CN102019141A - Process for purifying tail gas containing hydrothion by using liquid phase catalytic oxidation method - Google Patents
Process for purifying tail gas containing hydrothion by using liquid phase catalytic oxidation method Download PDFInfo
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- CN102019141A CN102019141A CN201010595609.XA CN201010595609A CN102019141A CN 102019141 A CN102019141 A CN 102019141A CN 201010595609 A CN201010595609 A CN 201010595609A CN 102019141 A CN102019141 A CN 102019141A
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- tail gas
- palladium
- reactor
- copper
- sulfide
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 239000007791 liquid phase Substances 0.000 title claims description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000746 purification Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 84
- 239000007789 gas Substances 0.000 claims description 73
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 58
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 56
- 229910052763 palladium Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 16
- 230000005587 bubbling Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000011552 falling film Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 239000005997 Calcium carbide Substances 0.000 abstract description 13
- 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 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 abstract 2
- 238000003795 desorption Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- -1 petroleum refining Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005504 petroleum refining Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000988 sulfur dye Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000001706 oxygenating effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 206010010741 Conjunctivitis Diseases 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 206010037508 Punctate keratitis Diseases 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 208000010513 Stupor Diseases 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 210000000196 olfactory nerve Anatomy 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a process for purifying tail gas containing hydrothion, which is energy-saving, environment-friendly, safe and economic. The technical process comprises the following steps: (1) preparation of a catalyst; and (2) the process for purifying the tail gas containing the hydrothion or catalytic oxidation purification process in which the hydrothion absorption and oxidation are carried out step by step. In the purification process provided by the invention, the hydrothion is oxidized to elemental sulfur so as to realize recycling, effectively solve the problem of hydrothion pollution, and provide a practical purification technique for yellow phosphorus exhausting gas, and tail gas and sewage gas of a sealed calcium carbide furnace. The process that hydrothion absorption and oxidation are carried out respectively on desorption of the hydrothion in the yellow phosphorus exhausting gas, the tail gas and sewage gas of the sealed calcium carbide furnace is adopted. The process is characterized in that the purified gas can be still used as the raw materials for other production links. The catalyst in the process has the advantages of high catalytic activity, good stability, good selectivity, and extensive application conditions, is easy to prepare, and is a clear technical process.
Description
Technical field
The present invention relates to the air pollution control technique field, particularly relate to the catalyzing, oxidizing and purifying method of hydrogen sulfide gas.
Background technology
Hydrogen sulfide (H
2S) be the foul gas that a kind of height stimulates strong rotten egg smell, the existence of hydrogen sulfide not only can cause equipment and corrosion of piping, catalyst poisoning in the gas, influences product quality, and can seriously be detrimental to health contaminated environment.The stink of hydrogen sulfide is very easily smelt, and the people is 0.01x10 to the susceptibility of hydrogen sulfide
-6G/m
3Low concentration (5x10
-6G/m
3Below) hydrogen sulfide mucous membrane and respiratory tract are had spread effect, can cause eye conjunctivitis, very easily absorbed simultaneously by lung and stomach and intestine, poisoning symptom takes place, cause histanoxia.Long-term contact low concentration H
2Headache, tired unable, failure of memory, insomnia, pectoralgia, cough can appear in S, feel sick and symptom such as diarrhoea, also keratitis punctata can occur.H
2S concentration is greater than 20x10
-6G/m
3The time belonged to dangerous values; Reach 200x10
-6G/m
3The time, can make the olfactory nerves complete paralysis; Concentration is greater than (700～1000) x10
-6G/m
3The time, the people can take place immediately stupor and because of respiratory paralysis dead immediately.H
2S can produce in phosphorus production, closed calcium carbide furnace as difficult purifying contaminated thing in technology such as calcium carbide, biogas fermentation, staple fibre, sulfur dye, petroleum refining, coal gas manufacturing, sewage disposal, papermaking and the organic matter decay process and produce.Not only cause environmental pollution, endangered health but also restricted production process control, safety in production and comprehensive utilization of waste materials.
At present, handle H both at home and abroad
2The method of S waste gas is a lot, generally can be divided into dry method, wet method and bioanalysis.
Dry method is to utilize H
2The reproducibility of S and combustibility are so that fixedly oxidant or absorbent come desulfurization or directly burning.Dry desulfurization is usually used in the processing of low sulfurous gas, and its equipment is simple, but equipment is huger, and needs a plurality of equipment handover operations, and desulfurizing agent is non-renewable, and cost is higher.This method comprises improved Claus method, iron processes, iron oxide process, zinc oxide method, manganese ore method, active carbon adsorption, sieve method, ion-exchange fibre method, electronics card irradiation, membrane separation process etc., desulfurizer therefor, catalyst have active carbon, iron oxide, zinc oxide, manganese dioxide and bauxite, also have molecular sieve, ion-exchange fibre etc. in addition.General recyclable sulphur, sulfur dioxide, sulfuric acid and sulfate.Patent CN1081930A (publication number) has announced that a kind of improved complex iron removes the technology of sulfide from admixture of gas, a kind of doctor solution and corresponding sulfur removal technology thereof by the multicomponent combination is provided, it is big to have saturated sulfur capacity, the absorption efficiency height, but desulfurizing agent needs regular regeneration or replacing, is not very economical generally.
Compare advantage such as wet desulphurization has that floor space is little, equipment is simple, easy to operate, small investment with dry desulfurization.Press the difference of desulfurizing agent, wet desulphurization can be divided into liquid absorption method and absorb oxidizing process two classes.The physical chemistry absorption process that the chemical absorption method that utilizes alkaline solution, the Physical Absorption method of utilizing organic solvent is arranged in the liquid absorption method and utilize Physical Absorption and chemical solvent simultaneously.Patent CN101062460A (publication number) has announced a kind of method of removing hydrogen sulfide from the mist that comprises low concentration hydrogen sulphide gas, and absorption liquid is selected from N-Propylene Glycol amine aqueous solution, monoethanolamine solution, diethanolamine solution and their mixture.This method equipment is simple, the desulfurizing agent cheapness, but desulfuration efficiency is not high, and pollutant is only transferred to liquid phase by gas phase; And absorb oxidizing process generally all is to add oxidant or catalyst in absorption liquid, makes the H of absorption
2S is oxidized to sulphur and makes solution regeneration in oxidizing tower (being regenerator).Absorption liquid commonly used has the aqueous solution of sodium carbonate, potash and ammonia, the aqueous solution or water slurry that oxidant commonly used or catalyst are made up of iron oxide, thioarsenate, iron cyanogen compound double salt and organic catalyst.
Bioanalysis is that the processing low concentration foul gas that gets up of developed recently is (as H
2S) comparatively effective method.Patent CN1218421A (publication number) has announced a kind of gas cleaning method that contains hydrogen sulfide, wherein use can sulfide oxidation autotrophy sulfide-oxidizing bacteria under high pH, handle the cleaning solution of using, thereby obtain elementary sulfur.Elementary sulfur is separated, and treated cleaning solution is looped back in the gas scrubbing step, desulfuration efficiency is up to 98%, even can reach 100%.Contain H with the bioanalysis processing
2S waste gas can be handled the gas of atm number, and the operational processes unit is controlled easily, and biomass accumulative total guarantees effective contaminant degradation ability, so it has certain application value.But equipment is many, and the cost height need add nutriments such as phosphorus, potassium, is not suitable for handling the H that contains of low concentration
2S gas.
Summary of the invention
The object of the present invention is to provide a kind of energy-saving and environmental protection, safe, the economic method that from sulfide hydrogen tail gas, removes hydrogen sulfide.Hydrogen sulfide is oxidized to elemental sulfur and realizes resource, and the pollution problem of also effectively removing hydrogen sulfide also provides practical purification techniques for yellow phosphoric tail gas, closed calcium carbide furnace tail gas and biogas simultaneously.
Liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method of the present invention is achieved in that and it is characterized in that containing following processing step:
1. preparation of catalysts:
Get cupric and palladium-containing catalyst respectively stirring and dissolving in concentration is 0%～30% acid, mix, filter the mixed catalytic agent solution, wherein the palladium mass concentration is 0.05～50g/L, copper mass concentration is 0.1～150g/L;
2. hydrogen sulfide absorption and the oxidation catalyzing, oxidizing and purifying technology of carrying out step by step:
Sulfide hydrogen tail gas is reacted with the mixed catalytic agent solution of being prepared that contains palladium, copper in 4～100 ℃ in the absorption tower, become the palladium simple substance of indissoluble after part palladium ion and the hydrogen sulfide haptoreaction, enter liquid phase and hydrogen sulfide is oxidized to elemental sulfur; Meanwhile, partial vulcanization hydrogen and copper ion generate the copper sulfide of indissoluble, and the generation of palladium simple substance and copper sulfide can make catalyst solution become black suspension,
The mixed catalytic agent solution that will absorb hydrogen sulfide is then sent into oxidizing tower and is carried out oxidation, blasts air or oxygen in oxidizing tower, and the hydrogen sulfide that is absorbed in the solution is existed with dissolved state, becomes elemental sulfur with oxygen generation oxidation reaction; Palladium simple substance then is oxidized to the divalence palladium ion; Copper sulfide is converted into copper sulphate, and the mixed solution after the oxidation is discharged from oxidizing tower, sends into the absorption tower again and recycles.
The acid of step described in 1. is hydrochloric acid, nitric acid or sulfuric acid, and described copper and palladium-containing catalyst are palladium bichloride or copper chloride.
The absorption tower of step described in 2. is turbulent contact absorber, tray absorption columns, bubble absorbing tower, venturi scrubber or stirs bubble absorbing tower that described oxidizing tower is packed column reactor, rapid ball absorption reactor thermally, plate-type reactor, bubbling reactor, falling film reactor or stirs bubbling reactor.
A kind of liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method is characterized in that containing following processing step:
1. preparation of catalysts:
Get cupric and palladium-containing catalyst respectively stirring and dissolving in concentration is 0%～30% acid, mix, filter the mixed catalytic agent solution, wherein the palladium mass concentration is 0.05～50g/L, copper mass concentration is 0.1～150g/L;
2. oxygenating-catalyzing, oxidizing and purifying technology:
Enter that the mol ratio of oxygen and hydrogen sulfide should if oxygen content is on the low side, adopt air or oxygen to mix with sulfide hydrogen tail gas greater than 2 in the sulfide hydrogen tail gas of catalyst oxidation reactor, the mol ratio that makes oxygen and hydrogen sulfide is greater than 2,
The above-mentioned sulfide hydrogen tail gas that regulates oxygen content and the mixed catalytic agent solution that contains palladium, copper that is mixed with are reacted in 4～100 ℃ in reactor, and hydrogen sulfide is oxidized to elemental sulfur and enters liquid phase in solution.
The acid of step described in 1. is hydrochloric acid, nitric acid or sulfuric acid, and described copper and palladium-containing catalyst are palladium bichloride or copper chloride.
The reactor of step described in 2. is packed column reactor, rapid ball absorption reactor thermally, plate-type reactor, bubbling reactor, falling film reactor or stirs bubbling reactor.
The advantage that present technique is compared with prior art had
1. the hydrogen sulfide that contains in the active height of catalyst of the present invention, good stability, the good yellow phosphoric tail gas of selectivity and the closed calcium carbide furnace tail gas is its difficult point of carrying out recycling as carbonizer's unstripped gas, and catalyst of the present invention can make the removal efficiency of hydrogen sulfide keep 100% for a long time in the purification of yellow phosphoric tail gas and closed calcium carbide furnace tail gas, the yellow phosphoric tail gas after the purification satisfy as in carbonizer's unstripped gas to the requirement of hydrogen sulfide content.The high activity, high stability and the high selectivity that possess as good catalyst have been shown;
2. catalyst of the present invention is prepared easily, the extensive different operating conditional request that adapts to temperature, pH, flow, oxygen concentration and the concentration of hydrogen sulfide scope of broad of application conditions, and hydrogen sulfide removes in the sulfide hydrogen tail gas that can be applicable to produce in yellow phosphoric tail gas, closed calcium carbide furnace tail gas, biogas fermentation, staple fibre, sulfur dye, petroleum refining, coal gas manufacturing, sewage disposal, the paper-making process;
3. the purification of hydrogen sulfide is to carry out under 4～100 ℃ cryogenic conditions among Qing Jie technical matters route the present invention, and hydrogen sulfide is oxidized to elemental sulfur in the purification process, and catalyst can be recycled, and has reduced the purification cost.
Description of drawings
Fig. 1 is that the present invention extracts H
2The S process flow diagram.
Among the figure: the 1-water scrubber; The 2-absorption tower; The 3-regenerator; The 4-centrifuge; The 5-washing water pump; 6-rich solution pump; The 7-lean pump; The 8-poor rich liquid heat exchanger; 9-lean solution cooler.
The specific embodiment
Technology contents of the present invention is as follows:
1) the required raw material of catalyst preparation
1. Cu-contained catalyst: elemental copper, cupric oxide, copper sulphate, copper nitrate, copper chloride, Schweinfurt green;
2. palladium-containing catalyst: simple substance palladium, palladium sulfate, palladium nitrate, palladium, palladium bichloride;
3. solvent: include hydrochloric acid, nitric acid or sulfuric acid;
2) object of the present invention's processing
Generation contains H
2The purification of the tail gas of S gas, include yellow phosphoric tail gas (tail gas consist of CO 85%～90%, CO
21～4%, H
21%～8%, N
22%～5%, H
2O 5%, H
2S 60～3000mg/m
3), (typical tail gas consists of (percent by volume): CO 80%～85%, H to closed calcium carbide furnace tail gas
27%, CO
21.5%, O
22%, N
27%, H
2S 100～850mg/m
3), biogas fermentation (CH
450%～80%, CO
220%～40%, N
20%～5%, H
21%, O
20.4%, H
2S 0.1%～3%), produce in the process such as staple fibre, sulfur dye, petroleum refining, coal gas manufacturing, sewage disposal, papermaking contain H
2S tail gas.
3) technical process of the present invention
1. preparation of catalysts
Get cupric and palladium-containing catalyst respectively stirring and dissolving in concentration is 0%～30% acid (hydrochloric acid or nitric acid or sulfuric acid), mix, filter the mixed catalytic agent solution.Wherein the palladium mass concentration is 0.05～50g/L, and copper mass concentration is 0.1～150g/L; Is good with palladium bichloride, copper chloride as catalyst, and acid is good with hydrochloric acid.
2. the process for purifying process of hydrogen sulfide in the sulfide hydrogen tail gas
Technology one: the catalyzing, oxidizing and purifying technology that hydrogen sulfide absorption and oxidation are carried out step by step
Owing to be rich in carbon monoxide in yellow phosphoric tail gas, the closed calcium carbide furnace tail gas, after purifying, can be used as valuable carbonizer's unstripped gas.Be rich in methane in the biogas fermentation, after purifying, can be used as fuel gas.If by purifying again after the oxygenating, then may also reduce the selectivity of catalyzing, oxidizing and purifying simultaneously owing to the oxygenating process is sneaked into more foreign gas.Therefore, to the technology that can adopt hydrogen sulfide absorption and oxidation to carry out step by step that removes of yellow phosphoric tail gas, closed calcium carbide furnace tail gas, hydrogen sulfide in methane, the feature of this technology is that purified gas is also as the raw material of other production links.
Sulfide hydrogen tail gas is reacted with the mixed catalytic agent solution of being prepared that contains palladium, copper in 4～100 ℃ in absorption tower (turbulent contact absorber or tray absorption columns or bubble absorbing tower or venturi scrubber or stirring bubble absorbing tower), become the palladium simple substance of indissoluble after part palladium ion and the hydrogen sulfide haptoreaction, enter liquid phase and hydrogen sulfide is oxidized to elemental sulfur; Meanwhile, partial vulcanization hydrogen and copper ion generate the copper sulfide of indissoluble.The generation of palladium simple substance and copper sulfide can make catalyst solution become black suspension.
The mixed catalytic agent solution that will absorb hydrogen sulfide is then sent into oxidizing tower (packed column reactor or rapid ball absorption reactor thermally or plate-type reactor or bubbling reactor or falling film reactor or stir bubbling reactor) and is carried out oxidation.In oxidizing tower, blast air or oxygen, make the hydrogen sulfide (existing) that is absorbed in the solution become elemental sulfur with oxygen generation oxidation reaction with dissolved state; Palladium simple substance then is oxidized to the divalence palladium ion; Copper sulfide is converted into copper sulphate.Mixed solution after the oxidation is discharged from oxidizing tower, sends into the absorption tower again and recycles.
Technology two: oxygenating-catalyzing, oxidizing and purifying technology
At the H that contains that produces in the processes such as staple fibre, sulfur dye, petroleum refining, coal gas manufacturing, sewage disposal, papermaking
2S tail gas, the tail gas industrial utilization of generation is worth not high, directly effluxes after purifying usually, so can take oxygenating-catalytic oxidation technology according to oxygen content in these tail gas and hydrogen sulfide content situation.
For guaranteeing hydrogen sulfide sufficient oxidation, purification in the liquid phase catalytic oxidation process, the mol ratio that enters oxygen and hydrogen sulfide in the sulfide hydrogen tail gas of catalyst oxidation reactor should be greater than 2, if oxygen content is on the low side, can adopt air or oxygen to mix with sulfide hydrogen tail gas, the mol ratio that makes oxygen and hydrogen sulfide is greater than 2.
The above-mentioned sulfide hydrogen tail gas that regulates oxygen content is reacted in 4～100 ℃ in reactor (packed column reactor or rapid ball absorption reactor thermally or plate-type reactor or bubbling reactor or falling film reactor or stirring bubbling reactor) with the mixed catalytic agent solution that contains palladium, copper that is mixed with, hydrogen sulfide is oxidized to elemental sulfur and enters liquid phase in solution, thereby realizes removing from sulfide hydrogen tail gas the purpose of hydrogen sulfide.
The principle of liquid phase catalytic oxidation is:
Embodiment 1: get the 2.1kg copper chloride and be dissolved in the 5L water, the 0.2kg palladium bichloride is dissolved in the hydrochloric acid of 5L 10%, both is mixed again, and filters, and discards filter residue, and gained filtrate is the mixed catalytic agent solution, and is standby.
Will be through being that main component, hydrogen sulfide content are 500～1150mg/m with the carbon monoxide after the alkali cleaning
3Yellow phosphoric tail gas with 10m
3/ h flow velocity feeds in the tower from spraying bottom, absorption tower, and the mixed catalytic agent solution 2L/min for preparing sprays into from spraying top, absorption tower, and gas-liquid conversed contact is in 20～40 ℃ of reactions down of tower temperature.The mixed catalytic agent solution that has absorbed hydrogen sulfide send into stir bubbling reactor and 4L/min flow velocity air at 20～40 ℃ of catalytic oxidations, it is recycling that the absorption liquid after the oxidation pumps into the absorption tower of spraying with pump again.After measured, hydrogen sulfide content is 0mg/m in the yellow phosphoric tail gas behind the absorption cleaning of spraying absorption tower
3
Embodiment 2: get in the hydrochloric acid that the 37.6g cupric oxide is dissolved in 5L 20%, the 50.0g palladium bichloride is dissolved in the 55L water, and both are mixed, and filters, and discards filter residue, and gained filtrate is the mixed catalytic agent solution, and is standby.
Will be through being that main component, hydrogen sulfide content are 100～850mg/m with the carbon monoxide after the dust removal process
3Closed calcium carbide furnace tail gas with 10m
3/ h flow velocity feeds from the venturi scrubber bottom, contacts with the mixed catalytic agent solution is reverse, reacts under 32 ℃.The mixed catalytic agent solution that has absorbed hydrogen sulfide is sent into and is stirred in the bubbling reactor at 32 ℃ down with the blowback venturi scrubber is recycling again behind the air catalytic oxidation of 8L/min flow velocity.After measured, hydrogen sulfide content is 0mg/m in the closed calcium carbide furnace tail gas after venturi scrubber purifies
3, and absorb operation continuously through 50h, after the purification of discharging by bubbling absorption column in the gas hydrogen sulfide content still be 0mg/m
3
Embodiment 3: get the 23.3g copper nitrate and be dissolved in the 0.9L water, 0.6g palladium simple substance is dissolved in the nitric acid of 0.1L 20%, and above-mentioned two kinds of solution are mixed, and filters, and obtains the mixed catalytic agent solution.It is standby in the bubble absorbing tower that the mixed catalytic agent solution is packed into.
Regulate sulfide hydrogen 1450mg/m
3Simulation gas in oxygen content, the mol ratio that makes oxygen and hydrogen sulfide is greater than 2, to simulate gas then and feed bubble absorbing tower with the speed of 20L/min and react with the mixed catalytic agent solution at 20 ℃, hydrogen sulfide content remains 0mg/m in the tail gas after the purification in 9h
3
Claims (6)
1. liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method is characterized in that containing following processing step:
1. preparation of catalysts:
Get cupric and palladium-containing catalyst respectively stirring and dissolving in concentration is 0%～30% acid, mix, filter the mixed catalytic agent solution, wherein the palladium mass concentration is 0.05～50g/L, copper mass concentration is 0.1～150g/L;
2. hydrogen sulfide absorption and the oxidation catalyzing, oxidizing and purifying technology of carrying out step by step:
Sulfide hydrogen tail gas is reacted with the mixed catalytic agent solution of being prepared that contains palladium, copper in 4～100 ℃ in the absorption tower, become the palladium simple substance of indissoluble after part palladium ion and the hydrogen sulfide haptoreaction, enter liquid phase and hydrogen sulfide is oxidized to elemental sulfur; Meanwhile, partial vulcanization hydrogen and copper ion generate the copper sulfide of indissoluble, and the generation of palladium simple substance and copper sulfide can make catalyst solution become black suspension,
The mixed catalytic agent solution that will absorb hydrogen sulfide is then sent into oxidizing tower and is carried out oxidation, blasts air or oxygen in oxidizing tower, and the hydrogen sulfide that is absorbed in the solution is existed with dissolved state, becomes elemental sulfur with oxygen generation oxidation reaction; Palladium simple substance then is oxidized to the divalence palladium ion; Copper sulfide is converted into copper sulphate, and the mixed solution after the oxidation is discharged from oxidizing tower, sends into the absorption tower again and recycles.
2. a kind of liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method according to claim 1 is characterized in that: the acid of step described in 1. is hydrochloric acid, nitric acid or sulfuric acid, and described copper and palladium-containing catalyst are palladium bichloride or copper chloride.
3. a kind of liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method according to claim 1, it is characterized in that: the absorption tower of step described in 2. is turbulent contact absorber, tray absorption columns, bubble absorbing tower, venturi scrubber or stirs bubble absorbing tower that described oxidizing tower is packed column reactor, rapid ball absorption reactor thermally, plate-type reactor, bubbling reactor, falling film reactor or stirs bubbling reactor.
4. liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method is characterized in that containing following processing step:
1. preparation of catalysts: get cupric and palladium-containing catalyst respectively stirring and dissolving in concentration is 0%～30% acid, mix, filter the mixed catalytic agent solution, wherein the palladium mass concentration is 0.05～50g/L, copper mass concentration is 0.1～150g/L;
2. oxygenating-catalyzing, oxidizing and purifying technology: enter that the mol ratio of oxygen and hydrogen sulfide should if oxygen content is on the low side, adopt air or oxygen to mix with sulfide hydrogen tail gas greater than 2 in the sulfide hydrogen tail gas of catalyst oxidation reactor, the mol ratio that makes oxygen and hydrogen sulfide is greater than 2,
The above-mentioned sulfide hydrogen tail gas that regulates oxygen content and the mixed catalytic agent solution that contains palladium, copper that is mixed with are reacted in 4～100 ℃ in reactor, and hydrogen sulfide is oxidized to elemental sulfur and enters liquid phase in solution.
5. a kind of liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method according to claim 4 is characterized in that: the acid of step described in 1. is hydrochloric acid, nitric acid or sulfuric acid, and described copper and palladium-containing catalyst are palladium bichloride or copper chloride.
6. a kind of liquid phase catalytic oxidation purification of sulphur-containing hydrogen tail gas method according to claim 4 is characterized in that: the reactor of step described in 2. is packed column reactor, rapid ball absorption reactor thermally, plate-type reactor, bubbling reactor, falling film reactor or stirs bubbling reactor.
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| CN102631832A (en) * | 2012-03-21 | 2012-08-15 | 浙江丽晶化学有限公司 | Slight hydrogen sulfide removal device and method in acidic gas |
| CN103111169A (en) * | 2013-03-14 | 2013-05-22 | 济钢集团有限公司 | Gas desulfurization method and automatically controlled desulfurization device |
| CN109381985A (en) * | 2018-11-21 | 2019-02-26 | 北京石油化工学院 | A kind of purifying treatment method of natural gas |
| CN109603434A (en) * | 2018-12-12 | 2019-04-12 | 中国成达工程有限公司 | A kind of purification process technique and device of yellow phosphoric tail gas |
| CN111362229A (en) * | 2020-04-24 | 2020-07-03 | 西南化工研究设计院有限公司 | Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas |
| CN114684793A (en) * | 2022-05-20 | 2022-07-01 | 黔南民族师范学院 | Method for preparing elemental sulfur from titanium gypsum, titanium white waste acid and yellow phosphorus tail gas |
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| CN102631832A (en) * | 2012-03-21 | 2012-08-15 | 浙江丽晶化学有限公司 | Slight hydrogen sulfide removal device and method in acidic gas |
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| CN111362229A (en) * | 2020-04-24 | 2020-07-03 | 西南化工研究设计院有限公司 | Method for preparing hydrogen for fuel cell from yellow phosphorus tail gas |
| CN114684793A (en) * | 2022-05-20 | 2022-07-01 | 黔南民族师范学院 | Method for preparing elemental sulfur from titanium gypsum, titanium white waste acid and yellow phosphorus tail gas |
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