CN101402020A - Method for purifying arsenic hydride gas in industrial waste gas - Google Patents
Method for purifying arsenic hydride gas in industrial waste gas Download PDFInfo
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- CN101402020A CN101402020A CNA2008102335076A CN200810233507A CN101402020A CN 101402020 A CN101402020 A CN 101402020A CN A2008102335076 A CNA2008102335076 A CN A2008102335076A CN 200810233507 A CN200810233507 A CN 200810233507A CN 101402020 A CN101402020 A CN 101402020A
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- molecular sieve
- industrial waste
- waste gas
- gas
- sieve catalyst
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- 239000007789 gas Substances 0.000 title claims abstract description 50
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002440 industrial waste Substances 0.000 title claims abstract description 15
- 229910000070 arsenic hydride Inorganic materials 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000002779 inactivation Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000005997 Calcium carbide Substances 0.000 abstract description 8
- 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 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 238000003915 air pollution Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000012823 chemical process development Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000007091 anti poisonous effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RSKPLCGMBWEANE-UHFFFAOYSA-N cacodyl Chemical group C[As](C)[As](C)C RSKPLCGMBWEANE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GIKLTQKNOXNBNY-OWOJBTEDSA-N lewisite Chemical compound Cl\C=C\[As](Cl)Cl GIKLTQKNOXNBNY-OWOJBTEDSA-N 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a method for purifying hydrogen arsenide in industrial waste gas, which comprises the following steps: firstly, a mixed modified solution of a cobalt phthalocyanine solution and one ion or a plurality of ions of Fe<3+>, Mn<2+> and Ni<2+> is prepared; secondly, molecular sieve is placed into the modified solution, and modified molecular sieve catalyst is obtained after impregnation, drying and calcination; and thirdly, the modified molecular sieve catalyst is placed into a fixed bed reactor, and the industrial waste gas, including 80 to 90 volume percent of CO, less than 2 volume percent of O2 and 500 to 1600 milligrams per cubic meter of AsH3, undergoes solid catalysis, oxidation and purification, so that the content of the hydrogen arsenide in the industrial waste gas is reduced to below 0.3 milligram per cubic meter. The modified molecular sieve catalyst has high low-temperature activity, can be used in complex industrial gas atmosphere containing CO, H2S, SO2, COS, PH3 and so on, and has good selectivity on AsH3. The method can be applied in factories such as large-scale coke-oven plants, yellow phosphorus manufacturing plants, calcium carbide plants, and provides a feasible path for air pollution control and monocarbide chemical process development of China.
Description
One, technical field
The present invention relates to the method for arsine gas in a kind of purified industrial waste gas, belong to the waste gas pollution control and treatment chemical technology field.
Two, background technology
Arsenic hydride is a colourless gas, belongs to the hypertoxic type material, and its toxicity is bigger 7 times than lewisite, and is bigger 400 times than cacodyl natrium arsenicum.In the industrial production, contain the smelting of arsenic ferrosilicon and when storing, contact humid air or water water the slag that puts out red-hot arsenic-containing ores and can produce arsenic hydride; Occasions such as the acid of the production of calcium carbide manufacturing, acetylene and use, metallic article is watered, charge in batteries, production synthetic dyestuffs all can produce arsenic hydride.Especially in calcium carbide was produced, the calcium carbide furnace gas that every production 1t calcium carbide produces was about 400m
3, it consists of: CO:80%～90%; CO
2: 0.2%～5%; N
2: 1%～2%; O
2: below 2%; AsH
3: 500～1500mg/m
3With concentration less than 300mg/m
3The existence of major impurity such as arsenic has limited that CO uses as high-quality Organic Chemicals gas in the tail gas in sulphur, the phosphorus impurities gas, particularly tail gas.Therefore, obtain highly purified CO gas, the materials such as arsenic hydride in the purified treatment calcium carbide stove exhaust are crucial.This is significant as the raw material of producing carbonizer's product, exploitation deep processed product and sustainable development to utilizing calcium carbide stove exhaust.The arsenic hydride maximum permissible concentration is 0.3mg/m in China (TJ36-79) workshop air in addition
3, therefore purifying arsenic hydride also becomes the protection health, eliminates a kind of necessary means of air-polluting.
Publication number is to disclose a kind of purification PH among the CN1076173
3And AsH
3Immesion active carbon, be used for the PH of purified hydrogen air-flow
3And AsH
3This method Immesion active carbon is to be carrier with the ature of coal granular activated carbon, and its dip composition has Cu, Hg, Cr, Ag.The preparation method is as follows for its Immesion active carbon: sieve is got the ature of coal granular activated carbon of certain particle size, uses CuSO
4, Cr
2O
3NH
4OH solution and AgNO
3Ethanolic solution fully mix, add down HgCl at 40-60 ℃
2, pressing the 70-80% liquid impregnation of active carbon water capacity, the pH of maceration extract is 8-13, and placed greater than 3 hours the dipping back, and said process carries out twice repeatedly, promptly gets Immesion active carbon.This method can reach international safe level 0.05PPm to the clean-up effect of arsenic hydride.
Publication number is to disclose a kind of be used for Hydrodearsenic Catalyst FeCuP alloy that the phosphine gas arsenic hydride removes and the application in dearsenification thereof among the CN101219388.Hydrodearsenic Catalyst is the FeCuP alloy with the oxidation-reduction method preparation.This alloy Cu content mass percent is 20%-35%, and P content mass percent is 0.9%-6.0%, and all the other are iron.Dearsenification step: in airtight gas circuit, feed the nitrogen deaeration, heating dearsenification reactor, the phosphine gas that will contain arsenic hydride feeds in the reactor that Hydrodearsenic Catalyst is housed and carries out dearsenification, gas after the dearsenification imports and is equipped with in the centrifuge tube of silver salt absorption liquid, take off centrifuge tube behind the 45min, add chloroform and supply 4mL, use the 1cm colorimetric cylinder, measure absorbance A in 520nm wavelength place.Carry out blank assay and control experiment simultaneously, calculate arsenic-removing rate.This method dearsenification temperature arsenic-removing rate in the time of 100 ℃ is 80.53%, and temperature arsenic-removing rate in the time of 120 ℃ is 93.34%, and temperature arsenic-removing rate in the time of 175 ℃ is 100%.
There is following problem in existing method: (1) only limits to PH in the air
3And AsH
3Or PH in the hydrogen stream
3And AsH
3Remove, do not relate to AsH under the reducing atmosphere of the industrial tail gas that contains CO
3Remove; (2) all be to only limit to remove simultaneously this two kinds of toxic and harmfuls, mixed-gas atmosphere is comparatively single; (3) the regeneration situation of Hydrodearsenic Catalyst and undeclared if Hydrodearsenic Catalyst can't be regenerated or regenerability is lower, then causes secondary pollution easily and increases cost.
At the problems referred to above, the present invention proposes modified molecular screen gas one solid catalysis oxidation, purification and contains a large amount of CO and O
2Volumn concentration is less than the arsenic hydride in 2% the industrial waste gas, with the AsH in the industrial gasses
3Reduce to 0.3mg/m
3Below.Be China's air pollution control and feasible way of carbonizer's process exploitation proposition.
Three, summary of the invention
The invention provides the method for arsine gas in a kind of purified industrial waste gas, as catalyst, the solid catalysis oxidation, purification contains a large amount of CO and O with molecular sieve modified back
2Volumn concentration is less than the arsenic hydride in 2% the industrial waste gas, with AsH wherein
3Reduce to 0.3mg/m
3Below.Be China's air pollution control and feasible way of carbonizer's process exploitation proposition.
The present invention finishes according to the following steps
1). Preparation of Catalyst: the preparation mass percent is 0.01%～0.1% phthalocyanine cobalt liquor, at room temperature stirs, and adds the Fe of 0.5～2mol/L in the time of stirring
3+The Mn of solution, 0.2～1mol/L
2+The Ni of solution and 0.1～0.5mol/L
2+In the solution one or more at room temperature continue to stir 0.5h then, obtain phthalocyanine cobalt and Fe
3+, Mn
2+, Ni
2+In the mixed and modified solution of one or more ions, described phthalocyanine cobalt liquor and Fe
3+The liquor capacity ratio is 20～100: 1, phthalocyanine cobalt liquor and Mn
2+Liquor capacity is than 20～50: 1; Phthalocyanine cobalt liquor and Ni
2+Liquor capacity is than 100～500: 1; With the modification liquid that obtains at room temperature ageing 24h make it behind the complete mixing modification liquid, molecular sieve is put into this modification liquid, in 20～40 ℃ constant temperature waters, stir 1h, at room temperature flood 48h after the stirring, then after filtration, filter residue is the presoma of modified molecular sieve catalyst, with its dry 24h under 90～120 ℃ temperature, put into roaster at last, and the temperature roasting 12h with 200～350 ℃ gets modified molecular sieve catalyst under the condition of anaerobic.
2). purification process: adding above prepared modified molecular sieve catalyst in fixed bed reactors, heat fixed bed reactors to 50～90 ℃, is 80%～90% with content for the CO volumn concentration, H
2S concentration is 100～200mg/m
3, SO
210～100mg/m
3, COS 100～200mg/m
3, PH
3100～150mg/m
3, AsH
3500～1600mg/m
3, the oxygen volumn concentration is that 0.2%～2% industrial waste gas feeds fixed bed reactors and carries out the adsorption cleaning reaction, assaying reaction device outlet AsH
3The concentration of gas is 0.3mg/m
3Below.
3). the catalyst regeneration process flow process will purify the catalyzer with water steam washing 3～6h of back inactivation, the dry 12h rear catalyst of just can regenerating under 100～150 ℃ temperature then, catalyst regeneration efficient is greater than 90%.
Advantage of the present invention is: producer's extensive use such as (1) modified molecular sieve catalyst can be in large-scale coke-oven plant, phosphorus production factory, calcium carbide factory, have the low temperature active height, and can contain CO, H
2S, SO
2, COS, PH
3Deng the complex industrial gas atmosphere in use, remove AsH wherein
3, have anti-poisonous impurity interference characteristic, and to AsH
3Has good selectivity; (2) catalyst can use under the condition of the long-pending percentage composition of oxysome≤2%; (3) adopting molecular sieve is that the prepared catalyst cost of support modification is lower, removes the performance height, and catalyst is renewable, still possesses catalytic performance preferably after the regeneration.
Four, the specific embodiment
Embodiment one: with mass percent is 0.01% phthalocyanine cobalt liquor, at room temperature mixes, and adding concentration in the time of stirring is the MnSO of 0.2mol/L
4Solution, its phthalocyanine cobalt liquor and MnSO
4The volume ratio of solution is 20: 1, at room temperature continues then to stir 0.5h, obtains phthalocyanine cobalt, Mn
2+The mixed and modified solution of ion, with the modification liquid that obtains at room temperature behind the ageing 24h, X type molecular sieve is put into this modification liquid, in 20 ℃ constant temperature waters, stir 1h then, at room temperature flood 48h after the stirring, behind the dipping after filtration, dry 24h under 90 ℃ baking temperature, put into roaster at last, and the temperature roasting 12h with 250 ℃ can purify used modified molecular sieve catalyst under the condition of anoxybiotic.The modified molecular sieve catalyst specific area can reach 323m
2/ g.
In fixed bed reactors,, feed CO:80%, the H of containing to be clean with the modified molecular sieve catalyst that makes in the above-mentioned condition with the insulation of 60 ℃ steady temperatures
2S:150mg/m
3, SO
2: 30mg/m
3, COS:150mg/m
3, PH
3: 130mg/m
3Closed electric furnace tail gas, wherein arsine gas concentration is 1500mg/m
3, reaction velocity is 800/h, with the gas chromatograph for determination of band TCD and PFD detector, behind adsorption cleaning arsine gas at 30h with inner outlet concentration less than 0.3mg/m
3, adsorption capacity can reach 12.2mg/g.
With the catalyzer with water steam washing 3h behind the inactivation, the dry 12h rear catalyst of just can regenerating under 110 ℃ temperature then, catalyst regeneration is imitated and is reached 96%, and promptly adsorption capacity is 96% of a fresh catalyst.
Embodiment two: with mass percent is 0.1% phthalocyanine cobalt liquor, at room temperature mixes, and adding concentration in the time of stirring is the FeCl of 1mol/L
3Solution, its phthalocyanine cobalt liquor and FeCl
3The volume ratio of solution is 30: 1, at room temperature continues then to stir 0.5h, obtains phthalocyanine cobalt, Fe
3+The mixed and modified solution of ion, with the modification liquid that obtains at room temperature behind the ageing 24h, Y zeolite is put into this modification liquid, in 40 ℃ constant temperature waters, stir 1h then, at room temperature flood 48h after the stirring, behind the dipping after filtration, dry 24h under 100 ℃ baking temperature, put into roaster at last, and the temperature roasting 12h with 300 ℃ can purify used modified molecular sieve catalyst under the condition of anoxybiotic.The modified molecular sieve catalyst specific area can reach 528m
2/ g.
In fixed bed reactors,, feed CO:85%, the H of containing to be clean with the modified molecular sieve catalyst that makes in the above-mentioned condition with the insulation of 80 ℃ steady temperatures
2S:120mg/m
3, SO
2: 15mg/m
3, COS:100mg/m
3, PH
3: 110mg/m
3Closed electric furnace tail gas, wherein arsine gas concentration is 800mg/m
3, reaction velocity is 1500/h, behind adsorption cleaning arsine gas at 36h with inner outlet concentration less than 0.3mg/m
3, adsorption capacity is 11.5mg/g.
With the catalyzer with water steam washing 4h behind the inactivation, the dry 12h rear catalyst of just can regenerating under 130 ℃ temperature then, catalyst regeneration is imitated and is reached 95%, and promptly adsorption capacity is 95% of a fresh catalyst.
Embodiment three: with mass percent is 0.1% phthalocyanine cobalt liquor, at room temperature mixes, and adds the FeCl of 2mol/L in the time of stirring
3The MnSO of solution, 1mol/L
4The NiCl of solution and 0.5mol/L
2Solution, its phthalocyanine cobalt liquor and FeCl
3, MnSO
4Solution, NiCl
2The volume ratio of solution was respectively 50: 1, and 40: 1,200: 1, at room temperature continue then to stir 0.5h, obtain phthalocyanine cobalt, Fe
3+, Mn
2+, Ni
2+The mixed and modified solution of ion, with the modification liquid that obtains at room temperature behind the ageing 24h, X type molecular sieve is put into this modification liquid, in 30 ℃ constant temperature waters, stir 1h then, at room temperature flood 48h after the stirring, behind the dipping after filtration, dry 24h under 120 ℃ baking temperature, put into roaster at last, and the temperature roasting 12h with 350 ℃ can purify used modified molecular sieve catalyst under the condition of anoxybiotic.The modified molecular sieve catalyst specific area can reach 356m
2/ g.
In fixed bed reactors,, feed CO:90%, the H of containing to be clean with the modified molecular sieve catalyst that makes in the above-mentioned condition with the insulation of 90 ℃ steady temperatures
2S:200mg/m
3, SO
2: 30mg/m
3, COS:200mg/m
3, PH
3: 150mg/m
3Closed electric furnace tail gas, wherein arsine gas concentration is 1600mg/m
3, reaction velocity is 2000/h, behind adsorption cleaning arsine gas at 48h with interior concentration less than 0.3mg/m
3, adsorption capacity can reach 14mg/g.
With the catalyzer with water steam washing 6h behind the inactivation, the dry 12h rear catalyst of just can regenerating under 150 ℃ temperature then, catalyst regeneration is imitated and is reached 98%, and promptly adsorption capacity is 98% of a fresh catalyst.
Claims (3)
1, the method for arsine gas in a kind of purified industrial waste gas, it is characterized in that: it is finished according to the following steps,
1). Preparation of Catalyst: the preparation mass percent is 0.01%～0.1% phthalocyanine cobalt liquor, at room temperature stirs, and adds the Fe of 0.5～2mol/L in the time of stirring
3+The Mn of solution, 0.2～1mol/L
2+The Ni of solution and 0.1～0.5mol/L
2+In the solution one or more at room temperature continue to stir 0.5h then, obtain phthalocyanine cobalt and Fe
3+, Mn
2+, Ni
2+In the mixed and modified solution of one or more ions, described phthalocyanine cobalt liquor and Fe
3+The liquor capacity ratio is 20～100: 1, phthalocyanine cobalt liquor and Mn
2+Liquor capacity is than 20～50: 1, and phthalocyanine cobalt liquor and Ni
2+Liquor capacity is than 100～500: 1, with the modification liquid that obtains at room temperature ageing 24h make it behind the mixing modification liquid, molecular sieve is put into this modification liquid, in 20～40 ℃ constant temperature waters, stir 1h, at room temperature flood 48h after the stirring, then after filtration, get the presoma of modified molecular sieve catalyst, with its dry 24h under 90～120 ℃ temperature, put into roaster at last, and the temperature roasting 12h with 200～350 ℃ gets modified molecular sieve catalyst under the condition of anaerobic.
2). purification process: add above prepared modified molecular sieve catalyst in fixed bed reactors, heating fixed bed reactors to 50～90 ℃ feed fixed bed reactors with industrial waste gas and carry out the adsorption cleaning reaction, and the assaying reaction device exports AsH
3The concentration of gas is 0.3mg/m
3Below, the processing of regenerating of the modified molecular sieve catalyst behind the inactivation.
2. the method for arsine gas in the purified industrial waste gas according to claim 1 is characterized in that: the modified molecular sieve catalyst behind the described inactivation is regenerated, and to handle be with its water steam washing 3-6h, dry 12h under 100-150 ℃ temperature then.
3. the method for arsine gas in the purified industrial waste gas according to claim 1 is characterized in that: the component content of described industrial waste gas is 80%～90% for the CO volumn concentration, H
2S concentration is 100～200mg/m
3, SO
210～100mg/m
3, COS 100～200mg/m
3, PH
3100～150mg/m
3, AsH
3500～1600mg/m
3, the oxygen volumn concentration is for being 0.2～2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102335076A CN101402020B (en) | 2008-10-30 | 2008-10-30 | Method for purifying arsenic hydride gas in industrial waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102335076A CN101402020B (en) | 2008-10-30 | 2008-10-30 | Method for purifying arsenic hydride gas in industrial waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101402020A true CN101402020A (en) | 2009-04-08 |
| CN101402020B CN101402020B (en) | 2012-02-15 |
Family
ID=40536267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102335076A Expired - Fee Related CN101402020B (en) | 2008-10-30 | 2008-10-30 | Method for purifying arsenic hydride gas in industrial waste gas |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102068994A (en) * | 2010-12-14 | 2011-05-25 | 昆明理工大学 | Catalyst and preparation method thereof |
| CN103551030A (en) * | 2013-10-31 | 2014-02-05 | 西南化工研究设计院有限公司 | Cleaning agent for removing phosphorous and arsenic in calcium carbide furnace exhaust, as well as preparation method and application thereof |
| CN107597115A (en) * | 2017-09-22 | 2018-01-19 | 昆明理工大学 | It is a kind of can high-efficient purification high concentration arsenic hydride catalyst and preparation method thereof |
| CN109759129A (en) * | 2019-01-15 | 2019-05-17 | 昆明理工大学 | A kind of Modification on Al PO4The preparation method and application of multistage porous molecular sieve |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032963C (en) * | 1993-02-20 | 1996-10-09 | 中国人民解放军防化研究院 | Impregnation active carbon for removing phosphine and hydrogen arsenide from hydrogen stream |
| CN101219388A (en) * | 2008-01-11 | 2008-07-16 | 南开大学 | Dearsenifying agent FeCuP alloy for removing arsenic hydride in phosphoretted hydrogen gas and uses thereof |
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2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068994A (en) * | 2010-12-14 | 2011-05-25 | 昆明理工大学 | Catalyst and preparation method thereof |
| CN102068994B (en) * | 2010-12-14 | 2013-03-06 | 昆明理工大学 | Catalyst and preparation method thereof |
| CN103551030A (en) * | 2013-10-31 | 2014-02-05 | 西南化工研究设计院有限公司 | Cleaning agent for removing phosphorous and arsenic in calcium carbide furnace exhaust, as well as preparation method and application thereof |
| CN103551030B (en) * | 2013-10-31 | 2016-01-06 | 西南化工研究设计院有限公司 | A kind ofly remove cleanser of phosphorus arsenic in calcium carbide stove exhaust and its preparation method and application |
| CN107597115A (en) * | 2017-09-22 | 2018-01-19 | 昆明理工大学 | It is a kind of can high-efficient purification high concentration arsenic hydride catalyst and preparation method thereof |
| CN109759129A (en) * | 2019-01-15 | 2019-05-17 | 昆明理工大学 | A kind of Modification on Al PO4The preparation method and application of multistage porous molecular sieve |
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| CN101402020B (en) | 2012-02-15 |
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