CN102059035B - Method for preparing high-purity H2 and PH3 from tail gas from generation of tetrakis hydroxymethyl phosphonium sulfate - Google Patents
Method for preparing high-purity H2 and PH3 from tail gas from generation of tetrakis hydroxymethyl phosphonium sulfate Download PDFInfo
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- CN102059035B CN102059035B CN201010560941A CN201010560941A CN102059035B CN 102059035 B CN102059035 B CN 102059035B CN 201010560941 A CN201010560941 A CN 201010560941A CN 201010560941 A CN201010560941 A CN 201010560941A CN 102059035 B CN102059035 B CN 102059035B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention discloses a method for preparing high-purity H2 and PH3 from tail gas from generation of tetrakis hydroxymethyl phosphonium sulfate, comprising the following steps of: firstly, primarily purifying the tail gas by a molecular sieve adsorption method to remove H2O, CO2 and CH2O, separating AsH3, FH3, HF, H2 and PH3 through cryogenic distillation so as to finally obtain the PH3 and H2 not less than 99.99% (grade 4N). Compared with the prior art, the invention realizes separation at low temperature by using a pure physical method according to different boiling points of different gas, avoids the risk of spontaneous combustion of hydrogen phosphide, prevents secondary pollution and effectively reduces emission of polluted gas. The obtained hydrogen phosphide can be returned to the system to reproduce high-purity etrakis hydroxymethyl phosphonium sulfate and hydrogen can be used as clean fuel. The invention reduces the production cost and energy consumption of the system, realizes the clean production of the etrakis hydroxymethyl phosphonium sulfate, effectively reduces the emission of harmful gas and changes waste into wealth.
Description
(1) technical field: the present invention relates to a kind ofly utilize industrial waste gas to carry out Separation and Recovery to produce H
2With PH
3Technology, specifically be to produce tail gas from tetra methylol sulfuric acid phosphorus to produce high-purity H
2With PH
3Method.
The (2) background technology: at present, the production process of tetra methylol sulfuric acid phosphorus is PH
3Gas and formaldehyde, sulfuric acid and water counter current contacting in synthetic tower absorbs the formaldehyde that its reaction end gas is accomplished by unreacted, part PH
3Gas, section H
2Gas and multiple gases impurity are formed, and the conventional treatment way is direct emptying or burning back emptying, and environment is polluted.High-purity PH
3Gas, H
2Gas is important chemical material, has higher economic value.The present invention is intended to various active ingredients in the separation and this tail gas of purifying, and effectively reduces noxious gas emission, with the purpose that realizes turning waste into wealth.
In the prior art, the preparation method of hydrogen phosphide usually adopts metaphosphoric acid pyrolysismethod or acid system, alkaline process, Hydrolyze method etc., is chemical method; Usually cause secondary pollution easily; And have the equipment investment height, perishable, shortcoming such as procedure of processing is many; There is the risk of spontaneous combustion in what is more important hydrogen phosphide, and operation easier is big; And the present invention is compared with prior art, adopts the method for pure physics, utilizes the boiling point of gas with various different, realize at low temperatures separating, and the risk of having avoided the hydrogen phosphide spontaneous combustion, and can not cause secondary pollution, be the new technology of comparatively economic environmental protection.Simultaneously; After tetra methylol sulfuric acid phosphorus tail gas separated; Can effectively reduce the discharging of dusty gas, but the hydrogen phosphide retrieval system production high-purity again tetra methylol sulfuric acid phosphorus that is obtained, and hydrogen can be used as clean fuel; Reduce production cost and system consumption, and realized the cleaner production of tetra methylol sulfuric acid phosphorus.In addition, the product hydrogen phosphide that is obtained is the special gas of a kind of important electron, is mainly used in the semi-conductive doping of n type, ion injection and chemical vapor deposition (CVD) etc.Also have that it is stifling at grain, also be widely used in the fields such as synthetic, the phosphorous glasses of phosphorus-containing compound and solar cell.PH
3Can be used for making non-crystal silicon solar cell, phosphosilicate glass passivation film etc., in synthetic phosphorus-containing matter and phosphorus Halides, also have certain application to have higher economic value.The inventive method has been opened up the another new way that hydrogen phosphide is produced.
The (3) summary of the invention: the object of the invention just provides a kind ofly to be produced tail gas from tetra methylol sulfuric acid phosphorus and produces high-purity H
2With PH
3Method; This method can effectively reduce noxious gas emission, turn waste into wealth, and separation acquisition purity reaches 99.99% H
2And PH
3Gas.The present invention includes following step:
A, system are prepared
In the piece-rate system device of mainly being made up of vacuum system, adsorption system, refrigeration system, distillation system and nitrogen heating system, open vacuum system at first makes I, II, III rectifying column in the distillation system reach the vacuum state of 2Kpa one by one; Open refrigeration system again, make I, II, III rectifying column in the distillation system all reduce to-90 ℃;
B, gas primary purifying
Under the normal temperature and pressure raw material tail gas is forced into the adsorption tower that gets into said adsorption system behind the 0.5MPa, gas flow rate is controlled at 50L/min-80L/min;
C, separation H
2
The gas that comes out from above-mentioned adsorption tower at first gets into the I rectifying column, in-90 ℃ environment, makes AsH
3, PH
3, three kinds of gas liquefactions of HF, and be deposited at the bottom of the tower H
2Gas concentrates on the tower middle and upper part, with H
2Gas is delivered in the hydrogen-holder and is stored, and closes the I rectifying column and makes it to quit work;
D, separation PH
3
In I rectifying column interlayer, introduce through heated nitrogen, give the AsH of rectifier bottoms
3, PH
3, three kinds of liquefaction of HF condensate liquid is heated to-75 ℃ slightly, opens the intake valve of II rectifying column; Liquid-vapor mixture in the I rectifying column is all entered in the II tower; Temperature be-75 ℃ in this moment II tower, further lowers the temperature through refrigeration machine and is maintained at-85 ℃, at this moment PH
3There is AsH with gas phase
3, HF still is in liquid phase, opens the III rectifying column afterwards, PH
3Get in the III rectifying column the final curing of condensing therein, the liquid AsH in the II tower
3, HF is drained into the waste gas storage tank after the nitrogen heating.Isolate few residual gas emptying in the III tower, solidify the PH in the III tower
3, after the nitrogen heating, make solid PH
3Liquefaction, and then enter in the hydrogen phosphide storage tank.
The system and device of realizing above-mentioned process comprises the tail gas gas holder, adsorption system, vacuum system, refrigeration system, distillation system, nitrogen heating system, H
2, PH
3Gas reservoir and waste gas storage tank; Said adsorption system comprises an adsorbing tower with molecular sieve, mainly is that tail gas is carried out primary purifying, to remove H
2O, CO
2, CH
2O; Between adsorption tower and tail gas gas holder, press is housed; Said vacuum system comprises a twin-stage water-ring vacuum pump, is mainly distillation system vacuum environment is provided; Said refrigeration system comprises a two-stage multiplex refrigerating machine, and three grades of cascade refrigeration machines are mainly the distillation system refrigeration cool-down; Said distillation system comprises I, II, III number three rectifying columns, is intended to utilize the heterogeneity of all gases to separate; Between rectifying column and refrigeration machine, cooler is housed back; Said nitrogen heating system comprises a nitrogen pressure machine and nitrogen heater, and the condensate liquids that are mainly in numbers three rectifying columns of I, II, III provide thermal source.The said equipment is installed connection by technological requirement to get final product.
Basic principle of the present invention is that at first tail gas adopts molecular sieve adsorption to carry out primary purifying, to remove H
2O, CO
2, CH
2O utilizes cryogenic rectification to isolate AsH then
3, PH
3, HF, H
2, PH
3, finally obtain being not less than the PH of 99.99% (4N level)
3, H
2
The (4) description of drawings
Fig. 1 is a technological process block diagram of the present invention.
The (5) specific embodiment:
Below in conjunction with Fig. 1, the practical implementation step of process of the present invention is described:
At first implement required piece-rate system device according to the process of the present invention of the technological process installation shown in Fig. 1, this device comprises the tail gas gas holder, adsorption system, vacuum system, refrigeration system, distillation system, nitrogen heating system, H
2, PH
3Gas reservoir and waste gas storage tank; Said adsorption system comprises a 3A adsorbing tower with molecular sieve, between adsorption tower and tail gas gas holder, press is housed; Said vacuum system comprises a SK series twin-stage water-ring vacuum pump; Said refrigeration system comprises a two-stage multiplex refrigerating machine, and three grades of cascade refrigeration machines, said distillation system comprise I, II, III number three rectifying columns; Between rectifying column and refrigeration machine, cooler is housed back; Said nitrogen heating system comprises a nitrogen pressure machine and nitrogen heater.
Each concrete equipment is modular system among the present invention, can order from associated production enterprise.
A, system are prepared
In above-mentioned piece-rate system device, at first open SK series twin-stage water-ring vacuum pump, make I, II, III rectifying column in the distillation system reach the vacuum state of 2Kpa one by one; Open two-stage multiplex refrigerating machine and three grades of cascade refrigeration machines in the refrigeration system again, make I, II, III rectifying column in the distillation system all reduce to-90 ℃; For down-stream is prepared;
B, gas primary purifying
Under the normal temperature and pressure tail gas in 44.6mol (1000L) the raw material tail gas gas holder is got into the 3A adsorbing tower with molecular sieve after booster fan is forced into 0.5MPa, gas flow rate is controlled at 50L/min-80L/min; H in the adsorption tower
2O, CO
2, CH
2O is removed.
C, separation H
2
The gas that comes out from above-mentioned adsorption tower at first gets into the I rectifying column, in-90 ℃ environment, makes AsH
3, PH
3, three kinds of gas liquefactions of HF, and be deposited at the bottom of the tower H
2Gas concentrates on the tower middle and upper part, and open and bleed blower fan with H this moment
2Gas is delivered in the hydrogen-holder and is stored, and closes the I rectifying column and makes it to quit work; Separate and obtain H
2Be 27.4mol, productive rate is 61.5%.
D, separation PH
3
Open the nitrogen pressure blower fan, in I rectifying column interlayer, introduce, give the AsH of rectifier bottoms through heated nitrogen
3, PH
3, three kinds of liquefaction of HF condensate liquid is heated to-75 ℃ slightly, opens the intake valve of II rectifying column; Liquid-vapor mixture in the I rectifying column is all entered in the II tower; Temperature be-75 ℃ in this moment II tower, further lowers the temperature through refrigeration machine and is maintained at-85 ℃, at this moment PH
3There is AsH with gas phase
3, HF still is in liquid phase, opens the III rectifying column afterwards, PH
3Get in the III rectifying column the final curing of condensing therein, the liquid AsH in the II tower
3, HF is drained into the waste gas storage tank after the nitrogen heating.Isolate few residual gas emptying in the III tower, solidify the PH in the III tower
3, after the nitrogen heating, make solid PH3 liquefaction, and then enter in the hydrogen phosphide storage tank.The final PH that obtains
3Be 15.79mol, productive rate is about 35.4%.Through check, separate the H that obtains
2, PH
3Purity all reaches 99.99%.
Claims (1)
1. produce tail gas from tetra methylol sulfuric acid phosphorus and produce high-purity H
2With PH
3Method,
It is characterized in that comprising the steps:
A, system are prepared
In the piece-rate system device of mainly being made up of vacuum system, adsorption system, refrigeration system, distillation system and nitrogen heating system, open vacuum system at first makes I, II, III rectifying column in the distillation system reach the vacuum state of 2kPa one by one; Open refrigeration system again, make I, II, III rectifying column in the distillation system all reduce to-90 ℃;
B, gas primary purifying
Under the normal temperature and pressure raw material tail gas is forced into the adsorption tower that gets into said adsorption system behind the 0.5MPa, gas flow rate is controlled at 50L/min-80L/min;
C, separation H
2
The gas that comes out from above-mentioned adsorption tower at first gets into the I rectifying column, in-90 ℃ environment, makes AsH
3, PH
3, three kinds of gas liquefactions of HF, and be deposited at the bottom of the tower H
2Gas concentrates on the tower middle and upper part, with H
2Gas is delivered in the hydrogen-holder and is stored, and closes the I rectifying column and makes it to quit work;
D, separation PH
3
In I rectifying column interlayer, introduce through heated nitrogen, give the AsH of rectifier bottoms
3, PH
3, three kinds of liquefaction of HF condensate liquid is heated to-75 ℃ slightly, opens the intake valve of II rectifying column; Liquid-vapor mixture in the I rectifying column is all entered in the II tower; Temperature be-75 ℃ in this moment II tower, further lowers the temperature through refrigeration machine and is maintained at-85 ℃, at this moment PH
3There is AsH with gas phase
3, HF still is in liquid phase, opens the III rectifying column afterwards, PH
3Get in the III rectifying column the final curing of condensing therein, the liquid AsH in the II tower
3, HF is drained into the waste gas storage tank after the nitrogen heating; Isolate few residual gas emptying in the III tower, solidify the PH in the III tower
3, after the nitrogen heating, make solid PH
3Liquefaction, and then enter in the hydrogen phosphide storage tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010560941A CN102059035B (en) | 2010-11-26 | 2010-11-26 | Method for preparing high-purity H2 and PH3 from tail gas from generation of tetrakis hydroxymethyl phosphonium sulfate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010560941A CN102059035B (en) | 2010-11-26 | 2010-11-26 | Method for preparing high-purity H2 and PH3 from tail gas from generation of tetrakis hydroxymethyl phosphonium sulfate |
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| Publication Number | Publication Date |
|---|---|
| CN102059035A CN102059035A (en) | 2011-05-18 |
| CN102059035B true CN102059035B (en) | 2012-10-17 |
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| CN114105112B (en) * | 2021-11-30 | 2024-03-12 | 湖北兴发化工集团股份有限公司 | Purification method of sodium hypophosphite byproduct phosphine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045195A (en) * | 2006-12-08 | 2007-10-03 | 昆明理工大学 | Liquid phase catalytic oxidation method for purifying tail gas containing phosphine |
| CN101672565A (en) * | 2009-08-13 | 2010-03-17 | 上海启元科技发展有限公司 | Method for preparing pure krypton and pure xenon by adopting full rectification |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128412A (en) * | 2001-10-22 | 2003-05-08 | Mitsui Chemicals Inc | Method for purifying silicon tetrafluoride |
| GB0814556D0 (en) * | 2008-08-11 | 2008-09-17 | Edwards Ltd | Purification of gas stream |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045195A (en) * | 2006-12-08 | 2007-10-03 | 昆明理工大学 | Liquid phase catalytic oxidation method for purifying tail gas containing phosphine |
| CN101672565A (en) * | 2009-08-13 | 2010-03-17 | 上海启元科技发展有限公司 | Method for preparing pure krypton and pure xenon by adopting full rectification |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-128412A 2003.05.08 |
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Address after: Huanggang City, Hubei province 435501 small town along the River Road on the north side of Huangmei County Patentee after: Hubei Lianxing chemical Limited by Share Ltd Address before: Huanggang City, Hubei province 435501 small town Huangmei County along the River Road, No. 108 Patentee before: Lianxing Chemical Co., Ltd. |
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Granted publication date: 20121017 Termination date: 20191126 |