CN101318099B - Process for removing organic sulfur in low-temperature condition - Google Patents
Process for removing organic sulfur in low-temperature condition Download PDFInfo
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- CN101318099B CN101318099B CN2008100586686A CN200810058668A CN101318099B CN 101318099 B CN101318099 B CN 101318099B CN 2008100586686 A CN2008100586686 A CN 2008100586686A CN 200810058668 A CN200810058668 A CN 200810058668A CN 101318099 B CN101318099 B CN 101318099B
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- organic sulfur
- absorption liquid
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- sulphur
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 19
- 125000001741 organic sulfur group Chemical group 0.000 title claims description 48
- 239000007788 liquid Substances 0.000 claims abstract description 62
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005864 Sulphur Substances 0.000 claims abstract description 36
- 230000008929 regeneration Effects 0.000 claims abstract description 33
- 238000011069 regeneration method Methods 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002912 waste gas Substances 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 230000004927 fusion Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 53
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000008439 repair process Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- 230000003009 desulfurizing effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical class OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- -1 methanation Chemical compound 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 108020001778 catalytic domains Proteins 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000003337 fertilizer Substances 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
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- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
Abstract
The invention provides a technological method for desorbing organic sulphur at low temperatures; wherein, the organic sulphur is hydrolyzed into H2 and CO2 and H2S is absorbed after being cooled by waste gas and absorbed by absorbing fluid for organic sulphur; the absorbing fluid for organic sulphur is regenerated by aerating gaseous CO, and the regenerated H2S is then aerated into H2S absorbing liquid so as to regenerate the H2S absorbing liquid in the air-blow method; the sulfur product can be obtained after the sulfur generated in the regeneration process goes through working procedures of centrifugal separation, washing, dehydration and fusion. The invention has the advantages that sulphur in the high-concentration organic sulphur waste gas can be effectively desorbed, with an absorbing and purifying efficiency more than 95 percent; meanwhile, the used catalysts, namely, the absorbing liquid for organic sulphur and H2S absorbing liquid are guaranteed for regeneration; the simple substance of sulphur absorbed by the catalyst can be effectively recycled at the same time of regeneration. The invention has simple process, small investment, low running cost and simple operation, requires low labor intensity, and does not pollute the environment.
Description
Technical field
The present invention relates to remove under a kind of cryogenic conditions the process of organic sulfur in cos, hydrogen sulfide and the carbon disulfide.Specifically be a kind of low temperature hydrolysis cos and carbon disulfide of being used for, and will produce or unstripped gas in the process of hydrogen sulfide stripping.
Background technology
Cos (COS) and hydrogen sulfide (H
2S) extensively being present in coal, oil, natural gas is unstripped gas, in the waste gas that carries out being produced when synthetic ammonia, methanol production and viscose rayon are produced.The existence of sulfide not only pollutes the environment, but also the meeting corrosion pipeline can cause the catalyst poisoning inactivation in the subsequent production process, thereby influence the quality of postorder chemical products.Especially in the commercial production of synthetic ammonia, they are the principal elements that make catalysqt deactivations such as methyl alcohol, methanation, ammonia synthesis.In recent years, along with the sustainable growth of economy, make energy supply and demand contradiction become increasingly conspicuous, the particularly rise of oil price causes some chemical fertilizer factories and the pure factory of couplet to have to adopt colm and sulphur coal gas making at a low price, and sulfur content increases in the unstripped gas thereby make.H
2S and COS are typical sulfide in these unstripped gas.Because COS is neutrality or faintly acid, its chemical property torpescence, the method that very difficult usefulness removes hydrogen sulfide removes it, brings new challenge therefore for existing desulfur technology.
Traditional fine desulfurizing technology mainly contains two kinds: a kind of is hydrogenation method, promptly at high temperature adopts cobaltmolybdate catalyst series connection zinc oxide, with COS and CS
2Change into H Deng organic sulfur
2S utilizes zinc oxide with H again
2S removes.This method process route is complicated, operating condition is harsh, energy consumption is big, investment cost is high, is difficult to promote in China.
Another kind is the organic sulfur hydrolyst of all developing both at home and abroad in recent years.Its course of reaction is: COS+H
2O → H
2S+CO
2, CS
2+ 2H
2O → 2H
2S+CO
2, under the effect of hydrolyst, utilize water vapour in the unstripped gas with COS and CS
2Be converted into the ripe H of treatment process
2Carry out subsequent treatment behind the S.
Relevant organic sulfur catalyzing hydrolysis Study on Technology mainly concentrates on middle low temperature both at home and abroad at present, discloses smart removal of organic sulfur of a kind of normal temperature and inorganic sulfur new technology like Chinese patent CN1067828A, is about to contain 0～30ppmH
2S and COS and CS
2Process gas earlier through one-level modified activated carbon or iron oxide desulfurization, absorb sulphur through the ordinary-temp hydrolysis catalyst 30～120 ℃ of following hydrolysis again, and then, make total sulfur＜0.1ppm in the smart processed gas through desulfurization under second level modified activated carbon or the iron oxide normal temperature.
Chinese patent CN1081424A discloses a kind of constant temperature fine desulfurizing production technology, is about to contain the H of 0～30ppm
2S+COS+CS
2Process gas,---water or steam heater are heated to 40～80 ℃, and---hydrolyst---cooling tower is cooled to normal temperature---desulfurizing agent sweetening process makes total sulfur＜0.1ppm in the smart processed gas through desulfurizing agent.
Chinese patent CN1130151A discloses a kind of inversion absorption type constant temperature fine desulfurizing technology, and it is with containing 0～30ppmH
2S+COS+CS
2Synthetic ammonia or petrochemical materials gas, the sweetening process of the desulfurizing agent through taking off inorganic sulfur and the desulfurizing agent of inversion absorption type removal of organic sulfur, at 20～60 ℃, smart desulfurization under normal pressure～10MPa pressure condition, total sulfur (H in the gas after the desulfurization
2S+COS+CS
2)＜0.1ppm.
Chinese patent CN1226873 discloses a kind of method that reclaims said compound except that hydrogen sulfide, sulfur dioxide, carbonyl sulfide and/or carbon disulfide sulfide contained in the desulfuration factory residual gas and with the form of sulphur.The process route of this method is with containing H with formation behind the residual gas catalyzing hydrolysis
2S and SO
2And do not contain COS and CS
2Water decomposition gas, after the cooling, the gas of this hydrolysis one of is introduced in parallel two Crouse's catalytic domains installing, another catalytic domain is used for regeneration, then cooling.The operating temperature of this technology is higher, is not easy to removing of organic sulfur under the cryogenic conditions.
Chinese patent CN1147010A discloses a kind of artificial coal gas constant temperature fine desulfurizing technology; It is characteristics high as organic sulfur content in the artificial coal gas of raw material (combustion) gas to industries such as electronics, chemical industry, metallurgy, complex shape; Adopt the multiple catalyst and the desulfurizing agent of Hubei Prov. Chemical Research Inst development and production; Under normal temperature or normal temperature～150 ℃, normal pressure～3.0MPa condition, with COS＜250mg/Nm in the coal gas
3, CS
2＜120mg/Nm
3, RSH＜8mg/Nm
3, thiophene＜10mg/Nm
3Be removed to total sulfur (with H
2The S meter) content difference≤112mg/Nm
3With≤7mg/Nm
3Two kinds of raw materials (combustion) gas.
Chinese patent CN1218421A discloses a kind of gas cleaning method to sulfide hydrogen or carbonyl sulfide, promptly adopts biological oxidation process to handle the sulfide in the waste gas cleaning solution, thereby obtains elementary sulfur.Elementary sulfur is separated, and treated cleaning solution is looped back in the gas scrubbing step.This method technology is complicated, and adaptability is relatively poor.
Chinese patent CN1323735A discloses the purification method of warm anti-sulphur hydrolysis organic sulfur in a kind of unstripped gas.And warm anti-sulfide hydrolysis in described tower, loading, this catalyst H in unstripped gas are set before unstripped gas decarburization and constant temperature fine desulfurizing with the middle temperature hydrolysis tower of anti-sulphur
2S50～10000ppm and COS20～1500ppm, O
2Content 0～0.6%, pressure normal pressure～30Mpa directly uses under 85～250 ℃ of conditions of temperature or after sulfuration, uses, and with organic sulfur in its hydrolytic purification gas, gas goes the decarburization of postorder operation then.
The technology of the organic sulfide removal that above-mentioned patent is mentioned only is applicable to the organic sulfur of low concentration mostly, and the solid catalyst of use all can not be regenerated, and organic sulfur transforms the H that generates
2S is prone to absorbed by solid catalyst, can not reclaim sulphur simple substance wherein.Particularly in current industrial chemicals shortage, under the situation of rise in oil price, sulphur is the important chemical raw materials for production, and the sulphur resource that reclaims in the sulphur-containing exhaust gas has important practical significance.
Summary of the invention
To the problem that removes of sulphur in (＞80%) the organic sulphur waste gas under the present high concentration CO atmosphere, the present invention provides that a kind of cost is low, efficient is high and takes into account the process of organic sulfur removal under the cryogenic conditions of recovery of regeneration and sulphur of catalyst.
The present invention accomplishes through following technical proposal: a kind of process of removing organic sulfur in low-temperature condition is characterized in that through the following step:
A, the waste gas that will contain organic sulfur are cooled to 20～100 ℃, are 100～500h by gas liquid ratio
-1Amount, waste gas is fed in the organic sulfur absorption liquid of following volume ratio, and makes it saturated, so that tempreture organic sulphur hydrolysis is become H
2S and CO
2, and absorb H
2S:
1mol/L hydroxide 0.01～10%
Ethanol 40～60%
Water surplus;
B, be 100～500h by gas liquid ratio
-1Amount, CO gas is fed in the organic sulfur absorption liquid of A step after saturated, carry out the regeneration of organic sulfur absorption liquid, the temperature of regeneration is 80～100 ℃, the recovery time is 5～8 hours, produces H in the time of regeneration
2S;
C, the H that B step regenerative process is produced
2S gas is 100～500h by gas liquid ratio
-1Amount, feed H
2In the S absorption liquid, absorb H
2S is to saturated, with H
2The S absorption liquid takes out and filters;
D, in the filtered fluid of C step, be 100～500h by gas liquid ratio
-1The amount bubbling air, carry out H with air Bubbling method of the prior art
2The regeneration of S absorption liquid, absorption liquid pH value to 8～9 after the regeneration of adjustment drum oxygen; The sulphur that regenerative process produces is through centrifugation, washing, dehydration, the fusion operation of prior art, get final product sulfur product.
Oxide in the organic sulfur absorption liquid of said A step is KOH, K
2CO
3, NaOH, Na
2CO
3, NaHCO
3, NH
4Among the OH one or more.
Hexahydropyridine, ethanol in the organic sulfur absorption liquid of said A step are chemical pure solution, and water is distilled water.
The H of said C step
2The S absorption liquid and the preparation as follows: at Fe
3+Content is in the solution of 0.03～0.06mol/L, is 10～50% amount by the mass ratio of Mn and Fe, adds Mn (NO
3)
2Or Mn (CH
3COO)
2Again by metal cations Fe
3+With the stabilizing agent integral molar quantity than the amount that is 15～50%, add in ethylenediamine tetra-acetic acid (EDTA), sulfosalicylic acid, the citric acid one or more, as the metal ion stabilizing agent; Use Na
2CO
3And NaHCO
3Adjustment pH value of solution value to 8～10 get H
2S GAS ABSORPTION liquid.
The present invention compared with prior art has advantage and effect: adopt such scheme, the sulphur in the ability effective elimination high concentrated organosulfur waste gas reaches more than 95% its absorption cleaning efficient, and can make catalyst system therefor simultaneously is organic sulfur absorption liquid, H
2The S absorption liquid obtains regeneration, can effectively reclaim the sulphur simple substance that absorbs in the catalyst in the time of regeneration, and this is in current industrial chemicals shortage, under the situation of rise in oil price; Can reclaim the sulphur resource in the sulphur-containing exhaust gas, make it to have important practical significance as important chemical raw materials for production---sulphur; Technology of the present invention is simple, small investment, and operating cost is low; Simple to operate, labour intensity is low, and is free from environmental pollution.
Description of drawings
Fig. 1 is a low temperature organic sulfur removal process chart.
Among the figure, 1 is impact flow reactor, and 2 is filter, and 3 is the sulphur foam tank, and 4 is regeneration tank, and 5 is centrifugal separator, and 6 is washer, and 7 is dehydrator, and 8 is sulfur melting kettle, and 9 is condenser, and 10 is cooling tower, and 11 is centrifugal pump, and 12 is air blast.
The specific embodiment
One, absorption liquid preparation:
1, organic sulfur absorption liquid and preparation thereof: with 5ml hexahydropyridine (chemical pure), 50ml ethanol (chemical pure), 1ml concentration is the KOH of 1mol/L and the organic sulfur absorption liquid that distilled water is mixed with 100ml, and is for use.
2, regeneration gas H
2The preparation of S absorption liquid: take by weighing 1.62 gram FeCl
3Mn (NO with 0.72 gram 50%
3)
2(element mol ratio Mn: Fe=0.2), together be dissolved in the 200mL deionized water, fully stirring and dissolving is processed Fe to solution
3+Concentration is the compound ion absorption liquid of 0.05mol/L; Interpolation 2.92 gram EDTA and 2.18 gram sulfosalicylic acids are done stabilizing agent (metal cations Fe
3+With stabilizing agent integral molar quantity ratio be 1: 2); Use NaCO
3And NaHCO
3The control pH value of solution is 9, and is for use.
Two, low temperature organic sulfur removal processing step is:
1, sulphur-containing exhaust gas (after wherein COS＜3000ppm=is cooled to 40 ℃, is equipped with in the reactor of the above-mentioned organic sulfur absorption liquid of 50ml with the gas flow feeding of 125ml/min, reacted 12 hours, make the organic sulfur absorption liquid saturated, so that tempreture organic sulphur hydrolysis is become H
2S and CO
2, and absorb H
2S;
2, be 150h by gas liquid ratio
-1Amount, regeneration gas CO is fed in the saturated organic sulfur absorption liquid of 1 step, under 80 ℃ of temperature, regenerated 6 hours, behind the organic sulfur regeneration of absorption solution under this condition, its purification efficiency is 100% still, produces H in the time of regeneration
2S;
3, the H that the regeneration of 2 steps is produced
2S presses the gas flow of 200mL/min, feeds the above-mentioned H of 50ml is housed
2In the impact flow reactor of S absorption liquid, wherein, the H that regeneration produces
2Hydrogen sulfide content in the S waste gas is 750mg/m
3, oxygen content is 10% (volume ratio), is under 60～70 ℃ in reaction temperature, H
2The S absorption liquid has reached 99% in the purification efficiency in the initial moment, is reflected in 500 minutes, and absorption cleaning efficient is all more than 98%, with H
2The S absorption liquid takes out and filters;
4, be 250h by gas liquid ratio
-1Amount, air is fed in the filtered fluid of 3 steps, adopt air Bubbling method of the prior art to carry out H
2The regeneration of S absorption liquid, the absorption liquid pH value to 8 after the regeneration of adjustment drum oxygen continues to react to purification efficiency and reaches 96.5%; The sulphur that regenerative process produces is through centrifugation, washing, dehydration, the fusion operation of prior art, get final product sulfur product.
Embodiment 2
One, absorption liquid preparation:
1, organic sulfur absorption liquid: with the hexahydropyridine of 10ml, the ethanol of 50ml, the concentration of 1ml is the Na of 1mol/L
2CO
3Be mixed with the organic sulfur absorption liquid of 100ml with distilled water, for use.
2, regeneration gas H
2S absorption liquid: take by weighing 1.62 gram FeCl
3With 0.87 gram Mn (CH
3COO)
2Be dissolved in the 200mL deionized water that (element mol ratio Mn: Fe=0.5), fully stirring and dissolving is processed Fe
3+Concentration is the solution of 0.05mol/L; Add 4.36 gram sulfosalicylic acids and 5.84 gram EDTA used as stabilizers (metal cations Fe
3+With stabilizing agent integral molar quantity ratio be 1: 4); Use NaCO
3And NaHCO
3The control pH value of solution is 10.
Two, low temperature organic sulfur removal processing step is:
1, is after the waste gas of COS＜3000ppm is cooled to 20 ℃ with sulphur-containing exhaust gas, feeds with the gas flow of 50ml/min and be equipped with in the reactor of the above-mentioned organic sulfur absorption liquid of 20ml, reacted 24 hours, make the organic sulfur absorption liquid saturated, so that tempreture organic sulphur hydrolysis is become H
2S and CO
2, and absorb H
2S;
2, regeneration gas CO (＞99%) is fed in the saturated organic sulfur absorption liquid of 1 step with the flow of 50ml/min, under 80 ℃ of temperature, regenerated 6 hours, behind the organic sulfur regeneration of absorption solution under this condition, its purification efficiency is 100% still, produces H in the time of regeneration
2S;
3, the H that the regeneration of 2 steps is produced
2S feeds 50mlH is housed with the gas flow of 300mL/min
2In the impact flow reactor of S absorption liquid, wherein, H
2Hydrogen sulfide content in the S waste gas is 1000mg/m
3, oxygen content is 15%, under 60 ℃ of temperature, after sustained response to treatment effeciency drops to 70%, absorption liquid is taken out filtration;
4, be 350h by gas liquid ratio
-1Amount, air is blasted in the filtered fluid of 3 steps, filtrating being roused oxygen regeneration, the absorption liquid pH value to 9 after the regeneration of adjustment drum oxygen continues to react to purification efficiency and reaches 96.5%; The sulphur that regenerative process produces is through centrifugation, washing, dehydration, the fusion operation of prior art, get final product sulfur product.。
Table 1 is the COS hydrolysis conversion of variable concentrations hexahydropyridine.
Table 2 is the COS hydrolysis conversion behind the different purge times.
The COS hydrolysis conversion of table 1 variable concentrations hexahydropyridine
COS hydrolysis conversion behind the different purge times of table 2
Claims (4)
1. the process of a removing organic sulfur in low-temperature condition is characterized in that through the following step:
A, the waste gas that will contain organic sulfur are cooled to 20～100 ℃, are 100～500h by gas liquid ratio
-1Amount, waste gas is fed in the organic sulfur absorption liquid of following volume ratio, and makes it saturated, so that tempreture organic sulphur hydrolysis is become H
2S and CO
2, and absorb H
2S:
B, be 100～500h by gas liquid ratio
-1Amount, CO gas is fed in the organic sulfur absorption liquid of A step after saturated, carry out the regeneration of organic sulfur absorption liquid, the temperature of regeneration is 80～100 ℃, the recovery time is 5～8 hours, produces H in the time of regeneration
2S;
C, the H that B step regenerative process is produced
2S gas is 100～500h by gas liquid ratio
-1Amount, feed H
2In the S absorption liquid, absorb H
2S is to saturated, with H
2The S absorption liquid takes out and filters;
D, in the filtered fluid of C step, be 100～500h by gas liquid ratio
-1The amount bubbling air, carry out H with the air Bubbling method
2The regeneration of S absorption liquid, absorption liquid pH value to 8～9 after the regeneration of adjustment bubbling; The sulphur that regenerative process produces is through centrifugation, washing, dehydration, fusion operation, get final product sulfur product.
2. the process of removing organic sulfur in low-temperature condition according to claim 1 is characterized in that the hydroxide in the organic sulfur absorption liquid of said A step is KOH, NaOH, NH
4Among the OH one or more.
3. the process of removing organic sulfur in low-temperature condition according to claim 1 is characterized in that hexahydropyridine, the ethanol in the organic sulfur absorption liquid of said A step is chemical pure solution, and water is distilled water.
4. the process of removing organic sulfur in low-temperature condition according to claim 1 is characterized in that the H of said C step
2The S absorption liquid and the preparation as follows: at Fe
3+Content is in the solution of 0.03～0.06mol/L, is 10～50% amount by the mass ratio of Mn and Fe, adds Mn (NO
3)
2Or Mn (CH
3COO)
2Again by metal cations Fe
3+With the stabilizing agent integral molar quantity than the amount that is 15～50%, add in edta edta, sulfosalicylic acid, the citric acid one or more, as the metal ion stabilizing agent; Use Na
2CO
3And NaHCO
3Adjustment pH value of solution value to 8～10 get H
2S GAS ABSORPTION liquid.
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| EA202192874A1 (en) | 2013-03-14 | 2022-01-19 | Стамикарбон Б.В. Эктин Андер Те Нейм Оф Мт Инновейшн Сентр | METHOD TO REMOVE COS AND CS2 |
| CN104629700B (en) * | 2015-02-03 | 2018-05-01 | 成都理工大学 | A kind of sulfur elimination for being used to produce water oil well and water-producing gas well |
| CN104910970A (en) * | 2015-05-22 | 2015-09-16 | 张玲 | Series-process coal gas desulfurization process method and desulfurization device therefor |
| EP3331634B8 (en) * | 2015-08-06 | 2023-06-21 | Fluor Technologies Corporation | Systems and methods for improved sulfur recovery from claus process tail gas |
| CN110835556A (en) * | 2019-11-29 | 2020-02-25 | 中冶南方都市环保工程技术股份有限公司 | Blast furnace gas wet desulphurization system and method |
| CN112263894A (en) * | 2020-11-26 | 2021-01-26 | 西南石油大学 | Ionic liquid desulfurization method and device for sulfur-containing gas |
| CN114191929B (en) * | 2021-12-24 | 2022-12-06 | 常州化工设计院有限公司 | Chemical tail gas treatment process |
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| CN1307498A (en) * | 1998-06-29 | 2001-08-08 | 巴斯福股份公司 | Method for removing acid gas components from gases |
| CN101091869A (en) * | 2007-04-06 | 2007-12-26 | 昆明理工大学 | Method for cleansing exhaust gas of sulfureted hydrogen in low concentration |
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| CN101091869A (en) * | 2007-04-06 | 2007-12-26 | 昆明理工大学 | Method for cleansing exhaust gas of sulfureted hydrogen in low concentration |
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