CN110339807B - 一种制备水化氯铝酸钙的方法 - Google Patents
一种制备水化氯铝酸钙的方法 Download PDFInfo
- Publication number
- CN110339807B CN110339807B CN201910479314.7A CN201910479314A CN110339807B CN 110339807 B CN110339807 B CN 110339807B CN 201910479314 A CN201910479314 A CN 201910479314A CN 110339807 B CN110339807 B CN 110339807B
- Authority
- CN
- China
- Prior art keywords
- aluminum chloride
- calcium
- stirring
- chloroaluminate
- centrifuging
- 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.)
- Active
Links
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011575 calcium Substances 0.000 title claims abstract description 25
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000292 calcium oxide Substances 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical group C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/164—Calcium aluminates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明涉及一种制备水化氯铝酸钙的方法，具体步骤为：按比例称取氯化铝、氢氧化钙或氧化钙、蒸馏水；将氢氧化钙或氧化钙溶于水中，不断搅拌，同时加入氯化铝，搅拌均匀后；离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心重复上述实验，如此反复冲洗沉淀物；将最终沉淀物放置烘箱烘干得到纯净的水化氯铝酸钙成品。该反应在常温下可以进行，操作简便，对反应釜没有要求，所获得水化氯铝酸钙比较纯净，且制备时间短暂。
Description
技术领域
本发明属于实验室合成Friedel盐技术领域，具体涉及一种制备水化氯铝酸钙的方法。
背景技术
水化氯铝酸钙(3CaO·A12O3·CaCl2·10H2O)又称Friedel盐，是水滑石类的双金属氢氧化物，具有独特的层状结构，主要表现为层间阴离子的可交换性、板层阳离子的可搭配性和孔径的可调变性，可以用来处理放射性、有毒物质及废水净化。许云峰、Dai、陆洋、Zhang、农成龙等人均研究了氯铝酸钙在水环境中Pb2+、Cd2+、Cr6+等重金属的吸附性能，研究表明水化氯铝酸钙对重金属的束缚作用主要表现为表面吸附和离子交换吸附。Shao研究表明氯铝酸钙对CrO4 2-能表现出有效的固化稳定化，产物为铬酸型氯铝酸钙。
目前来说，水化氯铝酸钙的合成方法有：将CaCl2、Ca(OH)2和铝酸盐水泥混合物在超声波下合成；在反应釜中加入水、聚氯化铝压滤残渣和氧化钙进行共聚反应，在反应过程中加入氟硅酸钠；一定比例的CaCl2、Ca(OH)2、三氧化二铝和铝酸钙在全返混爆发式成核反应器中合成。以上这些方法存在耗能大、效率低、原料昂贵等一些问题。
发明内容
本发明的目的是为了改进现有技术的不足而提供了一种制备水化氯铝酸钙的方法，制备方法更为简便，以改善现有技术中合成水化氯铝酸钙比较麻烦的问题。
本发明的技术方案为：一种制备水化氯铝酸钙的方法，具体步骤如下：
(1)、准确称取1摩尔份氯化铝、3-4摩尔份氢氧化钙或氧化钙、200-300摩尔份蒸馏水；
(2)、先将氢氧化钙或氧化钙加入水中，不断搅拌，呈白色悬浊液时，再加入氯化铝，搅拌均匀；
(3)、离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心，重复上述步骤反复冲洗沉淀物；
(4)、将最终沉淀物放置烘箱烘干。
优选步骤(1)所述的氢氧化钙或氧化钙、氯化铝都是分析纯，且氯化铝是无水氯化铝。
优选步骤(2)中加入氯化铝，搅拌时间为1-2min，确保反应物充分接触反应。
优选步骤(3)中冲洗沉淀物3-4次，确保产物的纯度。
优选步骤(4)中所述的烘箱温度为80-105℃。
本发明提供的制备水化氯铝酸钙的方法步骤简单，操作方便。
相对于现有技术，本发明包括以下有益效果：本发明利用氯化铝、氢氧化钙或氧化钙在蒸馏水中进行水化反应，合成水化氯铝酸钙，利用XRD(X射线衍射)分析的图谱可以证明合成成功。该反应在常温下可以进行，操作简便，对反应釜没有要求，所获得水化氯铝酸钙比较纯净，且制备时间短暂。
附图说明
图1为实施例1制备的水化氯铝酸钙的SEM图；
图2为实施例1制备的水化氯铝酸钙的XRD图；
图3为实施例1制备的水化氯铝酸钙的FT-IR图。
具体实施方式
下面通过具体的实施例对本发明做进一步的详细描述。
实施例1：
按摩尔数计，称取1份氯化铝，3份氢氧化钙，200份蒸馏水；将氢氧化钙溶于水中，不断搅拌，同时加入氯化铝，搅拌1min后；离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心重复上述实验，如此反复冲洗沉淀物3次；将最终沉淀物放置烘箱以105℃烘干得到成品。成品SEM图如图1所示，从图上可以看出成品成扁平层状六边形结构；XRD图如图2所示，从图上可以看出成品与标准卡片(PDF#89-8294)相吻合；FT-IR图如图3所示，从图上的这些特征峰都验证了的纯净度很高的氯铝酸钙的生成。
实施例2：
按摩尔数计，称取1份氯化铝，4份氢氧化钙，250份蒸馏水；将氢氧化钙溶于水中，不断搅拌，同时加入氯化铝，搅拌2min后；离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心重复上述实验，如此反复冲洗沉淀物4次；将最终沉淀物放置烘箱以95℃烘干得到成品。成品成扁平层状六边形结构，纯净度很高的氯铝酸钙，成品与标准卡片(PDF#89-8294)相吻合。
实施例3：
按摩尔数计，称取1份氯化铝，3份氧化钙，300份蒸馏水；将氧化钙溶于水中，不断搅拌，同时加入氯化铝，搅拌1.5min后；离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心重复上述实验，如此反复冲洗沉淀物3次；将最终沉淀物放置烘箱以85℃烘干得到成品。成品成扁平层状六边形结构；纯净度很高的氯铝酸钙，成品与标准卡片(PDF#89-8294)相吻合。
Claims (5)
1.一种制备水化氯铝酸钙的方法，具体步骤如下：
(1)、准确称取1摩尔份氯化铝、3-4摩尔份氢氧化钙或氧化钙、200-300摩尔份蒸馏水；
(2)、先将氢氧化钙或氧化钙加入水中，不断搅拌，呈白色悬浊液时，再加入氯化铝，搅拌均匀；
(3)、离心去除上层清液，再加入蒸馏水搅拌至浑浊态，继续离心，重复上述步骤反复冲洗沉淀物；
(4)、将最终沉淀物放置烘箱烘干。
2.根据权利要求 1中所述方法，其特征在于步骤(1)中所述的氯化铝是无水氯化铝。
3.根据权利要求 1中所述方法，其特征在于步骤(2)中加入氯化铝，搅拌时间为1-2min。
4.根据权利要求 1中所述方法，其特征在于步骤(3)中冲洗沉淀物3-4次。
5.根据权利要求 1中所述方法，其特征在于步骤(4)中所述的烘箱温度为80-105℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910479314.7A CN110339807B (zh) | 2019-06-04 | 2019-06-04 | 一种制备水化氯铝酸钙的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910479314.7A CN110339807B (zh) | 2019-06-04 | 2019-06-04 | 一种制备水化氯铝酸钙的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110339807A CN110339807A (zh) | 2019-10-18 |
| CN110339807B true CN110339807B (zh) | 2022-07-08 |
Family
ID=68181487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910479314.7A Active CN110339807B (zh) | 2019-06-04 | 2019-06-04 | 一种制备水化氯铝酸钙的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110339807B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114521552A (zh) * | 2022-02-25 | 2022-05-24 | 茂名市和亿化工有限公司 | 乙氧氟草醚-氯铝酸钙一步插层组装合成缓释剂的方法 |
| CN114804174A (zh) * | 2022-02-25 | 2022-07-29 | 茂名市和亿化工有限公司 | 水化氯铝酸钙结构重建合成乙氧氟草醚缓释剂方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108223A (ja) * | 1987-10-19 | 1989-04-25 | Fuji Kobunshi Kk | ポリパラフェニレンの合成法 |
| CN101519221A (zh) * | 2009-02-24 | 2009-09-02 | 上海大学 | 一种水化氯铝酸钙的合成方法 |
| CN102294219A (zh) * | 2011-03-01 | 2011-12-28 | 贵州黔新企业集团有限公司 | 一种采用电石渣为原料生产弗雷德盐乳液的方法 |
| CN102294218A (zh) * | 2011-03-01 | 2011-12-28 | 章兴华 | 一种生产弗雷德盐的方法 |
| CN104150518A (zh) * | 2014-08-05 | 2014-11-19 | 邵阳天堂助剂化工有限公司 | 水铝钙石合成方法及其水铝钙石基pvc复合热稳定剂 |
| CN104509531A (zh) * | 2014-11-17 | 2015-04-15 | 江苏隆昌化工有限公司 | 一种农药-氯铝酸钙缓释剂一步组装合成方法 |
-
2019
- 2019-06-04 CN CN201910479314.7A patent/CN110339807B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108223A (ja) * | 1987-10-19 | 1989-04-25 | Fuji Kobunshi Kk | ポリパラフェニレンの合成法 |
| CN101519221A (zh) * | 2009-02-24 | 2009-09-02 | 上海大学 | 一种水化氯铝酸钙的合成方法 |
| CN102294219A (zh) * | 2011-03-01 | 2011-12-28 | 贵州黔新企业集团有限公司 | 一种采用电石渣为原料生产弗雷德盐乳液的方法 |
| CN102294218A (zh) * | 2011-03-01 | 2011-12-28 | 章兴华 | 一种生产弗雷德盐的方法 |
| CN104150518A (zh) * | 2014-08-05 | 2014-11-19 | 邵阳天堂助剂化工有限公司 | 水铝钙石合成方法及其水铝钙石基pvc复合热稳定剂 |
| CN104509531A (zh) * | 2014-11-17 | 2015-04-15 | 江苏隆昌化工有限公司 | 一种农药-氯铝酸钙缓释剂一步组装合成方法 |
Non-Patent Citations (3)
| Title |
|---|
| Ca-Al水滑石的制备及其在铝酸钠溶液中的脱硅;马家玉等;《中国科学》;20100520;第40卷(第5期);第577-584页 * |
| Desilication of sodium aluminate solution by Friedel"s salt;Jiayu Ma et al.;《Hydrometallurgy》;20090831;第99卷;第225-230页 * |
| Friedel 盐对废水中低浓度Cd2+的吸附动力学;张娟娟等;《过程工程学报》;20120831;第12卷(第4期);第590-595页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110339807A (zh) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4656156A (en) | Adsorbent and substrate products and method of producing same | |
| Tong et al. | Transformation of alunite residuals into layered double hydroxides and oxides for adsorption of acid red G dye | |
| CN105753022B (zh) | 一种镁基层状复合氢氧化物的制备方法 | |
| CN110339807B (zh) | 一种制备水化氯铝酸钙的方法 | |
| JPH10503465A (ja) | ハイドロタルク石及びハイドロタルク石様化合物の二粉末合成 | |
| Pérez-Barrado et al. | Fast aging treatment for the synthesis of hydrocalumites using microwaves | |
| Fetter et al. | Sorption of 131 I− by hydrotalcites | |
| Radha et al. | Aging of trivalent metal hydroxide/oxide gels in divalent metal salt solutions: Mechanism of formation of layered double hydroxides (LDHs) | |
| Ma et al. | Performance and mechanism of Mg-Ca-Fe hydrotalcite-like compounds for fluoride removal from aqueous solution | |
| CN101357771A (zh) | 一种制备高比表面积拟薄水铝石微球的水热方法 | |
| CN108502897B (zh) | 一种Zr掺杂SBA-15介孔分子筛材料的光化学绿色合成方法 | |
| CN109692648B (zh) | 高效吸附水中硫酸根离子的吸附剂及其制备方法 | |
| JP5429843B2 (ja) | 八面体シート構造を有する光触媒材料 | |
| CN109052446B (zh) | 一种利用工业废渣为原料制备钙铝类水滑石的方法 | |
| RU2136593C1 (ru) | Аморфное производное каолина и способ его получения | |
| Zhou et al. | Insights into chloride sorption and phase transformation of the synthesized Ca-Al bimetallic oxides in flue gas desulfurization wastewater | |
| Khaldi et al. | Preparation of a well-ordered layered nanocomposite from zinc–aluminum–chloride layered double hydroxide and hydrogenophosphate by ion exchange | |
| CN110745849B (zh) | 一种硝酸根插层的镁铝水滑石制备方法 | |
| JPH06305724A (ja) | 合成多孔質材料及びその製造方法 | |
| Fuchida et al. | Experimental Investigation of Boron Removal Mechanism from Wastewater by Calcined Ettringite | |
| CN114229876A (zh) | 水滑石的制备方法 | |
| El-Korashy | Synthetic crystalline calcium silicate hydrate (I): cation exchange and caesium selectivity | |
| KR101130282B1 (ko) | 층상형 금속 이중층 수산화물 변이체 세피오사이트 화합물 및 그의 제조방법 | |
| Zhao et al. | Factors influencing the chloride removal of aqueous solution by calcined layered double hydroxides | |
| JP2000256011A (ja) | ベーマイト及びその製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |