CN111054205A - High-efficient fluorine recovery unit of wet process phosphoric acid - Google Patents
High-efficient fluorine recovery unit of wet process phosphoric acid Download PDFInfo
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- CN111054205A CN111054205A CN202010128222.7A CN202010128222A CN111054205A CN 111054205 A CN111054205 A CN 111054205A CN 202010128222 A CN202010128222 A CN 202010128222A CN 111054205 A CN111054205 A CN 111054205A
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Abstract
The invention discloses a wet-process phosphoric acid high-efficiency fluorine recovery device which mainly comprises a fluorine washer parallel-flow washing, a first-stage liquid foam separation, a pipeline parallel-flow washing, a second-stage cyclone separation, a third-stage liquid foam separation and automatic interlocking control of the whole process from water replenishing to fluosilicic acid production. The main equipment comprises a fluorine washer, a fluorine washer top layer sprayer, an in-tower annular sprayer, a pipeline separator, a pipeline sprayer, a tangential air inlet pipeline, a difluoro separator, a demister sprayer, a fluorine circulating pump, a fluorine sealing groove, a difluoro circulating pump, a pipeline pressure pump and related overflowing pipelines which are sequentially arranged on a gas phase pipeline, and a density meter, a liquid level meter, a pipeline separator flushing water replenishing valve and a demister flushing water replenishing valve which are required by realizing interlocking control. The whole process is fully automatically controlled, so that the yield of fluosilicic acid can be increased, the fluorine-containing sewage treatment cost is reduced, the fluorine escape amount is reduced, and the environment is improved.
Description
Technical Field
The invention relates to all the field of wet-process phosphoric acid production, in particular to a wet-process phosphoric acid high-efficiency fluorine recovery device.
Background
The fluorine is used as an associated resource in the phosphate ore and is scarce and precious. In the wet-process phosphoric acid production process, fluorine is mainly washed and recovered from phosphoric acid evaporation gas. With the rise of fluorine industry in recent years and the environmental protection requirement of new era, fluorine products are extracted from phosphate ore as far as possible, so that more economic values can be created, the treatment cost of fluorine-containing wastewater can be reduced, the pollution caused by the escape of fluorine into the air is reduced, and the environment is better protected.
The fluorine-containing gas evaporated in the wet-process phosphoric acid concentration process is difficult to recover due to large evaporation capacity, high gas temperature, high vacuum degree, too fast gas speed and the like. The existing wet-process fluorine phosphate recovery process adopts either single-tower cocurrent flow or countercurrent washing plus liquid foam separation or monofluorine pipeline cocurrent flow washing plus monofluorine tower countercurrent washing plus difluoro pipe cocurrent flow washing plus difluoro tower countercurrent washing. The former design adopts short washing flow, fluorine-containing gas is not cleaned, and the yield of gas-phase fluorine is low due to fast evaporation gas and low separation efficiency; the latter process is more obvious that silicon tetrafluoride can not be cleaned in a monofluorine washer, after the difluorofluorine washing, more silica gel is in a difluoro sealing groove, the air resistance in the washing tower is large, the washing liquid in the difluorofluorine tower is often pumped away, the fluosilicic acid concentration time is longer, and the gas phase fluorine yield is lower.
30 ten thousand tons of P produced per year2O5The fluorine recovery rate of the phosphoric acid concentrated evaporation gas is 80 percent, the concentration of dilute phosphoric acid is controlled to be 25 percent, the fluorine content is 2.1 percent, the concentration of concentrated product acid is controlled to be 48 percent, the fluorine content is 1.4 percent, and 1 ton of P is produced2O5About 55.5kg of fluosilicic acid is obtained, and 0.45t of fluorine escapes to the acidic circulating water every hour. To control the acidic circulating waterThe index of fluorine content is less than or equal to 3000ppm, and the index can be maintained only by supplementing and replacing process water with at least 151 cubes per hour. However, in the wet-process phosphoric acid production process, under the limitation of the water balance condition, the recycling of the slag yard pool water and other production wastewater needs to be fully considered, so the net displacement amount of the acidic circulating water is very small. If the fluorine content index of the acid circulating water needs to be completely controlled, only the fluorine-containing wastewater which cannot be replaced can be neutralized, and then the treated water is supplemented into the acid circulating water. In this way, the cost of wastewater treatment is very high. However, if the waste water containing fluorine is not replaced or replaced by other waste water (such as pool water) containing fluorine, the quality of the circulating water is increasingly poor, so that the production quality of the fluosilicic acid is unqualified, a cooling tower, a circulating water pump and overflowing parts thereof are corroded, system faults occur frequently, and the production environment and the surrounding environment are affected by acid rain floating of the cooling tower in serious cases.
Therefore, in order to change the current situation, efficient and environmentally friendly fluorine recovery technology needs to be developed.
Disclosure of Invention
The invention provides a fluorine recovery technical scheme of two-stage parallel flow and three-stage separation according to physicochemical properties of silicon tetrafluoride, hydrogen fluoride, water, fluosilicic acid and hydrated silicon dioxide and by combining parameters such as system vacuum degree, temperature, evaporation capacity, gas velocity and the like in the actual production process.
The technical scheme provided by the invention is a wet-process phosphoric acid high-efficiency fluorine recovery device which mainly comprises a fluorine scrubber parallel-flow washing, a first-stage liquid-foam separation, a pipeline parallel-flow washing, a second-stage cyclone separation, a third-stage liquid-foam separation and automatic interlocking control of the whole process from water replenishing to fluosilicic acid production. The main equipment comprises a fluorine washer, a fluorine washer top layer sprayer, an in-tower annular sprayer, a pipeline separator, a pipeline sprayer, a tangential air inlet pipeline, a difluoro separator, a demister sprayer, a fluorine circulating pump, a fluorine sealing groove, a difluoro circulating pump, a pipeline pressure pump and related overflowing pipelines which are sequentially arranged on a gas phase pipeline, and a density meter, a liquid level meter, a pipeline separator flushing water replenishing valve and a demister flushing water replenishing valve which are required by realizing interlocking control.
The connection mode of the main equipment is as follows:
arranging a top layer spray head of a fluorine washer and an inner ring type spray head in the tower in the fluorine washer, wherein the spraying direction of circulating liquid is consistent with the direction of air flow, a lower liquid pipeline of the fluorine washer is connected to a fluorine sealing groove, the fluorine sealing groove is provided with a fluorine circulating pump, an outlet pipeline of the fluorine circulating pump is provided with a densimeter, and the densimeter is interlocked with a fluosilicic acid discharge valve on the pipeline;
a pipeline separator is arranged at a washing outlet of the fluorine washer, a pipeline spray head is arranged in the pipeline separator, the pipeline separator is connected with the difluoro separator through a tangential air inlet pipeline, a downcomer of the difluoro separator is connected to a difluoro sealing groove, the difluoro sealing groove is provided with a difluoro circulating pump, and the difluoro circulating pump is connected to the pipeline spray head;
the bottom of the pipeline separator is provided with flushing water supplement, a difluoro circulating pump is communicated to a fluoro sealing groove through a bottom liquid receiving pipe of the pipeline separator, a pipeline separator flushing water supplement valve is arranged on the bottom liquid receiving pipe of the pipeline separator, a fluoro sealing groove liquid level meter is arranged on the fluoro sealing groove, and the fluoro sealing groove liquid level meter is interlocked with the pipeline separator flushing water supplement valve;
a demister is arranged at the upper part of the difluoro separator, pressurized flushing water supplement is arranged above the demister, and a demister flushing water supplement valve is arranged;
the difluoro sealing groove is provided with a difluoro sealing groove liquid level meter which is interlocked with the demister washing water replenishing valve; the foam remover flushing water replenishing valve is interlocked with the pipeline pressurizing pump.
A fluorine seal groove stirrer is arranged in the fluorine seal groove.
Through the interlocking control, the full-automatic control is realized by water replenishing, circulating absorption and fluosilicic acid discharging from the fluorine recovery device.
The device of the invention has the following working procedures: phosphoric acid fluorine-containing gas enters from the top of a fluorine scrubber, under the action of a fluorine circulating pump, washing liquid is fully contacted with the phosphoric acid fluorine-containing gas through spraying of a top layer spray head of the fluorine scrubber and an annular spray head in a tower, the gas is circularly absorbed and enters a pipeline separator through the gas absorbed by the fluorine scrubber, primary liquid-foam separation is realized, the separated gas is sprayed and washed by circulating liquid provided by a difluoro circulating pump before entering the difluoro separator, and the washed circulating liquid returns to a difluoro sealing groove from a downcomer of the difluoro separator. And the washed gas tangentially enters a difluoro separator for secondary cyclone separation, the separated gas passes through a demister for tertiary separation, and then enters a circulating water vacuum-pumping system. After continuous circulation absorption, the content of fluosilicic acid in the circulating liquid is gradually increased, and when the required concentration is reached, a discharge valve at the outlet of a fluorine circulating pump is automatically opened to send the fluosilicic acid to a fluosilicic acid storage tank. After fluosilicic acid is discharged, the liquid level of the fluorine sealing groove is used for conveying difluoro circulating liquid to be supplemented with water through the bottom of pipeline separation under the action of the difluoro circulating pump, and the liquid level of the difluoro sealing groove is supplemented with water through the demister through a pipeline pressure pump.
The invention has the beneficial effects that:
(1) the multi-layer spraying is arranged in the fluorine washer, the plurality of spray heads are installed, a tower parallel flow washing mode is adopted, the gas-liquid speed ratio in the tower is adjusted, the reaction contact time of silicon tetrafluoride gas and hydrofluoric acid is prolonged, the silicon tetrafluoride gas and the hydrofluoric acid are enabled to fully complete the reaction in the fluorine tower, the concentration of fluosilicic acid is increased rapidly, more finished fluosilicic acid products are generated, no silica gel is generated in a difluoro tank basically, and the extremely low silica gel content of the difluoro washing liquid is ensured.
(2) Set up the agitator in the fluorine seal groove, prevent that hydrogen fluoride and silicon tetrafluoride proportion from not matching among the phosphoric acid fluorine-containing gas, the silica gel of production is too much, and deposit seal groove bottom causes circulation washing liquid silica gel content increase in the twinkling of an eye, blocks up pipeline or shower nozzle.
(3) The outlet of the fluorine scrubber is provided with a pipeline separator, and in order to prevent or reduce liquid foam carried by high-speed airflow, the outlet of the fluorine scrubber is additionally provided with the pipeline separator for intercepting and collecting fluosilicic acid liquid drops taken away by the high-speed airflow.
(4) The bottom of the pipeline separator is provided with flushing water replenishing which comes from a difluoro sealing groove in order to avoid blocking the separator due to the possibility of silica gel generation in the monofluorine scrubber.
(5) And (2) performing parallel-flow washing on an air inlet pipeline of a difluoro separator, wherein fluorine-containing gas which is not cleaned in a fluorine tower and liquid foam which is not completely separated pass through a difluoro circulating liquid with a low temperature, a quick parallel-flow washing mode is adopted at the air inlet pipeline, washing conditions of low temperature, high pressure and full contact are provided, and residual fluorine in the gas is washed and recovered at the tail end.
(6) The gas tangentially enters the difluoro separator, after being sprayed and washed in the difluoro pipeline, the gas tangentially enters the difluoro separator, the gas velocity is reduced, the cyclone separation is carried out, and the liquid drops fall back along the wall of the device.
(7) The upper part of the difluoro separator is provided with the demister, and liquid drops entrained by the gas phase in the middle of the difluoro separator cannot fall back due to large gas quantity and high gas speed, so that the liquid drops are intercepted by installing the demister.
(8) The pressure boosting flushing water replenishing is arranged above the demister separator, intercepted liquid drops are flushed away, and meanwhile the demister is prevented from scaling.
(9) A densimeter is arranged on the fluorine circulating pipeline and is interlocked with the fluosilicic acid discharge valve. The densimeter sets an upper limit value and a lower limit value, the density of the monofluoro-cleaning solution reaches the upper limit value, the fluosilicic acid discharge valve is fully opened, and the fluosilicic acid discharge valve reaches the lower limit value, and is fully closed.
(10) The liquid level of a fluorine sealing groove is interlocked with a flushing water replenishing valve of the pipeline separator. And after the liquid level of the fluorine sealing groove reaches the upper limit value, the flushing water supplementing valve of the pipeline separator is opened, and after the liquid level of the fluorine sealing groove reaches the lower limit value, the flushing water supplementing valve is closed.
(11) The liquid level of the difluoro sealing groove is interlocked with the flushing water replenishing valve of the demister. And when the liquid level reaches the lower limit value, the demister flushing water supplementing valve is opened, and the liquid level reaches the upper limit value, and the flushing water supplementing valve is closed.
(12) The foam remover flushing water replenishing valve is interlocked with the pipeline pressurizing pump. When the foam remover flushing water replenishing valve is opened, the pipeline pressurizing pump is automatically started through interlocking; when the foam remover flushing water replenishing valve is closed, the pipeline pressurizing pump automatically stops.
Drawings
FIG. 1 is a schematic flow diagram of a wet-process phosphoric acid high-efficiency fluorine recovery device.
In the figure: 1. a fluorine scrubber; 2. a top shower nozzle of a fluorine scrubber; 3. an in-tower annular nozzle; 4. a pipeline separator; 5. a pipeline sprinkler; 6. a tangential inlet duct; 7. a difluoro separator; 8. a demister; 9. a demister spray head; 10. a fluorine circulating pump; 11. a fluorine seal groove; 12. a fluorine seal groove agitator; 13. a difluoro seal groove; 14. a difluoro circulating pump; 15. a densitometer; 16. a fluosilicic acid discharge valve; 17. a fluorine seal groove liquid level meter; 18. a difluoro sealing groove liquid level meter; 19. a pipeline separator flushing water replenishing valve; 20. a foam remover flushing water replenishing valve; 21. a pipeline pressurizing pump.
Detailed Description
In order to better understand the technical solution of the present invention, the detailed description of the embodiments of the fluorine recovery apparatus will be given with reference to the drawings and the reference numerals.
A wet-process phosphoric acid high-efficiency fluorine recovery device mainly comprises a fluorine scrubber parallel-flow washing part, a primary liquid-foam separation part, a pipeline parallel-flow washing part, a secondary cyclone separation part, a tertiary liquid-foam separation part and automatic interlocking control of the whole process from water replenishing to fluosilicic acid production; the main equipment comprises a fluorine scrubber 1, a top layer spray head 2 of the fluorine scrubber, an inner ring spray head 3 of a tower, a pipeline separator 4, a pipeline spray head 5, a tangential air inlet pipeline 6, a difluoro separator 7, a demister 8, a demister spray head 9, a fluorine circulating pump 10 providing a washing function, a fluorine sealing groove 11, a difluoro sealing groove 13, a difluoro circulating pump 14, a pipeline pressure pump 21 and related overflowing pipelines, and a densimeter, a liquid level meter, a pipeline separator washing water replenishing valve 19 and a demister washing water replenishing valve 20 which are required by realizing interlocking control, which are sequentially arranged on a gas phase pipeline; the connection mode of the main equipment is as follows:
a top layer spray head 2 of a fluorine washer and an inner ring type spray head 3 of a tower are arranged in the fluorine washer 1, the spraying direction of circulating liquid is consistent with the direction of air flow, a lower liquid pipeline of the fluorine washer is connected to a fluorine sealing groove 11, the fluorine sealing groove 11 is provided with a fluorine circulating pump 10, an outlet pipeline of the fluorine circulating pump 10 is provided with a densimeter 15, and the densimeter 15 is interlocked with a fluosilicic acid discharge valve 16 on the pipeline; a fluorine seal groove stirrer 12 is disposed in a fluorine seal groove 11.
A pipeline separator 4 is arranged at an outlet of a fluorine washer washing 1, a pipeline spray head 5 is arranged in the pipeline separator 4, the pipeline separator 4 is connected with a difluoro separator 7 through a tangential air inlet pipeline 6, a down-flow pipe of the difluoro separator 7 is connected to a difluoro sealing groove 13, the difluoro sealing groove 13 is provided with a difluoro circulating pump 14, and the difluoro circulating pump 14 is connected to the pipeline spray head 5;
the bottom of the pipeline separator is provided with flushing water supplement, a difluoro circulating pump 14 is communicated to a fluoro sealing groove 11 through a bottom liquid receiving pipe of the pipeline separator 4, the bottom liquid receiving pipe of the pipeline separator 4 is provided with a pipeline separator flushing water supplement valve 19, a fluoro sealing groove liquid level meter 17 is arranged on the fluoro sealing groove 11, and the fluoro sealing groove liquid level meter 17 is interlocked with the pipeline separator flushing water supplement valve 19;
a demister 8 is arranged at the upper part of the difluoro separator 7, a pressurizing flushing water supplement valve 20 is arranged above the demister 8;
a difluoro sealing groove liquid level meter 18 is arranged on the difluoro sealing groove 13, and the difluoro sealing groove liquid level meter 18 is interlocked with a demister flushing water replenishing valve 20; the demister flushing water replenishing valve 20 is interlocked with a pipe pressurizing pump 21.
The device of the invention is in operation: phosphoric acid fluorine-containing gas enters from the top of a fluorine scrubber 1, circulating liquid in a fluorine sealing groove 11 is sprayed by a top layer spray head 2 of the fluorine scrubber and an inner ring spray head 3 in the tower under the action of a fluorine circulating pump 10, the spraying direction of the circulating liquid is consistent with the air flow direction, the contact time of the cleaning liquid and the phosphoric acid fluorine-containing gas is longer, and the reaction of silicon tetrafluoride, hydrofluoric acid, silicon tetrafluoride and water is more sufficient. After the phosphoric acid fluorine-containing gas is washed by the circulating liquid, the gas flows back into a fluorine sealing groove 11 and is conveyed into a fluorine washer 1 by a fluorine circulating pump 10 to wash the gas continuously entering from a source. The washing and absorption are repeated and circulated in this way. A densimeter 15 is arranged on an outlet pipeline of a fluorine circulating pump 10, the densimeter 15 is interlocked with a fluosilicic acid discharge valve 16, and when the washing liquid reaches the required density, the fluosilicic acid discharge valve 16 is automatically opened and discharged to a fluosilicic acid storage tank.
Gas washed by a fluorine washer enters the pipeline separator 4 to realize primary liquid-foam separation, liquid after separation flows back to a fluorine sealing groove 11, gas after primary separation enters the difluoro separator 7, circulating liquid provided by a difluoro circulating pump 14 is sprayed and washed by a pipeline spray head 5, the washed circulating liquid returns to the difluoro sealing groove 13 from a downcomer of the difluoro separator 7 and is conveyed to the pipeline spray head 5 by the difluoro circulating pump 14, and the gas which continuously enters is circularly washed.
Gas after the pipeline shower nozzle washing enters into difluoro separator 7 through tangential intake pipe 6, carries out the second grade separation, and gas carries out tertiary separation through demister 8 after the separation, and like this, gas after two-stage cocurrent flow washing + tertiary liquid foam separation gets into vacuum pumping system. The separated liquid flows back into the difluoro seal groove 13.
After fluosilicic acid is discharged, the liquid level of a fluorine sealing groove 11 is reduced, the liquid level is interlocked with a pipeline separator washing water supplementing valve 19 through a fluorine sealing groove liquid level meter 17, when the liquid level is reduced to a certain lower limit value, the pipeline separator washing water supplementing valve 19 is automatically opened, and a difluoro circulating liquid is supplemented into a fluorine sealing groove 11 through a bottom liquid collecting pipe of a pipeline separator 4 by a difluoro circulating pump 14. When the liquid level in a fluorine seal groove 11 reaches a certain upper limit value, the pipeline separator flushing water-replenishing valve 19 is automatically closed. Because the fluorine sealing groove 11 is replenished with water, the density of the fluosilicic acid is reduced to a certain lower limit value, and the fluosilicic acid discharge valve 16 is automatically closed.
After water is replenished from the fluorine sealing groove 11, the liquid level of the difluoro sealing groove 13 is reduced, the difluoro sealing groove liquid level meter 18 is interlocked with the demister flushing water replenishing valve 20, the demister flushing water replenishing valve 20 is interlocked with the pipeline pressure pump 21, when the liquid level is reduced to a certain lower limit value, the demister flushing water replenishing valve 20 is automatically opened, the pipeline pressure pump 21 is started, and the fluorine recovery water replenishing water is used for flushing the demister 8 and replenishing water to the difluoro sealing groove 13. When the liquid level of the difluoro sealing groove 13 reaches a certain upper limit value, the demister flushing water supplementing valve 20 is automatically closed, and the pipeline pressurizing pump 21 is automatically stopped.
Considering that in the actual production process, because of the fluctuation of the concentration of phosphoric acid, when the proportion of silicon tetrafluoride and hydrogen fluoride in the fluorine-containing gas of phosphoric acid is not matched, more silicon gel is formed by the reaction of the excessive silicon tetrafluoride and water, and thus a fluorine seal groove stirrer 12 needs to be started to prevent the instantaneous higher solid content of the fluorine circulating liquid from blocking the spray head.
The device of the invention adopts a gas washing process technology, a liquid-foam separation technology and an automatic production control mode as core claims, can make relevant optimization measures within the spirit and the scope of the invention, and the optimization measures are regarded as the protection scope of the invention.
Claims (2)
1. The utility model provides a high-efficient fluorine recovery unit of wet process phosphoric acid which characterized in that: the device mainly comprises a parallel flow washing part of a fluorine washer, a primary liquid-foam separation part, a pipeline parallel flow washing part, a secondary cyclone separation part, a tertiary liquid-foam separation part and automatic interlocking control of the whole process from water replenishing to fluosilicic acid production; the main equipment comprises a fluorine scrubber (1), a fluorine scrubber top layer spray head (2), an in-tower annular spray head (3), a pipeline separator (4), a pipeline spray head (5), a tangential air inlet pipeline (6), a difluoro separator (7), a demister (8), a demister spray head (9), a fluorine circulating pump (10), a fluorine sealing groove (11), a difluoro sealing groove (13), a difluoro circulating pump (14), a pipeline pressure pump (21) and related overflow pipelines which are sequentially arranged on a gas phase pipeline, and a density meter, a liquid level meter, a pipeline separator flushing water supplementing valve (19) and a demister flushing water supplementing valve (20) which are required for realizing interlocking control; the connection mode of the main equipment is as follows:
a top layer spray head (2) of a fluorine washer and an inner ring-shaped spray head (3) of a tower are arranged in the fluorine washer (1), the spraying direction of circulating liquid is consistent with the direction of air flow, a lower liquid pipeline of the fluorine washer is connected to a fluorine sealing groove (11), the fluorine sealing groove (11) is provided with a fluorine circulating pump (10), an outlet pipeline of the fluorine circulating pump (10) is provided with a densimeter (15), and the densimeter (15) is interlocked with a fluosilicic acid discharge valve (16) on the pipeline;
a pipeline separator (4) is arranged at the outlet of a fluorine washer (1), a pipeline spray head (5) is arranged in the pipeline separator (4), the pipeline separator (4) is connected with a difluoro separator (7) through a tangential air inlet pipeline (6), a down-flow pipe of the difluoro separator (7) is connected to a difluoro sealing groove (13), the difluoro sealing groove (13) is provided with a difluoro circulating pump (14), and the difluoro circulating pump (14) is connected to the pipeline spray head (5);
the bottom of the pipeline separator is provided with flushing water supplement, a difluoro circulating pump (14) is communicated to a fluoro sealing groove (11) through a bottom liquid receiving pipe of the pipeline separator (4), the bottom liquid receiving pipe of the pipeline separator (4) is provided with a pipeline separator flushing water supplement valve (19), a fluoro sealing groove liquid level meter (17) is arranged on the fluoro sealing groove (11), and the fluoro sealing groove liquid level meter (17) is interlocked with the pipeline separator flushing water supplement valve (19);
a demister (8) is arranged at the upper part of the difluoro separator (7), a pressurizing flushing water supplement valve (20) is arranged above the demister (8);
a difluoro sealing groove liquid level meter (18) is arranged on the difluoro sealing groove (13), and the difluoro sealing groove liquid level meter (18) is interlocked with a demister flushing water replenishing valve (20); the demister flushing water replenishing valve (20) is interlocked with a pipeline pressurizing pump (21).
2. The high-efficiency fluorine recovery device for wet-process phosphoric acid according to claim 1, characterized in that: a fluorine seal groove agitator (12) is disposed within a fluorine seal groove.
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| CN202010128222.7A CN111054205A (en) | 2020-02-28 | 2020-02-28 | High-efficient fluorine recovery unit of wet process phosphoric acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023733A (en) * | 2021-05-07 | 2021-06-25 | 瓮福（集团）有限责任公司 | Fluosilicic acid production device and process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023733A (en) * | 2021-05-07 | 2021-06-25 | 瓮福（集团）有限责任公司 | Fluosilicic acid production device and process |
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