and carrier |
| CN106475023B (en) * | 2016-11-15 | 2019-05-28 | 中国海洋石油集团有限公司 | A kind of macropore holds the preparation method of aluminum oxide micro-sphere |
| CN106745121B (en) * | 2016-12-23 | 2017-12-19 | 鲁西催化剂有限公司 | A kind of preparation method of high-performance active oxidation aluminium ball |
| CN114988444A (en) * | 2022-04-29 | 2022-09-02 | 江苏晶晶新材料有限公司 | Preparation method of nano alumina microspheres special for antibiotic decolorization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1440194A (en) * | 1973-01-16 | 1976-06-23 | British Aluminium Co Ltd | Alumina sol |
| US4301033A (en) * | 1978-11-06 | 1981-11-17 | Nikki-Universal Co., Ltd. | High apparent bulk density gamma alumina carrier and method of manufacture of same |
| JPS6317220A (en) * | 1986-07-07 | 1988-01-25 | Mitsubishi Chem Ind Ltd | Production of microspherical alumina |
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| SU1771174A1 (en) * | 1990-04-06 | 1995-05-20 | Электрогорский филиал Всесоюзного научно-исследовательского института по переработке нефти | Method of preparing aluminium hydroxide pseudosol |
| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
-
2004
- 2004-11-26 CN CNB2004101554792A patent/CN100378001C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1440194A (en) * | 1973-01-16 | 1976-06-23 | British Aluminium Co Ltd | Alumina sol |
| US4301033A (en) * | 1978-11-06 | 1981-11-17 | Nikki-Universal Co., Ltd. | High apparent bulk density gamma alumina carrier and method of manufacture of same |
| JPS6317220A (en) * | 1986-07-07 | 1988-01-25 | Mitsubishi Chem Ind Ltd | Production of microspherical alumina |
| SU1771174A1 (en) * | 1990-04-06 | 1995-05-20 | Электрогорский филиал Всесоюзного научно-исследовательского института по переработке нефти | Method of preparing aluminium hydroxide pseudosol |
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
Non-Patent Citations (2)
| Title |
|---|
| 喷雾干燥装置的经济分析. 黄立新等.林产化工通讯，第3期. 1996 * |
| 离心式喷雾干燥制备纳米晶粉末的工艺原理及其影响因素. 马运柱等.硬质合金，第19卷第3期. 2002 * |
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|---|---|
| CN1631787A (en) | 2005-06-29 |
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Owner name: CHINESE ALUMINIUM CO., LTD. Free format text: FORMER OWNER: SHANDONG ALUMINIUM INDUSTRY CO., LTD. Effective date: 20071116 |
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Effective date of registration: 20071116 Address after: 100082 No. 62 North Main Street, Beijing, Xizhimen Applicant after: Aluminum Corporation of China Limited Address before: 255052 No. 1, five km road, Zhangdian District, Shandong, Zibo Applicant before: Shandong Aluminium Industry Co., Ltd. |
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