CN103406021A - Method for removing phosphine through double liquid phases - Google Patents
Method for removing phosphine through double liquid phases Download PDFInfo
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- CN103406021A CN103406021A CN2013103157081A CN201310315708A CN103406021A CN 103406021 A CN103406021 A CN 103406021A CN 2013103157081 A CN2013103157081 A CN 2013103157081A CN 201310315708 A CN201310315708 A CN 201310315708A CN 103406021 A CN103406021 A CN 103406021A
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- ionic liquid
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- phosphine
- liquid
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000007791 liquid phase Substances 0.000 title claims abstract description 22
- 229910000073 phosphorus hydride Inorganic materials 0.000 title abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 77
- 239000007789 gas Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000012159 carrier gas Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 229910052763 palladium Inorganic materials 0.000 claims description 25
- 239000003595 mist Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 13
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 claims description 3
- SORXVYYPMXPIFD-UHFFFAOYSA-N iron palladium Chemical compound [Fe].[Pd] SORXVYYPMXPIFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 11
- 239000010452 phosphate Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 34
- 230000008569 process Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- -1 hexafluorophosphate Chemical compound 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 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 6
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 229940006460 bromide ion Drugs 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000013517 stratification Methods 0.000 description 5
- 239000005997 Calcium carbide Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 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 description 4
- 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 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 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
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- PGYDGBCATBINCB-UHFFFAOYSA-N 4-diethoxyphosphoryl-n,n-dimethylaniline Chemical compound CCOP(=O)(OCC)C1=CC=C(N(C)C)C=C1 PGYDGBCATBINCB-UHFFFAOYSA-N 0.000 description 1
- 239000006009 Calcium phosphide Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
Abstract
The invention discloses a method for removing phosphine through double liquid phases. The method comprises the following steps: N2 is taken as carrier gas to mix tail gas containing phosphine (PH3) with oxygen thoroughly; then the mixed gas is pumped into ionic liquid; under the action of a catalyst, phosphine is subjected to a catalytic oxidation reaction to be oxidized into phosphoric acid by oxygen; then, the phosphoric acid enters aqueous phase, so as to achieve the purpose of removing phosphine. The method has the advantages as follows: the reaction occurs under the condition of low temperature and normal pressure; the reaction conditions are mild; after phosphine removing, phosphine is oxidized into a phosphate by-product; the phosphate by-product is made into phosphoric acid after being concentrated; the productivity of the phosphoric acid is high; the product can be separated from the catalyst; the catalyst can be recycled, so that the removing cost is lowered.
Description
Technical field
The present invention relates to a kind of method of Two Liquid Phases purifying hydrogen phosphide, belong to Air Pollution Control and changing waste into resources field.
Background technology
Hydrogen phosphide (PH
3) be a kind of foul smelling flavor, colourless, hypertoxic, carcinogenic gas, 10mg/m
3Contact 6 hours and just have poisoning symptom, 409 ~ 846mg/m
3The time, 0.5 ~ 1h occurs dead; Mainly result from the processes such as phosphorus production, the preparation of magnesium powder, acetylene production, Sodium hypophosphite production, semi-conductor industry production and the degraded of eutrophic lake bed mud, phosphine gas has caused atmosphere pollution, has endangered environmental and human health impacts.
At present, PH
3The purification of waste gas has the methods such as burning, wet oxidation absorption and sorption method, and firing method purifies PH
3Be more common in the traditional treatment method of yellow phosphoric tail gas, it is to utilize yellow phosphoric tail gas to contain 85% ~ 95% CO gas, has higher calorific value, the burning high temperature under by PH
3And other pollutant oxidation, purification, the method can not reclaim CO in yellow phosphoric tail gas, and the energy resource waste is large; Domestic and international relevant producer is to PH at present
3Treatment process be that it is mixed with air in combustion furnace, burning generates the phosphoric acid acid mist, water absorbs and makes phosphoric acid,diluted, this processing PH in absorption tower
3Traditional handicraft two shortcomings are arranged, the one, a small amount of PH in processing procedure
3With the phosphoric acid acid mist, enter in atmosphere, environment has been caused to certain pollution; The 2nd, PH
3All being converted into cheap phosphoric acid, i.e. quite a few raw material---yellow phosphorus has finally become cheap phosphoric acid rather than the higher sodium hypophosphite of price, has reduced the economic benefit of producing, and also has report to adopt firing method to remove PH
3Reactor, the PH of this reactor
3Purification efficiency can be near 100%, but its energy resource consumption is large, gas-powered is difficult, treating capacity is little.
The wet oxidation absorption process mainly comprises concentrated sulfuric acid oxidation absorption process, hypochlorite oxidation absorption process, phosphoric acid method, hydrogen peroxide method, permanganimetric method etc., and it is mainly to utilize PH
3Reproducibility and the oxidisability of oxidant, by redox reaction occurs, absorb PH
3Thereby, reach and purify PH
3Purpose; Wet method is in wet de-device, adopts absorbent to process poison gas, is usually used in the processing of the stifling rear poison gas of large storehouse, the gas treatment amount is large, department is comparatively common in the storage of grain, tobacco business, but has the etching problem of adsorption tower itself, and the recovery pollution problem of absorbent.
Absorption method can be divided into physisorphtion and chemiadsorption, physisorphtion is to utilize the adsorbent specific area to reach greatly surface free energy adsorbate is adsorbed, its adsorption capacity is lower, at present more multiplex is chemisorbed, and typical absorption method has Immesion active carbon catalytic oxidation and alternating temperature pressure swing adsorption method; At patent application (application number: disclose a kind of method that adopts fixed bed catalytic oxidation to purify yellow phosphoric tail gas CN 1398658A), wherein catalyst for catalytic oxidation adopts Immesion active carbon, Immesion active carbon catalytic oxidation purification efficiency is high, but while adopting the method dephosphorization, need to consume a large amount of active carbons, and need carry out the impregnation process of active carbon, although active carbon can regenerate, due to active carbon to P
2O
3And P
2O
5Adsorption capacity very strong, have the more difficult shortcoming of adsorbent reactivation, in addition, be subjected to other pollutant effects in unstripped gas, active carbon easily lost efficacy; (application number: CN 1345620A) announced a kind of method with the pressure swing adsorption purge yellow phosphoric tail gas, pressure-variable adsorption is to utilize under different pressures adsorbent to PH in patent application
3The difference of adsorption capacity is carried out PH
3Isolation of purified, the method technique is more complicated, investment is large, and wants lot of energy in the transformation process; The report that low-temperature adsorption, metal oxide absorption method are also arranged in addition, low-temperature adsorption be in a kind of employing cupric oxide, silica, aluminium oxide, zinc oxide at least a metal oxide after moulding as adsorbent, can use and remove PH under lower than 10 ℃
3A kind of adsorption method, the metal oxide absorption method is by PH
3High-temperature heating decomposes, utilize temperature higher than 100 ℃ of calcium oxide make complete decomposition and with decompose the elemental phosphorous generation calcium phosphide that generates to purify PH
3Method, the PH now had been reported
3In purification method, adopt the more of absorption method.
In addition, at patent application (application number: a kind of announced single liquid phase catalytic oxidation purifying tail gas containing phosphine CN 101045195A) method, wherein liquid phase is that catalyst obtains solution in water-soluble or sour, in liquid phase, hydrogen phosphide is carried out to catalytic oxidation, the content of oxygen and hydrogen phosphide is all lower in solution, affect absorption efficiency, to byproduct with catalyst, be difficult to separate, also mostly carry out on to screening of catalyst, can not improve the solubility of gas in water, and catalyst separates with the product difficulty, and product quality is short of to some extent.
Summary of the invention
The object of the present invention is to provide a kind of method of Two Liquid Phases purifying hydrogen phosphide, the method realizes as follows:
1, in the agent mol ratio of ionic liquid and catalysis be the ratio of 1:0.03 ~ 1:0.08 by catalyst dissolution in ionic liquid, the ratio that is 1:0.5 ~ 1:1.5 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and catalyst, abundant stirring reaction 20 ~ 40min, obtain pretreated ionic liquid at normal temperatures;
2, by the volume ratio of 1:1 ~ 1:3 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
3, press PH
3With N
2Volume ratio be the ratio of 1:3 ~ 1:7, with N
2For carrier gas passes in the gas blending tank hydrogen phosphide with after oxygen fully mixes, the ratio that is 1:20 ~ 1:30 in the volume ratio of ionic liquid and mist again is passed into mist in ionic liquid, reaction temperature is 30 ~ 90 ℃, reaction time is 6 ~ 8h, the volume percent content of oxygen is 6% ~ 12% in mist, collect tail gas after treatment, measure the wherein content of hydrogen phosphide.
Ionic liquid of the present invention can synthesize according to a conventional method, and concrete steps are as follows:
(1) be in molar ratio the ratio of 1:0.5:0.1 ~ 1:1:1.5 by 1-methylimidazole, bromination of n-butane, hexafluorophosphate or two fluoroform sulfimide salt mixing afterreaction, the reaction time is 2 ~ 4h, reaction temperature is 60 ~ 90 ℃;
(2) be that the ratio of 1:1 ~ 1:2 is mixed distilled water with reacted solution in step (1) by volume, stratification after stirring, after removing water, obtain mixed solution, repeatedly with distilled water, wash mixed solution, the bromide ion that washes away unreacted hexafluorophosphate or two fluoroform sulfimide salt and displace, until check water without precipitation with silver nitrate;
(3) by washed mixed liquor under vacuum dry 3 ~ 5 hours, baking temperature was 110 ℃ ~ 140 ℃, and the thick liquid that obtains colorless oil is ionic liquid;
Catalyst of the present invention is: palladium-containing catalyst, contain cuprous catalysis agent, iron-containing catalyst, copper-palladium mixed catalyst, iron-palladium mixed catalyst, wherein:
1. palladium-containing catalyst is a kind of in simple substance palladium, palladium sulfate, palladium nitrate, palladium, palladium bichloride;
2. containing the cuprous catalysis agent is stannous chloride, cuprous nitrate, a kind of in cuprous sulfate, cuprous acetate;
3. iron-containing catalyst is a kind of of fe, iron oxide, ferric sulfate, ferric nitrate, iron chloride, ferric acetate;
4. copper-palladium mixed catalyst is mixed in any proportion by copper catalyst and palladium catalyst, Cu-contained catalyst is a kind of in elemental copper, cupric oxide, copper sulphate, copper nitrate, copper chloride, Schweinfurt green, wherein, palladium-containing catalyst is a kind of in simple substance palladium, palladium sulfate, palladium nitrate, palladium, palladium bichloride;
5. iron-palladium mixed catalyst is mixed in any proportion by iron catalyst and palladium catalyst, wherein, iron-containing catalyst is a kind of in fe, iron oxide, ferric sulfate, ferric nitrate, iron chloride, ferric acetate, and palladium-containing catalyst is a kind of in simple substance palladium, palladium sulfate, palladium nitrate, palladium, palladium bichloride.
The present invention process to as if phosphine containing (PH
3) tail gas of gas, comprise the PH that contains produced in yellow phosphoric tail gas, closed calcium carbide furnace tail gas, the preparation of magnesium powder, Sodium hypophosphite production, feed fermentation, semi-conductor industry production and fumigant insect killing process
3Tail gas.
By gas flowmeter, control flow and gas ratio, mist is passed in ionic liquid, catalytic oxidation occurs, reaction principle is as follows:
The distribution coefficient of phosphate byproduct in water is higher than the distribution coefficient in ionic liquid, therefore the phosphate byproduct that reaction produces in ionic liquid can enter water, then in the suction concentration tower, finally in acid tank, make phosphoric acid, and after tail gas clean-up, discharge, then to supplementing water in absorption tower to continue purifying hydrogen phosphide.
The present invention compared with prior art has advantages of:
(1) in the present invention, ionic liquid and water form Two Liquid Phases, catalyst is dissolved in ionic liquid, after in ionic liquid, reacting, generate phosphate and enter mutually water from ionic liquid, realized separating of product and catalyst, products therefrom is comparatively pure, catalyst can be recycled, and has reduced the purification cost;
(2) Two Liquid Phases environment of the present invention is easy to preparation, applied range, and absorption efficiency is good, adaptable temperature, flow, oxygen concentration and PH
3Concentration range is wider, can be applicable to the purification of the phosphine-containing gas produced in the processes such as yellow phosphoric tail gas, closed calcium carbide furnace tail gas, the preparation of magnesium powder, Sodium hypophosphite production, acetylene production, feed fermentation, semi-conductor industry production;
(3) PH in the present invention
3Purification be to carry out under the cryogenic conditions of 30 ~ 90 ℃, the reaction condition gentleness, the hydrogen phosphide after purification is oxidized to the phosphate byproduct, makes phosphoric acid after concentrated.
The accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure, 1 is carrier gas N
2With contain PH
3Waste gas, the 2nd, O
2, the 3rd, gas blending tank, the 4th, absorption tower, the 5th, purified gas, the 6th, water, the 7th, ionic liquid, the 8th, supplementing water, the 9th, phosphate byproduct, the 10th, concentration tower, the 11st, acid tank.
The specific embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments, but protection domain of the present invention is not limited to described content.
Embodiment 1
1, the preparation of ionic liquid, concrete steps are as follows:
(1) be in molar ratio the ratio of 1:0.5:0.1 by 1-methylimidazole, bromination of n-butane and hexafluorophosphate mixing afterreaction, the reaction time is 2h, reaction temperature is 90 ℃;
(2) be that the ratio of 1:1 is mixed distilled water with reacted solution in step (1) by volume, stratification after stirring, after removing water, obtain mixed solution, repeatedly with distilled water, wash ionic liquid, the bromide ion that washes away unreacted hexafluorophosphate and displace, until check water without precipitation with silver nitrate;
(3) by washed ionic liquid under vacuum dry 5 hours, baking temperature was 110 ℃, and the thick liquid that obtains colorless oil is ionic liquid.
2, Two Liquid Phases catalyzing, oxidizing and purifying hydrogen phosphide, concrete steps are as follows:
(1) in ionic liquid and palladium sulfate mol ratio, be that the 1:0.03 ratio is dissolved in palladium sulfate in ionic liquid, the ratio that is 1:0.5 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and palladium sulfate, fully stir at normal temperatures 20min, namely obtain pretreated ionic liquid;
(2) by the volume ratio of 1:1 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
(3) press PH
3with N
2volume ratio be the ratio of 1:3, with N
2for carrier gas by yellow phosphoric tail gas (PH
3content is 890mg/m
3) pass in gas blending tank 3 with after oxygen fully mixes, the ratio that is 1:20 in the volume ratio of ionic liquid and mist is passed into mist in the 4 intermediate ion liquid of absorption tower, reaction temperature is 30 ℃, reaction time is 8h, the volume percent content of oxygen is 8% in mist, the phosphate byproduct 9 produced enters the rear discharge of water 6 and enters concentration tower 10, finally in acid tank 11, make phosphoric acid, and then add supplementing water 8 to continue absorption cleaning hydrogen phosphide (as shown in Figure 1) in absorption tower 4, after measured, in yellow phosphoric tail gas 5 after 4 absorption cleanings of absorption tower, Phosphine content is 27.3 mg/m
3, the productive rate of phosphoric acid is 91.2%.
1, the preparation of ionic liquid, concrete steps are as follows:
(1) be in molar ratio the ratio of 1:1:1.5 by 1-methylimidazole, bromination of n-butane and two fluoroform sulfimide salt mixing afterreaction, the reaction time is 4h, reaction temperature is 60 ℃;
(2) be that the ratio of 1:2 is mixed distilled water with reacted solution in step (1) by volume, stratification after stirring, after removing water, obtain mixed solution, repeatedly with distilled water, wash ionic liquid, the bromide ion that washes away unreacted pair of fluoroform sulfimide salt and displace, until check water without precipitation with silver nitrate;
(3) by washed ionic liquid under vacuum dry 3 hours, baking temperature was 140 ℃, and the thick liquid that obtains colorless oil is ionic liquid.
2, Two Liquid Phases catalyzing, oxidizing and purifying hydrogen phosphide, concrete steps are as follows:
(1) in ionic liquid and cuprous nitrate mol ratio, be that the 1:0.08 ratio is dissolved in cuprous nitrate in ionic liquid, the ratio that is 1:1.5 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and cuprous nitrate, fully stir at normal temperatures 40min, namely obtain pretreated ionic liquid;
(2) by the volume ratio of 1:3 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
(3) press PH
3with N
2volume ratio be the ratio of 1:5, with N
2for carrier gas will be closed calcium carbide stove exhaust (PH
3content is 950mg/m
3) pass in gas blending tank 3 with after oxygen fully mixes, the ratio that is 1:30 in the volume ratio of ionic liquid and mist is passed into mist in the 4 intermediate ion liquid of absorption tower, reaction temperature is 90 ℃, reaction time is 6h, the volume percent content of oxygen is 10% in mist, the phosphate byproduct 9 produced enters the rear discharge of water 6 and enters concentration tower 10, finally in acid tank 11, make phosphoric acid, and then add supplementing water 8 to continue absorption cleaning hydrogen phosphide in absorption tower 4, after measured, after 4 absorption cleanings of absorption tower to close Phosphine content in calcium carbide stove exhaust 5 be 28.5mg/m
3, the productive rate of phosphoric acid is 90.3%.
1, the preparation of ionic liquid, concrete steps are as follows:
(1) be in molar ratio the ratio of 1:1:1 by 1-methylimidazole, bromination of n-butane and two fluoroform sulfimide salt mixing afterreaction, the reaction time is 3h, reaction temperature is 80 ℃;
(2) be that the ratio of 1:1.4 is mixed distilled water with reacted solution in step (1) by volume, stratification after stirring, after removing water, obtain mixed solution, repeatedly with distilled water, wash ionic liquid, the bromide ion that washes away unreacted pair of fluoroform sulfimide salt and displace, until check water without precipitation with silver nitrate;
(3) by washed ionic liquid under vacuum dry 4 hours, baking temperature was 120 ℃, and the thick liquid that obtains colorless oil is ionic liquid.
2, Two Liquid Phases catalyzing, oxidizing and purifying hydrogen phosphide, concrete steps are as follows:
(1) in ionic liquid and iron chloride mol ratio, be that the 1:0.05 ratio is dissolved in iron chloride in ionic liquid, the ratio that is 1:0.8 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and iron chloride, fully stir at normal temperatures 25min, namely obtain pretreated ionic liquid;
(2) by the volume ratio of 1:2.5 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
(3) press PH
3with N
2volume ratio be the ratio of 1:7, with N
2for the tail gas (PH of carrier gas by the Sodium hypophosphite production generation
3content is 1200mg/m
3) pass in gas blending tank 3 with after oxygen fully mixes, the ratio that is 1:23 in the volume ratio of ionic liquid and mist is passed into mist in the 4 intermediate ion liquid of absorption tower, reaction temperature is 50 ℃, reaction time is 7.5h, the volume percent content of oxygen is 12% in mist, the phosphate byproduct 9 produced enters the rear discharge of water 6 and enters concentration tower 10, finally in acid tank 11, make phosphoric acid, and then add supplementing water 8 to continue absorption cleaning hydrogen phosphide in absorption tower 4, after measured, in the tail 5 that Sodium hypophosphite production after 4 absorption cleanings of absorption tower produces, Phosphine content is 36.0mg/m
3, the productive rate of phosphoric acid is 92.5%.
Embodiment 4
1, the preparation of ionic liquid, concrete steps are as follows:
(1) be in molar ratio the ratio of 1:1:1.5 by 1-methylimidazole, bromination of n-butane and hexafluorophosphate mixing afterreaction, the reaction time is 3h, reaction temperature is 70 ℃;
(2) be that the ratio of 1:1.6 is mixed distilled water with reacted solution in step (1) by volume, stratification after stirring, after removing water, obtain mixed solution, repeatedly with distilled water, wash ionic liquid, the bromide ion that washes away unreacted hexafluorophosphate and displace, until check water without precipitation with silver nitrate;
(3) by washed ionic liquid under vacuum dry 3.5 hours, baking temperature was 130 ℃, and the thick liquid that obtains colorless oil is ionic liquid.
2, Two Liquid Phases catalyzing, oxidizing and purifying hydrogen phosphide, concrete steps are as follows:
(1) the mixture mol ratio in ionic liquid and copper sulphate and palladium sulfate is that the 1:0.07 ratio is dissolved in copper sulphate and palladium sulfate in ionic liquid, wherein copper sulphate and palladium sulfate are the ratio mixing of 1:5 in mass ratio, the ratio that is 1:1.2 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and copper sulphate and sulfuric acid, fully stir at normal temperatures 30min, namely obtain pretreated ionic liquid;
(2) by the volume ratio of 1:1.5 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
(3) press PH
3with N
2volume ratio be the ratio of 1:4, with N
2for the carrier gas semi-conductor industry, produce the tail gas (PH produced
3content is 720mg/m
3) pass in gas blending tank 3 with after oxygen fully mixes, the ratio that is 1:27 in the volume ratio of ionic liquid and mist is passed into mist in the 4 intermediate ion liquid of absorption tower, reaction temperature is 70 ℃, reaction time is 7 h, the volume percent content of oxygen is 6% in mist, the phosphate byproduct 9 produced enters the rear discharge of water 6 and enters concentration tower 10, finally in acid tank 11, make phosphoric acid, and then add supplementing water 8 to continue absorption cleaning hydrogen phosphide in absorption tower 4, after measured, it is 21.6mg/m that semi-conductor industry after 4 absorption cleanings of absorption tower is produced Phosphine content in the tail gas 5 produced
3, the productive rate of phosphoric acid is 89.8%.
Claims (2)
1. the method for a Two Liquid Phases purifying hydrogen phosphide is characterized in that through following steps:
(1) in the mol ratio of ionic liquid and catalyst be the ratio of 1:0.03 ~ 1:0.08 by catalyst dissolution in ionic liquid, the ratio that is 1:0.5 ~ 1:1.5 in the mol ratio of ionic liquid and chelating agent tricresyl phosphate phosphatide again adds chelating agent tricresyl phosphate phosphatide in the mixed liquor of ionic liquid and catalyst, abundant stirring reaction 20 ~ 40min, obtain pretreated ionic liquid at normal temperatures;
(2) by the volume ratio of 1:1 ~ 1:3 by pretreated ionic liquid with put into reaction tower after water mixes, in reaction tower, form the layering Two Liquid Phases of ionic liquid and water;
(3) press PH
3With N
2Volume ratio be the ratio of 1:3 ~ 1:7, with N
2For carrier gas passes in the gas blending tank hydrogen phosphide with after oxygen fully mixes, the ratio that is 1:20 ~ 1:30 in the volume ratio of ionic liquid and mist again is passed into mist in ionic liquid, reaction temperature is 30 ~ 90 ℃, reaction time is 6 ~ 8h, the volume percent content of oxygen is 6% ~ 12% in mist, collect tail gas after treatment, measure the wherein content of hydrogen phosphide.
2. the method for Two Liquid Phases purifying hydrogen phosphide according to claim 1 is characterized in that: catalyst is palladium-containing catalyst, contain cuprous catalysis agent, iron-containing catalyst, copper-palladium mixed catalyst, iron-palladium mixed catalyst.
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