CN102431982A - Arsenic removing method of phosphoric acid - Google Patents
Arsenic removing method of phosphoric acid Download PDFInfo
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- CN102431982A CN102431982A CN2011102872114A CN201110287211A CN102431982A CN 102431982 A CN102431982 A CN 102431982A CN 2011102872114 A CN2011102872114 A CN 2011102872114A CN 201110287211 A CN201110287211 A CN 201110287211A CN 102431982 A CN102431982 A CN 102431982A
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- arsenic
- phosphoric acid
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Abstract
The invention relates to an arsenic removing method of phosphoric acid. According to the invention, H2S and phosphoric acid are directly subject to a reaction under a certain condition. The method comprises steps that: first, under a condition of heating, H2S is delivered into an arsenic removing reactor, and is subject to a reaction with phosphoric acid; a material obtained through reaction is delivered into a buffering tank; recovered H2S tail gas is then delivered into the buffering tank, such that arsenic removing is further carried out; the material obtained from the buffering tank is delivered into a centrifugal separator or a vacuum filter through a pump, and is filtered; an obtained filtrate is the required arsenic-removed phosphoric acid; the arsenic content of the filter residue is relatively high, such that the filter residue is used for preparing arsenic products or is subject to landfill processing; the tail gas obtained from the arsenic-removing process is directly delivered back to the buffering tank, and is subject to the arsenic removing reaction; or the tail gas is circulated, washed and absorbed in a washing tower by using an alkaline solution; when the tail gas reaches a discharging standard, the tail gas is discharged into the atmosphere. According to the invention, H2S is used for removing arsenic. The pollution of H2S to the environment can be reduced, the phosphoric acid arsenic removing cost can be reduced, other impurities such as metal ions can be prevented from being introduced, and the stability of the quality of the phosphoric acid products can be ensured. The method provided by the invention is advantaged in high arsenic-removing efficiency, convenient operation, sufficient utilization of materials, and substantial effects.
Description
Technical field
The present invention relates to the compound of phosphorus, further, relate to phosphoric acid, in particular to the arsenic removing method of phosphoric acid.
Background technology
As everyone knows, the Rock Phosphate (72Min BPL) majority all contains arsenic, processes phosphoric acid with Rock Phosphate (72Min BPL), no matter be hot method technology or wet processing, the arsenic content in the phosphoric acid all is higher than the industrial phosphoric acid index.Existing arsenic removing method mainly contains: 1. yellow phosphorus is carried out dearsenification earlier: with the direct dearsenification of thiophosphoric anhydride, its shortcoming is that thiophosphoric anhydride is to make with yellow phosphorus and sulphur in yellow phosphorus, the bad security incident that yellow phosphorus spontaneous combustion and poisoning very easily take place of control in the operating process; 2. dearsenification in phosphoric acid: be to react with sweetening agents such as sodium sulphite and phosphoric acid, this method can be better with the dearsenification effect, but can bring other impurity such as sodium to phosphoric acid.In the Chinese patent DB; Relevant application part only has " technology for removing arsenic in polyphosphoric acid " No. 200810157176.2; System adopts through in phosphoric acid solution, feeding hydrogen sulfide or adding sulfide (like sodium sulphite; Thiophosphoric anhydride), makes at a certain temperature to generate deposition, obtain low-arsenic phosphorus acid through filtering separation then.This method is primarily aimed at polyphosphoric acid, and this technical scheme is imperfect, does not disclose the content of many necessity, the TR that should control such as the suitable concentration of phosphoric acid, dearsenification reaction, reaction times etc., causes this technical scheme not implement.
Summary of the invention
The purpose of this invention is to provide a kind of phosphoric acid arsenic removing method, thereby overcome the defective in the prior art scheme, make phosphoric acid be able to real realization, and do not bring other impurity into, can not cause new pollution phosphoric acid with the hydrogen sulfide dearsenification.
Phosphoric acid arsenic removing method provided by the invention is to utilize H
2S directly and phosphoric acid react under certain condition, characteristics of the present invention comprise:
At first, under 50 ℃～90 ℃ conditions, in the dearsenification reactor drum, feed H
2S makes it and phosphatase reaction, and controlling reaction time is 0.2～1h; Reacted material gets into dashpot, in dashpot, continues to feed the H that reclaims
2S tail gas, further dearsenification, the control residence time is 0.2～2h; Reaction equation is following:
As
3+＋H
2S→As
2S
3↓
As
5+＋H
2S→As
2S
5↓
The material that comes out from dashpot filters through pump delivery to separating centrifuge or vacuum filter; Gained filtrating is exactly required dearsenification phosphoric acid; The filter residue arsenic content is higher, in order to process the arsenic goods or to adopt landfill disposal;
The tail gas of dearsenification operation directly returns in the dashpot, continues to participate in the dearsenification reaction; Or absorb in washing tower internal recycle washing with basic soln, enter atmosphere after reaching emission standard.
Above-mentioned H
2S is from synthetic ammonia installation, or the by product in barium sulphide and the production of other sulfide.
Temperature in the above-mentioned dearsenification reactor drum is preferably 60 ℃～70 ℃; The control residence time is preferably 0.2～2h in the above-mentioned dashpot; Contain H after the reaction
2The tail gas of S continues retrieval system.
Above-mentioned vacuum filter adopts single-stage or 2 grades or 3 grades of filtrations.
Above-mentioned basic soln is the NaOH aqueous solution or the soda ash aqueous solution or Ca (OH)
2The aqueous solution, its massfraction is controlled at 3%～20%.
The inventive method adopts H
2S is the dearsenification raw material, can solve H
2S can reduce phosphoric acid dearsenification cost again to the pollution of environment, especially can not bring other impurity such as metals ion into, has guaranteed the stable of phosphoric acid product quality, and the byproduct of reaction of generation also can use by oneself or take out; Technology circuit of the present invention is simple, and arsenic-removing rate is high, and easy to operate, material is fully utilized, and effect is obvious.
Embodiment
Embodiment 1
Under 50 ℃ of conditions, 1.2 times that press phosphoric acid arsenic content are calculated adding H
2The amount of S feeds H to the dearsenification reactor drum that phosphoric acid is housed
2S gas, reacted material gets into the dashpot of belt stirrer, with the H that extracts out through blower fan from the dearsenification reactive tank
2S gas is proceeded the dearsenification reaction, reaction 2h; The material that comes out from dashpot filters through pump delivery to filter, and gained filtrating is exactly dearsenification phosphoric acid.
Dearsenification result such as following table:
Embodiment 2
Under 90 ℃ of conditions, 1.2 times that press phosphoric acid arsenic content are calculated adding H
2The amount of S feeds H to the dearsenification reactor drum that phosphoric acid is housed
2S gas, reacted material gets into the dashpot of belt stirrer, with the H that extracts out through blower fan from the dearsenification reactive tank
2S gas is proceeded the dearsenification reaction, reaction 0.4h; The material that comes out from dashpot filters through pump delivery to filter, and gained filtrating is exactly dearsenification phosphoric acid.
Dearsenification result such as following table:
Embodiment 3
Under 70 ℃ of conditions, 1.2 times that press phosphoric acid arsenic content are calculated adding H
2The amount of S feeds H to the dearsenification reactor drum that phosphoric acid is housed
2S gas, reacted material gets into the dashpot of belt stirrer, with the H that extracts out through blower fan from the dearsenification reactive tank
2S gas is proceeded the dearsenification reaction, reaction 1h; The material that comes out from dashpot filters through pump delivery to filter, and gained filtrating is exactly dearsenification phosphoric acid.
Dearsenification result such as following table:
Claims (5)
1. a phosphoric acid arsenic removing method is to utilize H
2S directly and phosphoric acid react under certain condition, its characteristic comprises:
At first, under 50 ℃～90 ℃ conditions, in the dearsenification reactor drum, feed H
2S makes it and phosphatase reaction, and controlling reaction time is 0.2～1h; Reacted material gets into dashpot, in dashpot, continues to feed the H that reclaims
2S tail gas, further dearsenification, the control residence time is 0.2～2h;
The material that comes out from dashpot filters through pump delivery to separating centrifuge or vacuum filter; Gained filtrating is exactly required dearsenification phosphoric acid; The filter residue arsenic content is higher, in order to process the arsenic goods or to adopt landfill disposal;
The tail gas of dearsenification operation directly returns in the dashpot, continues to participate in the dearsenification reaction; Or absorb in washing tower internal recycle washing with basic soln, enter atmosphere after reaching emission standard.
2. the method for claim 1 is characterized in that said H
2S is from synthetic ammonia installation, or the by product in barium sulphide and the production of other sulfide.
3. the method for claim 1 is characterized in that the temperature in the said dearsenification reactor drum is preferably 60 ℃～70 ℃; The control residence time is preferably 0.2～2h in the above-mentioned dashpot; Contain H after the reaction
2The tail gas of S continues retrieval system.
4. the method for claim 1 is characterized in that said vacuum filter adopts single-stage or 2 grades or 3 grades of filtrations.
5. the method for claim 1 is characterized in that said basic soln is the NaOH aqueous solution or the soda ash aqueous solution or Ca (OH)
2The aqueous solution; Its massfraction is controlled at 3%～20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102872114A CN102431982A (en) | 2011-09-26 | 2011-09-26 | Arsenic removing method of phosphoric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102872114A CN102431982A (en) | 2011-09-26 | 2011-09-26 | Arsenic removing method of phosphoric acid |
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| CN102431982A true CN102431982A (en) | 2012-05-02 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701170A (en) * | 2012-06-15 | 2012-10-03 | 昆明川金诺化工股份有限公司 | Process method for removing arsenic from feed-grade calcium hydrogen phosphate prepared from wet-process phosphoric acid |
| CN102701165A (en) * | 2012-06-19 | 2012-10-03 | 瓮福（集团）有限责任公司 | Method for removing arsenic from electronic grade phosphoric acid generated by wet-process phosphoric acid |
| CN102849698A (en) * | 2012-09-28 | 2013-01-02 | 凯恩德利(北京)科贸有限公司 | Efficient arsenic removing method and device for phosphoric acid |
| CN103979510A (en) * | 2014-04-25 | 2014-08-13 | 防城港博森化工有限公司 | Dearsenization method in production of phosphoric acid |
| CN108910850A (en) * | 2018-09-25 | 2018-11-30 | 湖北兴福电子材料有限公司 | A kind of thermal method electron-level phosphoric acid arsenic removing method |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
| CN110540179A (en) * | 2019-09-03 | 2019-12-06 | 贵州开磷集团矿肥有限责任公司 | Method and equipment for removing harmful elements in wet-process phosphoric acid and derivative products thereof |
| CN112225188A (en) * | 2020-10-15 | 2021-01-15 | 中国五环工程有限公司 | Process for removing arsenic from phosphoric acid by wet method |
| CN112661128A (en) * | 2021-01-18 | 2021-04-16 | 瓮福（集团）有限责任公司 | Method for efficiently removing arsenic by wet-process purified phosphoric acid |
| CN115057419A (en) * | 2022-06-07 | 2022-09-16 | 瓮福（集团）有限责任公司 | Industrial-grade wet-process phosphoric acid dearsenification method |
| CN115072682A (en) * | 2022-06-07 | 2022-09-20 | 瓮福（集团）有限责任公司 | Feed-grade wet-process phosphoric acid dearsenification method |
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| EP0232766A2 (en) * | 1986-02-13 | 1987-08-19 | Hoechst Aktiengesellschaft | Process for eliminating heavy metals from mineral acids |
| JPH0648712A (en) * | 1992-07-31 | 1994-02-22 | Mitsui Toatsu Chem Inc | Purification of phosphoric acid solution |
| CN1483666A (en) * | 2003-05-12 | 2004-03-24 | 四川大学 | Method for preparing industrial grade and food grade phosphoric acid by wet method phosphoric acid |
| CN1843900A (en) * | 2006-05-08 | 2006-10-11 | 朱健 | Method for preparing electronic grade phosphoric acid by fusion crystallization method |
| CN101676201A (en) * | 2008-09-19 | 2010-03-24 | 胡金来 | Technology for removing arsenic in polyphosphoric acid |
-
2011
- 2011-09-26 CN CN2011102872114A patent/CN102431982A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| EP0232766A2 (en) * | 1986-02-13 | 1987-08-19 | Hoechst Aktiengesellschaft | Process for eliminating heavy metals from mineral acids |
| JPH0648712A (en) * | 1992-07-31 | 1994-02-22 | Mitsui Toatsu Chem Inc | Purification of phosphoric acid solution |
| CN1483666A (en) * | 2003-05-12 | 2004-03-24 | 四川大学 | Method for preparing industrial grade and food grade phosphoric acid by wet method phosphoric acid |
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Non-Patent Citations (1)
| Title |
|---|
| 陈思忠: "磷酸精制工艺研究与探讨", 《中国资源综合利用》, vol. 29, no. 8, 31 August 2011 (2011-08-31), pages 37 - 39 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701170A (en) * | 2012-06-15 | 2012-10-03 | 昆明川金诺化工股份有限公司 | Process method for removing arsenic from feed-grade calcium hydrogen phosphate prepared from wet-process phosphoric acid |
| CN102701165A (en) * | 2012-06-19 | 2012-10-03 | 瓮福（集团）有限责任公司 | Method for removing arsenic from electronic grade phosphoric acid generated by wet-process phosphoric acid |
| CN102849698A (en) * | 2012-09-28 | 2013-01-02 | 凯恩德利(北京)科贸有限公司 | Efficient arsenic removing method and device for phosphoric acid |
| CN102849698B (en) * | 2012-09-28 | 2014-07-16 | 凯恩德利(北京)科贸有限公司 | Efficient arsenic removing method and device for phosphoric acid |
| CN103979510A (en) * | 2014-04-25 | 2014-08-13 | 防城港博森化工有限公司 | Dearsenization method in production of phosphoric acid |
| CN108910850A (en) * | 2018-09-25 | 2018-11-30 | 湖北兴福电子材料有限公司 | A kind of thermal method electron-level phosphoric acid arsenic removing method |
| CN109678114A (en) * | 2019-02-19 | 2019-04-26 | 苏州晶瑞化学股份有限公司 | The minimizing technology of arsenic impurities in a kind of electronic grade hydrochloric acid |
| CN109678114B (en) * | 2019-02-19 | 2021-04-02 | 苏州晶瑞化学股份有限公司 | Method for removing arsenic impurity in electronic grade hydrochloric acid |
| CN110540179A (en) * | 2019-09-03 | 2019-12-06 | 贵州开磷集团矿肥有限责任公司 | Method and equipment for removing harmful elements in wet-process phosphoric acid and derivative products thereof |
| CN112225188A (en) * | 2020-10-15 | 2021-01-15 | 中国五环工程有限公司 | Process for removing arsenic from phosphoric acid by wet method |
| CN112225188B (en) * | 2020-10-15 | 2022-04-29 | 中国五环工程有限公司 | Process for removing arsenic from phosphoric acid by wet method |
| CN112661128A (en) * | 2021-01-18 | 2021-04-16 | 瓮福（集团）有限责任公司 | Method for efficiently removing arsenic by wet-process purified phosphoric acid |
| CN112661128B (en) * | 2021-01-18 | 2023-06-02 | 瓮福（集团）有限责任公司 | Method for efficiently removing arsenic in phosphoric acid by wet purification |
| CN115057419A (en) * | 2022-06-07 | 2022-09-16 | 瓮福（集团）有限责任公司 | Industrial-grade wet-process phosphoric acid dearsenification method |
| CN115072682A (en) * | 2022-06-07 | 2022-09-20 | 瓮福（集团）有限责任公司 | Feed-grade wet-process phosphoric acid dearsenification method |
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Application publication date: 20120502 |