CN102556973A - Method for producing hydrofluoric acid from fluorite as raw material - Google Patents
Method for producing hydrofluoric acid from fluorite as raw material Download PDFInfo
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- CN102556973A CN102556973A CN2012100410308A CN201210041030A CN102556973A CN 102556973 A CN102556973 A CN 102556973A CN 2012100410308 A CN2012100410308 A CN 2012100410308A CN 201210041030 A CN201210041030 A CN 201210041030A CN 102556973 A CN102556973 A CN 102556973A
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- sulfuric acid
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- fluorite
- acid
- leaching
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 44
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims description 43
- 239000010436 fluorite Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000002994 raw material Substances 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 113
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 239000010440 gypsum Substances 0.000 claims description 18
- 229910052602 gypsum Inorganic materials 0.000 claims description 18
- 150000004683 dihydrates Chemical class 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims 3
- 238000006115 defluorination reaction Methods 0.000 claims 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 239000002893 slag Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910001576 calcium mineral Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种以萤石为原料生产氢氟酸的方法，其制备过程在密闭反应设备中进行。具体操作如下：将萤石矿粉、磷酸和硫酸的混合溶液混合加入到密闭反应器进行反应，加入二水石膏作为晶种，控制硫酸浓度、P2O5含量和反应温度，来得到过滤和洗涤性能良好的二水石膏。反应过程中产生的HF气体经抽真空排出冷凝后，再经浓硫酸吸收脱水，并进一步精馏得到氢氟酸。脱氟后的浓硫酸用来补充分解所消耗的硫酸，和滤液一同返回新一轮萤石矿粉的浸出。本发明的优点在于实现了萤石矿物的高效分解，氟浸出率达到98％以上；基本实现了硫酸的循环利用，极大降低了浸出成本；浸出设备简单，操作方便，易于实现工业化。The invention discloses a method for producing hydrofluoric acid by using fluorite as a raw material, and the preparation process is carried out in closed reaction equipment. The specific operation is as follows: mix the mixed solution of fluorite mineral powder, phosphoric acid and sulfuric acid into a closed reactor for reaction, add dihydrate gypsum as a crystal seed, control the concentration of sulfuric acid, P2O5 content and reaction temperature to obtain filtration and Dihydrate gypsum with good washing properties. The HF gas produced in the reaction process is vacuumed out and condensed, then absorbed and dehydrated by concentrated sulfuric acid, and further rectified to obtain hydrofluoric acid. The concentrated sulfuric acid after defluorination is used to supplement the sulfuric acid consumed by the decomposition, and returns to a new round of fluorite powder leaching together with the filtrate. The invention has the advantages of realizing high-efficiency decomposition of fluorite minerals, and the leaching rate of fluorine reaches more than 98 percent; basically realizing the recycling of sulfuric acid and greatly reducing the cost of leaching; the leaching equipment is simple, easy to operate, and easy to realize industrialization.
Description
Technical field
The present invention relates to producing of hydrofluoric acid in the fluorine chemical field, be specifically a kind of be the method for raw material production hydrofluoric acid with the fluorite.
Background technology
Hydrofluoric acid has very widely at industry, national defence and aspect such as civilian to be used.As be used to produce freon refrigerant, fluorine resin, ALUMNIUM FLUORIDE etc., and in petroleum industry, be used as catalyzer, can also be as the raw material of the uranium hexafluoride that needs in nuclear industry and the Nuclear weapons production.
At present, the main method of production hydrofluoric acid is fluorite-sulfuric acid process.The thermodynamic tendency of sulfuric acid and fluorite reaction is very big, but the CaSO that reaction process generates
4Gu film can be coated on unreacted fluorite surface completely, and then influences further carrying out of reaction.Driven angle of mechanics improves leaching agent concentration and temperature of reaction, and to this reaction is favourable.In general industrial practice, its decomposition course at high temperature carries out, and the sulfuric acid concentration that is adopted is up to 95～100%, but still is difficult to from overcoming CaSO in essence
4Gu the coating effect of film contains CaF in the decompose slag that obtains
2Up to 5～10%, and, not only caused the waste of raw material, and polluted environment with about 14～15% free sulfuric acid.
In addition; The decomposition slip that contains sulfuric acid, hydrofluoric acid, calcium sulfate and undecomposed fluorite completely has very high tack to the internal surface of reactor drum; Will reduce the efficient of heat transfer and the processing power of equipment; Therefore, need to scrape off the reaction mixture that the internal surface at pre-reactor or rotary kiln adheres to, like this wearability of equipment is also had higher requirement through agitating vane or scraping device are installed.
Thereby press for the exploitation new, simple and effective fluorite decomposition technique.
In fact, be all the technology that sulfuric acid decomposes calcium mineral, once also be faced with the problem of calcium sulfate parcel when decomposing phosphatic rock in the production process of phosphoric acid by wet process.Once study the employing vitriol oil (98%) like U.S. Dai Weisen company and decomposed the method that phosphatic rock is produced phosphoric acid, but owing to the package action of calcium sulfate decomposes not thoroughly (Yue Keda 95%).
And at present the main flow technology of phosphoric acid by wet process has all adopted relatively low sulfuric acid concentration, and the crystal formation of taking measures to control product all kinds of technical process with pattern to reduce or to eliminate the inhibition of calcium sulfate to decomposition, to develop.Wherein use the most extensive to obtain dihydrate gypsum flow process thick, regular, that be easy to filter and wash.This type flow process is compared with top Dai Weisen company flow process, and sulfuric acid concentration has substantial degradation (30-50g/l), and this helps reducing the degree of supersaturation of calcium sulfate product in decomposition course.And the more important thing is because the product that ore decomposes is the phosphoric acid of higher concentration, but complexing calcium ions, thus the solubleness of calcium sulfate increased, reduced the sporadic nucleation speed of calcium sulfate.And adopted following adjustment measure: the degree of supersaturation that (1) provides the dihydrate gypsum crystal seed to reduce solution through the overfall effect, suppress homogeneous nucleation, promote heterogeneous nucleation; (2) provide a good mass transfer and relative homothermic to leach system.
And the sulfuric acid decomposition course of Calcium Fluoride (Fluorspan): decompose different with the sulfuric acid of phosphatic rock; What produce is hydrofluoric acid (volatilization is overflowed) but not phosphoric acid can not play the effect of complexing calcium, and the sulfuric acid concentration that adopts is also very high; Thereby cause a large amount of sporadic nucleations of calcium sulfate, parcel fluorite powder hinders reaction.
To this situation, the present invention has introduced high concentrations of phosphoric acid specially when sulfuric acid decomposes, and suitably reduces the decomposing solution sulfuric acid concentration, thereby has suppressed the nucleation of calcium sulfate.And the further temperature of reaction of finely regulating decomposing solution, also add dihydrate gypsum as crystal seed to promote heterogeneous nucleation, hinder the phenomenon of decomposing thereby eliminate, thoroughly decompose the fluorite mineral.
Separate the technology contrast with existing fluorite powder, slag of the present invention contains CaF
2Reduce greatly, excess sulfuric acid can reuse, and equipment is also greatly simplified.
In addition, during Wet-process Phosphoric Acid Production, the product phosphoric acid and the decomposing agents of generation all exist in solution; For obtaining high product quality; Can only remain after require decomposing 1～2% free sulfuric acid (Wu Peizhi. phosphoric acid by wet process. Chemical Industry Press, 1987,346-347).So the vitriolic consumption is just had strict restriction, this also is another lower odjective causes of various dihydrate gypsum flow process sulfuric acid concentrations; And during Acid of Hydrofluoric Acid Production, HF is gaseous state and overflows and separate with reactant sulfuric acid, also is unlikely to cause the product quality problem, and more excess sulfuric acid helps HF and overflows.Can adopt excessive sulfuric acid when therefore decomposing fluorite.As for decomposition nut liquid then can be in filtering separation behind the gypsum tailings acid of supplement consumed return decomposition, excess sulfuric acid does not have waste.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for raw material production hydrofluoric acid with the fluorite, and this method service temperature is low, and the fluorite rate of decomposition is high, and leaching agent can be realized reuse, reduces production costs greatly, and concrete operations are following:
A kind of is the method for raw material production hydrofluoric acid with the fluorite; Fluorite breeze and dihydrate gypsum crystal seed are joined in advance in the prepared phosphoric acid and sulfuric acid mixed solution; Confined reaction produces HF gas; Reaction finishes after-filtration decompose slag is separated with filtrating, returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to be consumed.
Described fluorite breeze contains CaF
2Mass percent is not less than 97%, and the particle diameter of mineral is less than 165 μ m.
Contain P in described phosphoric acid and the sulfuric acid mixed solution
2O
5Massfraction is 5%～35%, and sulfuric acid concentration is 100g/L～500g/L in described phosphoric acid and the sulfuric acid mixed solution.
The liquid-solid ratio 3: 1～10 of reaction: 1L/Kg,
Temperature of reaction is 60～100 ℃, and the reaction times is 1～8h.
The mass ratio of dihydrate gypsum add-on and fluorite breeze is 1: 1000～1: 10.
The HF gas that reaction produces through vacuumize discharge condensation after again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Decompose the leaching that the sulfuric acid that consumed and filtrating are together returned new round fluorite breeze through being used for after the defluorinate replenishing again to the vitriol oil after the HF dehydration.
The present invention has the following advantages:
1. under the high concentration phosphorus acid system, the fluorite breeze decomposes very thoroughly, and its rate of decomposition reaches more than 98%, amounts to slag and contains CaF
2Be reduced to 1.0 ± 0.5%, contain CaF far below slag in the existing technology
25～10% index;
2. excessive leaching agent sulfuric acid can be realized Returning utilization, decomposes to have obtained high-quality dihydrate gypsum, and the starting material that can be used for building greatly reduce the leaching cost;
3. leaching plant is simple, and is easy to operate, is easy to realize industriallization.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 decompose slag;
Fig. 2 is the SEM figure of embodiment 1 decompose slag.
Embodiment
Be described further below in conjunction with embodiment, following examples are intended to explain the present invention rather than to further qualification of the present invention.The absorption of HF gas, rectifying, the degassing etc. are operating as the operation of being familiar with of the same trade,, no longer detail among the embodiment for this reason.
Embodiment 1
The fluorite ore deposit (contains CaF
297.2%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 25%, controls sulfuric acid concentration at 200g/L, dihydrate gypsum crystal seed add-on 100g, and liquid-solid ratio 10: 1,90 ℃ of temperature of reaction, reaction times 4h, the XRD figure of the decompose slag that obtains and SEM figure are as depicted in figs. 1 and 2.With this understanding, CaF
2Rate of decomposition be 99.5%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 2
The filtrating that embodiment 2 is produced is mended and was decomposed the fluorite ore deposit into sulfuric acid afterwards to 200g/L and (contain CaF
297.2%), dihydrate gypsum crystal seed add-on 100g, liquid-solid ratio 10: 1,90 ℃ of temperature of reaction, reaction times 4h, with this understanding, CaF
2Rate of decomposition be 99.3%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 3
The fluorite ore deposit (contains CaF
297.2%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 35%, controls sulfuric acid concentration at 250g/L, dihydrate gypsum crystal seed add-on 10g, and liquid-solid ratio 5: 1,60 ℃ of temperature of reaction, reaction times 8h, with this understanding, CaF
2Rate of decomposition be 98.4%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 4
The fluorite ore deposit (contains CaF
297.2%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 20%, controls sulfuric acid concentration at 500g/L, dihydrate gypsum crystal seed add-on 1g, and liquid-solid ratio 8: 1,80 ℃ of temperature of reaction, reaction times 1h, with this understanding, CaF
2Rate of decomposition be 98.2%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 5
The fluorite ore deposit (contains CaF
298.4%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 35%, controls sulfuric acid concentration at 100g/L, dihydrate gypsum crystal seed add-on 10g, and liquid-solid ratio 3: 1,100 ℃ of temperature of reaction, reaction times 6h, with this understanding, CaF
2Rate of decomposition be 98.1%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 6
The fluorite ore deposit (contains CaF
298.4%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 10%, controls sulfuric acid concentration at 400g/L, dihydrate gypsum crystal seed add-on 50g, and liquid-solid ratio 4: 1,70 ℃ of temperature of reaction, reaction times 8h, with this understanding, CaF
2Rate of decomposition be 98.6%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 7
The fluorite ore deposit (contains CaF
298.4%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 30%, controls sulfuric acid concentration at 500g/L, dihydrate gypsum crystal seed add-on 40g, and liquid-solid ratio 5: 1,70 ℃ of temperature of reaction, reaction times 4h, with this understanding, CaF
2Rate of decomposition be 98.9%.The reaction after-filtration returns the leaching of new round fluorite breeze behind the sulfuric acid that filtrating benefit goes into to consume, the HF gas that produces in the reaction process is after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.
Embodiment 8
The fluorite ore deposit (contains CaF
298.4%) 1kg, preparation phosphoric acid and sulfuric acid mixed solution, P
2O
5Content is 20%, controls sulfuric acid concentration at 400g/L, dihydrate gypsum crystal seed add-on 50g, and liquid-solid ratio 6: 1,80 ℃ of temperature of reaction, reaction times 5h, with this understanding, CaF
2Rate of decomposition be 99.1%.Reaction after-filtration, the HF gas that produces in the reaction process are after vacuumizing the discharge condensation, and again through vitriol oil absorption dewatering, and further rectifying obtains hydrofluoric acid.Decompose the leaching that the sulfuric acid that consumed and filtrating are together returned new round fluorite breeze through being used for after the defluorinate replenishing again to the vitriol oil after the HF dehydration.
Claims (8)
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| CN 201210041030 CN102556973B (en) | 2012-02-22 | 2012-02-22 | A kind of method using fluorite as raw material to produce hydrofluoric acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826513A (en) * | 2012-09-03 | 2012-12-19 | 南通市明鑫化工有限公司 | Production process of hydrofluoric acid |
| CN103350985A (en) * | 2013-07-09 | 2013-10-16 | 安徽锦洋氟化学有限公司 | Anhydrous hydrogen fluoride production method |
| CN108147383A (en) * | 2018-01-05 | 2018-06-12 | 贵州川恒化工股份有限公司 | The defluorination method of phosphoric acid by wet process |
| CN110902697A (en) * | 2018-09-16 | 2020-03-24 | 张旭 | Process and device for preparing sodium fluoride or potassium fluoride from fluorite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982003848A1 (en) * | 1981-04-28 | 1982-11-11 | Boese Dieter | Process and device for manufacturing synthetic anhydrous calcium sulphate and pure hydrofluoric acid |
| CN1696050A (en) * | 2004-05-10 | 2005-11-16 | 四川大学 | A technology for preparing high-purity anhydrous hydrogen fluoride |
| CN102249193A (en) * | 2011-06-03 | 2011-11-23 | 无锡市东风化工厂 | Preparation method of hydrofluoric acid and special preparation equipment |
-
2012
- 2012-02-22 CN CN 201210041030 patent/CN102556973B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982003848A1 (en) * | 1981-04-28 | 1982-11-11 | Boese Dieter | Process and device for manufacturing synthetic anhydrous calcium sulphate and pure hydrofluoric acid |
| CN1696050A (en) * | 2004-05-10 | 2005-11-16 | 四川大学 | A technology for preparing high-purity anhydrous hydrogen fluoride |
| CN102249193A (en) * | 2011-06-03 | 2011-11-23 | 无锡市东风化工厂 | Preparation method of hydrofluoric acid and special preparation equipment |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826513A (en) * | 2012-09-03 | 2012-12-19 | 南通市明鑫化工有限公司 | Production process of hydrofluoric acid |
| CN103350985A (en) * | 2013-07-09 | 2013-10-16 | 安徽锦洋氟化学有限公司 | Anhydrous hydrogen fluoride production method |
| CN103350985B (en) * | 2013-07-09 | 2015-08-12 | 安徽锦洋氟化学有限公司 | A kind of anhydrous hydrogen fluoride production method |
| CN108147383A (en) * | 2018-01-05 | 2018-06-12 | 贵州川恒化工股份有限公司 | The defluorination method of phosphoric acid by wet process |
| CN110902697A (en) * | 2018-09-16 | 2020-03-24 | 张旭 | Process and device for preparing sodium fluoride or potassium fluoride from fluorite |
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