CN108910850A - A kind of thermal method electron-level phosphoric acid arsenic removing method - Google Patents
A kind of thermal method electron-level phosphoric acid arsenic removing method Download PDFInfo
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- CN108910850A CN108910850A CN201811115772.4A CN201811115772A CN108910850A CN 108910850 A CN108910850 A CN 108910850A CN 201811115772 A CN201811115772 A CN 201811115772A CN 108910850 A CN108910850 A CN 108910850A
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- Prior art keywords
- phosphoric acid
- dearsenicator
- passed
- hydrogen sulfide
- dearsenification
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of thermal method electron-level phosphoric acid arsenic removing method, the arsenic removing method is：Lead to nitrogen in sodium sulfide solution storage tank, after heating into storage tank without air, phosphoric acid is added and is reacted；Phosphoric acid is squeezed into dearsenicator by circulating pump, by the H of generation2S is passed through in dearsenicator；Sufficient phosphoric acid will be reacted in dearsenicator after filter, through High Purity Nitrogen qi exhaustion H2S gas enters phosphoric acid storage tank；The extra H that stripping goes out2S gas is absorbed with lye.De- H2Phosphoric acid after S gas enters phosphoric acid storage tank after cartridge filter, and arsenic content can be down to 10 ppb or less；The extra H that stripping goes out2S gas is absorbed with lye, avoids environmental pollution.By the phosphoric acid of this method dearsenification up to professional standard, it is applied to large scale integrated circuit industry.
Description
Technical field
The present invention relates to thermal method electron-level phosphoric acid technologies, especially thermal method electron-level phosphoric acid arsenic removing method.
Background technique
Electron-level phosphoric acid is semiconductor one of numerous high-purity chemicals reagents, is widely used in semicon industry,
It is one of chemicals important in wet etching, purity influences wafer micro-structure in etching process, electronic component yield,
Electrical property etc. is affected.
In recent years, super large-scale integration (IC) is quickly grown, and line width is more and more narrow, and wafer size is by 8 cun of development
12 cun, more even development is 16 cun, and chemical reagent purity requirement used in wafer cleaning and etching process is higher and higher,
Particle or metal ion in chemicals can cause conduction between microcircuit, to be allowed to short circuit, the lesser IC of line width scraps.
To avoid metal ion pollution in chip manufacturing, metal ion content must strict control in used chemicals.Its
Middle As belongs to VA race element, is wafer doped chemical, may penetrate into wafer in etching, causes electrically to change.Mesh
Preceding domestic production electron-level phosphoric acid technique is similar, and purification substantially uses physical method and chemical method, and As is removed more
It is difficult.
Summary of the invention
Present invention seek to address that deficiency of the prior art in terms of dearsenification, provides a kind of thermal method electron-level phosphoric acid dearsenification side
Method.The technical solution adopted by the present invention is that：
Utilize Na2H needed for S and phosphatase reaction generate dearsenification2S；
Na2S+2H3PO4==H2S+2NaH2PO4
(1) lead to nitrogen into sodium sulfide solution storage tank, after heating into storage tank without air, phosphoric acid is added and is reacted；Control
Na processed2The concentration of S is to guarantee H2The production quantity of S, by H2S is passed through dearsenicator；
(2) phosphoric acid is squeezed by dearsenicator by circulating pump, the H that step (1) is generated2S is passed through in dearsenicator；
(3) sufficient phosphoric acid will be reacted in dearsenicator in step (2) after filter, through High Purity Nitrogen qi exhaustion H2S gas into
Enter phosphoric acid storage tank；
(4) the extra H for going out stripping in step (3)2S gas is absorbed with lye.
Phosphoric acid quality concentration is higher than 85% in the step (1), step (2), and purity is greater than 99.999%.
Regulate and control Na in the step (1)2The mass concentration control of S is 5%~20%.
Reaction temperature is 60-80 DEG C in the step (1), and pressure is 90~150KPa in reactor tank, when pressure is higher than
Stop acid adding when 150KPa, continues acid adding when lower than 90KPa.
Phosphoric acid is squeezed into dearsenicator by the step (2), when dearsenicator phosphoric acid liquid level reaches 45%, opens dearsenification circulation
Pump, is passed through dearsenicator for hydrogen sulfide with 1000~3000L/h of flow, hydrogen sulfide is passed through time 1-5h.In further preferred scheme,
Phosphoric acid is squeezed into dearsenicator by the step (2), when dearsenicator phosphoric acid liquid level reaches 45%, dearsenification circulating pump is opened, by sulphur
Change hydrogen and dearsenicator is passed through with 1000~3000L/h of flow, hydrogen sulfide is passed through time 1-3h；When phosphoric acid liquid level reaches in dearsenicator
When 85%, phosphoric acid charging is closed, is passed through to hydrogen sulfide after finishing and phosphoric acid is squeezed into dearsenification mixing channel, to phosphorus in dearsenification mixing channel
After acid solution position reaches 45%, dearsenification pump is opened, hydrogen sulfide is passed through mixing channel, control vulcanization with flow for 2000~5000L/h
Hydrogen is passed through the time as 1-5h.
Described will react sufficient phosphoric acid after filter in dearsenification mixing channel in step (2), through High Purity Nitrogen qi exhaustion H2S
Gas enters phosphoric acid storage tank；The extra H that stripping goes out2S gas is absorbed with lye.
De- H2Phosphoric acid after S gas enters phosphoric acid storage tank after cartridge filter, and arsenic content can be down to 10ppb or less；It blows
The extra H of abjection2S gas is absorbed with lye, avoids environmental pollution.
2NaOH+H2S=Na2S+2H2O
The technology of the present invention principle is：Na2S is added phosphoric acid and prepares H2S, by H2The electron level phosphorus that mass fraction is 85% is added in S
Acid, the arsenic of pentavalent are reduced to trivalent arsenic in acid condition, precipitating are generated, by the electron level phosphorus that low arsenic content is obtained by filtration
Acid.Its key reaction is：
Na2S+2H3PO4==H2S+2NaH2PO4(1)
2H3AsO4+5H2S==As2S5+8H2O(2)
2H3AsO3+3H2S==6H2O+As2S3↓(3)
Pb2++H2S==PbS ↓+2H+(4)
It mainly includes As that reaction, which generates precipitating,2S3, the metal sulfides such as S and PbS, arsenic slag need to be collected and be isolated, give place
The mechanism of reason ability is handled.
Arsenic removing method of the present invention can effectively remove the metallic element that electrical property can be influenced in electron-level phosphoric acid, reach
The standard of IC industrial application at present.
Specific embodiment
Na of the present invention2The mass concentration of S can there are many, the flow of hydrogen sulfide and to be passed through the time all alterable, below by
The present invention is further described in detail for specific embodiment, and compares each embodiment and illustrate advantage of the invention.
Certain factory is using the patent of invention to thermal method electron-level phosphoric acid dearsenification, and specific step is as follows：
(1) liquid level that 20%~50% is added water into vulcanized sodium preparing tank, adds vulcanized sodium solid, and control vulcanized sodium is molten
Liquid concentration 5%~15%, and steam heating is opened, solution temperature is at 60~80 DEG C in control vulcanized sodium preparing tank；To vulcanized sodium
After being completely dissolved, sodium sulfide solution is passed through vulcanization hydrogen reactor, it is complete first will to vulcanize air in hydrogen reactor and pipeline with nitrogen
After total replacement, rear slowly into vulcanization hydrogen reactor, addition phosphoric acid prepares hydrogen sulfide gas, while observing pressure in tank, works as pressure
Stop acid adding when higher than 150KPa, continues acid adding when lower than 90KPa；
(2) phosphoric acid in phosphoric acid buffer tank is squeezed into dearsenicator, when dearsenicator phosphoric acid liquid level reaches 45%, opens dearsenification
Circulating pump, and hydrogen sulfide inlet valve is opened, hydrogen sulfide flow is adjusted to 1000~3000L/h, leads to the control of hydrogen sulfide time and exists
1-3h stops when phosphoric acid liquid level reaches 85% in dearsenicator into acid.To hydrogen sulfide is logical finish after phosphoric acid squeezed into dearsenification mix
Close slot, after phosphoric acid liquid level reaches 45% in dearsenification mixing channel, open dearsenification pump, hydrogen sulfide be passed through flow be adjusted to 2000~
5000L/h, control hydrogen sulfide are passed through the time, lead to the control of hydrogen sulfide time in 1~5h；
(3) when lautertuns liquid level 30%~90%, open filter pump, before a set filter install 5 μm of filter cores, when its pressure
When difference reaches 245~277KPa, filter core is replaced in time, and later group installs 1 μm of filter core, and sampling analysis coloration, works as color after filtering
When spending unqualified can at grade one filter and sheet frame circulating filtration, until qualified；
(4) when fluid reservoir phosphoric acid liquid level reaches 80% or so, heater, by sour temperature control system at 60~75 DEG C, and it is same
When be passed through nitrogen aeration, the aeration cycle time be greater than 12 hours；
(5) stripping is gone out into extra H2The phosphoric acid of S enters phosphoric acid storage tank by cartridge filter, and arsenic content can be down to
5ppb；
(6) the extra H that stripping goes out2S gas is absorbed by three sodium hydroxides, and the vulcanized sodium of generation enters vulcanized sodium preparation
Reuse in tank；
(7) arsenic slag transfers to the mechanism with processing qualification to be handled after collecting.
Following example one illustrates Na of the present invention by Experimental comparison2S content prepares the advantage of hydrogen sulfide arsenic removal,
Experiment is using Na in rate-determining steps (1)2The amount of S component is as a comparison case：
First comparative example, by Na2The control of S mass concentration is 5%, the H of preparation2S is passed through dearsenicator dearsenification.
Second comparative example, by Na2The control of S mass concentration is 7.5%, the H of preparation2S is passed through dearsenicator dearsenification.
Third comparative example, by Na2The control of S mass concentration is 10%, the H of preparation2S is passed through dearsenicator dearsenification.
4th comparative example, by Na2The control of S mass concentration is 12.5%, the H of preparation2S is passed through dearsenicator dearsenification.
5th comparative example, by Na2The control of S mass concentration is 15%, the H of preparation2S is passed through dearsenicator dearsenification.
In embodiment two, pass through the removal of dearsenicator in rate-determining steps (2), the flow optimization arsenic of dearsenification mixing channel hydrogen sulfide
Rate.
First comparative example will be passed through the flow control of dearsenicator hydrogen sulfide in 1000L/h, be passed through the H of dearsenification mixing channel2S stream
Amount control is in 2000L/h.
Second comparative example will be passed through the flow control of dearsenicator hydrogen sulfide in 1500L/h, be passed through the H of dearsenification mixing channel2S stream
Amount control is in 3000L/h.
Third comparative example will be passed through the flow control of dearsenicator hydrogen sulfide in 2000L/h, be passed through the H of dearsenification mixing channel2S stream
Amount control is in 3500L/h.
4th comparative example will be passed through the flow control of dearsenicator hydrogen sulfide in 2500L/h, be passed through the H of dearsenification mixing channel2S stream
Amount control is in 4000L/h.
5th comparative example will be passed through the flow control of dearsenicator hydrogen sulfide in 3000L/h, be passed through the H of dearsenification mixing channel2S stream
Amount control is in 5000L/h.
In embodiment three, time-optimized arsenic is passed through by dearsenicator in rate-determining steps (2), dearsenification mixing channel hydrogen sulfide
Removal rate.
First comparative example controls the hydrogen sulfide time for being passed through dearsenicator in 1h, when being passed through the hydrogen sulfide of dearsenification mixing channel
Between control in 1h.
The hydrogen sulfide time for being passed through dearsenicator is controlled in 1.5h, is passed through the hydrogen sulfide of dearsenification mixing channel by the second comparative example
Time controls in 2h.
Third comparative example controls the hydrogen sulfide time for being passed through dearsenicator in 2h, when being passed through the hydrogen sulfide of dearsenification mixing channel
Between control in 3h.
The hydrogen sulfide time for being passed through dearsenicator is controlled in 2.5h, is passed through the hydrogen sulfide of dearsenification mixing channel by the 4th comparative example
Time controls in 4h.
5th comparative example controls the hydrogen sulfide time for being passed through dearsenicator in 3h, when being passed through the hydrogen sulfide of dearsenification mixing channel
Between control in 5h.
The Na of the above mass concentration2S produces H2After S, it is passed through the H of the above flow2S is to dearsenification mixing channel, and when controlling dearsenification
Between, it is measured through overtesting, aforementioned present invention first embodiment, second embodiment and 3rd embodiment and its comparative example are corresponding
Indices are as shown in table 1：
Table 1
Explanation：1,2,3 be respectively embodiment 1, embodiment 2, embodiment 3.
A, b, c, d, e are respectively comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5.
Arsenic removing method of the invention is described in detail above, the foregoing is merely specific embodiment parties of the invention
Formula is not intended to limit the scope of protection of the present invention, and on the basis of the present invention, can be made some modifications or improvements to it, this is right
It is obvious for those skilled in the art.Therefore, these modifications made without departing from theon the basis of the spirit of the present invention
Or improve, it falls within the scope of the claimed invention.
Claims (8)
1. a kind of thermal method electron-level phosphoric acid arsenic removing method, which is characterized in that steps are as follows for its dearsenification：
（1）Lead to nitrogen into sodium sulfide solution storage tank, after heating into storage tank without air, phosphoric acid is added and is reacted；
（2）Phosphoric acid is squeezed into dearsenicator by circulating pump, by step（1）The H of generation2S is passed through in dearsenicator；
（3）By step（2）The sufficient phosphoric acid of reaction is after filter in middle dearsenicator, through High Purity Nitrogen qi exhaustion H2S gas enters phosphoric acid
Storage tank；
（4）By step（3）The extra H that middle stripping goes out2S gas is absorbed with lye.
2. thermal method electron-level phosphoric acid arsenic removing method according to claim 1, which is characterized in that step（1）, step（2）In
Phosphoric acid quality concentration is higher than 85%, and purity is greater than 99.9999%.
3. thermal method electron-level phosphoric acid arsenic removing method according to claim 1, which is characterized in that step（1）Middle regulation Na2S's
Mass concentration control is 5% ~ 20%.
4. thermal method electron-level phosphoric acid arsenic removing method according to claim 1, which is characterized in that step（1）Middle reaction temperature
It is 60-80 DEG C, pressure is 90 ~ 150KPa in reactor tank, stops acid adding when pressure is higher than 150KPa, continues when lower than 90KPa
Acid adding.
5. thermal method electron-level phosphoric acid arsenic removing method according to claim 1, which is characterized in that step（2）Middle hydrogen sulfide is logical
The flow for entering dearsenicator is 2000 ~ 5000L/h, and being passed through the time is 1 ~ 5h.
6. thermal method electron-level phosphoric acid arsenic removing method according to claim 5, which is characterized in that step（2）Phosphoric acid is squeezed into
Dearsenicator opens dearsenification circulating pump when dearsenicator phosphoric acid liquid level reaches 45%, and hydrogen sulfide is logical with 1000 ~ 3000 L/h of flow
Enter dearsenicator, hydrogen sulfide is passed through time 1-5h.
7. thermal method electron-level phosphoric acid arsenic removing method according to claim 1, which is characterized in that step（2）Phosphoric acid is squeezed into
Dearsenicator opens dearsenification circulating pump when dearsenicator phosphoric acid liquid level reaches 45%, and hydrogen sulfide is logical with 1000 ~ 3000 L/h of flow
Enter dearsenicator, hydrogen sulfide is passed through time 1-3h；When phosphoric acid liquid level reaches 85% in dearsenicator, phosphoric acid charging is closed, to hydrogen sulfide
It is passed through after finishing and phosphoric acid is squeezed into mixing channel, after phosphoric acid liquid level reaches 45% in slot to be mixed, dearsenification pump is opened, by dearsenicator
Interior hydrogen sulfide is that 2000 ~ 5000L/h is passed through mixing channel with flow, and control hydrogen sulfide is passed through the time as 1-5h.
8. thermal method electron-level phosphoric acid arsenic removing method according to claim 7, which is characterized in that by step（2）Middle mixing channel
After the interior sufficient phosphoric acid of reaction is filtered, through High Purity Nitrogen qi exhaustion H2S gas enters phosphoric acid storage tank；The extra H that stripping goes out2S
Gas is absorbed with lye.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811115772.4A CN108910850A (en) | 2018-09-25 | 2018-09-25 | A kind of thermal method electron-level phosphoric acid arsenic removing method |
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| CN201811115772.4A CN108910850A (en) | 2018-09-25 | 2018-09-25 | A kind of thermal method electron-level phosphoric acid arsenic removing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809378A (en) * | 2019-03-27 | 2019-05-28 | 重庆万盛川东化工有限公司 | Phosphoric acid for food production technology |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2109970A1 (en) * | 1971-03-03 | 1972-09-07 | Knapsack Ag | Process and device for the continuous dearsenation of polyphosphoric acid |
| WO2005003026A1 (en) * | 2003-07-01 | 2005-01-13 | Nippon Chemical Industrial Co.,Ltd. | High purity phosphoric acid and method for production thereof |
| CN102431982A (en) * | 2011-09-26 | 2012-05-02 | 瓮福（集团）有限责任公司 | Arsenic removing method of 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 |
| 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 |
| CN105271150A (en) * | 2015-10-22 | 2016-01-27 | 昆明理工大学 | Method for removing arsenic through industrial phosphoric acid |
-
2018
- 2018-09-25 CN CN201811115772.4A patent/CN108910850A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2109970A1 (en) * | 1971-03-03 | 1972-09-07 | Knapsack Ag | Process and device for the continuous dearsenation of polyphosphoric acid |
| WO2005003026A1 (en) * | 2003-07-01 | 2005-01-13 | Nippon Chemical Industrial Co.,Ltd. | High purity phosphoric acid and method for production thereof |
| CN102431982A (en) * | 2011-09-26 | 2012-05-02 | 瓮福（集团）有限责任公司 | Arsenic removing method of 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 |
| 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 |
| CN105271150A (en) * | 2015-10-22 | 2016-01-27 | 昆明理工大学 | Method for removing arsenic through industrial phosphoric acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809378A (en) * | 2019-03-27 | 2019-05-28 | 重庆万盛川东化工有限公司 | Phosphoric acid for food production technology |
| 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 |
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Application publication date: 20181130 |