CN104941422B - A kind of processing method of phosphine gas - Google Patents
A kind of processing method of phosphine gas Download PDFInfo
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- CN104941422B CN104941422B CN201510250297.1A CN201510250297A CN104941422B CN 104941422 B CN104941422 B CN 104941422B CN 201510250297 A CN201510250297 A CN 201510250297A CN 104941422 B CN104941422 B CN 104941422B
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- absorbing liquid
- phosphine
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Abstract
The present invention relates to a kind of processing method of phosphine gas, belong to technical field of waste gas treatment.This method is absorbed including the gas of phosphine containing is initially entered into absorption tower by absorbing liquid, and the solution after absorption is reacted with limewash again；Described absorption is realized by the absorption tower with specific structure; using method of the present invention and it is aided with corresponding equipment; the final phosphine waste gas for causing discharge changes into the phosphate fertilizer that can be reused; basically reach the discharge of hydrogen phosphide " zero " content; avoid atmosphere pollution; and it can be the invention for all having positive effect to protection health and atmospheric environment with the secondary fertilizer utilized to generate.
Description
Technical field
The present invention relates to a kind of processing method of phosphine gas, belong to technical field of waste gas treatment.
Background technology
Hydrogen phosphide is a kind of poisonous and hazardous gas, the characteristics of with high toxicity, spontaneous combustion, there is obvious injury to human body,
Producing and using the unit of hydrogen phosphide, if directly discharged to phosphine gas, atmosphere pollution can be caused, therefore to hydrogen phosphide
The absorption and processing of waste gas are particularly important.
In currently available technology to phosphine waste gas carry out absorption cleaning apparatus and method mainly have combustion method, wet method and
Dry method.Wherein combustion method is traditional hydrogen phosphide processing method, and generation of burning is blended in incinerator by hydrogen phosphide and air
Phosphoric acid smog, gained smog is passed through the phosphoric acid that technical grade is made in absorption tower, but the shortcoming of the method is that incinerator is added using electricity
Heat, belongs to high-energy equipment, and the phosphoric acid smog of generation has stronger corrosivity, and each section of temperature difference of incinerator to reactor
Greatly, it is unfavorable for safety in production, also there is gas leakage.Wet-treating hydrogen phosphide is to use sodium hypochlorite for absorbent, raw
Into relatively stable phosphoric acid salt, have the disadvantage：The accessory substance chlorine for producing big quantitative response causes secondary pollution, it is hypochlorous chemically
Matter is unstable, is extremely easy in decomposition, fails, it is necessary to frequently change absorbing liquid, increases extra cost.Dry process hydrogen phosphide is using work
Property charcoal hydrogen phosphide is adsorbed, but without change hydrogen phosphide chemical property, weak point be absorption after activated carbon to adopt
With or burning or parsing method carry out post-processing, however it remains pollution problem.Above method either chemical transfer method and
Absorption method, mostly more or less causes a certain degree of secondary pollution.
The content of the invention
In view of the deficiencies of the prior art, the present invention proposes a kind of processing method of phosphine gas, using this hair
Bright described method and it is aided with corresponding equipment, the final phosphine waste gas for causing discharge changes into the phosphorus that can be reused
Fertilizer, basically reaches the discharge of hydrogen phosphide " zero " content, it is to avoid atmosphere pollution, and generate can with the secondary fertilizer utilized.
A kind of processing method of phosphine gas of the present invention, this method includes first entering the gas of phosphine containing
Enter absorption tower to be absorbed by absorbing liquid, absorb the solution after phosphine gas and reacted again with limewash；
Described absorption is realized by following absorption tower：Outside the absorption tower, including tower body, tower body from down to up successively
Provided with leakage fluid dram, gas feed, overfall, absorbing liquid import and gas vent；Air inlet is sequentially provided with inside tower body from the bottom to top
Shower nozzle, orifice plate, baffle ring and cloth liquid disk；Air inlet spray head is connected with gas feed；Cloth liquid disk and absorbing liquid inlet communication；In tower body
There is absorbing liquid in portion；
Described absorbing liquid is the aqueous solution that hydrogen peroxide and sulfuric acid are constituted.
Its specific handling process is：Gas containing hydrogen phosphide enters air inlet spray head by gas feed, in air inlet
It is dispersed in absorbing liquid and is reacted in the presence of shower nozzle, hydrogen peroxide reacts in acid condition with hydrogen phosphide, tool
The reaction equation of body is：
2H2O2+PH3=H3PO2+2H2O
3H2O2+PH3=H3PO3+3H2O
Air inlet spray head of the present invention can be carried out preliminary disperse to the gas of phosphine containing.Gas is in absorbing liquid
Continue to rise, by the orifice plate inside tower body, be dispersed into some small and weak air-flows, absorbing liquid is presented in the presence of air-flow and set out
Absorbing liquid above blister state, i.e. orifice plate is mixed with the air-flow of phosphine containing, and a foam layer state is presented, gas-liquid is added
Contact area, increases reaction probabilities so that hydrogen phosphide can be fully absorbed.Between orifice plate and overfall of the present invention
Height be tower height 2/3-3/5, that is to say, that the height of whole froth bed is the 2/3-3/5 of tower height, it is ensured that gas-liquid contact
Have enough reaction strokes so that hydrogen phosphide can absorbed liquid fully absorb；The aperture of the absorption tower aperture plate is 1mm-
3mm, percent opening is not less than 30%, preferably 30%-40%, it is ensured that the gas of phosphine containing is dispersed into more tiny gas
Stream, increases gas liquid interfacial area.
In order to be further ensured that preferable assimilation effect, the absorbing liquid described in determination is groped by inventor's test of many times
The mass fraction of middle hydrogen peroxide is 3%-5%；The concentration of sulfuric acid is 0.25mol/L.Inhaled in the absorption tower under static conditions
The height of liquid is received higher than orifice plate height, less than the height of overfall.The gas orifice tower flow velocity on the absorption tower is 0.02m/sec-
0.05m/sec.The tower height on the absorption tower is 7 with tower diameter ratio:1~10:1.
Further, the overfall on absorption tower of the present invention can be connected with tower body bottom so that the absorption of overflow
Liquid can be again returned to tower body and be utilized.
In actual production running, after operation a period of time, if during absorption hypervolia in absorption tower, can
So that absorbing liquid part to be discharged by the leakage fluid dram of tower body bottom.
Absorbing liquid of the present invention is prepared using the conventional method of this area.Can in concrete processing procedure
To be controlled using following methods to the absorbability of absorbing liquid：(1) measurement hydrogen peroxide (H2O2) content judged, use
Iodimetric titration capacity analysis hydrogen peroxide (H2O2) content, work as H2O2Concentration ＜ 0.2%~0.3%, hydrogen peroxide is mended
Fill；(2) concentration of measurement discharge phosphine gas, when discharge capacity is more than 1 μm of ol/mol, if process conditions do not change,
To hydrogen peroxide (H2O2) supplemented.
After being absorbed by froth bed, the content of hydrogen phosphide very little in handled gas, in order to avoid in gas
Hydrogen phosphide absorb incomplete, the gas after being absorbed by froth bed continues to rise, the absorbing liquid shape under the distribution of cloth liquid disk
Inversely contacted into " liquid film " and the gas risen, hydrogen phosphide therein is further absorbed, in order to ensure to rise
Gas and " liquid film " between abundant contact, the lower section of cloth liquid disk is provided with baffle ring, and the diameter of described cloth liquid disk is more than folding
The internal diameter of ring is flowed, the gas of rising all can rise and divide with cloth liquid disk from the endoporus of baffle ring in the presence of baffle ring
The liquid that cloth gets off is contacted so that the hydrogen phosphide of residual is fully absorbed again, it is ensured that clean-up effect.
The present invention by froth bed and the double-absorption of " liquid film ", the phosphine gas that is remained in final gas it is micro- its
It is micro-, more than 99% absorptivity can be reached, the gas after absorption tower absorbs is discharged from the gas vent at the top of tower body.This
Invention is applied to phosphine containing and does not contain the processing of the gas of other reducing substanceses.
Absorb the absorbing liquid after phosphine gas and reaction generation calcium sulfate-calcium phosphate emulsion further carried out with limewash,
The reaction end pH value is 6.The composition of the emulsion is identical with calcium superphosphate composition, thus can be used as phosphate fertilizer, can also
Add the organic matters such as other potash fertilizer, directly apply to agricultural, as can be used for courtyard greening and crops etc..The emulsion can
Directly to use or use the supernatant liquor reusable edible after decorating film, precipitation to prepare absorbing liquid after precipitation, liquid is not produced
Calcium superphosphate content ＞ 25%, conversion ratio ＞ 90% in discharge, the emulsion after conversion.
In summary, it is an advantage of the invention that substantially completely absorbing phosphine waste gas, the toxicity of hydrogen phosphide is minimized,
It is almost nil, and be converted to the secondary utilization of fertilizer progress that can be reused.Be by it is useless be converted to it is useful, by poisonous conversion
Into process that is nontoxic, turning waste into wealth, and input cost is relatively low, is a utilization ratio height, to protection health and air
Environment all has the invention of positive effect.
Brief description of the drawings
Fig. 1 is the structural representation on absorption tower of the present invention；
Fig. 2 is the structural representation of orifice plate of the present invention.
In figure：1st, tower body, 2, gas feed, 3, overfall, 4, absorbing liquid import, 5, gas vent, 6, air inlet spray head, 7,
Orifice plate, 8, baffle ring, 9, cloth liquid disk, 10, leakage fluid dram.
Embodiment
Embodiment 1
A kind of processing method of phosphine gas, this method includes the gas of phosphine containing initially entering absorption tower process
Absorbing liquid is absorbed, and is absorbed the solution after phosphine gas and is reacted again with limewash；
Described absorption is realized by following absorption tower：Outside the absorption tower, including tower body 1, tower body 1 from down to up according to
It is secondary to be provided with leakage fluid dram 10, gas feed 2, overfall 3, absorbing liquid import 4 and gas vent 5；Inside tower body 1 from top to bottom successively
Provided with air inlet spray head 6, orifice plate 7, baffle ring 8 and cloth liquid disk 9；Air inlet spray head 6 is connected with gas feed 2；Cloth liquid disk 9 and absorbing liquid
Import 4 is connected；There is absorbing liquid inside tower body 1；
Described absorbing liquid is the aqueous solution that hydrogen peroxide and sulfuric acid are constituted；The quality of hydrogen peroxide in described absorbing liquid
Fraction is 5%；The concentration of sulfuric acid is 0.25mol/L.
Height between described orifice plate 7 and overfall 3 is the 2/3 of tower height.
The gas void tower flow velocity on the absorption tower is 0.02m/sec.
The aperture of the absorption tower aperture plate 7 is 3mm, percent opening 30%.
The tower height on the absorption tower is 7 with tower diameter ratio:1
The height of absorbing liquid is higher than the height of orifice plate 7 under static conditions in the absorption tower.
The diameter of described cloth liquid disk 9 is more than the internal diameter of baffle ring 8.
It is 6 to absorb the solution after phosphine gas with limewash reaction end pH value.
Embodiment 2
A kind of processing method of phosphine gas, this method includes the gas of phosphine containing initially entering absorption tower process
Absorbing liquid is absorbed, and is absorbed the solution after phosphine gas and is reacted again with limewash；
Described absorption is realized by following absorption tower：Outside the absorption tower, including tower body, tower body from down to up successively
Provided with leakage fluid dram, gas feed, overfall, absorbing liquid import and gas vent；Air inlet is from top to bottom sequentially provided with inside tower body
Shower nozzle, orifice plate, baffle ring and cloth liquid disk；Air inlet spray head is connected with gas feed；Cloth liquid disk and absorbing liquid inlet communication；In tower body
There is absorbing liquid in portion；
Described absorbing liquid is the aqueous solution that hydrogen peroxide and sulfuric acid are constituted；The quality of hydrogen peroxide in described absorbing liquid
Fraction is 3%；The concentration of sulfuric acid is 0.25mol/L.
Height between described orifice plate and overfall is the 3/5 of tower height.
The gas void tower flow velocity on the absorption tower is 0.03m/sec.
The aperture of the absorption tower aperture plate is 1mm, percent opening 40%.
The tower height on the absorption tower is 8 with tower diameter ratio:1
The height of absorbing liquid is higher than orifice plate height under static conditions in the absorption tower.
The diameter of described cloth liquid disk is more than the internal diameter of baffle ring.
It is 6 to absorb the solution after phosphine gas with limewash reaction end pH value.
Embodiment 3
A kind of processing method of phosphine gas, this method includes the gas of phosphine containing initially entering absorption tower process
Absorbing liquid is absorbed, and is absorbed the solution after phosphine gas and is reacted again with limewash；
Described absorption is realized by following absorption tower：Outside the absorption tower, including tower body, tower body from down to up successively
Provided with leakage fluid dram, gas feed, overfall, absorbing liquid import and gas vent；Air inlet is from top to bottom sequentially provided with inside tower body
Shower nozzle, orifice plate, baffle ring and cloth liquid disk；Air inlet spray head is connected with gas feed；Cloth liquid disk and absorbing liquid inlet communication；In tower body
There is absorbing liquid in portion；
Described absorbing liquid is the aqueous solution that hydrogen peroxide and sulfuric acid are constituted；The quality of hydrogen peroxide in described absorbing liquid
Fraction is 4%；The concentration of sulfuric acid is 0.25mol/L.
Height between described orifice plate and overfall is the 2/3 of tower height.
The gas void tower flow velocity on the absorption tower is 0.05m/sec.
The aperture of the absorption tower aperture plate is 2mm, percent opening 35%.
The tower height on the absorption tower is 10 with tower diameter ratio:1
The height of absorbing liquid is higher than orifice plate height under static conditions in the absorption tower.
The diameter of described cloth liquid disk is more than the internal diameter of baffle ring.
It is 6 to absorb the solution after phosphine gas with limewash reaction end pH value.
Claims (5)
1. a kind of processing method of phosphine gas, it is characterised in that：This method includes initially entering the gas of phosphine containing
Absorption tower is absorbed by absorbing liquid, is absorbed the solution after phosphine gas and is reacted again with limewash；
Described absorption is realized by following absorption tower：The absorption tower, including tower body (1), tower body (1) it is outside from down to up according to
It is secondary to be provided with leakage fluid dram (10), gas feed (2), overfall (3), absorbing liquid import (4) and gas vent (5)；Tower body (1) is internal
Air inlet spray head (6), orifice plate (7), baffle ring (8) and cloth liquid disk (9) are sequentially provided with from the bottom to top；Air inlet spray head (6) enters with gas
Mouth (2) connection；Cloth liquid disk (9) is connected with absorbing liquid import (4)；There is absorbing liquid inside tower body (1)；
Described absorbing liquid is the aqueous solution that hydrogen peroxide and sulfuric acid are constituted；
Height between described orifice plate (7) and overfall (3) is the 2/3-3/5 of tower height；
The height of absorbing liquid is higher than orifice plate (7) height under static conditions in the absorption tower；
The diameter of described cloth liquid disk (9) is more than the internal diameter of baffle ring (8)；
The aperture of the absorption tower aperture plate (7) is 1mm-3mm, and percent opening is not less than 30%.
2. a kind of processing method of phosphine gas according to claim 1, it is characterised in that：Mistake in described absorbing liquid
The mass fraction of hydrogen oxide is 3%-5%；The concentration of sulfuric acid is 0.25mol/L.
3. a kind of processing method of phosphine gas according to claim 1, it is characterised in that：The gas on the absorption tower
Void tower flow velocity is 0.02m/sec-0.05m/sec.
4. a kind of processing method of phosphine gas according to claim 1, it is characterised in that：The tower height on the absorption tower
It is 7 with tower diameter ratio:1~10:1.
5. a kind of processing method of phosphine gas according to claim 1, it is characterised in that：Absorb after phosphine gas
Solution and limewash reaction end pH value be 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510250297.1A CN104941422B (en) | 2015-05-15 | 2015-05-15 | A kind of processing method of phosphine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510250297.1A CN104941422B (en) | 2015-05-15 | 2015-05-15 | A kind of processing method of phosphine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104941422A CN104941422A (en) | 2015-09-30 |
| CN104941422B true CN104941422B (en) | 2017-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510250297.1A Expired - Fee Related CN104941422B (en) | 2015-05-15 | 2015-05-15 | A kind of processing method of phosphine gas |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376597A (en) * | 2017-07-11 | 2017-11-24 | 山东海新石油化工有限公司 | A kind of desulfurizer |
| CN108341405A (en) * | 2018-01-16 | 2018-07-31 | 湖北兴福电子材料有限公司 | A kind of device and method that the phosphorous off-gas recovery of yellow phosphorus storage tank recycles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2456822Y (en) * | 2000-11-02 | 2001-10-31 | 都江堰科环新技术灭虫服务中心 | Phosphine gas colleciton processor |
| CN101337157A (en) * | 2008-08-12 | 2009-01-07 | 昆明理工大学 | Purification method of low concentration phosphine waste gas |
| CN101352653A (en) * | 2008-08-12 | 2009-01-28 | 昆明理工大学 | Low-temperature micro-oxygen purification method for removing harmful gas in yellow phosphorus tail gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2549415B2 (en) * | 1988-04-19 | 1996-10-30 | 協和化工株式会社 | Method for removing arsine and / or phosphine |
| GB9607066D0 (en) * | 1996-04-03 | 1996-06-05 | Ici Plc | Purification process |
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2015
- 2015-05-15 CN CN201510250297.1A patent/CN104941422B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2456822Y (en) * | 2000-11-02 | 2001-10-31 | 都江堰科环新技术灭虫服务中心 | Phosphine gas colleciton processor |
| CN101337157A (en) * | 2008-08-12 | 2009-01-07 | 昆明理工大学 | Purification method of low concentration phosphine waste gas |
| CN101352653A (en) * | 2008-08-12 | 2009-01-28 | 昆明理工大学 | Low-temperature micro-oxygen purification method for removing harmful gas in yellow phosphorus tail gas |
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| CN104941422A (en) | 2015-09-30 |
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