CN105384182A - 一种氧化铝微球的制备方法 - Google Patents
一种氧化铝微球的制备方法 Download PDFInfo
- Publication number
- CN105384182A CN105384182A CN201510659381.9A CN201510659381A CN105384182A CN 105384182 A CN105384182 A CN 105384182A CN 201510659381 A CN201510659381 A CN 201510659381A CN 105384182 A CN105384182 A CN 105384182A
- Authority
- CN
- China
- Prior art keywords
- alumina
- suspension
- sphere
- aluminum oxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000499 gel Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000011806 microball Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- -1 aluminum ions salts Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000000017 hydrogel Substances 0.000 claims description 3
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 8
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229920002148 Gellan gum Polymers 0.000 abstract 2
- 239000000216 gellan gum Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 235000010492 gellan gum Nutrition 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种氧化铝微球的制备方法，其特征在于：将氧化铝前驱体加入到65-90℃的结冷胶溶液中，形成氧化铝前驱体-结冷胶悬浮液；将上述悬浮液加入80-100℃油相中进行高速搅拌，冷却后加入阳离子溶液继续搅拌可得到凝胶微球，将凝胶微球洗涤、干燥、焙烧可得到氧化铝微球。该法具有成型速度快，制备过程无污染，生产成本低等优势，而且操作步骤简单，易于实现工业化生产，产品磨耗较低，颗粒尺寸满足多种反应器要求。
Description
技术领域
本发明属于催化剂载体领域，涉及一种氧化铝微球的制备方法，尤其是一种利用结冷胶与金属离子溶液形成凝胶的特性制备氧化铝微球。
技术背景
γ-氧化铝具有较大的比表面，可调控的孔结构及良好的热稳定性能、吸附性能，广泛用于催化剂载体及其吸附剂。目前球形氧化铝的制备方法主要有：喷雾造粒，滚动成型、油(氨)柱成型及水柱成型。其中喷雾干燥制备氧化铝微球的粒径为几十微米到几百微米，但此法制备的产品粒度分布不均匀，且存在较多的粉尘，环境污染严重。滚动成型难以制备微米级的颗粒。油(氨)柱成型及水柱成型产品的颗粒尺寸均大于几百微米。当球形氧化铝应用于流化床中时，要求的颗粒粒径在几十微米至几千微米，且样品的耐磨性能要求较高。
中国专利201210376310.4中，以脲醛树脂微球作为模板吸附铝离子，然后在环氧丙烷的开环作用下使铝离子发生羟联反应和阳联反应，制备氧化铝微球。此法所用原料模板的成本较高，交联时间需要4-5小时，生产效率较低。
中国专利201310057670.2中，利用静电纺丝技术制备氧化铝微球，粒径在0.1-1μm。但此工艺的生产效率较低，控制因素(电压、电流、纺丝距离、湿度、温度等)较多，设备的输出电压为20-30KV且成本较高，苛刻的实验条件及较高的生产成本难以实现工业化生产。
结冷胶是一种阴离子型线性多糖，具有平行的双螺旋结构，胶体链为4个基本单元重复聚合组成，基本单元由一份子的鼠李糖和葡萄糖全算及两分子的葡萄糖构成，并可与金属阳离子的溶液形成凝胶。
发明内容
本发明的目的是提供一种新型的制备氧化铝微球的方法，以解决技术背景中所述的工艺复杂、生产成本高及难以实现工业化生产等问题，同时产品的磨耗较低，粒度相对较为集中，满足多种反应器要求。
本发明的技术方案概述如下：
一种氧化铝微球的制备方法，包括以下步骤：
将氧化铝前驱体、结冷胶分散于去离子水中，然后加热至65～90℃，使结冷胶充分溶解，形成混悬液；将上述混悬液加入到80～100℃油相中进行高速搅拌10～30min，然后在搅拌作用下将体系冷却至10-30℃后，加入阳离子溶液继续搅拌形成凝胶微球；将凝胶微球取出进行洗涤、干燥、焙烧得到氧化铝微球；所述氧化铝前驱体在浆液中的固含量为5-30wt％，结冷胶含量为0.1-5wt％。
所述氧化铝前驱体为拟薄水铝石、薄水铝石、氧化铝水凝胶或者纳米氧化铝溶胶中的一种或多种。
所述油相为煤油、石蜡油中的一种或者多种，混悬液与油相的体积比为1:1～10。
所述搅拌速度为500-1000rpm。
所述阳离子溶液为钾、钠或铝离子的盐溶液，阳离子总浓度为0.1-0.5mol/L。。
本发明方法与现有技术相比，其有益效果如下：
1)本发明利用浆液加入油相中，在高速搅拌作用下可形成球形的小液滴，该法操作简便，再利用结冷胶与阳离子形成凝胶，进一步固化，得到凝胶微球。
2)该法通过控制混悬液与油相的体积比，可控制形成的氧化铝微球颗粒的尺寸在50μm-1000μm可调，且颗粒尺寸相对集中，磨耗较低。
3)原料及过程绿色、无污染，是一种低成本制备高性能氧化铝微球的方法，易于实现工业化生产。
具体实施方式
下面结合具体实施例对本发明一种氧化铝微球的制备方法作进一步说明，但并不因此而限制本发明。
实施例1
(1)将100g拟薄水铝石样品加入到70℃的300ml结冷胶水溶液(浓度2％)中，拟薄水铝石在浆液中的固含量为25％，形成拟薄水铝石-结冷胶悬浮液。
(2)将上述混悬液加入到90℃煤油中，且煤油的体积为300ml，开启搅拌速度500rpm，搅拌时间15min，将体系冷却到25℃。
(3)加入铝离子溶液继续搅拌，铝离子总浓度为0.1mol/L，可以得到凝胶微球。
(4)将凝胶颗粒洗涤后，在100℃下干燥10h，550℃焙烧4h，得到的氧化铝微球的性质见表1。
实施例2
按照实施例1中的步骤制备氧化铝微球，不同的是加入的铝源为氧化铝水凝胶，且在浆液中的固含量为10％，得到的微球性质见表1。
实施例3
按照实施例1中的步骤制备氧化铝微球，不同的是加入的油相为石蜡油，得到的微球的性质见表1。
实施例4
按照实施例1中的步骤制备氧化铝微球，混悬液与油相的体积比变为1:5，得到的微球的性质见表1。
实施例5
按照实施例1中的步骤制备氧化铝微球，混悬液与油相的体积比变为1:10，得到的微球的性质见表1。
实施例6
按照实施例1中的步骤制备氧化铝微球，不同的是加入的阳离子为钾离子，得到的微球的性质见表1。
实施例7
按照实施例1中的步骤制备氧化铝微球，不同的是阳离子铝离子在浆液中的浓度为0.4mol/L,得到的微球的性质见表1。
表1氧化铝微球物性结果
| 实施例 | 粒径(μm) | 磨耗(％) |
| 1 | 730-820 | 0.2 |
| 2 | 290-400 | 0.31 |
| 3 | 720-850 | 0.23 |
| 4 | 450-550 | 0.28 |
| 5 | 50-160 | 0.35 |
| 6 | 690-810 | 0.44 |
| 7 | 580-690 | 0.05 |
Claims (5)
1.一种氧化铝微球的制备方法，其特征在于，按照以下的工艺步骤进行：将氧化铝前驱体、结冷胶分散于去离子水中，然后加热至65～90℃，使结冷胶充分溶解，形成混悬液；将上述混悬液加入到80～100℃油相中进行高速搅拌10～30min，然后在搅拌作用下将体系冷却至10-30℃后，加入阳离子溶液继续搅拌形成凝胶微球；将凝胶微球取出进行洗涤、干燥、焙烧得到氧化铝微球；所述氧化铝前驱体在浆液中的固含量为5-30wt％，结冷胶含量为0.1-5wt％。
2.按照权利要求1所述方法，其特征在于，所述的氧化铝前驱体为拟薄水铝石、薄水铝石、氧化铝水凝胶或者纳米氧化铝溶胶中的一种或多种。
3.按照权利要求1所述方法，其特征在于，所述的油相为煤油、石蜡油中的一种或者多种，所述混悬液与所述油相的体积比为1:1～10。
4.按照权利要求1所述方法，其特征在于，所述的搅拌速度为500-1000rpm。
5.按照权利要求1所述方法，其特征在于，所述阳离子溶液为钾、钠或铝离子的盐溶液，阳离子总浓度为0.1-0.5mol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510659381.9A CN105384182B (zh) | 2015-10-12 | 2015-10-12 | 一种氧化铝微球的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510659381.9A CN105384182B (zh) | 2015-10-12 | 2015-10-12 | 一种氧化铝微球的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384182A true CN105384182A (zh) | 2016-03-09 |
| CN105384182B CN105384182B (zh) | 2017-04-26 |
Family
ID=55417024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510659381.9A Active CN105384182B (zh) | 2015-10-12 | 2015-10-12 | 一种氧化铝微球的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384182B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400427A (zh) * | 2018-12-26 | 2019-03-01 | 湖北航天化学技术研究所 | 一种高燃速气体发生剂的制粒工艺 |
| CN110203953A (zh) * | 2019-07-15 | 2019-09-06 | 清华大学 | 一种γ-氧化铝微球及其制备方法 |
| CN116161688A (zh) * | 2022-12-12 | 2023-05-26 | 雅安百图高新材料股份有限公司 | 一种纳米球形氧化铝制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105524A (zh) * | 2008-07-23 | 2011-06-22 | 的里雅斯特大学 | 由多糖基体和金属纳米颗粒组成的三维纳米复合物材料以及其制备和用途 |
| CN104353502A (zh) * | 2014-11-12 | 2015-02-18 | 中国海洋石油总公司 | 一种大孔容球形氧化铝的制备方法 |
| CN104402028A (zh) * | 2014-11-12 | 2015-03-11 | 中国海洋石油总公司 | 一种球形氧化铝的油水柱成型方法 |
-
2015
- 2015-10-12 CN CN201510659381.9A patent/CN105384182B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105524A (zh) * | 2008-07-23 | 2011-06-22 | 的里雅斯特大学 | 由多糖基体和金属纳米颗粒组成的三维纳米复合物材料以及其制备和用途 |
| CN104353502A (zh) * | 2014-11-12 | 2015-02-18 | 中国海洋石油总公司 | 一种大孔容球形氧化铝的制备方法 |
| CN104402028A (zh) * | 2014-11-12 | 2015-03-11 | 中国海洋石油总公司 | 一种球形氧化铝的油水柱成型方法 |
Non-Patent Citations (1)
| Title |
|---|
| 任凌波等: "《生物化工产品生产工艺技术及应用》", 30 June 2001 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400427A (zh) * | 2018-12-26 | 2019-03-01 | 湖北航天化学技术研究所 | 一种高燃速气体发生剂的制粒工艺 |
| CN109400427B (zh) * | 2018-12-26 | 2021-02-02 | 湖北航天化学技术研究所 | 一种高燃速气体发生剂的制粒工艺 |
| CN110203953A (zh) * | 2019-07-15 | 2019-09-06 | 清华大学 | 一种γ-氧化铝微球及其制备方法 |
| CN116161688A (zh) * | 2022-12-12 | 2023-05-26 | 雅安百图高新材料股份有限公司 | 一种纳米球形氧化铝制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384182B (zh) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104760968B (zh) | 一种纳米级有机膨润土的制备方法 | |
| CN106492867B (zh) | g-C3N4量子点敏化TiO2纳米管的制备方法 | |
| CN104261462B (zh) | 一种微纳二氧化锡实心球的制备方法 | |
| CN105289433A (zh) | 一种规模化制备过渡金属氧化物多孔微球的方法 | |
| CN104477953B (zh) | 一种球形氧化铝的成型方法 | |
| CN105384182A (zh) | 一种氧化铝微球的制备方法 | |
| CN102643592A (zh) | 聚苯胺改性介孔分子筛防腐涂料的制备方法 | |
| CN105895192A (zh) | 低温导电银浆及其制备方法 | |
| CN103771429A (zh) | 一种利用共模板剂合成多孔球形二氧化硅的方法 | |
| CN104292236A (zh) | 三维多孔g-C3N4材料的制备方法 | |
| CN107828313B (zh) | 一种含改性氧化石墨烯的环氧树脂涂料及其制备方法 | |
| EP3677548A1 (en) | Method for manufacturing ultra-porous nano-sio2 | |
| CN106167270A (zh) | 一种介孔θ‑氧化铝球形载体的制备方法 | |
| CN102815733A (zh) | 一种纳米勃姆石及其制备方法 | |
| CN105521806A (zh) | 一种scr烟气脱硝催化剂及其制备方法 | |
| CN101417258B (zh) | 用于超细功能粉体制备的湿法精确分级工艺 | |
| CN102107899B (zh) | 一种片状γ相纳米氧化铝的制备方法 | |
| CN106362775B (zh) | 一种基于硫化钼的高效光催化制备氢气的纳米材料及制备方法 | |
| CN104353503B (zh) | 一种球形硅铝复合载体的制备方法 | |
| CN104437556B (zh) | 一种合成乙酸正丁酯催化剂的制备方法 | |
| CN103145172A (zh) | 一种yolk/shell结构碱式硫酸铜的制备方法 | |
| CN105195070B (zh) | 一种分子筛微球的制备方法 | |
| CN107746068A (zh) | 一种二氧化硅改性硫酸钡粉体的制备方法 | |
| CN105080603B (zh) | 一种硝基苯选择性加氢制苯胺用催化剂及其制备方法、使用方法 | |
| CN105295446A (zh) | 一种超疏水粉末的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB02 | Change of applicant information |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: CHINA NATIONAL OFFSHORE OIL Corp. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161014 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |