CN103691289B - The processing method of molten sulfur pond tail gas in a kind of claus process - Google Patents
The processing method of molten sulfur pond tail gas in a kind of claus process Download PDFInfo
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- CN103691289B CN103691289B CN201410026037.1A CN201410026037A CN103691289B CN 103691289 B CN103691289 B CN 103691289B CN 201410026037 A CN201410026037 A CN 201410026037A CN 103691289 B CN103691289 B CN 103691289B
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- subsider
- tail gas
- molten sulfur
- sulphur
- desulfurizing agent
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 67
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 38
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 29
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 15
- 230000008929 regeneration Effects 0.000 claims abstract description 15
- 238000011069 regeneration method Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010926 purge Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 230000001172 regenerating effect Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 116
- 229910052742 iron Inorganic materials 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000002738 chelating agent Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 229910001447 ferric ion Inorganic materials 0.000 claims description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- STNSYZSNIYTNMI-UHFFFAOYSA-N azane;[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound N.OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O STNSYZSNIYTNMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003899 bactericide agent Substances 0.000 claims description 5
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 5
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 5
- 229940111695 potassium tartrate Drugs 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 claims description 5
- -1 DTPMPA Chemical compound 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001472 potassium tartrate Substances 0.000 claims description 4
- 235000011005 potassium tartrates Nutrition 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 229940032912 zephiran Drugs 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000003500 flue dust Substances 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 238000010790 dilution Methods 0.000 description 12
- 239000012895 dilution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 5
- 235000018553 tannin Nutrition 0.000 description 5
- 229920001864 tannin Polymers 0.000 description 5
- 239000001648 tannin Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 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 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- BWNMWDJZWBEKKJ-UHFFFAOYSA-M benzyl-docosyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 BWNMWDJZWBEKKJ-UHFFFAOYSA-M 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 208000029039 cyanide poisoning Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical class Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
Abstract
The invention discloses the processing method of molten sulfur pond tail gas in a kind of claus process, air purges the molten sulfur pond of Cross unit, molten sulfur pond tail gas mixing air enters absorption supergravity reactor, and the desulfurization agent with coming from subsider, removes the evacuate air of hydrogen sulfide; Reduction-state desulfurizing agent containing sulphur realizes desulfurizer regeneration under the effect of purging air; Desulfurizing agent blowback subsider after regeneration, sulphur is deposited to rapidly bottom subsider and forms sulphur slurry; Sulphur slurry forms solid sulfur, filtrate blowback subsider, and the regenerative sulfur binding liquid pump in subsider enters to absorb supergravity reactor, enter next circulation, the present invention makes tail gas qualified discharge, and the Claus tail gases of any tolerance can process, there is no tail gas incinerator, decrease the discharge of flue dust in air; Handling rate is high, and mass transfer intensity is high, and equipment volume is little, and floor space is few; Decrease sulphur loss; Security performance is high, environmental friendliness, does not have the three wastes to produce; Stable operation, reliable.
Description
Technical field:
The present invention relates to a kind of processing method of tail gas, particularly relate to the processing method of molten sulfur pond tail gas in a kind of claus process.
Background technology:
Current domestic recovery technology of sulfur, the overwhelming majority adopts thermal transition+secondary low-temperature catalyzed conversion claus process, and the advantage technique of claus process is simple, and be applicable to maximize and the device realizing high automation and produce, device efficiency is high.But due to the restriction by chemical balance under reaction temperature and reversible reaction, sulfur recovery rate is the highest also can only reach 96-97%, still has the sulphur of 3-4% with SO
2form enter air, after increase tail gas hydrogenation treating apparatus, sulfur recovery rate can reach 99.7%.Still be difficult to guarantee satisfied new discharging standards.In addition in actual production process, do not reach initial designs ability owing to producing load, cause the flow of tail gas and the larger fluctuation of composition to change, not only cause the rising of cost, also result in exceeding standard of tail gas sulfur content.
The H comprised in molten sulfur pond in claus process
2s gas, progressively discharges in Molten sulphur cooling procedure, is discharged in air, is to cause one of reason that Claus tail gases sulfur content exceeds standard.Claus tail gases has large-minded, that hydrogen sulfide content is little feature, and conventional treatment process not easily reaches new discharging standards.
Goal of the invention:
The object of the invention is to overcome the deficiency of prior art and molten sulfur pond exhaust gas treating method in a kind of claus process is provided, making tail gas qualified discharge.Vent gas treatment rate of the present invention is high, and mass transfer intensity is high, and equipment volume is little, and floor space is few; Decrease sulphur loss; Security performance is high, environmental friendliness, does not have the three wastes to produce; Stable operation, reliable.
Object of the present invention can be reached by following measure: the processing method of molten sulfur pond tail gas in a kind of claus process, it is characterized in that it is under super gravity field, the method using the molten sulfur pond tail gas of novel chelated iron liquid phase oxidation to claus process device to process, comprises the steps:
, desulfurizing agent is pumped in subsider;
, air purges the molten sulfur pond of Cross unit, molten sulfur pond tail gas mixing air enters absorption supergravity reactor, and contact at the wire packing of rotor with the desulfurizing agent come from subsider, hydrogen sulfide is oxidized to elemental sulfur, Fe in desulfurizing agent
3+become Fe
2+, the gas removing hydrogen sulfide is emptying through supergravity reactor built-in filter;
, reduction-state desulfurizing agent containing sulphur is absorbing Fe under the effect at purging air in supergravity reactor
2+become Fe
3+, realize desulfurizer regeneration; Desulfurizing agent blowback subsider after regeneration, sulphur is deposited to rapidly bottom subsider and forms sulphur slurry;
, sulphur slurry to be pumped into vacuum filter from subsider outlet at bottom and to form solid sulfur, filtrate blowback subsider;
, regenerative sulfur binding liquid pump in subsider enters to absorb supergravity reactor, enters next circulation.
In order to realize object of the present invention further, the described desulfurizing agent containing chelates ferric ions contains following component: chelated iron catalyst, chelating agent, surfactant, chelating agent protective agent, bactericide, alkali lye, water, chelated iron catalyst concn scope: 350 ~ 10000ppm in desulfurizing agent; Chelating agent concentrations scope: 400 ~ 15000ppm; Surfactant concentration ranges: 1 ~ 1000ppm; Concentration of sterilant scope: 1 ~ 1000ppm; Chelating agent protective agent concentration range: 10 ~ 100000ppm; Alkali concn scope: 0.1 ~ 1mol/L; The volume ratio of chelating agent/chelated iron catalyst is 1 ~ 5; PH value of solution is 8 ~ 10.
In order to realize object of the present invention further, described chelated iron catalyst is the mixture of chelated iron, alcohol and water, and the mol ratio of alcohol/chelating Fe is 0.1 ~ 5, and in solution, the content of iron is 350 ~ 10000ppm.
In order to realize object of the present invention further, described chelated iron is HEDP, EDTMPS, DTPMPA, EDDHA, STPP, NTA, Na
3nTA, EDTA, HEDTA, Na
3hEDTA, Na
4at least one in EDTA, gluconic acid sodium salt, sodium metasilicate, potassium tartrate, natrium citricum and soluble ferric iron salt FeCl
3, Fe
2(SO
4)
3, Fe (NO
3)
3, FeNH
4(SO
4) in the chelate of at least one, the mol ratio of chelate ligand/Fe is 1 ~ 10; Alcohol is at least one in micromolecular secondary alcohol, the tertiary alcohol, reproducibility alcohol, as the tert-butyl alcohol, isopropyl alcohol, isoamyl alcohol, glucitol, sorbierite, sweet mellow wine etc.;
In order to realize object of the present invention further, described chelating agent is HEDP, EDTMPS, DTPMPA, EDDHA, STPP, NTA, Na
3nTA, EDTA, HEDTA, Na
3hEDTA, Na
4at least one in EDTA, gluconic acid sodium salt, sodium metasilicate, potassium tartrate, natrium citricum.
In order to realize object of the present invention further, described surfactant to be carbon number be 5 ~ 20 straight chain alcohol or polyalcohol at least one.Mainly C
5h
11oH, C
5h
12o
2, C
6h
13oH, C
6h
14o
2, C
6h
12o
2, C
8h
11oH, C
12h
25one or more mixtures of OH;
In order to realize object of the present invention further, described bactericide is at least one in wide-spectrum bactericide zephiran, as docosyl dimethyl benzyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, two dodecyl dimethyl ammonium chlorides etc.;
In order to realize object of the present invention further, described chelating agent protective agent is at least one of KI, KCl, KBr; Can produce hydroxyl radical free radical in hydrogen sulfide stripping process, destroy the stable of chelating agent, the protectant effect of chelating agent is the hydroxyl radical free radical produced in Absorption Desulfurization process, makes chelating agent be in stable state all the time.
In order to realize object of the present invention further, described alkali lye is KOH, NaOH; In doctor solution, add alkali lye, make doctor solution system keep pH to be stabilized between 8 ~ 10.
Air bubbling purging process is adopted for molten sulfur pond tail gas, utilizes the bleed mode of pressurization of roots blower to enter absorption supergravity reactor.In the gas treatment equipment of molten sulfur pond, purge the air capacity making to enter in absorption supergravity reactor owing to using air enough large, do not need separately to establish regeneration reactor, absorption and regeneration are all carried out in absorption reactor thermally, arrange subsider.
The present invention can produce following good effect compared with the prior art: the present invention is under a kind of super gravity field, and use the method for novel chelated iron liquid phase oxidation process claus process molten sulfur pond tail gas, it is by following advantage:
, any tolerance tail gas can process, there is no tail gas incinerator, decrease the discharge of flue dust in air;
, vent gas treatment rate is high, after process, in tail gas, hydrogen sulfide content is less than 1ppm, reaches national requirements for environmental protection;
, mass transfer intensity is high, equipment volume is little, and floor space is few;
, doctor solution in the reactor the time of staying short, decrease sulphur loss;
, security performance is high, do not use any poisonous chemical substance, in sulfur product, there is no hydrogen sulfide gas, avoid the danger that operating personnel are poisoning;
, environmental friendliness, do not have the three wastes to produce;
, open, stop easily, steady state operation can be reached within a few minutes;
, reliable, device does not block, can long-term operation.
Accompanying drawing illustrates:
Fig. 1 is process chart of the present invention;
Detailed description of the invention: the specific embodiment of the present invention is elaborated below in conjunction with accompanying drawing:
The preparation of desulfurizing agent:
1, by FeCl
3, NTA, potassium tartrate, the tert-butyl alcohol according to mol ratio be 1:2.5:1:1.5 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 14g/L.Get chelated iron catalyst concentrates 37.5mL, NTA chelating agent concentrate 56.25mL and be diluted to 1500mL, in dilution, total concentration of iron is 350ppm, in dilution, add C
5h
12o
20.15g, KCl0.15g, KOH8.5g make desulfurizing agent;
2, by Fe
2(SO
4)
3, EDTA, HEDTA, natrium citricum, isoamyl alcohol according to mol ratio be 1:2:1.5:1:1:1.5 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 56g/L.Get chelated iron catalyst concentrates 267mL, EDTA and HEDTA chelating agent concentrate 321mL and be diluted to 1500mL, in dilution, total concentration of iron is 10000ppm, in dilution, add C
5h
12o
20.9g, KCl0.6g, KOH8.5g make desulfurizing agent;
3, by Fe (NO
3)
3, HEDP, NTA, gluconic acid sodium salt, glucitol according to mol ratio be 1:1:1:1:1 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 35g/L, get chelated iron catalyst concentrates 21.5mL, Na
4eDTA chelating agent concentrate 33mL is diluted to 1500mL, and in dilution, total concentration of iron is 500ppm, in dilution, add C
5h
12o
20.3g, KCl0.3g, KOH8.5g make desulfurizing agent;
4, by Fe (NO
3)
3, HEDP, DTPMPA, sorbierite, the tert-butyl alcohol according to mol ratio be 1:2:1:0.5:0.5 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 56g/L, get chelated iron catalyst concentrates 27mL, HEDTA chelating agent concentrate 32mL and be diluted to 1500mL, in dilution, total concentration of iron is 1000ppm, in dilution, add C
5h
12o
20.3g, C
12h
25oH0.15g, KBr0.3g, KI0.15g, KOH8.5g make desulfurizing agent;
5, by FeCl
3, Fe
2(SO
4)
3, Fe (NO
3)
3, EDTMPS, DTPMPA, sorbierite according to mol ratio be 1:1:0.5:2:1:1 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 56g/L.Get chelated iron catalyst concentrates 107mL, Na
3hEDTA chelating agent concentrate 210mL is diluted to 1500mL, and in dilution, total concentration of iron is 4000ppm, in dilution, add C
5h
12o
20.5g, C
6h
12o
20.3g, KI0.5g, KOH8.5g make desulfurizing agent;
6, by FeCl
3, Fe (NO
3)
3, STPP, HEDTA, sweet mellow wine, the tert-butyl alcohol according to mol ratio be 1:1:2:1:1:1 ratio mixing, make the chelated iron catalyst concentrates that total concentration of iron is 56g/L.Get chelated iron catalyst concentrates 227mL, EDTA, HEDTA chelating agent concentrate 280mL and be diluted to 1500mL, in dilution, total concentration of iron is 8500ppm, in dilution, add C
5h
12o
20.5g, C
6h
12o
20.3g, C
8h
11oH0.3g, KCl0.3g, KBr0.3g, KI0.15g, KOH8.5g makes desulfurizing agent.
Embodiment: the processing method of a kind of molten sulfur pond vent gas treatment, it comprises the steps:
, the desulfurizing agent of above-mentioned preparation is pumped in subsider;
, with air purge molten sulfur pond, in molten sulfur pond, gas and vapor permeation air enters absorption supergravity reactor through booster fan, contact at the wire packing of rotor with the desulfurizing agent come from subsider, the chelates ferric ions that hydrogen sulfide is desulfurized in agent is oxidized to sulphur, ferric ion is reduced to ferrous ion, and the gas removing hydrogen sulfide is emptying through supergravity reactor built-in filter; ;
, reduction-state desulfurizing agent containing sulphur contacts absorbing the air come with air inlet in supergravity reactor, ferrous ion is oxidized to ferric ion, realizes desulfurizer regeneration; Recycling desulfurizer containing sulphur enters subsider by regeneration liquid pump, and sulphur is deposited to rapidly bottom subsider and forms sulphur slurry;
, sulphur slurry by sulphur stock pump enter vacuum filter formed solid sulfur, in filtrate blowback subsider;
, regenerative sulfur binding liquid in subsider entered by recycle liquid pump and absorbs supergravity reactor and carry out next one and circulate.
Adopt above-mentioned desulfurizing agent, with the claus process molten sulfur pond tail gas of the method process variable concentrations of embodiment 1, result is as shown in table 1:
Table 1 result
| Numbering | Molten sulfur pond concentration of hydrogen sulfide % | Fluid flow m 3/h | Desulfurization/regeneration temperature DEG C | Purified gas hydrogen sulfide content ppm |
| 1 | 0.015 | 3 | 45/45 | 0.0 |
| 2 | 0.032 | 3 | 45/45 | 0.1 |
| 3 | 0.067 | 3 | 45/45 | 0.1 |
| 4 | 0.138 | 3 | 45/45 | 0.0 |
| 5 | 0.179 | 3 | 45/45 | 0.1 |
| 6 | 0.230 | 3 | 45/45 | 0.0 |
Theoretically, tannin process, modified ADA method, PDS method, OR-GREEN method, FD method, LO-CAT method are all applicable to the present invention, but tannin process, modified ADA method, PDS method, equipment needed thereby are many, alkali consumption is large in complex operation, course of reaction, investment is large; FD method sulfosalicylic acid Complexing Iron used is catalyst, and the recovery time grows and catalyst is easily degraded, and technology investment is large; PDS method has the danger of hydrogen cyanide poisoning and alkali consumption is large; Although OR-GREEN method and the technological process of LO-CAT method are simply, the catalyst used is unstable, easily degrades, and increases investment cost.
Below for process concentration of hydrogen sulfide be the molten sulfur pond tail gas of 0.032% time, respectively under super gravity field with tannin process, modified ADA method, FD method, PDS method, LO-CAT method, OR-GREEN method and the inventive method process, result is as shown in table 2.
Table 2 comparing result
| Numbering | Process names | Dominant catalyst | Purified gas hydrogen sulfide content ppm |
| 1 | Tannin process | Tannin extract catalyst | 26 |
| 2 | Modified ADA method | Improvement anthraquinone disulphonate | 32 |
| 3 | FD method | Sulfosalicylic acid Complexing Iron | 49 |
| 4 | PDS method | PDS catalyst | 58 |
| 5 | LO-CAT method | Complexing Iron | 5 |
| 6 | OR-GREEN method | Complexing Iron | 17 |
| 7 | Novel chelating iron processes | Novel chelated iron | 0.1 |
Desulfurizing agent in above-described embodiment can also adopt other existing desulfurizing agents containing chelates ferric ions; above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that the common engineers and technicians in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (4)
1. the processing method of molten sulfur pond tail gas in claus process, is characterized in that it is under super gravity field, and the method using the molten sulfur pond tail gas of chelated iron liquid phase oxidation to claus process device to process, comprises the steps:
(1), the desulfurizing agent containing chelates ferric ions is pumped in subsider; The described desulfurizing agent containing chelates ferric ions contains following component: chelated iron catalyst, chelating agent, surfactant, chelating agent protective agent, bactericide, alkali lye, water, chelated iron catalyst concn scope: 350 ~ 10000ppm in desulfurizing agent; Chelating agent concentrations scope: 400 ~ 15000ppm; Surfactant concentration ranges: 1 ~ 1000ppm; Concentration of sterilant scope: 1 ~ 1000ppm; Chelating agent protective agent concentration range: 10 ~ 100000ppm; Alkali concn scope: 0.1 ~ 1mol/L; The volume ratio of chelating agent/chelated iron catalyst is 1:1 ~ 5:1; PH value of solution is 8 ~ 10; Described chelated iron is HEDP, EDTMPS, DTPMPA, EDDHA, STPP, NTA, Na
3nTA, HEDTA, Na
3hEDTA, Na
4at least one in EDTA, gluconic acid sodium salt, sodium metasilicate, potassium tartrate and soluble ferric iron salt FeCl
3, Fe
2(SO
4)
3, Fe (NO
3)
3, FeNH
4(SO
4) in the chelate of at least one, the mol ratio of chelate ligand/Fe is 1 ~ 10; Alcohol is at least one in micromolecular secondary alcohol, the tertiary alcohol, reproducibility alcohol; Described chelating agent is HEDP, EDTMPS, DTPMPA, EDDHA, STPP, NTA, Na
3nTA, HEDTA, Na
3hEDTA, Na
4at least one in EDTA, gluconic acid sodium salt, sodium metasilicate, potassium tartrate; Described chelated iron catalyst is the mixture of chelated iron, alcohol and water, and the mol ratio of alcohol/chelating Fe is 0.1 ~ 5, and in solution, the content of iron is 350 ~ 10000ppm;
(2), air purges the molten sulfur pond of Cross unit, and molten sulfur pond tail gas mixing air enters absorption supergravity reactor, and contact at the wire packing of rotor with the desulfurizing agent come from subsider, hydrogen sulfide is oxidized to elemental sulfur, Fe in desulfurizing agent
3+become Fe
2+, the gas removing hydrogen sulfide is emptying through supergravity reactor built-in filter;
(3) Fe under the effect of the reduction-state desulfurizing agent, containing sulphur at purging air in absorption supergravity reactor
2+become Fe
3+, realize desulfurizer regeneration; Desulfurizing agent blowback subsider after regeneration, sulphur is deposited to rapidly bottom subsider regeneration reactor and forms sulphur slurry;
(4), sulphur slurry is pumped into vacuum filter from subsider regeneration reactor outlet at bottom and forms solid sulfur, filtrate blowback subsider regeneration reactor;
(5) the regenerative sulfur binding liquid pump, in subsider regeneration reactor enters to absorb supergravity reactor, enters next circulation.
2. the processing method of molten sulfur pond tail gas in a kind of claus process according to claim 1, it is characterized in that described surfactant to be carbon number be 5 ~ 20 straight chain alcohol or polyalcohol at least one.
3. the processing method of molten sulfur pond tail gas in a kind of claus process according to claim 1, is characterized in that described bactericide is zephiran.
4. the processing method of molten sulfur pond tail gas in a kind of claus process according to claim 1, is characterized in that described chelating agent protective agent is at least one of KI, KCl, KBr.
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| CN106731593A (en) * | 2016-08-03 | 2017-05-31 | 石家庄市滕泰环保设备有限公司 | Hydrogen sulfide removal system under aerobic conditions |
| CN107500253A (en) * | 2017-09-08 | 2017-12-22 | 中冶焦耐(大连)工程技术有限公司 | A kind of claus tail-gas clean-up technique |
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| US6610264B1 (en) * | 1992-04-15 | 2003-08-26 | Exxonmobil Oil Corporation | Process and system for desulfurizing a gas stream |
| CN1960940A (en) * | 2004-03-03 | 2007-05-09 | 国际壳牌研究有限公司 | Process for the high recovery efficiency of sulfur from an acid gas stream |
| CN101874968A (en) * | 2009-12-31 | 2010-11-03 | 中北大学 | Iron complex desulfurizer suitable for super-gravity desulfurization |
| CN102151476A (en) * | 2011-03-29 | 2011-08-17 | 武汉国力通化工环保科技有限公司 | Method for removing hydrogen sulfide in gas phase through oxidization under high gravity field |
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| US6610264B1 (en) * | 1992-04-15 | 2003-08-26 | Exxonmobil Oil Corporation | Process and system for desulfurizing a gas stream |
| CN1960940A (en) * | 2004-03-03 | 2007-05-09 | 国际壳牌研究有限公司 | Process for the high recovery efficiency of sulfur from an acid gas stream |
| CN101874968A (en) * | 2009-12-31 | 2010-11-03 | 中北大学 | Iron complex desulfurizer suitable for super-gravity desulfurization |
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