CN102951611A - Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises - Google Patents
Method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises Download PDFInfo
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- CN102951611A CN102951611A CN2012105653611A CN201210565361A CN102951611A CN 102951611 A CN102951611 A CN 102951611A CN 2012105653611 A CN2012105653611 A CN 2012105653611A CN 201210565361 A CN201210565361 A CN 201210565361A CN 102951611 A CN102951611 A CN 102951611A
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Abstract
The invention discloses a method for preparing anhydrous hydrogen fluoride by utilizing fluorine-containing waste liquid or fluorosilicic acid in phosphate fertilizer enterprises, and the method is characterized in that ammonia (or ammonium carbonate) is reacted with 5% to 30% fluorine-containing waste gas absorption liquid or fluorosilicic acid, the reaction is ended when the pH value is 7 to 8, reaction mass is filtered to obtain ammonium fluoride solution, and the ammonium fluoride solution is used for absorbing silicon tetrafluoride (SiF4) in tail gas to obtain ammonium fluoride solution; the ammonium fluoride solution is evaporated, concentrated and centrifugally filtered to obtain solid ammonium fluorosilicate; and the solid ammonium fluorosilicate has acidolysis reaction with 92% to 99% concentrated sulfuric acid to produce mixed gas of SiF4 and hydrogen fluoride (HF), the mixed gas is washed, purified and condensed to obtain the anhydrous hydrogen fluoride, and the SiF4 is used for preparing ammonium fluosilicate. The water in the fluorine-containing waste gas absorption liquid or the fluorosilicic acid is removed in the preparation step of the ammoniuim fluosilicate, so that the anhydrous hydrogen fluoride product is easy to obtain; the acidolysis waste solution can be returned to be equivalently used in a phosphate fertilizer production system; and the effectiveness for utilizing the fluorine in phosphate ore can be realized.
Description
Technical field
The present invention relates to the technology of preparing of fluorine chemical industry anhydrous hydrogen fluoride in the chemical field, relate in particular to a kind of technological method that utilizes the fluorine-containing waste liquid of phosphatic fertilizer company or silicofluoric acid to prepare anhydrous hydrogen fluoride.
Background technology:At present, the main production method of anhydrous hydrogen fluoride for industrial use is with fluorite (Calcium Fluoride (Fluorspan) CaF
2) and the vitriol oil be raw material, be heated to 500 ℃, reaction generates hydrogen fluoride gas, by distilation, obtains anhydrous hydrogen fluoride after the liquefaction, the calcium sulfate that generates after the reaction is as industrial waste residue disposal.Take the technology of silicofluoric acid as the raw material production anhydrous hydrogen fluoride, except adopting the sulfuric acid pyrolysis method, urn good fortune blue sky, Guizhou fluorine chemical limited-liability company utilize silicofluoric acid to produce the anhydrous hydrogen fluoride both at home and abroad, also there are not other ripe industrialization technologies.
For a long time, industry thinks that always fluorite is the main source of fluorine resource.Whole world fluorite reserves are about 600,000,000 tons, calculate by 50% fluorine content, and the fluorine total amount is also only had an appointment 300,000,000 tons.And approximately 60,000,000,000 tons of known Rock Phosphate (72Min BPL) reserves in the world, the fluorine content in the Rock Phosphate (72Min BPL) is 2%～4%, corresponding fluorine total amount is 1,200,000,000 ~ 2,400,000,000 tons.The fluorite resource reserves that China has now been verified (ore is by the single fluorite average grade 54% in the whole nation) have 1.55 * 10
5Kt, and China's fluorine resource associated with phosphate rock reserves just are equivalent to 2.12 * 10
6～2.59 * 10
6Fluorine stock number in the kt fluorite ore is 13.67～16.71 times that China has verified the fluorite reserves.The Rock Phosphate (72Min BPL) amount of annual exploitation reaches more than 5,000 ten thousand tons, and the association fluorine has more than 150 ten thousand tons.On the other hand, fluorite is a kind of non-renewable strategic resources, and country has carried out and no longer provided new fluorite production licence, and quota exports relevant policies such as (export quotas are also reducing year by year).Along with the minimizing of fluorite resource, the Fluorspar Powder supply is becoming tight day, and the price of Fluorspar Powder is also high with one the tunnel, and this will make Fluorspar Powder-Production By Sulfuric Acid Process hydrofluoric acid or anhydrous hydrogen fluoride be subject to greatly restriction even stop production.Therefore, effectively utilizing fluorine resource in the phosphorus ore, take silicofluoric acid as the raw material production anhydrous hydrogen fluoride, is the inevitable choice of China's fluorine chemical sustainable development.
Along with the high speed development of Chinese fluorine chemical industry, fluorite resource is further exhausted, rationally recycles fluorine resource abundant in the phosphorus ore day by day important.The present invention prepares the various patented technologies of anhydrous hydrogen fluoride by silicofluoric acid inside and outside the comparator, propose the present technique method.
At present produce hydrofluoric patented technology with the silicofluoric acid of phosphatic fertilizer company by-product more, mainly be divided into direct method and indirect method, direct method is to utilize sulfuric acid directly to decompose silicofluoric acid to prepare hydrogen fluoride; Indirect method is first silicofluoric acid to be converted into the fluoride salts such as Neutral ammonium fluoride, prepares hydrogen fluoride with sulfuric acid reaction again.No matter be direct method and indirect method, a problem that all will face is from the silicofluoric acid to the anhydrous hydrogen fluoride, how to remove the water in the raw material, obtains anhydrous product.Existing a lot of technology is exactly owing to the water of failing to remove in the raw material, can only obtain water hydrofluoric acid.Therefore, utilize silicofluoric acid to produce anhydrous hydrogen fluoride, dehydration technique is crucial.
Summary of the invention:
The purpose of this invention is to provide the method that the fluorine-containing waste liquid of a kind of phosphatic fertilizer company or silicofluoric acid prepare anhydrous hydrogen fluoride, water in waste gas containing fluoride absorption liquid or the silicofluoric acid is got rid of by concentrated ammonium silicofluoride, can make the very low hydrogen fluoride of water content and silicon tetrafluoride mixed gas with the vitriol oil acidolysis solid ammonium silicofluoride stage again, easily obtain the anhydrous hydrogen fluoride product; The acidolysis raffinate returns the utilization of production of phosphate fertilizer system.Waste gas containing fluoride absorption liquid or silicofluoric acid in the production of phosphate fertilizer are utilized effectively.
Technological method of the present invention is as follows:
(1) with waste gas containing fluoride absorption liquid or the silicofluoric acid reaction of ammonia (or volatile salt) with 5%～30%W/W, control pH value 7～8 is reaction end, generates Neutral ammonium fluoride and silicon-dioxide, filters the ammonolysis reaction material and obtains ammonium fluoride solution and silicon-dioxide byproduct.Ammonium fluoride solution is as the raw material of subsequent technique, and the silicon-dioxide wash water is used for the make-up solution of the fluorine absorption system of Phosphoric Acid Concentration, and the silicon-dioxide byproduct can further recycle.
The main chemical reactions principle that relates to is:
(2) ammonium fluoride solution of producing in the above-mentioned steps (1) is for the tail gas of absorption step (5), NH
4SiF in F and the tail gas
4Reaction obtains ammonium fluosilicate solution;
The main chemical reactions principle that relates to is:
①?
②?
(3) ammonium fluosilicate solution that obtains in the above-mentioned steps (2) obtains the solid ammonium silicofluoride through the low pressure evaporation concentration.Evaporation vacuum tightness is 55kPa～80kPa, and temperature of charge is 70 ℃～50 ℃.
(4) the solid ammonium silicofluoride that obtains in the above-mentioned steps (3) is with H
2SO
4Content is that 92%～99% the vitriol oil carries out acidolysis reaction under hot conditions, produces SiF
4With the mixed gas of HF, the acidolysis raffinate returns the production of phosphate fertilizer system equivalent and uses.Sulphuric acid is with H
2SO
4Count 100%～150%W/W of theoretical amount; Sulphuric acid is with H
2SO
4Count 100%～150%W/W of theoretical amount; The acidolysis SiF that under vacuum condition, volatilizees
4And HF, vacuum degree control is at 55kPa～85kPa, and temperature is controlled at 120 ℃～140 ℃; As the acidolysis SiF that under normal pressure, volatilizees
4During with HF, then temperature should be controlled at 140 ℃～175 ℃.
The main chemical reactions principle that relates to is:
(5) hydrogen fluoride that obtains in the above-mentioned steps (4) and the mixed gas of silicon tetrafluoride obtain anhydrous hydrogen fluoride after washing, purification, condensation, mainly contain SiF in the tail gas
4Gas.Indication concentration of the present invention all adopts concentration expressed in percentage by weight.
The present invention removes the water in waste gas containing fluoride absorption liquid or the silicofluoric acid at the ammonium silicofluoride preparatory phase, can make the very low acidolysis gas of water content in the acidolysis hydrogen fluoride processed stage, easily obtains the anhydrous hydrogen fluoride product.The acidolysis raffinate returns the production of phosphate fertilizer system equivalent and uses.Byproduct silicon-dioxide foreign matter content is low, is easy to carry out deep processing and becomes the filler white carbon black.Only be a small amount of fluorine that the liquid foam is taken out of in the concentrated waste water that produces, be easy to process.This invention technology has realized effective utilization of fluorine resource associated with phosphate rock.
Description of drawings:
Fig. 1 is the process flow diagram of the inventive method.Schematic diagram mainly comprises: the ammonolysis reaction (I) that step (1) is carried out with ammonia (or volatile salt) and waste gas containing fluoride absorption liquid or silicofluoric acid; Ammonium fluoride solution absorbs SiF in the tail gas in the step (2)
4The tail gas of gas generation ammonium fluosilicate solution absorbs, ammonium fluosilicate solution production (II); Ammonium fluosilicate solution adds concentrated ammonium fluosilicate solution concentrated (III) in the step (3); Solid ammonium silicofluoride and the vitriol oil carry out the solid ammonium silicofluoride acidolysis (IV) of acidolysis reaction in the step (4); SiF
4, the HF condensation of gas, obtain HF condensation, the rectifying (V) of anhydrous hydrogen fluoride after refining.
Embodiment:
Embodiment 1
With the fluorine silicofluoric acid reaction of ammonia (or volatile salt) and 20%, control pH value 7.5 is reaction end, generates Neutral ammonium fluoride and silicon-dioxide, filters the ammonolysis reaction material and obtains ammonium fluoride solution and silicon-dioxide byproduct; Ammonium fluoride solution is used for absorbing tail gas SiF
4, obtain ammonium fluosilicate solution; Ammonium fluosilicate solution obtains the solid ammonium silicofluoride through the low pressure evaporation concentration, and evaporation vacuum tightness is 75kPa, and temperature of charge is about 55 ℃～58 ℃.Obtain content after the centrifuge dehydration of solid ammonium silicofluoride greater than 92% solid ammonium silicofluoride; Solid ammonium silicofluoride and 98% the vitriol oil carry out acidolysis reaction and produce SiF
4With the mixed gas of HF, sulphuric acid is with H
2SO
4Count 120% of theoretical amount, the acidolysis hydrogen fluoride that under vacuum condition, volatilizees, vacuum degree control is at 55kPa～80kPa, and temperature of reaction is controlled at 140 ℃～120 ℃; The acidolysis raffinate returns the production of phosphate fertilizer system equivalent and uses; The SiF that acidolysis obtains
4After washing, purification, condensation, obtain anhydrous hydrogen fluoride with the mixed gas of HF; Mainly contain SiF in the cool solidifying rear tail gas
4Gas, tail gas is for the preparation of ammonium silicofluoride; After rectifying, obtain HF content greater than 99.90% anhydrous hydrogen fluoride finished product with obtaining anhydrous hydrogen fluoride after the condensation.
Anhydrous hydrogen fluoride per ton (100%HF) norm quota of consumption
The fluorine yield is greater than 88%.
Embodiment 2
Except the acidolysis process using hydrogen fluoride that volatilizees under normal pressure, outside temperature of reaction was controlled at approximately 170 ℃, all the other were with embodiment 1.
Claims (8)
1. the fluorine-containing waste liquid of phosphatic fertilizer company or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that following these steps to carrying out:
(1) with waste gas containing fluoride absorption liquid or the silicofluoric acid reaction of ammonia (or volatile salt) with 5%～30%W/W, control pH value 7～8 is reaction end, generates Neutral ammonium fluoride and silicon-dioxide, filters the ammonolysis reaction material and obtains ammonium fluoride solution and silicon-dioxide byproduct;
(2) ammonium fluoride solution of producing in the above-mentioned steps (1), the tail gas for absorption step (5) obtains ammonium fluosilicate solution;
(3) ammonium fluosilicate solution that obtains in the above-mentioned steps (2) is that 55kPa～80kPa, temperature of charge are that evaporation concentration produces the ammonium silicofluoride crystal under 70 ℃～50 ℃ the condition in vacuum tightness, obtains the solid ammonium silicofluoride after the centrifuging;
(4) the solid ammonium silicofluoride that obtains in the above-mentioned steps (3) is with H
2SO
4Content is that 92%～99% the vitriol oil carries out acidolysis reaction, produces SiF
4Mixed gas with HF; Sulphuric acid is with H
2SO
4Count 100%%～150% of theoretical amount; The acidolysis SiF that under vacuum condition, volatilizees
4And HF, vacuum degree control is at 55kPa～85kPa, and temperature is controlled at 120 ℃～140 ℃; As the acidolysis SiF that under normal pressure, volatilizees
4During with HF, temperature is controlled at 140 ℃～175 ℃;
(5) SiF that obtains in the above-mentioned steps (4)
4Obtain anhydrous hydrogen fluoride with the mixed gas of HF through washing, purification, condensation, after refining, mainly contain SiF in the tail gas
4Return in the above-mentioned steps (2) for the preparation of ammonium silicofluoride.
2. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that the wash water of washing silicon-dioxide in the step (1) is as the make-up solution of Phosphoric Acid Concentration fluorine absorption system.
3. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that optimal conditions in step (3) operation is that the vacuum tightness of solution evaporation concentration systems is 70kPa～80kPa, temperature of charge is about 55 ℃～65 ℃.
4. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that the acidolysis raffinate of step (4) returns the use of production of phosphate fertilizer system equivalent.
5. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that the sulphuric acid of step (4) is with H
2SO
4Count 120%～130% my W/W of theoretical amount.
6. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, the acidolysis that it is characterized in that step (4) SiF that volatilizees under vacuum condition
4And HF, vacuum degree control is at 70kPa～80kPa, and temperature is controlled at 125 ℃～135 ℃.
7. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, the acidolysis that it is characterized in that step (4) SiF that also can volatilize under normal pressure
4And HF, temperature is controlled at 160 ℃～170 ℃.
8. the fluorine-containing waste liquid of a kind of phosphatic fertilizer company as claimed in claim 1 or silicofluoric acid prepare the method for anhydrous hydrogen fluoride, it is characterized in that mainly containing SiF in the tail gas of step (5)
4Gas is sent into step (2) and is absorbed with the ammonium fluoride solution of step (1).
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445074A (en) * | 2014-12-11 | 2015-03-25 | 云南省化工研究院 | Method for preparing anhydrous hydrogen fluoride and coproducing silicon tetrafluoride by treating diluted hydrofluosilicic acid through solvent extraction method |
| CN106006560A (en) * | 2016-05-23 | 2016-10-12 | 禄丰天宝磷化工有限公司 | Method for preparing hydrogen fluoride in feed grade calcium hydrophosphate production process |
| CN106145043A (en) * | 2016-06-29 | 2016-11-23 | 云南磷化集团有限公司 | The method that the fluorine-containing waste liquid of a kind of phosphorous chemical industry prepares low concentration hydrofluoric acid |
| CN106185817A (en) * | 2016-07-12 | 2016-12-07 | 中南大学 | A kind of method reclaiming Fluohydric acid. from fluorine-containing silicic acid waste water |
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN109179328A (en) * | 2018-08-29 | 2019-01-11 | 福建瓮福蓝天氟化工有限公司 | A kind of decoloration process of phosphoric acid fluosilicic acid as byproduct production anhydrous hydrogen fluoride |
| CN109353988A (en) * | 2018-11-12 | 2019-02-19 | 贵州开磷氟硅化工有限责任公司 | The method that ammonium fluoride and the concentrated sulfuric acid are mixed with high concentration of hydrofluoric acid |
| CN109574017A (en) * | 2018-11-23 | 2019-04-05 | 贵州开磷氟硅化工有限责任公司 | A method of SiF4 and anhydrous hydrogen fluoride are prepared by raw material of fluosilicic acid |
| CN110950359A (en) * | 2020-01-07 | 2020-04-03 | 贵州瓮福蓝天氟化工股份有限公司 | Method for preparing sodium fluoride and by-product high-performance white carbon black |
| CN111153387A (en) * | 2020-03-03 | 2020-05-15 | 衢州市鼎盛化工科技有限公司 | Method and equipment for recovering fluorine-containing waste liquid of acid-washed coal |
| CN112320803A (en) * | 2020-10-27 | 2021-02-05 | 贵州省化工研究院 | Method for producing solid ammonium fluosilicate by using fluosilicic acid in phosphoric acid |
| CN115010092A (en) * | 2022-07-20 | 2022-09-06 | 湖北九宁化学科技有限公司 | Method for recycling CVD dust in semiconductor industry |
| CN115072666A (en) * | 2022-06-23 | 2022-09-20 | 中石化南京工程有限公司 | System and method for preparing anhydrous hydrogen fluoride from fluosilicic acid |
| WO2023202270A1 (en) * | 2022-04-20 | 2023-10-26 | 贵州新东浩化工材料科技有限公司 | Method for graded utilization of fluorine and silicon resources in phosphate ore |
| US11891344B2 (en) | 2022-04-20 | 2024-02-06 | Chtem Limited | Methods for graded utilization of fluorine and silicon resources in phosphate ores |
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| CN104445074A (en) * | 2014-12-11 | 2015-03-25 | 云南省化工研究院 | Method for preparing anhydrous hydrogen fluoride and coproducing silicon tetrafluoride by treating diluted hydrofluosilicic acid through solvent extraction method |
| CN106006560A (en) * | 2016-05-23 | 2016-10-12 | 禄丰天宝磷化工有限公司 | Method for preparing hydrogen fluoride in feed grade calcium hydrophosphate production process |
| CN106145043A (en) * | 2016-06-29 | 2016-11-23 | 云南磷化集团有限公司 | The method that the fluorine-containing waste liquid of a kind of phosphorous chemical industry prepares low concentration hydrofluoric acid |
| CN106185817A (en) * | 2016-07-12 | 2016-12-07 | 中南大学 | A kind of method reclaiming Fluohydric acid. from fluorine-containing silicic acid waste water |
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN109179328A (en) * | 2018-08-29 | 2019-01-11 | 福建瓮福蓝天氟化工有限公司 | A kind of decoloration process of phosphoric acid fluosilicic acid as byproduct production anhydrous hydrogen fluoride |
| CN109353988A (en) * | 2018-11-12 | 2019-02-19 | 贵州开磷氟硅化工有限责任公司 | The method that ammonium fluoride and the concentrated sulfuric acid are mixed with high concentration of hydrofluoric acid |
| CN109574017A (en) * | 2018-11-23 | 2019-04-05 | 贵州开磷氟硅化工有限责任公司 | A method of SiF4 and anhydrous hydrogen fluoride are prepared by raw material of fluosilicic acid |
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| CN111153387A (en) * | 2020-03-03 | 2020-05-15 | 衢州市鼎盛化工科技有限公司 | Method and equipment for recovering fluorine-containing waste liquid of acid-washed coal |
| CN112320803A (en) * | 2020-10-27 | 2021-02-05 | 贵州省化工研究院 | Method for producing solid ammonium fluosilicate by using fluosilicic acid in phosphoric acid |
| CN112320803B (en) * | 2020-10-27 | 2022-05-13 | 贵州省化工研究院 | Method for producing solid ammonium fluosilicate by using fluosilicic acid in phosphoric acid |
| WO2023202270A1 (en) * | 2022-04-20 | 2023-10-26 | 贵州新东浩化工材料科技有限公司 | Method for graded utilization of fluorine and silicon resources in phosphate ore |
| US11891344B2 (en) | 2022-04-20 | 2024-02-06 | Chtem Limited | Methods for graded utilization of fluorine and silicon resources in phosphate ores |
| CN115072666A (en) * | 2022-06-23 | 2022-09-20 | 中石化南京工程有限公司 | System and method for preparing anhydrous hydrogen fluoride from fluosilicic acid |
| CN115072666B (en) * | 2022-06-23 | 2023-08-18 | 中石化南京工程有限公司 | System and method for preparing anhydrous hydrogen fluoride from fluosilicic acid |
| CN115010092A (en) * | 2022-07-20 | 2022-09-06 | 湖北九宁化学科技有限公司 | Method for recycling CVD dust in semiconductor industry |
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Inventor after: Tian Juan Inventor after: Ma Fubo Inventor after: Zhou Changping Inventor after: Chen Wenxing Inventor before: Chen Wenxing Inventor before: Tian Juan Inventor before: Zhou Changping |
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