CN108455616A - A kind of fluosilicic acid dechlorination method and device - Google Patents
A kind of fluosilicic acid dechlorination method and device Download PDFInfo
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- CN108455616A CN108455616A CN201711384793.1A CN201711384793A CN108455616A CN 108455616 A CN108455616 A CN 108455616A CN 201711384793 A CN201711384793 A CN 201711384793A CN 108455616 A CN108455616 A CN 108455616A
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- fluosilicic acid
- acid
- gas
- fluosilicic
- hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
Abstract
The invention discloses a kind of fluosilicic acid dechlorination method and device, this method heats raw material fluosilicic acid, so that it is evaporated to gas, then cooled down to it, and fluosilicic acid gas is cooled into liquid fluosilicic acid at first, to realize the separation with hydrogen chloride gas.Fluosilicic acid and hydrogen chloride heating evaporation are gas by it, then the boiling-point difference of fluosilicic acid and hydrogen chloride gas is utilized, fluosilicic acid is first liquefied and obtains fluosilicic acid liquid, and hydrogen chloride still exists in gaseous form, the acidic circulation water absorbing hydrogen chloride gas for finally utilizing garden phosphoric acid workshop to provide, the acidic circulation water for absorbing hydrogen chloride gas return again to phosphoric acid workshop recycling.The concentration that chloride in fluosilicic acid can effectively be removed, the case where avoiding having to abandon because of fluosilicic acid chloride concentration height completely, the consumption of fluosilicic acid raw material reduces by 10% when compared to original technology production anhydrous hydrogen fluoride.
Description
Technical field
The invention belongs to chemical fields, are related to the purifying of wet process phosphoric acid by-product fluosilicic acid, and specially a kind of fluosilicic acid removes
Chlorine method and device.
Background technology
The fast development of Phosphate Fertilizer Industry, realizes most optimum distribution of resources, improves industrial concentration, but Wet Processes of Phosphoric Acid
Batch is built up, a large amount of fluosilicic acid of by-product.The usual manner of recycling fluosilicic acid be generate fluosilicate or fluoride salt, although
It is simple for process, but added value of product is low, and market is obviously inadequate to the eupepsy of product, utilization ratio is low.
My company successfully produces anhydrous hydrogen fluoride using fluosilicic acid as raw material, and technique is：It will be from the dilute of phosphate fertilizer plant
Fluosilicic acid first passes around dearsenification device and removes objectionable impurities arsenic, and one is obtained by concentration subsequently into fluosilicic acid concentration systems
The dense fluosilicic acid for determining concentration, after being separated by filtration, dense fluosilicic acid enters reactor and is mixed with the concentrated sulfuric acid, generates ocratation, fluorine
Change the mixed gas such as hydrogen, after being absorbed with the concentrated sulfuric acid, ocratation enters concentration systems and absorbed；Sulfuric acid after reaction contains greatly
Hydrogen fluoride is measured, detaches hydrogen fluoride with sulfuric acid through distilling, high and low boiling contaminants is removed by purification, rectifying, obtains anhydrous fluorination
Hydrogen production.The technique does not also clean to raw material fluosilicic acid, but directly carries out concentrate.During production, find
Chloride in fluosilicic acid can produce anhydrous hydrogen fluoride to form interference, especially in the link and later use of fluosilicic acid concentrate height
The fluosilicic acid of concentration prepares the link of hydrogen fluoride with sulfuric acid reaction so that part fluosilicic acid has to abandon because chlorinity is too high
It uses, causes to waste, influence the yield of anhydrous hydrogen fluoride；Therefore the content for reducing chloride in raw material fluosilicic acid is very necessary
's.
Invention content
It is an object of the invention to provide a kind of fluosilicic acid dechlorination method and devices；Raw material fluosilicic acid is purified, can be kept away
Exempt from the waste of fluosilicic acid, and improves the yield of anhydrous hydrogen fluoride.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of fluosilicic acid dechlorination method, to raw material
Fluosilicic acid is heated, and so that it is evaporated to gas, is then cooled down to it, and fluosilicic acid gas is cooled into liquid at first
Fluosilicic acid, to realize the separation with hydrogen chloride gas.
Raw material fluosilicic acid is heated, so that it is evaporated to gas, then it is cooled down, fluosilicic acid gas is most
It is first cooled into liquid fluosilicic acid, to realize the separation with hydrogen chloride gas.
Further, temperature rises to 107.5 DEG C or more when heating.
Further, fluosilicic acid gas cooling becomes the temperature collected after liquid fluosilicic acid at 20-35 DEG C.
Further, fluosilicic acid is condensed into other remaining gases after liquid and is absorbed using aqueous solution.Preferred water
Solution is the acidic circulation water from phosphoric acid workshop.Phosphoric acid containing 1-2% in acidic circulation water.
In addition, if the effect after primary dechlorination does not reach requirement, obtained liquid fluosilicic acid can be regard as original again
Material fluosilicic acid carries out heating vaporization and refrigerated separation, and after primary or multiplicating, dechlorination effect is more preferable.
The invention further relates to the devices to be dechlorinated to fluosilicic acid using the above method, including set gradually heat exchanger,
Condenser and packed tower, packed tower top are equipped with washing lotion import, and bottom is equipped with washing lotion outlet, and washing lotion outlet passes through pipeline and pump connects
It is connected to washing lotion import.Packed tower lower part is additionally provided with washing lotion supply port.
Further, the heat exchanger is graphite heat exchanger, and shell side walks superheated steam, superheat steam temperature 170-
220℃.Pressure is 0.8Mpa, and flow is 5 tons/h, and the addition of raw material fluosilicic acid is 15-20m3/h.
Further, the shell side of the condenser walks chilled water, chilled water temperature≤7 DEG C.Flow is 20m3/h,
Further, the washing lotion used in the packed tower is the acidic circulation water in phosphoric acid workshop, waits for hydrochloric acid in acidic circulation water
Concentration returns to phosphoric acid workshop recycling after reaching 15wt%.
Further, reduce hydrogen chloride using the tetrafluoro Pall ring of DN50 in packed tower and hydrogen fluoride mistake is produced to fluosilicic acid
Interference in journey promotes hydrogen fluoride output.
Then the present invention utilizes fluosilicic acid and hydrogen chloride gas by being gas by fluosilicic acid and hydrogen chloride heating evaporation
Fluosilicic acid is first liquefied and obtains fluosilicic acid liquid by boiling-point difference, and hydrogen chloride still exists in gaseous form, finally utilizes garden phosphorus
The acidic circulation water absorbing hydrogen chloride gas that sour workshop provides, the acidic circulation water for absorbing hydrogen chloride gas return again to phosphoric acid vehicle
Between recycle.
Beneficial effects of the present invention：
1, the concentration of chloride in fluosilicic acid can be effectively removed, the effect once to dechlorinate can at least reduce by 80% or more, repeatedly
Can reach after repeating reduces chlorinity 99%；The case where avoiding having to abandon because of fluosilicic acid chloride concentration height completely, compares
The consumption of fluosilicic acid raw material reduces by 10% when original technology produces anhydrous hydrogen fluoride.
2, by the removal of chloride in raw material fluosilicic acid, material quality is improved so that the fluosilicic acid and sulfuric acid of high concentration
Reaction efficiency when reaction prepares hydrogen fluoride gets a promotion, anhydrous hydrogen fluoride volume increase 5%.
3, using phosphoric acid workshop acidic circulation water as the absorbent of chloride, the chloride of gas phase is substantially with hydrogen chloride
Form exists, and the dissolubility of hydrogen chloride in water is extremely strong, and the selective effect using acidic circulation water absorbing hydrogen chloride is very good,
And the acidic circulation water after absorbing hydrogen chloride can also be utilized further, avoid wasting, and mitigate environmental protection pressure.
4, using the technique, moreover it is possible to while the other impurities in raw material fluosilicic acid are removed, such as remove iodine and arsenic therein.
5, in addition, packing support structure and liquid distribution trough are arranged also in packed tower used, it can be ensured that packed tower
Fastness, further extend packed tower service life.
Description of the drawings
Fig. 1 is the device of the invention structural schematic diagram.
Fig. 2 is the process flow chart of the present invention.
Specific implementation mode
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Embodiment 1：
Raw material fluosilicic acid is taken, its ingredient is analyzed, following component is contained：Fluosilicic acid 18wt%, chlorion 1.5wt%, iodine
20mg/L, arsenic 10mg/L, phosphorus pentoxide 0.1%, remaining is water.
As shown in Figs. 1-2, which is added in heat exchanger, heat exchange vaporization, wherein mistake is carried out with superheated steam
For the temperature of hot steam entrance at 200-220 DEG C, pressure 0.8Mpa, flow is 5 tons/h, and the addition of raw material fluosilicic acid is
20m3/h, the gas after vaporization are passed through in condenser, and heat exchange cooling is carried out with chilled water, and fluosilicic acid is condensed into liquid at first, are received
The liquid fluosilicic acid temperature collected be 30 DEG C, remaining gas by packed tower to being washed with acidic circulation water, finally
Remaining tail gas discharge.Acidic circulation water comes from phosphoric acid workshop, is recycled in packed tower, is returned after concentration of hydrochloric acid reaches 15%
Rephosphorization acid workshop recycles.New acidic circulation water is filled into from the bottom of packed tower as needed.System during entire dechlorination
For micro-vacuum state, gauge pressure is shown as -3 ~ -5KPa.
Obtained liquid fluosilicic acid is detected, and ingredient therein is as follows：Fluosilicic acid 18.5wt%, chlorion 0.3wt%, iodine
6 mg/L, arsenic 5mg/L, phosphorus pentoxide 0.1%, remaining is water.
Embodiment 2：
Dechlorination operation is carried out again to the obtained liquid fluosilicic acid in embodiment 1, specific steps are finally obtained with embodiment 1
Ingredient in liquid fluosilicic acid is as follows：Fluosilicic acid 18.8wt%, chlorion 0.1wt%, iodine 4mg/L, arsenic 3mg/L, phosphorus pentoxide
0.08%, remaining is water.
Embodiment 3：
Raw material fluosilicic acid is taken, its ingredient is analyzed, following component is contained：Fluosilicic acid 24wt%, chlorion 2.5wt%, iodine
25mg/L, arsenic 12mg/L, phosphorus pentoxide 0.2%, remaining is water.
As shown in Figs. 1-2, which is added in heat exchanger, heat exchange vaporization, wherein mistake is carried out with superheated steam
For the temperature of hot steam entrance at 170-200 DEG C, pressure 0.8Mpa, flow is 5 tons/h, and the addition of raw material fluosilicic acid is
15m3/h, the gas after vaporization are passed through in condenser, and heat exchange cooling is carried out with chilled water, and fluosilicic acid is condensed into liquid at first, are received
The liquid fluosilicic acid temperature integrated as 25-35 DEG C, remaining gas by packed tower to being washed with acidic circulation water, most
Remaining tail gas discharge afterwards.Acidic circulation water comes from phosphoric acid workshop, is recycled in packed tower, waits for that concentration of hydrochloric acid reaches 15wt%
Phosphoric acid workshop is returned to afterwards to recycle.New acidic circulation water is filled into from the bottom of packed tower as needed.During entire dechlorination
System is micro-vacuum state, and gauge pressure is shown as -3 ~ -5KPa.
Obtained liquid fluosilicic acid is detected, and ingredient therein is as follows：Fluosilicic acid 25wt%, chlorion 0.4wt%, iodine
10mg/L, arsenic 6mg/L, phosphorus pentoxide 0.2%, remaining is water.
Embodiment 4：
Raw material fluosilicic acid is taken, its ingredient is analyzed, following component is contained：Fluosilicic acid 20wt%, chlorion 2wt%, iodine 20mg/
L, arsenic 12mg/L, phosphorus pentoxide 0.1%, remaining is water.
The raw material fluosilicic acid is added in heat exchanger, heat exchange vaporization, wherein superheated steam entrance are carried out with superheated steam
Temperature at 190-210 DEG C, pressure 0.8Mpa, flow is 5 tons/h, and the addition of raw material fluosilicic acid is 18m3/h, after vaporization
Gas be passed through in condenser, carry out heat exchange cooling with chilled water, fluosilicic acid is condensed into liquid at first, the liquid fluorine silicon being collected into
Sour temperature is 20-30 DEG C, remaining gas is by the way that, to being washed with acidic circulation water, last remaining tail gas is arranged in packed tower
Go out.Acidic circulation water comes from phosphoric acid workshop, is recycled in packed tower, and phosphoric acid workshop is returned to after concentration of hydrochloric acid reaches 15wt%
It recycles.New acidic circulation water is filled into from the bottom of packed tower as needed.System is tiny structure shape during entire dechlorination
State, gauge pressure are shown as -3 ~ -5KPa.
Obtained liquid fluosilicic acid is detected, and ingredient therein is as follows：Fluosilicic acid 25wt%, chlorion 0.3wt%, iodine
10mg/L, arsenic 8mg/L, phosphorus pentoxide 0.1%, remaining is water.
Claims (10)
- A kind of method 1. fluosilicic acid dechlorinates, it is characterised in that：Raw material fluosilicic acid is heated, so that it is evaporated to gas, then It is cooled down, fluosilicic acid gas is cooled into liquid fluosilicic acid at first, to realize the separation with hydrogen chloride gas.
- 2. according to the method described in claim 1, it is characterized in that：Temperature rises to 107.5 DEG C or more when heating.
- 3. according to the method described in claim 1, it is characterized in that：Fluosilicic acid gas cooling is collected after becoming liquid fluosilicic acid Temperature is at 20-35 DEG C.
- 4. according to the method described in claim 1, it is characterized in that：Fluosilicic acid is condensed into remaining other gases use after liquid Aqueous solution is absorbed.
- 5. according to the method described in claim 4, it is characterized in that：The aqueous solution is the acidic circulation from phosphoric acid workshop Water.
- 6. according to the method described in claim 1-5 any one, it is characterised in that：Obtained liquid fluosilicic acid is used as original again Material fluosilicic acid carries out heating vaporization and refrigerated separation again.
- 7. the device that the method according to claim 1-6 any one dechlorinates to fluosilicic acid, it is characterised in that：Including Heat exchanger, condenser and the packed tower set gradually, packed tower top are equipped with washing lotion import, and bottom is equipped with washing lotion outlet, washing lotion Outlet is connected to washing lotion import by pipeline and pump.
- 8. device according to claim 7, it is characterised in that：The heat exchanger is graphite heat exchanger, and shell is walked overheat and steamed Vapour, superheat steam temperature are 170-220 DEG C.
- 9. device according to claim 7, it is characterised in that：The shell side of the condenser walks chilled water, chilled water temperature ≤7℃。
- 10. device according to claim 7, it is characterised in that：The washing lotion used in the packed tower is phosphoric acid workshop Acidic circulation water returns to phosphoric acid workshop after concentration of hydrochloric acid in acidic circulation water reaches 15wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711384793.1A CN108455616A (en) | 2017-12-20 | 2017-12-20 | A kind of fluosilicic acid dechlorination method and device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711384793.1A CN108455616A (en) | 2017-12-20 | 2017-12-20 | A kind of fluosilicic acid dechlorination method and device |
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| CN108455616A true CN108455616A (en) | 2018-08-28 |
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| CN201711384793.1A Pending CN108455616A (en) | 2017-12-20 | 2017-12-20 | A kind of fluosilicic acid dechlorination method and device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252770A (en) * | 2020-04-26 | 2020-06-09 | 贵州瓮福蓝天氟化工股份有限公司 | Method for removing chlorine from fluosilicic acid |
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| JP2005119956A (en) * | 2003-09-25 | 2005-05-12 | Showa Denko Kk | Method of manufacturing tetrafluorosilane |
| CN1646669A (en) * | 2002-03-05 | 2005-07-27 | 卡拉利研究股份有限公司 | Method for treating carbonaceous materials |
| CN101827642A (en) * | 2007-09-04 | 2010-09-08 | Memc电子材料有限公司 | Method for treatment of a gas stream containing silicon tetrafluoride and hydrogen chloride |
| CN103848426A (en) * | 2014-02-25 | 2014-06-11 | 瓮福（集团）有限责任公司 | Method for concentrating fluosilicic acid by utilizing vacuum falling film evaporation method |
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2017
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Patent Citations (4)
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|---|---|---|---|---|
| CN1646669A (en) * | 2002-03-05 | 2005-07-27 | 卡拉利研究股份有限公司 | Method for treating carbonaceous materials |
| JP2005119956A (en) * | 2003-09-25 | 2005-05-12 | Showa Denko Kk | Method of manufacturing tetrafluorosilane |
| CN101827642A (en) * | 2007-09-04 | 2010-09-08 | Memc电子材料有限公司 | Method for treatment of a gas stream containing silicon tetrafluoride and hydrogen chloride |
| CN103848426A (en) * | 2014-02-25 | 2014-06-11 | 瓮福（集团）有限责任公司 | Method for concentrating fluosilicic acid by utilizing vacuum falling film evaporation method |
Non-Patent Citations (2)
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| 吴建军: "偏磷酸钾肥料生产工艺", 云南化工, vol. 29, no. 5, pages 147 - 9 * |
| 曹骐等: "磷化工副产氟硅酸的利用及无水氟化氢的生产研究进展", 无机盐工业, vol. 42, no. 5, pages 1 - 4 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252770A (en) * | 2020-04-26 | 2020-06-09 | 贵州瓮福蓝天氟化工股份有限公司 | Method for removing chlorine from fluosilicic acid |
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