CN102311122A - Silicic acid purification method - Google Patents
Silicic acid purification method Download PDFInfo
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- CN102311122A CN102311122A CN201110220439A CN201110220439A CN102311122A CN 102311122 A CN102311122 A CN 102311122A CN 201110220439 A CN201110220439 A CN 201110220439A CN 201110220439 A CN201110220439 A CN 201110220439A CN 102311122 A CN102311122 A CN 102311122A
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- silicic acid
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Abstract
The invention provides a silicic acid purification method, comprising the following steps of 1) treatment of cationic resin; 2) treatment of anionic resin; 3) preparation of sodium silicate solution; 4) preparation of silicic acid; 5) acidification of silicic acid; 6) second treatment of cationic resin; 7) adjusting of pH; and 8) purification of silicic acid. The silicic acid purification method of the invention increases a removal rate of aluminum element from 6% to 94%, a removal rate of magnesium element from 27% to 61.5%, a removal rate of calcium element from 40% to 90%. A pH of the purified silicic acid is adjusted to 4 by organic base, so as to avoid silicic acid gelatin caused by salt generated from neutralization of inorganic base and acid; and the purified silicic acid has obviously reduced metal impurities, improved stability and is beneficial to silica solution synthesis using silicic acid as a raw material.
Description
Technical field
The present invention relates to a kind of silicic acid purification process, specifically, relate to the purification process of the raw materials of silica sol silicic acid that is used to prepare polishing fluid, belong to chemical technology field.
Background technology
In chemically machinery polished (CMP), employed polishing fluid be with the silicon dioxide colloid in the silicon sol as abrasive material, and the semiconductor material performance influence of the purity of silicon dioxide colloid after to polishing is very big.If can reduce metal element content in the silicon sol of traditional technology preparation; Mainly be Ca, Mg, Al etc.; Just can keep away polishing residual these metallic elements of material surface later, thereby avoid a series of problems of causing because of these metallic elements, the raising product percent of pass.In the building-up process of silicon sol, if contain high-valency metal elements such as Ca, Mg, Al in the raw material, they tend to get in the netted space of silicon sol with the form of oxyhydroxide, therefore are difficult to remove through simple method.And these metallic impurity in the process of polishing, can interact with other chemical substances in the polishing fluid, change existence form, enter into polishing fluid again, thereby pollute, and influence polishing effect.Therefore, ion exchange method is owing to contain more impurity in its raw water glass, and its synthetic silicon sol also contains more impurity, therefore can't be used in the higher finishing polish of purity requirement.
Directly handle silicic acid or silicon sol with the combination of resin cation(R.C.) or positive negatively charged ion, effect is all undesirable, reason be pH value greater than 4 condition under, most metals are to exist with hydroxide form, are difficult to removal with the method for IX.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art, improve a kind of silicic acid purification process.
Silicic acid purification process of the present invention may further comprise the steps:
1) processing of resin cation(R.C.)
Brand-new strong acid type cationic resin is cleaned; Spend the night with the NaOH solution soaking of 5wt% earlier; Be washed till pH7-8 with zero(ppm) water, use 11% hydrochloric acid soln soaked overnight again, use zero(ppm) water clean to the pH value be 5～6; The strong acid type cationic resin of so handling well is filled two resin columns, i.e. post 1 and post 2;
2) processing of resin anion(R.A)
Brand-new strong base resin anion(R.A) is cleaned, spend the night with the NaOH solution soaking of 5wt%, be washed till pH7-8 with zero(ppm) water, fill resin column 3, promptly post 3;
3) preparation of water glass solution
Water intaking glass is mixed with the 2-6wt% water glass solution with zero(ppm) water, and is subsequent use;
4) preparation of silicic acid
With water glass solution, make its post 1 of flowing through and filling resin with certain flow rate, during effluent PH is 3-4, collect solution 1;
5) acidifying of silicic acid
With the 1-10wt% inorganic acid solution pH value of solution 1 is adjusted to 0.1～3, stirred 0.5-10h hour; 6) resin cation(R.C.) is handled for the second time
Post 2 with the solution after the acidifying 1 is flowed through and filled resin cation(R.C.) with certain flow rate obtains solution 2;
7) pH regulator
Use an amount of organic bases to be added in the solution 2, regulate the pH value, obtain solution 3 to 3-4 with certain interpolation speed;
8) purifying of silicic acid
Make it through post 3 with certain flow rate solution 3, obtain the silicic acid behind the final purifying.
Preferably, in the described silicic acid purification process,
Said modulus of water glass is 1.
Said resin cation(R.C.) is a Na type highly acidic resin, and the granularity of resin is at 0.25-1.25mm.
The said acidifying mineral acid that is used for is hydrochloric acid, sulfuric acid or nitric acid.
The flow through flow velocity of post 2 of said solution 1 is 5L/h-10L/h.
When the pH value of post 2 effluent begins to descend, for collecting the starting point of solution 2; When effluent pH value remains unchanged, for collecting the terminal point of solution 2.
Employed organic bases is TMAH, choline, pyridine, thanomin or diethylenetriamine.
The speed of the organic alkaline solution of said interpolation is 1g/h-60g/h.
The flow through flow velocity of post 3 of said solution 3 is 5L/h-10L/h.
When the pH value of post 3 effluent begins to rise, for collecting the starting point of final purifying silicic acid; When effluent pH value remains unchanged, for collecting the terminal point of final purifying silicic acid.
Principle of the present invention is:
The form that metal exists in water is relevant with pH.With Al is example
There is following balance Al in aluminium in basic soln
3++ 3OH
- 
Al (OH)
3
When pH=10, C [OH then
-]=10
-4Mol/L
Al (OH)
3Solubleness be 3*10
-33Mol/L, by white lake solution solubility product formula:
KspAl?=C[Al
3+]*（?C[OH
-]）
3
Can calculate Al under this pH
3+Content be to the maximum: 3*10
-21Mol/L
When pH=2, C [OH then
-]=10
-12Mol/L, then Al under this pH
3+Content be to the maximum: 3*10
3Mol/L that is to say under acidic conditions, Al (OH)
3Can not be present in the aqueous solution, but with Al
3+Form exist.
The pH value of silicic acid is adjusted to 0.1～3, makes Al (OH)
3Be converted into Al
3+, removing Al through resin cation(R.C.)
3+, can reach the purpose of purifying.
Silicic acid purification process of the present invention; The pH value of silicic acid is transferred to 0.1～3,, pass through resin cation exchange again so that metallic element wherein is converted into ionic species by the metal hydroxides form; Remove metallic element; Adding organic bases adjusting pH is 3-4, and the silicic acid after will handling is again finally prepared highly purified silicic acid through the strong base resin anion(R.A).Through the silicic acid that the inventive method is handled, can the clearance of aluminium element be brought up to 94% by 6%, the clearance of magnesium elements is brought up to 61.5% by 27%, the clearance of calcium constituent is brought up to 90% by 40%.Be adjusted to 4 with the silicic acid pH value of organic bases after with purifying; Can avoid the use of mineral alkali and cause silicic acid gel with the salt that the acid neutralization generates; Silicic acid metallic impurity behind the purifying obviously reduce, and have increased the stability of silicic acid, and being beneficial to silicic acid is that the silicon sol that raw material carried out is synthetic.
Method of the present invention has following technique effect:
1, start with from the purifying of raw material silicic acid, most of metallic impurity of avoiding from the source get into the silicon sol building-up process.If the product silicon sol is carried out the purifying of similar technology, because under the alkaline condition, metallic impurity exist with hydroxide form,, can mix that it is inner to get into colloid along with the growth of silicon sol, be difficult to remove through simple IX;
2, analyzed, verified the relation of metal existence form and pH value of solution objectively.When solution is when alkalescence, metallic impurity exist with hydroxide form, and it is lower to be difficult to the rate of removing through resin cation exchange.The present invention is according to this principle, and pH turns down with silicic acid, makes metal hydroxides fully be converted into the metals ion form.Then improved clearance effectively through resin cation(R.C.) again;
3, the pH of reduction silicic acid will make silicic acid play pendulum, easily gel.Therefore the silicic acid pH after the present invention adopts organic bases to handle regulates back 3-4 again, has guaranteed the stability of silicic acid.Simultaneously, if use mineral alkali to regulate pH, acid-base neutralisation generates salt, and same unfavorable to stablizing of silicic acid, the generation of inorganic salt has been avoided in the employing of organic bases;
4, make at last and to have passed through acidifying-resin cation(R.C.)-organic bases and regulate silicic acid behind the pH through resin anion(R.A), further purifying silicic acid.
Embodiment
Embodiment 1
Present embodiment mesosilicic acid purification process comprises the following steps:
1. the processing of resin cation(R.C.)
Brand-new strong acid type cationic resin is cleaned; Spend the night with the NaOH solution soaking of 5wt% earlier; Be washed till pH7-8 with zero(ppm) water, use 11% hydrochloric acid soln soaked overnight again, use zero(ppm) water clean to the pH value be 5～6; The strong acid type cationic resin of so handling well is filled two resin columns, i.e. post 1 and post 2;
2. the processing of resin anion(R.A)
Brand-new strong base resin anion(R.A) is cleaned, spend the night, be washed till pH7-8, fill resin column 3 (post 3) with zero(ppm) water with the NaOH solution soaking of 5wt%.
3. the preparation of water glass solution
Water intaking glass is mixed with the 3wt% water glass solution with zero(ppm) water, and is subsequent use
4. the preparation of silicic acid
With the water glass solution of 3wt%, make its post 1 of flowing through and filling resin with the 5L/h flow velocity, collect solution 1, when effluent pH greater than 4 the time, stop to collect.
5. the acidifying of silicic acid
Solution 1 is used the 10wt% hcl acidifying, and regulating the pH value is 1, stirs 1 hour.
6. resin cation(R.C.) is handled for the second time
Post 2 with the solution after the acidifying 1 is flowed through and filled resin cation(R.C.) with the flow velocity of 5L/h obtains solution 2.7.pH regulate
Be added in the solution 2 with 10g/h interpolation speed with the 10wt% choline, regulate pH value to 3, obtain solution 3.
8. the purifying of silicic acid
Make it through post 3 with the flow velocity of 5L/h solution 3, obtain the silicic acid behind the final purifying.
ICP result is following in experiment:
Embodiment 2
Present embodiment mesosilicic acid purification process comprises the following steps:
1. the processing of resin cation(R.C.)
Brand-new strong acid type cationic resin is cleaned; Spend the night with the NaOH solution soaking of 5wt% earlier; Be washed till pH7-8 with zero(ppm) water, use 11% hydrochloric acid soln soaked overnight again, use zero(ppm) water clean to the pH value be 5～6; The strong acid type cationic resin of so handling well is filled two resin columns (post 1, post 2).
2. the processing of resin anion(R.A)
Brand-new strong base resin anion(R.A) is cleaned, spend the night, be washed till pH7-8, fill resin column 3 (post 3) with zero(ppm) water with the NaOH solution soaking of 5wt%.
3. the preparation of water glass solution
Water intaking glass is mixed with 2% water glass solution with zero(ppm) water, and is subsequent use
4. the preparation of silicic acid
With water glass solution, make its post 1 of flowing through and filling resin with the 10L/h flow velocity, collect solution 1, when effluent pH greater than 4 the time, stop to collect.
5. the acidifying of silicic acid
With solution 1 usefulness 10wt% nitric acid acidifying, regulating the pH value is 2, stirs 5 hours.
6. resin cation(R.C.) is handled for the second time
Post 2 with the solution after the acidifying 1 is flowed through and filled resin cation(R.C.) with the flow velocity of 10L/h obtains solution 2.7.pH regulate
Be added in the solution 2 with 5g/h interpolation speed with the 10wt% TMAH, regulate pH value to 3, obtain solution 3.
8. the purifying of silicic acid
Make it through post 3 with the flow velocity of 10L/h solution 3, obtain the silicic acid behind the final purifying.
ICP result is following in experiment:
Embodiment 3
Present embodiment mesosilicic acid purification process comprises the following steps:
1. the processing of resin cation(R.C.)
Brand-new strong acid type cationic resin is cleaned; Spend the night with the NaOH solution soaking of 5wt% earlier; Be washed till pH7-8 with zero(ppm) water, use 11% hydrochloric acid soln soaked overnight again, use zero(ppm) water clean to the pH value be 5～6; The strong acid type cationic resin of so handling well is filled two resin columns (post 1, post 2).
2. the processing of resin anion(R.A)
Brand-new strong base resin anion(R.A) is cleaned, spend the night, be washed till pH7-8, fill resin column 3 (post 3) with zero(ppm) water with 5% NaOH solution soaking.
3. the preparation of water glass solution
Water intaking glass is mixed with 2.6% water glass solution with zero(ppm) water, and is subsequent use
4. the preparation of silicic acid
With water glass solution, make its post 1 of flowing through and filling resin with the 8L/h flow velocity, collect solution 1, when effluent pH greater than 4 the time, stop to collect.
5. the acidifying of silicic acid
Solution 1 is used 10% sulfuric acid acidation, and regulating the pH value is 3, stirs 10 hours.
6. resin cation(R.C.) is handled for the second time
Post 2 with the solution after the acidifying 1 is flowed through and filled resin cation(R.C.) with the flow velocity of 8L/h obtains solution 2.7.pH regulate
Be added in the solution 2 with 30g/h interpolation speed with the 10wt% thanomin, regulate pH value to 4, obtain solution 3.
8. the purifying of silicic acid
Make it through post 3 with the flow velocity of 8L/h solution 3, obtain the silicic acid behind the final purifying.
ICP result is following in experiment:
Claims (10)
1. a silicic acid purification process is characterized in that, may further comprise the steps:
1) processing of resin cation(R.C.)
Brand-new strong acid type cationic resin is cleaned; Spend the night with the NaOH solution soaking of 5wt% earlier; Be washed till pH7-8 with zero(ppm) water, use 11% hydrochloric acid soln soaked overnight again, use zero(ppm) water clean to the pH value be 5～6; The strong acid type cationic resin of so handling well is filled two resin columns, i.e. post 1 and post 2;
2) processing of resin anion(R.A)
Brand-new strong base resin anion(R.A) is cleaned, spend the night with the NaOH solution soaking of 5wt%, be washed till pH7-8 with zero(ppm) water, fill resin column 3, promptly post 3;
3) preparation of water glass solution
Water intaking glass is mixed with the 2-6wt% water glass solution with zero(ppm) water, and is subsequent use;
4) preparation of silicic acid
With water glass solution, make its post 1 of flowing through and filling resin with certain flow rate, during effluent PH is 3-4, collect solution 1;
5) acidifying of silicic acid
With the 1-10wt% inorganic acid solution pH value of solution 1 is adjusted to 0.1～3, stirred 0.5-10h hour; 6) resin cation(R.C.) is handled for the second time
Post 2 with the solution after the acidifying 1 is flowed through and filled resin cation(R.C.) with certain flow rate obtains solution 2;
7) pH regulator
Use an amount of organic bases to be added in the solution 2, regulate the pH value, obtain solution 3 to 3-4 with certain interpolation speed;
8) purifying of silicic acid
Make it through post 3 with certain flow rate solution 3, obtain the silicic acid behind the final purifying.
2. silicic acid purification process according to claim 1 is characterized in that, said modulus of water glass is 1.
3. silicic acid purification process according to claim 1 is characterized in that, said resin cation(R.C.) is a Na type highly acidic resin, and the granularity of resin is at 0.25-1.25mm.
4. silicic acid purification process according to claim 1 is characterized in that, the said acidifying mineral acid that is used for is hydrochloric acid, sulfuric acid or nitric acid.
5. silicic acid purification process according to claim 1 is characterized in that, the flow through flow velocity of post 2 of said solution 1 is 5L/h-10L/h.
6. silicic acid purification process according to claim 1 is characterized in that, when the pH value of post 2 effluent begins to descend, for collecting the starting point of solution 2; When effluent pH value remains unchanged, for collecting the terminal point of solution 2.
7. silicic acid purification process according to claim 1 is characterized in that, employed organic bases is TMAH, choline, pyridine, thanomin or diethylenetriamine.
8. silicic acid purification process according to claim 1 is characterized in that, the speed of the organic alkaline solution of said interpolation is 1g/h-60g/h.
9. silicic acid purification process according to claim 1 is characterized in that, the flow through flow velocity of post 3 of said solution 3 is 5L/h-10L/h.
10. silicic acid purification process according to claim 1 is characterized in that, when the pH value of post 3 effluent begins to rise, for collecting the starting point of final purifying silicic acid; When effluent pH value remains unchanged, for collecting the terminal point of final purifying silicic acid.
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|---|---|---|---|
| CN201110220439A CN102311122A (en) | 2011-08-03 | 2011-08-03 | Silicic acid purification method |
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|---|---|---|---|
| CN201110220439A CN102311122A (en) | 2011-08-03 | 2011-08-03 | Silicic acid purification method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043671A (en) * | 2012-12-27 | 2013-04-17 | 上海新安纳电子科技有限公司 | Production method for polysilicic acid |
| CN104591192A (en) * | 2014-12-24 | 2015-05-06 | 上海新安纳电子科技有限公司 | Method for preparing high-purity silicic acid |
| CN106810287A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of method for improving big thickness fiber reinforcement quartz composite density |
| CN108002393A (en) * | 2017-12-27 | 2018-05-08 | 上海新安纳电子科技有限公司 | A kind of method that Ludox polishing fluid using recycling prepares silicic acid |
| CN111334255A (en) * | 2018-12-19 | 2020-06-26 | 阳江市惠尔特新材料科技有限公司 | Preparation method of high-purity silica sol and silica sol prepared by preparation method |
| CN111732106A (en) * | 2020-06-02 | 2020-10-02 | 青岛海湾科技产业研究院有限公司 | Method for preparing active silicic acid and silica sol |
| CN112299424A (en) * | 2020-09-29 | 2021-02-02 | 航天特种材料及工艺技术研究所 | Method for preparing low-metal-content high-purity silicic acid |
| CN113372630A (en) * | 2020-03-10 | 2021-09-10 | 旭化成株式会社 | Conjugated diene polymer composition and tire |
| CN115611284A (en) * | 2021-07-13 | 2023-01-17 | 航天特种材料及工艺技术研究所 | Method for preparing high-purity silicic acid |
-
2011
- 2011-08-03 CN CN201110220439A patent/CN102311122A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043671A (en) * | 2012-12-27 | 2013-04-17 | 上海新安纳电子科技有限公司 | Production method for polysilicic acid |
| CN103043671B (en) * | 2012-12-27 | 2014-12-03 | 上海新安纳电子科技有限公司 | Production method for polysilicic acid |
| CN104591192A (en) * | 2014-12-24 | 2015-05-06 | 上海新安纳电子科技有限公司 | Method for preparing high-purity silicic acid |
| CN106810287A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of method for improving big thickness fiber reinforcement quartz composite density |
| CN106810287B (en) * | 2015-11-30 | 2020-06-16 | 航天特种材料及工艺技术研究所 | Method for improving density of large-thickness fiber reinforced quartz composite material |
| CN108002393A (en) * | 2017-12-27 | 2018-05-08 | 上海新安纳电子科技有限公司 | A kind of method that Ludox polishing fluid using recycling prepares silicic acid |
| CN111334255A (en) * | 2018-12-19 | 2020-06-26 | 阳江市惠尔特新材料科技有限公司 | Preparation method of high-purity silica sol and silica sol prepared by preparation method |
| CN111334255B (en) * | 2018-12-19 | 2021-08-31 | 阳江市惠尔特新材料科技有限公司 | Preparation method of high-purity silica sol and silica sol prepared by preparation method |
| CN113372630A (en) * | 2020-03-10 | 2021-09-10 | 旭化成株式会社 | Conjugated diene polymer composition and tire |
| CN111732106A (en) * | 2020-06-02 | 2020-10-02 | 青岛海湾科技产业研究院有限公司 | Method for preparing active silicic acid and silica sol |
| CN112299424A (en) * | 2020-09-29 | 2021-02-02 | 航天特种材料及工艺技术研究所 | Method for preparing low-metal-content high-purity silicic acid |
| CN115611284A (en) * | 2021-07-13 | 2023-01-17 | 航天特种材料及工艺技术研究所 | Method for preparing high-purity silicic acid |
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Application publication date: 20120111 |