CN1821314A - A kind of preparation method of superfine cerium oxide for polishing - Google Patents
A kind of preparation method of superfine cerium oxide for polishing Download PDFInfo
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- oxalic acid
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 43
- 238000005498 polishing Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- -1 cerium ion Chemical class 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 18
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 5
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
一、技术领域1. Technical field
本发明涉及一种抛光用超细氧化铈的制备方法，属于稀土化合物的制备技术领域。The invention relates to a preparation method of ultrafine cerium oxide for polishing, and belongs to the technical field of preparation of rare earth compounds.
二、背景技术2. Background technology
在工业领域中广泛使用抛光粉。稀土抛光粉的使用可追溯到第一次世界大战，美国和加拿大率先使用以氧化铈为主要成分的稀土抛光粉，用于精密军用仪器镜头的研磨，取代了氧化铁抛光粉。氧化铈抛光粉具有抛光速度高、作业污染少、抛光质量高等优点。正是由于稀土抛光粉的开发，使玻璃研磨表面的精度得到了很大程度的改善，从而使稀土抛光粉在世界上被广泛的利用。现在氧化铈在抛光粉上的应用已占了氧化铈整个应用量的近一半，已成为氧化铈应用的最大领域。Polishing powders are widely used in industrial fields. The use of rare earth polishing powder can be traced back to World War I. The United States and Canada took the lead in using rare earth polishing powder with cerium oxide as the main component for grinding precision military instrument lenses, replacing iron oxide polishing powder. Cerium oxide polishing powder has the advantages of high polishing speed, less operation pollution and high polishing quality. It is precisely because of the development of rare earth polishing powder that the precision of glass grinding surface has been greatly improved, so that rare earth polishing powder is widely used in the world. Now the application of cerium oxide in polishing powder has accounted for nearly half of the total application of cerium oxide, and has become the largest application field of cerium oxide.
稀土抛光粉正在增长的市场是在光掩模领域上的应用，光掩模(又称遮光膜)是用特种玻璃如硅酸盐玻璃制成的，这种玻璃需要研磨和抛光，技术要求极其严格。抛光后的玻璃表面镀铬，然后在上面反向印刷电路，最后再将电路投射表面喷镀阻光层的半导体芯片上。光掩模的抛光要求比较高，要用粒度分布均匀、形状一致性好的超细氧化铈进行抛光。The growing market for rare earth polishing powder is the application in the field of photomasks. Photomasks (also known as light-shielding films) are made of special glasses such as silicate glass. This glass needs to be ground and polished, and the technical requirements are extremely high. strict. The surface of the polished glass is chrome-plated, and then the circuit is reverse printed on it, and finally the circuit is projected on the semiconductor chip with a light-blocking layer sprayed on the surface. The polishing requirements of photomasks are relatively high, and ultrafine cerium oxide with uniform particle size distribution and good shape consistency should be used for polishing.
抛光粉的制备一般分为固相反应法和沉淀—煅烧法。超细氧化铈抛光粉的制备多采用沉淀—煅烧法。The preparation of polishing powder is generally divided into solid-state reaction method and precipitation-calcination method. The preparation of ultrafine cerium oxide polishing powder mostly adopts precipitation-calcination method.
美国专利5543126公开了一种合成氧化铈颗粒的方法，它是利用碱性物质将含氢氧化铈(IV)与硝酸盐的水性介质调节至pH值为8～11，并在压力下且温度控制在100～200℃加热该含水物质，得到氧化铈的粒度在0.03至5微米之间。该方法的前驱体是氢氧化铈，且粒度分布较宽，抛光效果不好。U.S. Patent No. 5,543,126 discloses a method for synthesizing cerium oxide particles. It uses an alkaline substance to adjust the aqueous medium containing cerium hydroxide (IV) and nitrate to a pH value of 8 to 11, and under pressure and temperature control The aqueous mass is heated at 100-200°C to obtain cerium oxide with a particle size between 0.03 and 5 microns. The precursor of this method is cerium hydroxide, and the particle size distribution is wide, so the polishing effect is not good.
中国台湾专利328068公开了混合硝酸铈(III)并快速加热至70～100℃，调节pH值为5～10之间，且在该温度下保温0.2～20小时，得到10至80纳米的氧化铈粉体。该方法的前驱体也是氢氧化铈，且粒度太细，不适合做抛光粉使用。China Taiwan Patent No. 328068 discloses mixing cerium (III) nitrate and rapidly heating to 70-100°C, adjusting the pH value between 5-10, and keeping it at this temperature for 0.2-20 hours to obtain cerium oxide of 10-80 nanometers Powder. The precursor of this method is also cerium hydroxide, and the particle size is too fine to be used as polishing powder.
上述方法有的需要高温高压设备，价格昂贵，没有大量生产的经济价值；有的不适合大规模生产。而粒径在10nm～3μm之间，比表面积小于50m2/g的超细氧化铈抛光粉的制备还没有报导。Some of the above methods require high-temperature and high-pressure equipment, which are expensive and have no economic value for mass production; some are not suitable for large-scale production. However, the preparation of ultrafine cerium oxide polishing powder with a particle size between 10 nm and 3 μm and a specific surface area of less than 50 m 2 /g has not been reported yet.
三、发明内容3. Contents of the invention
本发明的目的是在于提供一种制备比表面积小，粒度分布均匀、形状一致性好，成本较低的抛光用超细氧化铈的方法。The purpose of the present invention is to provide a method for preparing superfine cerium oxide for polishing with small specific surface area, uniform particle size distribution, good shape consistency and low cost.
本发明的目的由如下技术方案实现：The purpose of the present invention is achieved by the following technical solutions:
(1).用一种酸溶解铈的碳酸盐或氧化物，或用水溶解铈的硝酸盐、氯化物或硫酸盐制成铈的盐溶液，特别是硝酸盐溶液A；(1). Dissolve cerium carbonate or oxide with a kind of acid, or dissolve cerium nitrate, chloride or sulfate with water to make cerium salt solution, especially nitrate solution A;
(2).该铈盐溶液A中，铈离子的浓度为0.1～2.0mol/l，氢离子浓度为0.001～1mol/l；(2). In the cerium salt solution A, the concentration of cerium ions is 0.1 to 2.0 mol/l, and the concentration of hydrogen ions is 0.001 to 1 mol/l;
(3).向该铈盐溶液中加入分散剂G，形成溶液B；(3). Add dispersant G to the cerium salt solution to form solution B;
(4).取一种碱性物质H配成溶液C；(4). Take a kind of alkaline substance H to make solution C;
(5).将溶液B与溶液C混合进行化学反应，反应时间为10～180分钟，控制反应终点的pH值为5～10，化学反应后生成的沉淀物再经搅拌10～100分钟，形成悬浮液D；(5). Mix solution B and solution C for chemical reaction. The reaction time is 10-180 minutes, and the pH value at the end of the reaction is controlled to be 5-10. Suspension D;
(6).取草酸、草酸铵或碱金属草酸盐配成含草酸的溶液E；(6). Take oxalic acid, ammonium oxalate or alkali metal oxalate to make solution E containing oxalic acid;
(7).将悬浮液D和草酸溶液E充分接触进行化学反应，反应时间为20～200分钟，控制反应终点的pH值为1～5，化学反应后生成的沉淀物再经搅拌5～100分钟，得到沉淀物；(7). Fully contact the suspension D and the oxalic acid solution E to carry out the chemical reaction. The reaction time is 20 to 200 minutes, and the pH value at the end of the reaction is controlled to be 1 to 5. Minutes, get precipitate;
(8).该沉淀物经过滤、洗涤、干燥，得到氧化铈的前驱体F；(8). The precipitate is filtered, washed and dried to obtain a precursor F of cerium oxide;
(9).该前驱体F在600～1000℃下灼烧2～10小时，即得到抛光用超细氧化铈产品。(9). The precursor F is burned at 600-1000° C. for 2-10 hours to obtain an ultrafine cerium oxide product for polishing.
分散剂G是至少一种有机表面活性物质。Dispersant G is at least one organic surface-active substance.
分散剂G的加入量是：氧化铈重量的1～12％。The added amount of the dispersant G is: 1-12% of the weight of the cerium oxide.
碱性物质H是氨水、脲、碳酸氢铵、碳酸铵、碱金属氢氧化物、碱金属的碳酸盐或碱金属的酸式碳酸盐。The basic substance H is ammonia water, urea, ammonium bicarbonate, ammonium carbonate, alkali metal hydroxide, alkali metal carbonate or alkali metal acid carbonate.
碱性物质H配制成水溶液C，特别是C的浓度为0.15～8mol/l。The alkaline substance H is formulated into an aqueous solution C, especially the concentration of C is 0.15-8 mol/l.
草酸溶液E的浓度是0.1～2mol/l。The concentration of the oxalic acid solution E is 0.1-2 mol/l.
氧化铈的前驱体F在600～1000℃下灼烧2～10小时，其升温速度是50～500℃。The precursor F of cerium oxide is fired at 600-1000° C. for 2-10 hours, and the heating rate is 50-500° C.
本发明的优点是：通过制备含有铈离子的盐溶液A，然后在该溶液中加入分散剂G，形成溶液B。取一种碱性物质H配成溶液C。将溶液B与溶液C混合进行化学反应，反应时间为10～180分钟，控制反应终点的pH值为5～10，化学反应后生成的沉淀物再经搅拌10～100分钟，形成悬浮液D。取、草酸铵或碱金属草酸盐草酸配成含草酸的溶液E。将悬浮液D和草酸溶液E充分接触进行化学反应，反应时间为20～200分钟，控制反应终点的pH值为1～5，化学反应后生成的沉淀物再经搅拌5～100分钟。然后过滤、洗涤、干燥该沉淀物，最后在600～1000℃下灼烧2～10小时，其升温速度是50～500℃，可得到粒径在10nm～3μm之间，比表面积小于50m2/g的超细氧化铈。The advantage of the present invention is that solution B is formed by preparing salt solution A containing cerium ions, and then adding dispersant G to the solution. Take an alkaline substance H to make solution C. Mix solution B and solution C for chemical reaction, the reaction time is 10-180 minutes, control the pH value at the end of the reaction to 5-10, and the precipitate formed after the chemical reaction is stirred for 10-100 minutes to form suspension D. Take, ammonium oxalate or alkali metal oxalate oxalic acid to make solution E containing oxalic acid. Suspension D and oxalic acid solution E are fully contacted for chemical reaction, the reaction time is 20-200 minutes, the pH value at the end of the reaction is controlled to be 1-5, and the precipitate formed after the chemical reaction is stirred for 5-100 minutes. Then filter, wash, and dry the precipitate, and finally burn it at 600-1000°C for 2-10 hours, the heating rate is 50-500°C, and the particle size can be between 10nm and 3μm, and the specific surface area is less than 50m 2 / g of ultrafine cerium oxide.
本发明采用可工业化的共沉淀方法进行沉淀，经沉淀、过滤、干燥、焙烧等步骤制备超细氧化铈，先用氨水、碳酸氢铵等碱性物质进行沉淀，得到小颗粒的沉淀物，然后用草酸转型，可以控制超细氧化铈产品的晶型，使其适合于抛光。同时本发明制备抛光用超细氧化铈，比表面积小，粒度分布均匀、形状一致性好，成本较低。还可用工业碳酸铈、工业碳铵、工业氨水、工业草酸等为原料，适合工业化生产，此方法的成本较低。The present invention adopts the industrialized co-precipitation method for precipitation, and prepares superfine cerium oxide through steps such as precipitation, filtration, drying, roasting, etc., and firstly uses alkaline substances such as ammonia water and ammonium bicarbonate for precipitation to obtain small particle precipitates, and then Transformation with oxalic acid can control the crystal form of ultra-fine cerium oxide products, making them suitable for polishing. At the same time, the invention prepares superfine cerium oxide for polishing, has small specific surface area, uniform particle size distribution, good shape consistency and low cost. Industrial cerium carbonate, industrial ammonium bicarbonate, industrial ammonia water, industrial oxalic acid, etc. can also be used as raw materials, which is suitable for industrial production, and the cost of this method is relatively low.
四、附图说明4. Description of drawings
图1为本发明方法制备氧化铈的激光粒度图；Fig. 1 is the laser particle size figure that the inventive method prepares cerium oxide;
图2为本发明方法制备氧化铈的及扫描电镜图：Fig. 2 is that the inventive method prepares cerium oxide and scanning electron micrograph:
五、具体的实施方式5. Specific implementation
实施例1：Example 1:
将2.2kg碳酸铈(CeO2≥45％)用1.23LHNO3溶解，并加5.48L去离子水制成溶液A，在其中加29.7g聚乙二醇形成溶液B。取6.76L2.5mol/L的NH4HCO3成溶液C。然后在搅拌的情况下，将溶液C滴加到溶液B中，在滴加过程中，溶液的pH值不断升高，待溶液C滴完后，反应体系的pH值为6.5；此时生成白色沉淀，再搅拌该沉淀0.2小时，成悬浮液D。取2.86kg草酸用19.1L去离子水配成溶液E。然后将E滴加到悬浮液D中，在滴加过程中，溶液的pH值不断降低，待溶液E滴完后，反应体系的pH值为2.2，继续搅拌0.1小时，将沉淀过滤，并用去离子水洗涤3～4次，然后将沉淀置于100℃静态空气中干燥8小时，再在650℃焙烧2小时，升温速度为100℃/小时，产品为氧化铈，比表面积是35.6m2/g(美国Coulter SA3100比表面积分析仪测得)，其粒度D50为0.355μm(美国Coulter LS230激光粒度仪测得)。2.2 kg of cerium carbonate (CeO 2 ≥ 45%) was dissolved in 1.23 L of HNO 3 , and 5.48 L of deionized water was added to form solution A, and 29.7 g of polyethylene glycol was added to form solution B. Take 6.76L of 2.5mol/L NH 4 HCO 3 to form solution C. Then, under the condition of stirring, solution C is added dropwise to solution B. During the process of dropping, the pH value of the solution increases continuously. After solution C is dropped, the pH value of the reaction system is 6.5; at this time, a white Precipitate, and stir the precipitate for 0.2 hours to form suspension D. Take 2.86kg oxalic acid and make solution E with 19.1L deionized water. Then E was added dropwise to the suspension D. During the dropwise addition, the pH value of the solution decreased continuously. After the solution E was dropped, the pH value of the reaction system was 2.2. Continue stirring for 0.1 hour, filter the precipitate, and use Wash with ion water for 3 to 4 times, then dry the precipitate in static air at 100°C for 8 hours, then bake at 650°C for 2 hours, the heating rate is 100°C/hour, the product is cerium oxide, and the specific surface area is 35.6m 2 / g (measured by U.S. Coulter SA3100 specific surface area analyzer), and its particle size D50 is 0.355 μm (measured by U.S. Coulter LS230 laser particle size analyzer).
实施例2：Example 2:
将2.5kg Ce(NO3)3·6H2O和4.80L去离子水制成溶液A，在其中加31.9g聚乙二醇形成溶液B。取8.13L1.5mol/L的NaHCO3成溶液C。然后在搅拌的情况下，将溶液C滴加到溶液B中，在滴加过程中，溶液的pH值不断升高，待溶液C滴完后，反应体系的pH值为5.8；此时生成白色沉淀，再搅拌该沉淀0.5小时，成悬浮液D。取3.125kg草酸用25L去离子水配成溶液E。然后将E滴加到悬浮液D中，在滴加过程中，溶液的pH值不断降低，待溶液E滴完后，反应体系的pH值为2.5，继续搅拌0.2小时，将沉淀过滤，并用去离子水洗涤3～4次，然后将沉淀置于800℃静态空气中干燥12小时，再在600℃焙烧2小时，升温速度为150℃/小时，产品为氧化铈，比表面积是42.3m2/g(美国Coulter SA3100比表面积分析仪测得)，其粒度D50为0.336μm(美国Coulter LS230激光粒度仪测得)。2.5kg Ce(NO 3 ) 3 ·6H 2 O and 4.80L deionized water were used to prepare solution A, and 31.9g polyethylene glycol was added to form solution B. Take 8.13L of 1.5mol/L NaHCO 3 into solution C. Then, under the condition of stirring, solution C is added dropwise to solution B. During the process of dropping, the pH value of the solution increases continuously. After solution C is dropped, the pH value of the reaction system is 5.8; at this time, a white Precipitate, and stir the precipitate for 0.5 hours to form suspension D. Take 3.125kg oxalic acid and make solution E with 25L deionized water. Then E was added dropwise to the suspension D. During the dropwise addition, the pH value of the solution decreased continuously. After the solution E was dropped, the pH value of the reaction system was 2.5. Continue stirring for 0.2 hours, filter the precipitate, and use Wash with ion water for 3 to 4 times, then dry the precipitate in static air at 800°C for 12 hours, then bake at 600°C for 2 hours, the heating rate is 150°C/hour, the product is cerium oxide, and the specific surface area is 42.3m 2 / g (measured by U.S. Coulter SA3100 specific surface area analyzer), and its particle size D50 is 0.336 μm (measured by U.S. Coulter LS230 laser particle size analyzer).
实施例3：Example 3:
将0.8kg氧化铈(CeO2≥99％)用1.00LHNO3溶解，并加4.65L去离子水制成溶液A，在其中加28g聚乙二醇形成溶液B。取4.67L3.0mol/L的氨水成溶液C。然后在搅拌的情况下，将溶液C滴加到溶液B中，在滴加过程中，溶液的pH值不断升高，待溶液C滴完后，反应体系的pH值为7.5；此时生成棕色沉淀，再搅拌该沉淀0.2小时，成悬浮液D。取1.08kg草酸用5.4L去离子水配成溶液E。然后将E滴加到悬浮液D中，在滴加过程中，溶液的pH值不断降低，待溶液E滴完后，反应体系的pH值为1.5，继续搅拌0.2小时，将沉淀过滤，并用去离子水洗涤3～4次，然后将沉淀置于120℃静态空气中干燥10小时，再在700℃焙烧2小时，升温速度为200℃/小时，产品为氧化铈，比表面积是28.2m2/g(美国Coulter SA3100比表面积分析仪测得)，其粒度D50为0.149μm(美国CoulterLS230激光粒度仪测得)，见附图1、附图2。Dissolve 0.8 kg of cerium oxide (CeO 2 ≥99%) in 1.00 L of HNO 3 , add 4.65 L of deionized water to make solution A, and add 28 g of polyethylene glycol to it to form solution B. Take 4.67L of 3.0mol/L ammonia water to form solution C. Then, under the condition of stirring, solution C is added dropwise to solution B. During the dropping process, the pH value of the solution increases continuously. After solution C is dropped, the pH value of the reaction system is 7.5; at this time, a brown Precipitate, and stir the precipitate for 0.2 hours to form suspension D. Take 1.08kg oxalic acid and make solution E with 5.4L deionized water. Then E was added dropwise to the suspension D. During the dropwise addition, the pH value of the solution decreased continuously. After the solution E was dropped, the pH value of the reaction system was 1.5. Continue stirring for 0.2 hours, filter the precipitate, and use Wash with ion water for 3 to 4 times, then dry the precipitate in static air at 120°C for 10 hours, then bake at 700°C for 2 hours, the heating rate is 200°C/hour, the product is cerium oxide, and the specific surface area is 28.2m 2 / g (U.S. Coulter SA3100 specific surface area analyzer measures), its particle size D 50 is 0.149 μm (U.S. Coulter LS230 laser particle size analyzer measures), see accompanying drawing 1, accompanying drawing 2.
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| CN101541912B (en) * | 2006-11-20 | 2012-12-12 | Lg化学株式会社 | Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
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| CN103754923A (en) * | 2014-01-28 | 2014-04-30 | 内蒙古科技大学 | Method for preparing superfine cerium oxide |
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| DD154010A1 (en) * | 1980-11-03 | 1982-02-17 | Adolf Kaller | PROCESS FOR PRODUCING COARSE-BROKEN COMPOUNDS OF FINE-CRYSTALLINE CERDIOXIDE HYDRATES |
| TW311905B (en) * | 1994-07-11 | 1997-08-01 | Nissan Chemical Ind Ltd | |
| US6596042B1 (en) * | 2001-11-16 | 2003-07-22 | Ferro Corporation | Method of forming particles for use in chemical-mechanical polishing slurries and the particles formed by the process |
| CN100337926C (en) * | 2002-10-28 | 2007-09-19 | 日产化学工业株式会社 | Cerium oxide particles and process for the production thereof |
| DE10337199A1 (en) * | 2003-08-13 | 2005-03-10 | Degussa | cerium oxide powder |
| CN1321896C (en) * | 2004-04-14 | 2007-06-20 | 北京方正稀土科技研究所有限公司 | Process for preparing nano cerium dioxide |
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| CN101541912B (en) * | 2006-11-20 | 2012-12-12 | Lg化学株式会社 | Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
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| CN106029572A (en) * | 2013-12-16 | 2016-10-12 | 罗地亚经营管理公司 | Liquid suspension of cerium oxide particles |
| CN103754923A (en) * | 2014-01-28 | 2014-04-30 | 内蒙古科技大学 | Method for preparing superfine cerium oxide |
| CN103754923B (en) * | 2014-01-28 | 2016-08-17 | 内蒙古科技大学 | The preparation method of fine cerium oxide |
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| CN115403064A (en) * | 2022-09-20 | 2022-11-29 | 中国科学院长春应用化学研究所 | Cerium oxide and preparation method thereof |
| CN115403064B (en) * | 2022-09-20 | 2023-10-13 | 中国科学院长春应用化学研究所 | Cerium oxide and preparation method thereof |
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