CN102716653A - Method for purifying phosphine tail gas from fumigation - Google Patents
Method for purifying phosphine tail gas from fumigation Download PDFInfo
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- CN102716653A CN102716653A CN2011100783154A CN201110078315A CN102716653A CN 102716653 A CN102716653 A CN 102716653A CN 2011100783154 A CN2011100783154 A CN 2011100783154A CN 201110078315 A CN201110078315 A CN 201110078315A CN 102716653 A CN102716653 A CN 102716653A
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- phosphine
- hydrogen phosphide
- tail gas
- purifying
- ultraviolet light
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Abstract
This invention discloses a method for purifying phosphine tail gas by fumigating, which belongs to the filed of air purification. The invention provides a method for purifying the phosphine fumigating tail gas, which comprises the following steps of: irradiating the phosphine fumigating tail gas by a vacuum UV light source for converting the phosphine intophosphoric acid; and then, causing the tail gas to pass through an active filter for absorbing the phosphoric acid and decomposing ozone . The method has a high efficiency of purifying the phosphine, low energy consumption , large air flow processing amount and a simple process. The application of the invention can be used in processing phosphine fumigating tail gas in large air flow and has a higher practical value.
Description
Technical field
The invention belongs to the air purifying process field, particularly relate to the purification of low-concentration hydrogen phosphide in the air, be mainly used in tobacco, the hydrogen phosphide vent gas treatment when grain storage is fumigated insect protected.
Background technology
In agricultural products storage processes such as grain, tobacco, medicinal material, dry fruit, grow various insects easily, utilize hydrogen phosphide that the storage storehouse is fumigated processing; Good disinsection effect; Easy to use, cost is low, and is less residual and residue is nontoxic; Be safest fumigant, all be used as unique fumigant at a plurality of national hydrogen phosphide and use.
Hydrogen phosphide is a kind of hypertoxic gas; The not treated direct discharging of air of phosphine containing in the storehouse after the stifling operation; Might the human or animal of periphery be damaged, if do not discharge, the hydrogen phosphide of low concentration also can be oxidized to the phosphate compound of various valence states gradually in air; Though toxicity reduces, can corrode the air-conditioning exhaust system.Therefore, fumigation exhaust gas need carry out purified treatment.
Phosphine gas is difficult to be adsorbed, but it has very strong reproducibility, so the method that the purification of tail gas containing phosphine mainly adopts oxidation to absorb handles, and mainly adopts two kinds of technologies of dry method and wet method.
Wet processing is in the absorption tower, with oxidizing solution hydrogen phosphide to be absorbed, and solution comprises the concentrated sulfuric acid, liquor potassic permanganate, liquor natrii hypochloritis, hydrogen peroxide, SPA etc., and oxidant wherein is consumptive.For strengthened purification efficient, adopt the spray mode.The purification efficiency of hydrogen phosphide is directly related with the concentration of oxidant, and in order to reach higher purification efficiency, the consumption of oxidant will be higher than the consumption of hydrogen phosphide far away, causes the waste of oxidant.In the Chinese patent (ZL 200610048889.6); Mention a kind of purification method of hydrogen phosphide; Utilization contains the aqueous solution or the acid solution of Cu, Pd as catalyst, can recycle, and has reduced operating cost; But need between hydrogen phosphide absorbing catalyst oxidation regeneration technology, switch, reclaim also difficulty of catalyst.Hydrogen phosphide by solution absorption after, form the mixture of phosphoric acid, phosphate and oxidant, could separate or utilization again through complicated aftertreatment technology.The energy consumption of wet processing is high, and the work air quantity is less, is not suitable for the purification of big air quantity, low-concentration phosphorus-containing hydrogen air.
Dry process utilizes the chemical reactivity or the reproducibility of hydrogen phosphide, and the corresponding chemical substance of dipping makes the hydrogen phosphide chemisorbed on adsorbent.Mention a kind of active carbon that has flooded Cu, Hg, Cr, Ag in the Chinese patent (ZL 93101650.9), can be used for hydrogen phosphide and arsenic hydride that semicon industry produces, but the protection finite capacity.The Ni ion dipping adsorbent (application number 200910094498.1) that Chinese patent is mentioned; Or Cu ion dipping adsorbent (application number 200910094501.X); Or Co ion dipping adsorbent (application number 2,009 1 0094502.4), or alkaline-earth halide impregnated zeolite adsorbents adsorb, (application number 200810058666.7); Though need not add noble metal (AgO) or heavy metal promoter such as (Hg0, Cd0); But adsorbance is too low, every gram adsorbent to the adsorbance of hydrogen phosphide less than 20mg, poor practicability.In a word, with the chemiadsorption purifying hydrogen phosphide, the problem that the ubiquity adsorption capacity is little, the adsorbent inactivation is fast.
Patent CN 1 398658A (publication number) discloses a kind of method that adopts fixed bed catalytic oxidation to purify yellow phosphoric tail gas; Develop catalyst series and be used for catalysis absorption hydrogen phosphide impurity; Its principle is to utilize the strong reducing property of hydrogen phosphide and the reaction of the active component on the active carbon to generate diphosphorus trioxide and phosphorus pentoxide; And utilize active carbon the adsorbance of diphosphorus trioxide and phosphorus pentoxide to be realized the deep purifying of yellow phosphoric tail gas much larger than these characteristics of hydrogen phosphide; Shortcoming is to need strict oxygen or the air that quantitatively adds in yellow phosphoric tail gas, has strengthened operation, control difficulty.
In addition; Patent CN 101559322A (publication number) has proposed the hydrogen phosphide ultraviolet degradation method; Purify but be difficult to be applied to the strong wind amount phosphine gas by the treating apparatus that this method is set up, and if the product after the photodissociation do not handle and just be back in the warehouse, still can work the mischief to facility in the storehouse.
In a word, present hydrogen phosphide treatment process is main with wet oxidation, and operating procedure is complicated, and it is little to handle air quantity, the product difficult treatment, though and the dry method absorbing process is simple to operate, adsorbent is little to the adsorbance of hydrogen phosphide, can not sizable application.
Summary of the invention
To the problem that present hydrogen phosphide purification technology exists, the present invention proposes the dry oxidation technology of hydrogen phosphide, in gas phase, makes phosphatization
Hydrogen-oxygen turns to phosphoric acid, uses the method for active carbon class adsorbent purifying phosphoric acid again.
At first, phosphine fumigation exhaust gas shines with vacuum ultraviolet light source, and airborne moisture and oxygen produce the ozone (O of strong oxidizing property
3) and hydroxyl radical free radical (OH), hydrogen phosphide and ozone and hydroxyl radical free radical generation oxidation reaction generate phosphoric acid.Its chemical reaction process is shown below:
O
2+hv→2O·
·O+O
2→O
3
O·+H
2O→2·OH
PH
3+8·OH→H
3PO
4+4H
2O
·4O
3+PH
3→H
3PO
4+4O
2
The phosphoric acid that produces exists with the form of phosphoric acid mist in air.
Then, the air that contains the phosphoric acid mist feeds active carbon filter, and the phosphoric acid mist is absorbed, and remaining ozone is decomposed by active carbon bed, the cleaned air passes discharging.
Vacuum ultraviolet light source is xenon lamp, halogenation xenon lamp or low pressure mercury lamp.
Because the oxidation reaction of hydrogen phosphide is carried out in gas phase; Overcome the shortcoming that the liquid phase oxidation technique energy consumption is big, air quantity is little, purification efficiency is low, operating procedure is complicated; Again because the target that charcoal absorption purifies is a phosphoric acid class higher-boiling compound; Rather than hydrogen phosphide, overcome the problem that the hydrogen phosphide adsorption capacity is little in the dry process, working life is short.This technology has following characteristics:
(1) the processing air quantity is big, energy consumption is low
The oxidation of hydrogen phosphide is carried out in the air pipeline of ventilating system, and resistance is little, except that blower fan, does not need other power-equipments, does not take warehouse space, and normal temperature and pressure is operation down, and energy consumption is low;
(2) purification efficiency is high
Vacuum-ultraviolet light makes airborne oxygen and water reaction generate ozone (O
3) and hydroxyl radical free radical (OH); With airborne hydrogen phosphide generation homogeneous chemical reaction, reaction speed is fast, and the efficient that is converted into phosphoric acid is high; And active carbon has very big adsorption capacity and very high purification efficiency to phosphoric acid, thereby makes the present invention to hydrogen phosphide very high purification efficiency arranged.
(3) long service life
The reaction reagent of hydrogen phosphide oxidation is airborne oxygen and steam, does not use catalyst, has also avoided catalysqt deactivation to the influence in service life, and its service life is relevant with the life-span of light source, and present light source life can reach more than 8000 hours.
Particularly, the present invention adopts following mode to accomplish the purification of hydrogen phosphide: in air-conditioning duct or air pipeline, vacuum ultraviolet light source is installed, vacuum ultraviolet light source can send wavelength less than the 200nm ultraviolet light; Decompose airborne steam and oxygen and produce ozone and hydroxyl radical free radical, oxidation hydrogen phosphide generates phosphoric acid, then; Let postradiation air pass through active carbon filter; Absorb phosphoric acid wherein, and ozone decomposition, the cleaned air passes discharging.
Description of drawings
Fig. 1: hydrogen phosphide purification device
1, air pipeline; 2, vacuum ultraviolet light source; 3, active carbon filter
The specific embodiment
Embodiment 1
As shown in Figure 1, air pipeline (1) is the stainless steel cylinder of diameter 20cm, long 60cm, sectional area 314cm
2, vacuum ultraviolet light source (2) is that a power is the 23W low pressure mercury lamp, hangs on the center of air pipeline (1), and active carbon filter (3) is for to be the cylindrical tube of diameter 4cm, and the coal mass active carbon of interior dress particle diameter 1.5mm loads thickness 6cm.
The variable concentrations phosphine gas takes place respectively, at the gas with various flow, investigates the clean-up effect of the present invention to hydrogen phosphide, the concentration of hydrogen phosphide in test active carbon filter (3) tail gas, the purification efficiency of calculating hydrogen phosphide, result of the test is as shown in table 1.
Table 1 power is that the 23W low pressure mercury lamp is to the hydrogen phosphide purification effect
Embodiment 2
Air pipeline (1) is in series sectional area 314cm by two stainless steel cylinders of diameter 20cm, long 60cm
2, vacuum ultraviolet light source (2) is that two power are the 23W low pressure mercury lamp, hangs on two stainless steel cylindrical center positions respectively, and active carbon filter (3) is for to be the cylindrical tube of diameter 6cm, and the coal mass active carbon of interior dress particle diameter 1.5mm loads thickness 6cm.Compare with embodiment 1, air pipeline length doubles in this example, and air quantity also doubles, and the irradiation power of unit are is identical, and irradiation time is also identical, and is as shown in table 2 to the hydrogen phosphide purification result of the test.
Table 2 power is that the low pressure mercury lamp of 46W is to the hydrogen phosphide purification effect
Embodiment 3
Air pipeline (1) surrounds for iron sheet, cross section is foursquare hollow cuboid, length of side 25cm, long 60cm, sectional area 625cm
2, vacuum ultraviolet light source (2) is a low pressure mercury lamp that power is 23W, hangs on the middle position of cuboid, active carbon filter (3) is the cylindrical tube of diameter 6cm, the coal mass active carbon of interior dress particle diameter 1.5mm, filling thickness 6cm.Compare with embodiment 1, the sectional area of this routine air pipeline doubles, and air quantity also doubles, and irradiation power is identical.As shown in table 2 to the hydrogen phosphide purification result of the test.
92 watts of table 3 low pressure mercury lamp power are to the hydrogen phosphide purification effect
Handle for big air quantity, certain density phosphine fumigation exhaust gas; Can set purification efficiency according to the result of the test of embodiment 1～3, under the situation that guarantees irradiation time and irradiation power; Purifier is amplified, and active carbon filter can be selected the various commercial model of nominal air delivery for use.
Claims (2)
1. phosphine fumigation exhaust gas purification method, it is characterized in that this method may further comprise the steps: at first, phosphine concentration is 50～1000mg/m
3Fumigation exhaust gas, through vacuum ultraviolet light source (2) irradiation, irradiation time 10～200s makes hydrogen phosphide wherein be oxidized to phosphoric acid, the sectional area 300～10000cm of air pipeline (1) in air pipeline (1)
2, long 60～2500cm; Then, fumigation exhaust gas is through active carbon filter (3) emptying.
2. according to claims 1 described exhaust purifying method, it is characterized in that vacuum ultraviolet light source is xenon lamp, halogenation xenon lamp or low pressure mercury lamp, can send the ultraviolet light of wavelength less than 200nm, power is 20～5000W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100783154A CN102716653A (en) | 2011-03-30 | 2011-03-30 | Method for purifying phosphine tail gas from fumigation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100783154A CN102716653A (en) | 2011-03-30 | 2011-03-30 | Method for purifying phosphine tail gas from fumigation |
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| Publication Number | Publication Date |
|---|---|
| CN102716653A true CN102716653A (en) | 2012-10-10 |
Family
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|---|---|---|---|
| CN2011100783154A Pending CN102716653A (en) | 2011-03-30 | 2011-03-30 | Method for purifying phosphine tail gas from fumigation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474909A (en) * | 2015-08-26 | 2017-03-08 | 江苏华正环保科技有限公司 | A kind of dry type phosphine fumigation exhaust gas purify technique |
| CN108097009A (en) * | 2018-01-02 | 2018-06-01 | 昆明理工大学 | It is a kind of to purify phosphine gas and the method for recycling phosphoric acid in uncontrollable discharge environment |
| CN110052137A (en) * | 2019-05-09 | 2019-07-26 | 上海烟草集团有限责任公司 | A kind of phosphine gas method for innocent treatment and its device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076173A (en) * | 1993-02-20 | 1993-09-15 | 中国人民解放军防化研究院 | The Immesion active carbon of purifying hydrogen phosphide, hydrogen arsenide in the hydrogen stream |
| CN1951544A (en) * | 2005-10-21 | 2007-04-25 | 福建新大陆环保科技有限公司 | Method and apparatus for photochemical degradation of organic gas |
| WO2007137856A2 (en) * | 2006-05-31 | 2007-12-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalytically-active activated carbons doped with metal salts and use thereof |
| CN101559322A (en) * | 2009-05-18 | 2009-10-21 | 河南工业大学 | Photodegradation device of phosphine fumigation exhaust gas |
| CN101654232A (en) * | 2009-08-27 | 2010-02-24 | 昆明理工大学 | Method for adsorbing and purifying PH3 under reducing condition |
-
2011
- 2011-03-30 CN CN2011100783154A patent/CN102716653A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076173A (en) * | 1993-02-20 | 1993-09-15 | 中国人民解放军防化研究院 | The Immesion active carbon of purifying hydrogen phosphide, hydrogen arsenide in the hydrogen stream |
| CN1951544A (en) * | 2005-10-21 | 2007-04-25 | 福建新大陆环保科技有限公司 | Method and apparatus for photochemical degradation of organic gas |
| WO2007137856A2 (en) * | 2006-05-31 | 2007-12-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalytically-active activated carbons doped with metal salts and use thereof |
| CN101559322A (en) * | 2009-05-18 | 2009-10-21 | 河南工业大学 | Photodegradation device of phosphine fumigation exhaust gas |
| CN101654232A (en) * | 2009-08-27 | 2010-02-24 | 昆明理工大学 | Method for adsorbing and purifying PH3 under reducing condition |
Non-Patent Citations (1)
| Title |
|---|
| 张忠良等: "真空紫外光解—活性炭吸附去除甲苯及副产物臭氧", 《中国环境科学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474909A (en) * | 2015-08-26 | 2017-03-08 | 江苏华正环保科技有限公司 | A kind of dry type phosphine fumigation exhaust gas purify technique |
| CN108097009A (en) * | 2018-01-02 | 2018-06-01 | 昆明理工大学 | It is a kind of to purify phosphine gas and the method for recycling phosphoric acid in uncontrollable discharge environment |
| CN110052137A (en) * | 2019-05-09 | 2019-07-26 | 上海烟草集团有限责任公司 | A kind of phosphine gas method for innocent treatment and its device |
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Application publication date: 20121010 |