CN103043671A - Production method for polysilicic acid - Google Patents
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- CN103043671A CN103043671A CN2012105800678A CN201210580067A CN103043671A CN 103043671 A CN103043671 A CN 103043671A CN 2012105800678 A CN2012105800678 A CN 2012105800678A CN 201210580067 A CN201210580067 A CN 201210580067A CN 103043671 A CN103043671 A CN 103043671A
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Abstract
The invention provides a production method for polysilicic acid. The method comprises the following steps: using excessive water glass to improve the resin exchange efficiency through the cation exchange; reducing the regenerant specific consumption and improving the finished product purity through collocation of weak acid type cation exchange resin and strong acid type cation exchange resin; backwards flowing the water glass to guarantee the flow smoothness through the weak acid type cation exchange resin; using exchanged flushing liquid to dilute concentrated water glass in order to improve the utilization rate of the water glass and reduce the waste water emission; and using collected acid residual liquid and generated flushing liquid for the next cycle of resin regeneration in order to further reduce the consumption of acid for regeneration and reduce the waste water neutralization cost. The method has the advantages of low regenerant specific consumption, high finished product purity, low consumption of de-ionized water and low waste water treatment cost, and has very remarkable commercial value.
Description
Technical field
The invention belongs to the inorganic fine chemicals production field, specifically a kind of for the manufacture of the production method of silicon sol (comprising for semiconductor die garden and other chemically machinery polished abrasive silica) with the poly-silicic acid of raw material, more precisely a kind ofly save the deionized water consumption, reduce regenerant consumption, improve the water glass utilization ratio, the method for the poly-silicic acid metal element content of control.
Background technology
Production method for the manufacture of silicon sol has a variety of at present, specifically comprise water glass ion exchange method, water glass electroosmose process, water glass acid directly neutralisation, silica gel high-temperature digestion method, elemental silicon dissolution method and organosilicon hydrolyzation method, and a large amount of employings of commercialization is water glass ion exchange method, silica gel high-temperature digestion method, elemental silicon dissolution method and organosilicon hydrolyzation method.
The organosilicon hydrolyzation method has simple, the easy to control the quality system of technique, advantage that facility investment is few, but needing the organosilicon with costliness is raw material, production cost is higher than other several methods far away, and product only is applied to field (such as chemical-mechanical polishing of semiconductor) that purity is had high requirements; The elemental silicon dissolution method has the advantage that technique is simple, facility investment is few equally, but residual solids particle difficulty or ease are separated clean and be can not get widespread use (such as chemical-mechanical polishing of semiconductor, high light printing paper) in the reactant, and only are applied to the fields such as refractory materials, exterior coating; Although the silica gel dissolution method has technique simply and the advantage of low equipment investment equally, because the deficiency that particle diameter is less and metal element content is high is not used widely equally; Facility investment is large although the water glass ion exchange method has, the deficiency of complex process, is used widely owing to raw material is cheap.
As everyone knows, exchangable ion and effects of ion exist running balance at exchange process on the exchange resin, and the exchange degree between the ion depends on concentration difference between exchange resin kind, exchange ion radius size and the exchange ion.
Traditional water glass ion exchange method has dual mode in poly-this step of silicic acid of preparation: swap-on-the-fly and exchange column exchange process.
Swap-on-the-fly comprises following steps: 1. add a certain amount of R-H strong acid type resin in reaction vessel, and then add a certain amount of rare water glass solution and stir, hydrogen ion on sodium in the solution (or potassium) ion and the resin is through ion-exchange and so that water glass changes poly-silicic acid into, then separation resin and poly-silicic acid; 2. resin adds separation resin and the rinsing liquid that contains poly-silicic acid (rinsing liquid that contains poly-silicic acid discharges after treatment as waste water) behind the water rinse; 3. resin stirs after adding diluted acid, the hydrogen ion exchange in (or potassium) ion of the sodium on the resin and the diluted acid, then separation resin and regenerated liquid (regenerated liquid is used as direct discharging of waste water after neutralizing treatment); 4. resin adds separation resin and rinsing liquid (rinsing liquid is as waste water discharging after neutralization) behind the water rinse.
Analyze the dynamic exchange process and be not difficult to find following several respects problem: 1. a certain amount of R-H strong acid type resin and water glass carry out ion-exchange under whipped state, positively charged ion in the solution and the positively charged ion on the resin reach running balance, hydrogen ion on the resin fails to be fully used, the commutative water glass of unit volume resin becomes the ratio of silicic acid lower, kish element in the poly-silicic acid of gained (be sodium element with sodium silicate, be potassium element with potash water glass) content is higher; 2. clean for the poly-silicic acid rinsing that will be attached on the resin after the resins exchange, need to consume a certain amount of deionized water, be attached to simultaneously that poly-silicic acid on the resin enters rinsing liquid and as discharge of wastewater, the silicon-dioxide in the poly-silicic acid is not fully used; When 3. resin adds diluted acid stirring regeneration, positively charged ion in the solution and the positively charged ion on the resin reach running balance, hydrogen ion in the solution fails to be fully used, cause the regenerator specific consumption high, solution behind the regeneration ending (being regenerated liquid) acid number is too high, need to consume more alkaline matter ability qualified discharge after neutralization meets environmental requirement, cause cost for wastewater treatment to increase; 4. be that the regenerated liquid rinsing that will be attached on the resin totally need consume more deionized water after the regeneration, the processing of the rinsing liquid that produces has increased again expense with discharging.
Adopt swap-on-the-fly, the silicon sol of 1 ton of 30% solid content of every production (take poly-silicic acid concentration 5% as example) needs to consume deionized water〉15m
3, 30% hydrochloric acid 0.6t, use in waste water treatment alkali lye be (with OH
-The mol number calculates)〉2.7kmol, waste discharge〉14.3m
3, silicon-dioxide utilization ratio＜94% in the water glass, metallic element (sodium or potassium) content in the poly-silicic acid of gained〉and 100ppm.
The exchange column exchange process comprises following steps: 1. a certain amount of rare water glass R-H strong acid type cationic resin layer of flowing through gets poly-silicic acid; 2. the deionized water resin layer flushing exchange resin of flowing through gets washing fluid (containing residuary water glass and poly-silicic acid), and washing fluid discharges after neutralizing treatment as waste water; 3. a certain amount of dilute acid streams is carried out resin regeneration through resin layer, gets regenerated liquid (comprising the acidic solution that the regeneration later stage is not fully utilized), and regenerated liquid discharges after neutralizing treatment as waste water; 4. get acid debris with the deionized water rinsing resin layer, acid debris is discharged after neutralizing treatment as waste water.
Adopt the exchange column exchange process, the silicon sol of 1 ton of 30% solid content of every production (take poly-silicic acid concentration 5% as example) needs to consume deionized water 10 ~ 12m
3, 30% hydrochloric acid, 0.40 ~ 0.45t, use in waste water treatment alkali lye consume (with OH
-The mol number calculates) 1.06 ~ 1.47kmol, waste discharge 9.3 ~ 11.3m
3, silicon-dioxide utilization ratio 93 ~ 96% in the water glass, metallic element (sodium or potassium) content 50 ~ 100ppm in the poly-silicic acid of gained.
The exchange column exchange process is compared with swap-on-the-fly has following several respects advantage: 1. concentration difference significantly increases between resin and effects of ion, exchange is more abundant with regeneration, the regenerator specific consumption obviously descends, unit volume resins exchange water glass quantity increases, and the kish constituent content descends in the poly-silicic acid; 2. in the resin cleaning process, because to wash alternative rinsing, the wash-down water consumption obviously descends.
Yet the exchange column exchange process also exists the deficiency of following several respects: 1. deionized water consumption is also more; 2. the regenerator specific consumption is also higher; 3. the water glass utilization ratio is also lower; 4. wastewater discharge is also more with the alkali lye of processing waste water consumption; 5. the kish constituent content also fails to reach the requirement of producing hyperpure silicasol in the poly-silicic acid of gained.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of poly-silicic acid production method, be used for to solve that the consumption of prior art deionized water is many, the regenerator specific consumption greatly, the water glass utilization ratio is low, discharge of wastewater is many, cost for wastewater treatment is high and poly-silicic acid in the high problem of kish constituent content.
For achieving the above object, the invention provides a kind of poly-silicic acid production method, comprise following 7 steps:
1) cationic exchange: excessive rare water glass solution adverse current is through R-H weak-type resin-column, the R-H strong acid type resin exchange column of flowing through again, must gather respectively silicic acid and alkalescence recovery liquid, described poly-silicic acid pH＜7.0 or metal element content＜1-50ppm(decide according to product requirement) the part effluent liquid, it is remainder effluent liquid except poly-silicic acid that described alkalescence reclaims liquid;
2) flushing: wash exchange column with a certain amount of deionized water in the spray mode, get washing fluid A;
3) resin regeneration: with the excessive dilute acid streams weak-type exchange column of behind the strong acid type exchange column, flowing through again, respectively regenerated liquid and acid raffinate; Described regenerated liquid is pH〉3 part effluent liquid, described acid raffinate is for remaining the part effluent liquid except regenerated liquid;
4) flushing: wash exchange column with a certain amount of deionized water in the spray mode, get washing fluid B;
5) alkalescence reclaims liquid and is used as rare water glass and is used at first ion-exchange in the production cycle and recycles in next round;
6) washing fluid A is used as deionized water and is used for the raw material concentrated sodium silicate being configured to rare water glass and recycling;
7) acid raffinate and washing fluid B merge and to be used as diluted acid and to be used at first resin regeneration in the production cycle and to recycle in next round.
The strong acid type resin of the R-H strong acid type resin exchange column described in the step 1) is 001 * 7 resin, and the weak-type resin in the described R-H weak-type resin-column is acrylic resin.
Excessive rare water glass described in the step 1) refers to sodium ion in rare water glass solution (potash water glass is potassium ion) mole number greater than 0.7 times of exchange capacity of resin, and more excellent is 0.7 ~ 1.5 times, and best is 1.1 ~ 1.5 times.
The constituent content of kish described in the step 1) is decided (common＜as 1-50ppm), usually to reach＜1ppm according to production technique of the present invention according to product needed.
Step 2) and step 4) described in a certain amount of deionized water rinsing exchange column of usefulness in the deionized water consumption be less than 2.0 times of resin layer volumes, 1.0 ~ 1.5 times of more excellent is resin layer volume, 1.2 ~ 1.3 times of best is resin layer volume.
The excessive diluted acid of usefulness described in the step 3) refers to that hydrionic mole number summation is 1.0 ~ 1.3 times of exchange capacity of resin in the diluted acid, and more excellent is that 1.05 ~ 1.10 times of resins exchange are held.
The present invention adopts the weak-type resin to reduce the regenerator specific consumption, control metal element content in the poly-silicic acid with strong acid type resin, in exchange process, guarantee that with the reflux type weak-type cationic exchange coloum of flowing through flow process is unimpeded, recycling alkalescence recovery liquid and washing fluid A reuse acid raffinate and washing fluid B and consume and the minimizing cost for wastewater treatment with acid to reduce to regenerate to improve the water glass utilization ratio, save deionized water consumption, to reduce discharge of wastewater.
Compare with the exchange column exchange process with existing swap-on-the-fly, the present invention has great advantage at the aspects such as metal element content, deionized water consumption, regenerator specific consumption, minimizing cost for wastewater treatment.
At first, adopt swap-on-the-fly, rare water glass solution is added R-H strong acid type resin to rare water glass gradually be transformed into poly-silicic acid under whipped state, the hydrogen ion utilization ratio only is 50 ~ 60% on the resin; Adopt the exchange column exchange process, above-mentioned same rare water glass solution high R-H strong acid type resin layer to water glass of 1.5 ~ 2.0m of flowing through is transformed into poly-silicic acid, the hydrogen ion utilization ratio on the resin layer also only is 60 ~ 70%; As above-mentioned same rare water glass solution being adopted excessive exchange process exchange of the present invention, reclaim liquid to alkalescence and flow to end from exchange column, at this moment hydrionic utilization ratio in the resin 93%.Obviously, excessive exchange process is compared the hydrogen ion utilization ratio and has been improved at least 33 percentage points with swap-on-the-fly; Excessive exchange process is compared hydrogen and has been improved at least 23 percentage points from utilization ratio with the exchange column exchange process.
Secondly, adopt swap-on-the-fly, metallic element (sodium or potassium) content is common in the poly-silicic acid〉100ppm, the poly-silicic acid that the method obtains can not directly be made high-purity silicasol, and described high-purity silicasol is metallic element＜10ppm in the silicon sol of 30% solid content; Adopt the exchange column exchange process, obtain early stage in the poly-silicic acid of part metal element content usually＜0.1ppm, along with the metal element content that carries out gradually that exchanges raises gradually, metal element content is usually at 0.2 ~ 1.0ppm in the poly-silicic acid that obtains when the water glass exchange capacity reaches 50% resins exchange amount, metal element content is at 1.0 ~ 5ppm during to 60% resins exchange amount, the average content of (pH＜7 parts is during the theoretical exchange capacity of about 70% resin) metallic element is 50 ~ 100ppm in the poly-silicic acid of all acidic moieties that obtain; Adopt a kind of poly-silicic acid production method of the present invention, can effectively control metal element content＜50ppm in the poly-silicic acid.
Again, swap-on-the-fly and exchange column exchange process are after the water glass exchange finishes, the residuary water glass solution that 10 ~ 15% resinite accumulated amounts are still arranged in the resin, the commutative 2.1L modulus of 1L strong acid type resin (001 * 7 resin) is 3.4, dioxide-containing silica is that the rare water glass solution of 7g/100ml becomes poly-silicic acid, and the water glass solution that remains in the resin after each exchange finishes is 4.8 ~ 7.1% of water glass solution total amount; Adopt swap-on-the-fly, need use the deionized water greater than 2.0 times of resin volumes could the resin rinsing is clean after the water glass exchange finishes, satisfy the regeneration requirement; Adopt the exchange column exchange process, need at least the deionized water of 2.0 times of resin volumes resin could be rinsed well with traditional continuous water inlet flushing after the water glass exchange finishes; And as above-mentioned purging method adopted the spraying process of one of using in the present invention, the liquid level that does not exceed resin layer when spray irrigation exists, the wash-down water consumption will be reduced to 0.7 ~ 1.2 times of resin volume.Obviously, adopt spray irrigation of the present invention not only to save the wash-down water consumption but also improved flush efficiency, simultaneously the present invention is used as deionized water with washing fluid A the raw material concentrated sodium silicate is configured to rare water glass, has not only improved the water glass utilization ratio, but also has avoided the generation of flushing waste water.
In addition, lot of documents and practice show when resin regeneration, adopt strong acid type resin (such as 001 * 7 resin) regenerator specific consumption higher (1.9 ~ 3.1), and weak-type resin (such as acrylic resin) regenerator specific consumption less (1.05 ~ 1.1); Under alkaline condition, the strong acid type resin exchange rate is higher than again the weak-type resin.The present invention successively by weak-type and strong acid type exchange column, so that the hydrogen ion in the resin is fully exchanged, has guaranteed effective control of metallic element in the poly-silicic acid with excessive water glass simultaneously thus; Again excessive dilute acid soln is passed through strong acid type exchange column and weak-type exchange column successively during regeneration, so that the hydrogen ion in the acid maximizes the use; The acid raffinate of collecting when regenerating simultaneously and the washing fluid B behind the regeneration ending merge as diluted acid next round in the production cycle at first for resin regeneration and take full advantage of.
Simultaneously, experiment shows that when rare water glass solution passed through the weak-type exchange column through following current, the resin volume can expand gradually, and exchange liquid flows and slows down, and finally causes solution to flow; Adopt countercurrent exchange method of the present invention, effectively avoided resin to expand and the flow velocity that causes reduces, so that exchange is carried out smoothly.
Embodiment
Below by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be used by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change under the spirit of the present invention not deviating from.
Embodiment 1
Preparatory period circulation (exchange column preparation)
1) in the DN50 exchange column, adds R-H strong acid type resin (001 * 7 resin) and claim exchange column A to height 1.5m(); In the exchange column of DN50, add the R-H acrylic resin and claim exchange column B to height 1.0m().15 moles of described two exchanging column resin exchange capacity ≈, resin layer volume ≈ 5L (R-H).
2) the delivery number is 3.4, SiO
2Content is the rare water glass solution 35L(1.37 of 6g/100ml times resins exchange total amount), adverse current is through exchange column B successively, and the exchange column A that flows through again gets respectively the poly-silicic acid a of 19L and 15.6L alkalescence and reclaims wherein cull layer 0.4L of liquid b(, following situation is identical), this moment, the resin layer volume became ≈ 6L.
3) be equivalent to 1.0 times of resin layer volumes with 6L() deionized water successively spray irrigation exchange column B and exchange column A, get washing fluid c6L, washing fluid dilutes concentrated sodium silicate as deionized water.
4) get 16L concentration be the rare HCl aqueous solution of 1.0mol/L (being equivalent to 1.07 times of resins exchange amounts) successively through exchange column A and exchange column B, respectively regenerated liquid e (pH〉3 parts) 13L and the regeneration of acid raffinate f (pH＜3 parts) 3L(next cycle with).
5) with 6L deionized water successively spray irrigation exchange column A and exchange column B, get washing fluid g6L, washing fluid g uses in the next cycle resin regeneration.
The 1st loop cycle (normal circulation)
6) get 15.6L alkalescence and reclaim liquid b, the exchange column B of adverse current behind a upper end cycle successively, the exchange column A behind the upper end cycle of flowing through again, alkalescence reclaim liquid b add finish after, water glass 25L after the above-mentioned dilution of continuation adding gets respectively the poly-silicic acid a1 of 25L and 15.6L alkalescence recovery liquid b1.
7) with 6L deionized water successively spray irrigation exchange column B and exchange column A, get 6L washing fluid c1, washing fluid c1 dilutes concentrated sodium silicate as deionized water.
8) get the acid raffinate f of 3L (pH＜3 parts) and 6L washing fluid g flow through successively exchange column A and exchange column B, continuing after add finishing to add 15L concentration is the rare HCl aqueous solution of 1.0mol/L, respectively 20L regenerated liquid e1 (pH〉3 parts) and 4L acidity raffinate f1.
9) with 6L deionized water successively following current spray irrigation exchange column A and exchange column B, get 6L washing fluid g1.
Constantly circulate by step 6) to step 9).
The poly-silicic acid that above-mentioned each cycle obtains can make 30% silicon sol 5.0kg, is converted to silicon sol deionized water per ton consumption and waste water and is produced as 4.0m
3, in and waste water consumption alkali lye 0.004kmol, regeneration is with 30% hydrochloric acid consumption 0.37t, the silicon-dioxide utilization ratio is 99.2% in the water glass.
Embodiment 2
Preparatory period circulation (exchange column preparation)
1) in the DN50 exchange column, adds R-H strong acid type resin (001 * 7 resin) and claim exchange column A to height 1.5m(); In the exchange column of DN50, add the R-H acrylic resin and claim exchange column B to height 1.0m().5 moles of described two exchanging column resin exchange capacity ≈, the resin layer volume is ≈ 5L (R-H).
2) the delivery number is 3.4, SiO
2Content is rare water glass solution 35L(1.37 times exchange capacity of resin of 6g/100ml), adverse current is through exchange column B and the exchange column A that flows through successively, get respectively the poly-silicic acid a(metallic element of 7L＜1ppm part) and 27.6L alkalescence recovery liquid b, this moment, the resin layer volume became ≈ 6L.
3) with 6L deionized water successively spray irrigation exchange column B and exchange column A, get 6L washing fluid c, washing fluid c is used for the dilution concentrated sodium silicate as deionized water.
4) get rare HCl aqueous solution that 16L concentration is 1.0mol/L (1.07 times of resins exchange amounts) flow through successively exchange column A and exchange column B, respectively 13L regenerated liquid e (pH〉3 part) and the acid raffinate f of 3L (pH＜3 partly).
5) with 6L deionized water successively spray irrigation exchange column A and exchange column B, get 6L washing fluid g.
The 1st loop cycle (normal circulation)
6) get 27.6L alkalescence recovery liquid B, adverse current is through exchange column B and exchange column A successively, and after adding finished, continuation added dilution water glass 25L, got respectively 25L and gathered silicic acid a1(metallic element＜1ppm part) and alkalescence recovery liquid b127.6L.
7) with 6L deionized water successively spray irrigation exchange column B and exchange column A, get 6L washing fluid c1.
8) get the acid raffinate f of 3L (pH＜3 parts) and 6L washing fluid g flow through successively exchange column A and exchange column B, continue to add the rare HCl aqueous solution of 15L (1.0mol/L), respectively 21L regenerated liquid e1 (pH〉3 parts) and 3L acidity raffinate f1.
9) with 6L deionized water successively spray irrigation exchange column A and exchange column B, get 6L washing fluid g1.
By 6) to 9) step constantly circulates.
The poly-silicic acid that above-mentioned each cycle obtains can make 30% silicon sol 5.0kg, is converted to silicon sol deionized water per ton consumption and waste water and is produced as 4.2m
3, in and waste water consumption alkali lye 0.004kmol, regeneration is with 30% hydrochloric acid consumption 0.37t, the silicon-dioxide utilization ratio is 99.2% in the water glass, metal element content＜1ppm in the silicic acid, metal element content＜5ppm in the 30% solid content silicon sol.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not is used for restriction the present invention.Any person skilled in the art scholar all can be under spirit of the present invention and category, and above-described embodiment is modified or changed.Therefore, have in the technical field under such as and know that usually the knowledgeable modifies or changes not breaking away from all equivalences of finishing under disclosed spirit and the technological thought, must be contained by claim of the present invention.
Claims (5)
1. poly-silicic acid production method may further comprise the steps:
1) cationic exchange: excessive rare water glass solution adverse current is through R-H weak-type cationic exchange coloum, the R-H strong-acid type cation exchange column of flowing through again, must gather respectively silicic acid and alkalescence recovery liquid, described poly-silicic acid is pH less than 7 or the effluent liquid of metal element content＜1-50ppm, and it be remainder effluent liquid except gathering silicic acid that described alkalescence reclaims liquid;
2) flushing: wash exchange column with deionized water in the spray mode, get washing fluid A;
3) resin regeneration: with the excessive dilute acid streams R-H weak-type exchange column of behind R-H strong acid type exchange column, flowing through again, respectively regenerated liquid and acid raffinate, described regenerated liquid is pH〉3 effluent liquid, described acid raffinate is remainder effluent liquid except regenerated liquid;
4) flushing: wash exchange column with deionized water in the spray mode, get washing fluid B;
5) alkalescence reclaims liquid and is used as rare water glass and is used at first ion-exchange in the production cycle and recycles in next round;
6) washing fluid A is used as deionized water and is used for the raw material concentrated sodium silicate being configured to rare water glass and recycling;
7) acid raffinate and washing fluid B merging was used as diluted acid and is used at first resin regeneration in next production cycle.
2. a kind of poly-silicic acid production method according to claim 1, it is characterized in that: the weak-type resin in the described R-H weak-type cationic exchange coloum is acrylic resin, and the strong acid type resin in the described R-H strong-acid type cation exchange column is 001 * 7 resin.
3. a kind of poly-silicic acid production method according to claim 1, it is characterized in that: the excessive rare water glass described in the step 1), refer to that the mole number of sodium ion in rare water glass (with potash water glass time be potassium ion) is greater than 0.7 times of exchange capacity of resin, 0.7～1.5 times of more excellent is exchange capacity of resin, 1.1 ~ 1.5 times of best is exchange capacity of resin.
4. a kind of poly-silicic acid production method according to claim 1, it is characterized in that: step 2) and step 4) described in the deionized water consumption of deionized water rinsing exchange column less than 2.0 times of resin layer volumes, 1.0～1.5 times of more excellent is resin layer volume, 1.2～1.3 times of best is resin layer volume.
5. a kind of poly-silicic acid production method according to claim 1, it is characterized in that: the excessive diluted acid of the usefulness described in the step 3) refers to that hydrionic mole number summation is 1.0 ~ 1.3 times of exchange capacity of resin in the diluted acid, and more excellent is that 1.05～1.10 times of resins exchange are held.
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| 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 |
| CN110217799A (en) * | 2018-03-02 | 2019-09-10 | 中国石油化工股份有限公司 | Silica solution and preparation method thereof |
| CN110217799B (en) * | 2018-03-02 | 2020-12-18 | 中国石油化工股份有限公司 | Silica sol and preparation method thereof |
| CN114868638A (en) * | 2022-04-21 | 2022-08-09 | 王进 | Paddy field water changing control method and system |
| CN114868638B (en) * | 2022-04-21 | 2023-09-29 | 王进 | Paddy field water change control method and system |
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