CN101337157A - Purification method of low concentration phosphine waste gas - Google Patents
Purification method of low concentration phosphine waste gas Download PDFInfo
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- CN101337157A CN101337157A CNA200810058808XA CN200810058808A CN101337157A CN 101337157 A CN101337157 A CN 101337157A CN A200810058808X A CNA200810058808X A CN A200810058808XA CN 200810058808 A CN200810058808 A CN 200810058808A CN 101337157 A CN101337157 A CN 101337157A
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 32
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 16
- 239000002912 waste gas Substances 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 230000005587 bubbling Effects 0.000 claims abstract description 12
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 38
- 239000012153 distilled water Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- -1 rare earth cerium oxide Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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Abstract
The invention provides a method for purifying the exhaust gas with low concentration of phosphine. The method is characterized in that an absorption liquid and a solid catalyst are put into a bubbling reactor according to the ratio of 100 ml:1-3 g; the gas containing low-concentration phosphine is allowed to enter the reactor; the reaction temperature is controlled to be 40 DEG C to 80 DEG C; phosphine is purified in the bubbling reactor; and the tail gas after purification has the concentration of phosphine as low as 50 mg/m<3>. The method has the advantages as follows: (1) the method is simple, the operability is strong, the purification efficiency is improved, and the purification cost is reduced; (2) the catalyst is easy to separate, reclaim and reuse; (3) the bubbles in the bubbling reactor are tiny and uniform, thereby strengthening the dissolution of phosphine in the absorption liquid; (4) the reaction conditions are mild and easy to implement; and (5) phosphoric acid can be reclaimed for re-implement of changing waste into resource.
Description
Technical field
The present invention relates to atmosphere pollution purification techniques field, specifically a kind of purification method of low concentration phosphine waste gas.
Background technology
All contain hydrogen phosphide in many chemical industry tail gas that are rich in carbon monoxide, as the tail gas of the tail gas of phosphorus production, acetylene production, calcium carbide furnace gas etc.In order to utilize the carbon monoxide in the tail gas to produce high value-added product, just must remove hydrogen phosphide.Hydrogen phosphide is colourless hypertoxic gas, very easily causes various C
1Chemical catalyst is poisoned, and can make the corrosion of boiler material impaired, has a strong impact on the recycling of these tail gas.Hydrogen phosphide is a kind of gas that is difficult to purify, and the method for industrial existing purifying hydrogen phosphide has dry method and wet method two big classes at present, as firing method, absorption method and catalytic oxidation etc.
Firing method is traditional purification method, the mode of Chang Yidian days lamps, and the chimney stack high with 30m enters atmosphere with exhaust combustion.This method gas treatment amount is little, and energy-output ratio is big, and serious environment pollution is greatly wasted the carbon monoxide resource.
Absorption method such as active carbon oxidation absorption method, generation catalytic reactions such as the phosphorus on activated carbon surface in oxygen and the tail gas, hydrogen phosphide are adsorbed, and this square law device poor operability causes the secondary pollution of phosphorous active carbon easily.Hypochlorite oxidation is owned by France in the solution oxide absorption process, is to utilize liquor natrii hypochloritis's phosphorous oxide and hydrogen phosphide, generates the oxide of phosphorus, is absorbed by alkali lye again, and this method purification efficiency and oxidant are active and alkali lye absorption efficiency relation is very big, the device poor operability.
Chinese patent CN1398658A discloses the method that a kind of yellow phosphoric tail gas fixed bed catalytic oxidation purifies, and tail gas is tentatively removed the oxide of the elemental phosphorous and phosphorus of part by alkali cleaning, enters the catalytic oxidation fixed bed, catalyzing, oxidizing and purifying phosphorus and hydrogen phosphide again after heating up.This subtraction unit equipment complexity also needs extra oxygenating to heat up, and certain deficiency is arranged.The efficient of this several method purifying hydrogen phosphide is not high, the flow process complexity, and cause secondary pollution easily.Chinese patent CN101045195A discloses a kind of method of liquid phase catalytic oxidation purifying tail gas containing phosphine, and wherein used catalyst system and catalyzing is a liquid phase, and catalyst has used precious metal chemical complex.The cost height of this method catalyst, the not easily separated recovery of product and catalyst.
Summary of the invention
The purpose of this invention is to provide the low-concentration hydrogen phosphide in a kind of catalytic wet air oxidation (CWAO) cleaning of off-gas of reaction condition gentleness.
The catalytic wet air oxidation purifying hydrogen phosphide, be by in bubbling reactor, adding liquid phase absorption liquid and solid catalyst, adopting the heterogeneous catalysis mode, the low-concentration hydrogen phosphide in the cleaning of off-gas, make the phosphatization Hydrogen Energy oxidized under the condition of low temperature, little oxygen, reach the purpose of cleaning of off-gas.
The particular content of catalytic wet air oxidation is to use the big solution of hydrogen phosphide solubility as absorption liquid, with the micro amount of oxygen that contains in the tail gas as oxidant, be that active component prepares catalysis of solid catalyst hydrogen phosphide and is oxidized to phosphoric acid with the transistion metal compound, CWO is reflected in the bubbling reactor and carries out, and enhancing gas contacts with absorption liquid and catalyst.
The present invention considers the resistance to mass tranfer of hydrogen phosphide between gas-liquid-solid three-phase, adopts copper ammon solution as absorption liquid.The concrete purification process of hydrogen phosphide is as follows:
1. pending gas is: the tail gas that contains low-concentration hydrogen phosphide gas, comprise that yellow phosphoric tail gas, closed calcium carbide furnace tail gas, sodium hypophosphite production and other are the tail gas that produces in the chemical process of raw material with phosphorus or coal, the content of hydrogen phosphide is 800mg/m in these tail gas
3～1000mg/m
3, oxygen content is 0.5%～1%.
2. processing method: absorption liquid and solid catalyst are put into bubbling reactor, addition is: catalyst is 1～3g: 100mL (mass volume ratio) than absorption liquid, reaction temperature is controlled at 40～80 ℃, the gas that contains low-concentration hydrogen phosphide is converted into phosphoric acid through CWO in bubbling reactor, remaining gas enters the tail gas absorption bottle from reactor outlet, enters at last in the atmosphere, and hydrogen phosphide content can drop to 50mg/m in the tail gas after the purification
3
3. prepare catalyst and absorption liquid:
1) catalyst: the method with prior art prepares the support type copper oxide catalyst, adds support type cupric oxide cerium oxide catalyst, the cupric oxide iron oxide mixed oxide catalyst of rare-earth element cerium.That is:
By the element mol ratio is aluminum nitrate, copper nitrate or the ferric nitrate that took by weighing respectively in 2: 1～1: 4, with the aluminum nitrate dissolved in distilled water, adds volume fraction and is 5%～10% ammoniacal liquor and produce aluminum hydroxide sol; With copper nitrate or ferric nitrate dissolved in distilled water, be added in the aluminum hydroxide sol and stir, add volume fraction again and be 5%～10% ammoniacal liquor to there being the precipitation generation again, left standstill after the high-speed stirred aging 6 hours, with gained precipitation with dry after the distilled water washing, suction filtration three times, dried solid porphyrize 400 ℃ of following roastings 3 hours loading type ferric oxide or copper oxide catalyst;
By the element mol ratio is aluminum nitrate, copper nitrate or ferric nitrate, the cerous nitrate that took by weighing respectively in 200: 200: 1～50: 50: 1, with the aluminum nitrate dissolved in distilled water, adds volume fraction and is 5%～10% ammoniacal liquor and make aluminum hydroxide sol; With copper nitrate or ferric nitrate dissolved in distilled water, with the cerous nitrate dissolved in distilled water, be added in the aluminum hydroxide sol mixed solution of copper nitrate and cerous nitrate or the mixed solution of ferric nitrate and cerous nitrate and stirring, add volume fraction again and be 5%～10% ammoniacal liquor to there being the precipitation generation again, left standstill after the high-speed stirred aging 6 hours, with dry after the distilled water washing, suction filtration three times, dried solid porphyrize made loading type ferric oxide or the copper oxide catalyst that adds rare earth cerium oxide in 3 hours 400 ℃ of following roastings with gained precipitation;
By the element mol ratio is to take by weighing certain amount of ferric nitrate and copper nitrate in 1: 2～1: 4, prepare iron nitrate solution and copper nitrate solution with dissolved in distilled water respectively, two solution are mixed, and in mixed solution, add sodium carbonate liquor to precipitating fully, with distilled water washing precipitation and filtration, repetitive operation 3～4 times, oven dry precipitation is then also ground, and the gained particle is produced catalyst 300～500 ℃ of following roastings.
2) absorption liquid: the bigger copper ammon solution of preparation hydrogen phosphide solubility.
Get the copper-bath of a certain amount of 1mol/L, dripping volume fraction in copper-bath is 5% ammoniacal liquor, makes copper sulphate change the Kocide SD precipitation just fully into, and the Kocide SD precipitation with the distilled water washing, is filtered 3～4 times; After Kocide SD precipitation after washing filtered was dried, to be 5% ammoniacal liquor precipitation all dissolved that to prepare volume fraction with distilled water diluting be 5%～20% copper ammon solution with volume fraction again.
The present invention compares with known technology and has the following advantages:
1. method is simple, and is workable, improved purification efficiency, reduced the purification cost;
2. catalyst is easy to separate and reclaims, and utilizes again;
3. bubble is small and even in the blistering reaction, is beneficial to strengthen the dissolving of hydrogen phosphide in absorption liquid;
4. the reaction condition gentleness is easy to realize;
5. can reclaim phosphoric acid, realize changing waste into resources once more.
Description of drawings
Fig. 1 is purification method (catalytic wet air oxidation) the experiment flow figure of low concentration phosphine waste gas of the present invention.
Among the figure, 1-N
2, 2-PH
3, 3-O
2, 4-pressure-reducing valve, 5-spinner flowmeter, 6-blending tank, 7-stop valve, the threeway of 8-glass, 9-bubbling reactor, 10-water-bath, 11-tail gas absorption bottle.
The specific embodiment
Embodiment 1:
The preparation catalyst: by the element mol ratio is to take by weighing aluminum nitrate and copper nitrate at 1: 1, the aluminum nitrate dissolved in distilled water, and the adding volume fraction is that 5% ammoniacal liquor is produced aluminum hydroxide sol; The copper nitrate dissolved in distilled water, be added in the aluminum hydroxide sol, and then to add volume fraction be that 5% ammoniacal liquor is to there being the precipitation generation again, left standstill after the high-speed stirred aging 6 hours, with dry after the distilled water washing, suction filtration three times, dried solid porphyrize was 400 ℃ of following roastings 3 hours with gained precipitation.
The preparation absorption liquid: get the copper-bath of 10 milliliters of 1mol/L, adding 4～5 drop volume marks in copper-bath is 5% ammoniacal liquor, makes copper sulphate change the Kocide SD precipitation just fully into, and the Kocide SD precipitation is washed, filtered 3～4 times with distilled water; After Kocide SD precipitation after washing filtered was dried, to be 5% ammoniacal liquor precipitation all dissolved that to prepare volume fraction with distilled water diluting be 10% copper ammon solution with volume fraction again.
Purification method: get the catalyst that above-mentioned absorption liquid of 100ml and 2g prepare and put into bubbling reactor, hydrogen phosphide content is 800mg/m
3, oxygen content be 1% waste gas from the reactor inlet air inlet, gas flow is 200ml/min, reaction temperature is controlled at 75 ℃.Reaction process as shown in Figure 1.
Clean-up effect: the initial purge efficient after the processing can reach about 95%, and along with the continuation of reaction, purification efficiency descends gradually, and purification efficiency was still more than 75% when reaction proceeded to the 60min left and right sides.
Embodiment 2:
The preparation catalyst: by the element mol ratio is to take by weighing ferric nitrate and copper nitrate at 1: 2, prepare iron nitrate solution and copper nitrate solution with dissolved in distilled water respectively, two solution are mixed, and to add mass fraction in mixed liquor be 10% sodium carbonate liquor to precipitation fully, with distilled water washing precipitation and filtration, repetitive operation 3～4 times, oven dry precipitation is then also ground, and the gained particle is made catalyst at 400 ℃ of following roasting 4h.
The preparation absorption liquid: get the copper-bath of 10 milliliters of 1mol/L, adding volume fraction in copper-bath is 10% ammoniacal liquor, makes copper sulphate change the Kocide SD precipitation just fully into, and the Kocide SD precipitation with the distilled water washing, is filtered 3～4 times; After Kocide SD precipitation after washing filtered was dried, to be 10% ammoniacal liquor precipitation all dissolved that to prepare volume fraction with distilled water diluting be 15% copper ammon solution with volume fraction again.
Purification method: get the 70ml absorption liquid and the 2g catalyst is put into bubbling reactor, hydrogen phosphide content is 800mg/m
3, oxygen content is that 1% waste gas is from the reactor inlet air inlet.Gas flow is 150ml/min, and reaction temperature is controlled at about 65 ℃.Concrete reaction process as shown in Figure 1.
Clean-up effect: at gas flow is 150ml/min, and reaction temperature is to react under the condition about 75 ℃, and the initial purge efficient of hydrogen phosphide reaches 96.3%, and along with the lasting purification efficiency of reaction descends, reaction 60min after-purification efficient reduces to 70%.
Embodiment 3:
The preparation catalyst: by the element mol ratio is to take by weighing aluminum nitrate, copper nitrate and cerous nitrate at 100: 100: 1, prepares copper nitrate solution with the dissolved in distilled water aluminum nitrate, and the adding volume fraction is that 10% ammoniacal liquor is produced aluminum hydroxide sol; Copper nitrate and cerous nitrate are used dissolved in distilled water respectively, and join in the aluminum hydroxide sol successively, add volume fraction and be 10% ammoniacal liquor to there being the precipitation generation again, leave standstill aging 6h after the high-speed stirred, with dry after the distilled water washing, suction filtration three times, dried solid porphyrize is at 350 ℃ of following roasting 4h with gained precipitation.
The preparation absorption liquid: get the copper-bath of 10 milliliters of 1mol/L, adding volume fraction in copper-bath is 5% ammoniacal liquor, makes copper sulphate change the Kocide SD precipitation just fully into, and the Kocide SD precipitation with the distilled water washing, is filtered 3～4 times.After Kocide SD precipitation after washing filtered was dried, to be 5% ammoniacal liquor precipitation all dissolved that to prepare volume fraction with distilled water diluting be 20% copper ammon solution with volume fraction again.
Purification method: get the catalyst that above-mentioned absorption liquid of 100ml and 2g make and put into bubbling reactor, hydrogen phosphide content is 1000mg/m
3, oxygen content is that 1% waste gas enters reactor, and gas flow is 250ml/min, and reaction temperature is controlled at below 90 ℃.
Reaction temperature is the purification efficiency of the hydrogen phosphide purification efficiency of hydrogen phosphide (when beginning reaction) as shown in the table simultaneously not, by in the table as can be seen, purification efficiency reached more than 95% when reaction temperature was elevated to 80 ℃ of left and right sides.
Claims (6)
1, a kind of purification method of low concentration phosphine waste gas, it is characterized in that: absorption liquid and solid catalyst are put into bubbling reactor, addition is: catalyst is 1～3g: 100mL than absorption liquid, make the gas that contains low-concentration hydrogen phosphide enter into reactor, reaction temperature is controlled at 40～80 ℃, the purification of hydrogen phosphide is carried out in bubbling reactor, and hydrogen phosphide content can be reduced to 50mg/m in the tail gas after the purification
3
2, the purification method of low concentration phosphine waste gas according to claim 1, it is characterized in that Preparation of catalysts is: be aluminum nitrate, copper nitrate or the ferric nitrate that took by weighing respectively in 2: 1～1: 4 by the element mol ratio, with the aluminum nitrate dissolved in distilled water, add volume fraction and be 5%～10% ammoniacal liquor and produce aluminum hydroxide sol; With copper nitrate or ferric nitrate dissolved in distilled water, be added in the aluminum hydroxide sol and stir, add volume fraction again and be 5%～10% ammoniacal liquor to there being the precipitation generation again, left standstill after the high-speed stirred aging 6 hours, with gained precipitation with dry after the distilled water washing, suction filtration three times, dried solid porphyrize 400 ℃ of following roastings 3 hours loading type ferric oxide or copper oxide catalyst.
3, the purification method of low concentration phosphine waste gas according to claim 1, it is characterized in that Preparation of catalysts is: be aluminum nitrate, copper nitrate or ferric nitrate, the cerous nitrate that took by weighing respectively in 200: 200: 1～50: 50: 1 by the element mol ratio, with the aluminum nitrate dissolved in distilled water, add volume fraction and be 5%～10% ammoniacal liquor and make aluminum hydroxide sol; With copper nitrate or ferric nitrate dissolved in distilled water, with the cerous nitrate dissolved in distilled water, be added in the aluminum hydroxide sol mixed solution of copper nitrate and cerous nitrate or the mixed solution of ferric nitrate and cerous nitrate and stirring, add volume fraction again and be 5%～10% ammoniacal liquor to there being the precipitation generation again, left standstill after the high-speed stirred aging 6 hours, with dry after the distilled water washing, suction filtration three times, dried solid porphyrize made loading type ferric oxide or the copper oxide catalyst that adds rare earth cerium oxide in 3 hours 400 ℃ of following roastings with gained precipitation.
4, the purification method of low concentration phosphine waste gas according to claim 1, it is characterized in that Preparation of catalysts is: by the element mol ratio is to take by weighing certain amount of ferric nitrate and copper nitrate in 1: 2～1: 4, prepare iron nitrate solution and copper nitrate solution with dissolved in distilled water respectively, two solution are mixed, and in mixed solution, add sodium carbonate liquor to precipitating fully, with distilled water washing precipitation and filtration, repetitive operation 3～4 times, oven dry precipitation is then also ground, and the gained particle is produced catalyst 300～500 ℃ of following roastings.
5, the purification method of low concentration phosphine waste gas according to claim 1, the preparation that it is characterized in that absorption liquid is: the copper-bath of getting a certain amount of 1mol/L, dripping volume fraction in copper-bath is 5% ammoniacal liquor, make copper sulphate change the Kocide SD precipitation just fully into, the Kocide SD precipitation with the distilled water washing, is filtered 3～4 times; After Kocide SD precipitation after washing filtered was dried, to be 5% ammoniacal liquor precipitation all dissolved that to prepare volume fraction with distilled water diluting be 5%～20% copper ammon solution with volume fraction again.
6, the purification method of low concentration phosphine waste gas according to claim 1 is characterized in that the gas flow that gas enters into reactor is 150～250ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810058808XA CN101337157B (en) | 2008-08-12 | 2008-08-12 | Purification method of low concentration phosphine waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810058808XA CN101337157B (en) | 2008-08-12 | 2008-08-12 | Purification method of low concentration phosphine waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101337157A true CN101337157A (en) | 2009-01-07 |
| CN101337157B CN101337157B (en) | 2012-01-11 |
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| CN102311302A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Copper salt absorption liquid for desorbing hydrogen phosphide from ethane and propene in gas phase and application thereof |
| CN102311301A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and application thereof |
| CN101773777B (en) * | 2009-12-29 | 2012-10-31 | 昆明理工大学 | Method for removing hydrogen phosphide by wet catalytic air oxidation |
| CN104190250A (en) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | Purification method of methyne phosphate |
| CN104941422A (en) * | 2015-05-15 | 2015-09-30 | 山东省计量科学研究院 | Hydrogen phosphide gas treatment method |
| CN104941613A (en) * | 2015-06-15 | 2015-09-30 | 武汉轻工大学 | Preparation method of supported flower-shaped copper oxide and method for deeply removing hydrogen phosphide from yellow phosphorus tail gas |
| CN108557818A (en) * | 2018-05-03 | 2018-09-21 | 安徽顺达环保科技股份有限公司 | A method of the dedusting ash discharged using iron and steel enterprise prepares activated carbon |
| CN108786412A (en) * | 2017-04-27 | 2018-11-13 | 北京化工大学 | A kind of method of complex system and jet stream combination oxidation removal hydrogen phosphide |
| CN113893679A (en) * | 2021-10-28 | 2022-01-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Purifying agent for tail gas of CIGS thin-film battery and preparation method thereof |
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| US5527517A (en) * | 1994-11-23 | 1996-06-18 | Philip Morris Incorporated | Liquid scrubbing of gas-phase contaminants |
| CN100482322C (en) * | 2006-12-08 | 2009-04-29 | 昆明理工大学 | Liquid phase catalytic oxidation method for purifying tail gas containing phosphine |
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| CN101773777B (en) * | 2009-12-29 | 2012-10-31 | 昆明理工大学 | Method for removing hydrogen phosphide by wet catalytic air oxidation |
| CN102311302A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Copper salt absorption liquid for desorbing hydrogen phosphide from ethane and propene in gas phase and application thereof |
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| CN102311302B (en) * | 2010-06-29 | 2013-09-25 | 中国石油化工股份有限公司 | Copper salt absorption liquid for desorbing hydrogen phosphide from ethane and propene in gas phase and application thereof |
| CN102311301B (en) * | 2010-06-29 | 2013-09-25 | 中国石油化工股份有限公司 | Copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and application thereof |
| CN104190250A (en) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | Purification method of methyne phosphate |
| CN104941422A (en) * | 2015-05-15 | 2015-09-30 | 山东省计量科学研究院 | Hydrogen phosphide gas treatment method |
| CN104941422B (en) * | 2015-05-15 | 2017-08-08 | 山东省计量科学研究院 | A kind of processing method of phosphine gas |
| CN104941613A (en) * | 2015-06-15 | 2015-09-30 | 武汉轻工大学 | Preparation method of supported flower-shaped copper oxide and method for deeply removing hydrogen phosphide from yellow phosphorus tail gas |
| CN108786412A (en) * | 2017-04-27 | 2018-11-13 | 北京化工大学 | A kind of method of complex system and jet stream combination oxidation removal hydrogen phosphide |
| CN108557818A (en) * | 2018-05-03 | 2018-09-21 | 安徽顺达环保科技股份有限公司 | A method of the dedusting ash discharged using iron and steel enterprise prepares activated carbon |
| CN108557818B (en) * | 2018-05-03 | 2021-11-19 | 安徽顺达环保科技股份有限公司 | Method for preparing activated carbon by utilizing fly ash discharged by iron and steel enterprises |
| CN113893679A (en) * | 2021-10-28 | 2022-01-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Purifying agent for tail gas of CIGS thin-film battery and preparation method thereof |
| CN113893679B (en) * | 2021-10-28 | 2023-07-21 | 中建材玻璃新材料研究院集团有限公司 | Purifying agent for CIGS thin film battery tail gas and preparation method thereof |
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