CN108295622A - Composite desulfurizing agent and the method that deep desulfuration is carried out to sulfurous gas - Google Patents
Composite desulfurizing agent and the method that deep desulfuration is carried out to sulfurous gas Download PDFInfo
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- CN108295622A CN108295622A CN201810090325.1A CN201810090325A CN108295622A CN 108295622 A CN108295622 A CN 108295622A CN 201810090325 A CN201810090325 A CN 201810090325A CN 108295622 A CN108295622 A CN 108295622A
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- sulfur
- gas
- desulfurizing agent
- tower
- composite desulfurizing
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- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 70
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 146
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 74
- 239000005864 Sulphur Substances 0.000 claims abstract description 57
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 35
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003457 sulfones Chemical class 0.000 claims abstract description 14
- 150000003462 sulfoxides Chemical group 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims description 79
- 229910052717 sulfur Inorganic materials 0.000 claims description 79
- 239000002904 solvent Substances 0.000 claims description 28
- 125000001741 organic sulfur group Chemical group 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- -1 acrylic ester Chemical class 0.000 claims description 7
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 2
- 229940043237 diethanolamine Drugs 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 239000012744 reinforcing agent Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 abstract 1
- 235000001508 sulfur Nutrition 0.000 description 49
- 230000023556 desulfurization Effects 0.000 description 40
- 230000008569 process Effects 0.000 description 37
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 29
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005504 petroleum refining Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 101000720907 Pseudomonas savastanoi pv. phaseolicola Ornithine carbamoyltransferase 1, anabolic Proteins 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- GCXZDAKFJKCPGK-UHFFFAOYSA-N heptane-1,2-diol Chemical class CCCCCC(O)CO GCXZDAKFJKCPGK-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical class OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 150000003544 thiamines Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
A kind of method that the present invention provides composite desulfurizing agent and carries out deep desulfuration to sulfurous gas, wherein composite desulfurizing agent include：Sulfone or sulfoxide：2~40 parts, organic amine desulfurizer：2~30 parts, the monohydric alcohol or dihydric alcohol of C3~C8：0~20 part, hardening agent：5~90 parts；Wherein, hardening agent is selected from least one of N N-formyl morpholine Ns, N methyl pyrrolidones, polyethylene glycol, triethylene glycol, tetraethylene glycol and propene carbonate.Composite desulfurizing agent provided by the present invention can realize that deep removal, the method for carrying out deep desulfuration to sulfurous gas using above-mentioned composite desulfurizing agent also have the advantages that scrap build expense is low, operation energy consumption is low to hydrogen sulfide simultaneously with organic sulphur components in sulfurous gas.
Description
Technical field
The present invention relates to the deep desulfuration technology of sulfurous gas more particularly to a kind of realize to the hydrogen sulfide in tail gas of sulphur
With organic sulphur components simultaneously deep removal composite desulfurizing agent and to sulfurous gas carry out deep desulfuration method.
Background technology
The regulation effect of sulfur-containing tail gas is an important factor for influencing discharge gas quality all the time, and usual way is pair
Sulfur-containing tail gas is first through desulfurization process to wherein sulfur content down to a certain degree, then by burning the high-altitude in the form of sulfur-containing oxide
Discharge.Sulfur-containing tail gas refers to the sulfurous gas of all kinds of processing unit discharges, and source difference causes tail gas composition to have difference, sulphur meeting
With elemental sulfur, sulfide and organic sulfur (such as COS, CS2Deng) form presence, so tail gas desulfurization needs to take into account all kinds of sulfur-bearings
The property of substance, farthest reduces total sulfur content, to meet gas discharge standard.
In various sulfur-containing tail gas, of greatest concern should be tail gas of sulphur, be the sour gas warp generated from oil refining process
The discharge product of sulphur recovery process, the desulfurization of tail gas of sulphur and the research of post-processing technology also do not stop always.It is net from desulfurization
Change effect to consider, that relatively generally acknowledges and use at present surely belongs to " hydrogenating reduction+hydramine absorb ", that is, well known SCOT and
Super-SCOT techniques enter SCOT reactions to tail gas of sulphur (from sulphur recovery process or other processing units) desulfidation tail gas
Device implements hydrogenating reduction, and under the action of hydrogenation catalyst, sulphur and sulfide in tail gas are transformed into hydrogen sulfide, and Process Gas is through cold
But (being usually chilling) contacts into desulfuration absorbing tower with alcohol amine solvent afterwards, and hydrogen sulfide and partial CO 2 are absorbed, tail gas
In total sulfur can significantly reduce and (300ppm can be less than), enter back into discharged in burning link.
The implementation of new gas discharge standard《GB31570-2015 petroleum refining industry pollutant emission standards》Regulation, burns
SO in being discharged after burning2Control standard from 960mg/Nm3Must not be increased to and is higher than 100mg/Nm3, and some environmental carrying capacities are limited
Developed area be even more that the index is increased to 50mg/Nm3, therefore higher want is proposed to the deep desulfuration of tail gas
It asks.In view of total sulfur content sulphur existing for hydrogen sulfide and the organic sulfur speciation of this kind of sulfur-containing tail gas, had been reported that at present and
The deep desulfuration of implementation includes the treatment technology for two class Sulfurs, it is ensured that SO in control discharge2Level.
Most of sulphur and sulfide can be effectively removed by hydrogenating reduction and hydramine solvent absorption, also part can be made organic
Sulphur, which is realized, to be removed, but organic sulfur COS and CS in gas2It is converted to H by chemical means2S difficulty is larger, in common chilling
Being taken off with amine waits the removal efficiency during processing very low, is usually no more than 30%, absorbs pressure although theoretically can also pass through to improve
Power increases and absorbs the means such as series and reach the absorption for strengthening organic sulfur, controls organic sulfur content in incineration gases, but to it is existing more
New transformation require it is high, based on mostly alkali is de- or amine takes off measure with device, needing to add after burning process, in investment height
While, also result in equipment etching problem and alkaline residue pollution.So for the environmental protection standard for coping with increasingly stringent, it is more at present to adopt
Or, successively there is Complexing Iron, ionic liquid, the ammonia process of desulfurization, flue gas alkali in high temperature thermal incineration tailing gas post-processing technology
Technique etc. is washed, though these techniques are effective to promoting desulfurization, respectively there is shortcoming in practical applications.
The basic principle that iron process is complexed is contacted with hydrogen sulfide containing gas by Complexing Iron solvent, and Oxidation of Hydrogen Sulfide is
Elemental sulfur, the ferric ion in catalyst are reduced to ferrous ion.Again by blasting air into catalyst solution, profit
By oxidation of divalent iron ion it is ferric ion with the oxygen in air, is recycled after making catalyst regeneration.The technology has
The advantages that hydrogen sulfide extrusion rate is high, easy to operate, the cycle of operation is long.But the medicament such as surface for needing supplement to be lost in operating process
Activating agent, fungicide, pH conditioning agents (alkali) etc..Because being limited by product quality, it is suitable for Small-sized Sulfur Recovery Plant and improves tail
Gas decontamination index or stand-by provision as Small-sized Sulfur Recovery Plant.
The ionic liquid that ionic liquid technique uses is to add a small amount of activation based on organic cation and inorganic anion
The aqueous solution that agent, antioxidant form.Ionic liquid sulfur dioxide absorption at low temperature, by titanium dioxide in absorbent under high temperature
Sulfur regeneration comes out, to achieve the purpose that sulfur dioxide in removing and recovered flue gas.Ionic liquid cyclic absorption technique desulfurization is imitated
Rate is high, has very high selectivity to sulfur dioxide.But since the sulfur dioxide corrosion of technique abjection is stronger,
It is more demanding to the material in system, cause construction investment larger；On the other hand, the brine waste which generates is more, is
Moisturizing of uniting is larger, while increasing the cost of sewage disposal.
Ammonia desulfurizing process makees absorbent with liquefied ammonia or ammonium hydroxide, absorbs the sulfur dioxide in flue gas after sulphur part processed is burned,
Tail gas after absorption directly arranges air, and the air that the ammonium sulfite solution of generation is blasted forces oxidation to generate ammonium sulfate,
Ammonium sulfate can be used as chemical fertilizer raw material use after relevant treatment.One of ammonia flue gas desulfurization technique category Novel clean technology.
But a large amount of ammonium sulfate of by-product, investment is relatively high, and refinery can consider full factory's flue gas desulfurization situation, unified to consider ammonium sulfate
Refined part reduces investment；Additionally there are serious aerosol problems.
Flue gas alkaline cleaning procedure is tower top after removing most of hydrogen sulfide and partial CO 2 by desulfuration absorbing tower
The cleaning of off-gas of discharge enters tail gas furnace burning, and remaining hydrogen sulfide and carbonyl sulfide in cleaning of off-gas are completely converted into dioxy
Change sulphur, rear flue gas enters sodium hydroxide absorption tower and carries out chilling and sulfur dioxide absorption, the purifying smoke after sulfur dioxide absorption
It is emptied through absorbing tower top row inflator.Though the technology can realize the minimum discharge of sulfur recovery tail gas, technological process is longer, system
Complex, construction investment and public work consumption are all bigger；Secondly, sodium sulphate caused by sodium hydroxide absorption technique is useless
Water is bigger, considerably increases the cost of sewage disposal.
The new type low temperature catalytic desulfurizing technology technology is using the suction-operated in activated carbon gap by the SO in flue gas2It inhales
Attached enrichment obtains the SO of high concentration2Gas, and loaded Cu, Fe, V, Al isoreactivity catalyst component on absorbent charcoal carrier.Flue gas
In SO2、H2O、O2It is attracted in the hole of catalyst, becomes active molecule under the action of active catalytic components,
With SO2Reaction generates SO3, single step reaction of going forward side by side generation sulfuric acid.The technique has lower compared with high desulfurization efficiency height, operating cost
Advantage, but catalyst timeliness is low, needs frequent more catalyst changeout, since by-product sulfuric acid causes pipeline investment big, anti-corrosion
High cost.
Therefore it provides a kind of new desulfurization agent prescription and mating deep desulfuration technique, make processed gas reach even remote
It is provided less than gas discharge standard, while not increasing the equipment investment burden of enterprise also, be the reality faced in current actual production
Border problem.
Invention content
In view of the above-mentioned drawbacks in the prior art, the present invention provides a kind of composite desulfurizing agent and carries out depth to sulfurous gas
The method of desulfurization can not only realize the deep desulfuration of hydrogen sulfide and organic sulfur simultaneously, but also low with scrap build expense
The advantages of.
To realize said effect, present invention firstly provides a kind of composite desulfurizing agents, include the component of following parts by weight：
Sulfone or sulfoxide：2~40 parts, organic amine desulfurizer：2~30 parts, the monohydric alcohol or dihydric alcohol of C3~C8：0~20 part,
Hardening agent：5~90 parts；
Wherein, hardening agent is selected from N- N-formyl morpholine Ns, N-Methyl pyrrolidone, polyethylene glycol, triethylene glycol, tetraethylene glycol and carbonic acid
At least one of acrylic ester.
The study found that said components are carried out reasonable disposition, obtained composite desulfurizing agent has very outstanding inventor
Desulfurization effect, deep removal while capable of disposably realizing the organic sulfurs such as hydrogen sulfide and COS, so as to get processed gas in
Hydrogen sulfide content is less than 5mg/Nm3, the content of organic sulfur is less than 20mg/Nm3(all in terms of sulphur), sulfide content summation are equivalent
SO2Less than 50mg/Nm3, well below gas discharge standard《GB31570-2015 petroleum refining industry pollutant emission standards》's
It is required that so as to which processed gas is directly discharged in air, avoid tail gas of sulphur is carried out again to burn bring it is new
Problem of environmental pollution, and saved energy consumption.
Also, above-mentioned composite desulfurizing agent to sulfide carry out deep removal while, also maintain to carbon dioxide compared with
Low absorptivity avoids in conventional amine sulfur removal technology, in deep removal H2Caused CO during S2Altogether suction rate increase,
The drawbacks of sour gas quality reduces, does not influence the normal operating of follow-up sulphur unit etc..
Therefore, composite desulfurizing agent provided by the present invention has very strong fit to the sulfide content in sulfurous gas
Ying Xing, can be suitable for current sulphur recovery and amine takes off the worst sulfur-containing tail gas that technology generates, the wherein content of hydrogen sulfide
Even up to arrive 3000mg/Nm3, more particularly to be suitable for sulfur-containing tail gas through SCOT techniques, i.e., the hydrogenated reduction of tail gas of sulphur and
The desulfurization process of product after hydramine absorption.
Specifically, the hydrogenated reduction of tail gas of sulphur generally contains hydrogen sulfide and COS simultaneously in the product after hydramine absorption
Equal organic sulfurs, it is also possible to which the content containing a small amount of carbon dioxide, wherein hydrogen sulfide can reach 300mg/Nm3。
Unless otherwise instructed, in the present invention, Nm3It refer to the gas volume of the normal atmosphere pressure at 25 DEG C, 1；Wherein N generations
Table standard conditions (Normal Condition), the i.e. condition of air are a standard atmospheric pressure, and temperature is 25 DEG C, relative humidity
It is 0%.
Specifically, the sulfone in above-mentioned composite desulfurizing agent or sulfoxide, can be common sulfone or sulfoxide in petrochemical industry
Class solvent, wherein sulfone such as can be at least one of sulfolane, methyl sulfolane and oil sulfone；Sulfoxide can be dimethyl
Sulfoxide and/or diethyl sulfoxide.Inventor the study found that the polarity of sulfone used or sulfoxide is bigger, hold by the desulfurization of composite desulfurizing agent
Amount is more prominent.
The presence of above-mentioned sulfone or sulfoxide and hardening agent thoroughly absorbs while capable of realizing organic sulfur and hydrogen sulfide,
In specific implementation process of the present invention, sulfone or the quality sum of sulfoxide and hardening agent account for the 40~90% of composite desulfurizing agent quality, into
One step is 40%~80%, for example usually controllable sulfone or sulfoxide account for the 15~35% of composite desulfurizing agent quality, and hardening agent accounts for multiple
The 25~45% of desulfurizing agent quality are closed, to ensure that the composite desulfurizing agent has the adaptability of highly stable sulfur speciation variation.
Organic amine desulfurizer in above-mentioned composite desulfurizing agent can improve composite desulfurizing agent to H2The adaptation of S contents fluctuation
Property.It can be specifically hydramine desulfurizing agent, can also be other organic amines.It is used in specific implementation process of the present invention
Organic amine desulfurizer is selected from isopropylamine, methyl diethanolamine (MDEA), monoethanolamine (MEA), diisopropanolamine (DIPA) (DIPA), diethyl
At least one of hydramine (DEA) and diglycolamine (DGA).
The monohydric alcohol or dihydric alcohol of C3~C8 in above-mentioned composite desulfurizing agent can improve composite desulfurizing agent to COS contents
The adaptability of fluctuation, therefore the addition of above-mentioned monohydric alcohol or dihydric alcohol can be rationally adjusted according to the content of COS in sulfurous gas.
According to specific production practices, if the content of COS is not higher than 60mg/Nm in sulfurous gas3, may be selected it is few plus be even not added with C3~
The monohydric alcohol or dihydric alcohol of C8.Certainly, to reach better desulfurization effect, the aromatic hydrocarbon of suitable C6~C12 can also be added.Hair
A person of good sense controls 5~20%, not only the study found that working as mass percentage of the aromatic hydrocarbon of C6~C12 in composite desulfurizing agent
There is removal effect more outstanding to COS, but also do not influence the removing of hydrogen sulfide and other sulfide, have ideal
Desulfurization effect.
Above-mentioned monohydric alcohol can be specifically branched-chain alcoho, i.e. a certain hydrogen atom on the branched paraffin of C3~C8 is taken by hydroxyl
The product in generation, such as isoamyl alcohol can be specifically 3- methyl-1-butanols, can also be 2-methyl-1-butene alcohol；Dihydric alcohol specifically may be used
To be the dihydric alcohol of C4~C8, i.e., the product that certain two hydrogen atom on the linear paraffin of C4~C8 is replaced by hydroxyl, such as
Heptandiol can be specifically 1,7- heptandiols, can also be 1,2- heptandiols.
The all components of above-mentioned composite desulfurizing agent are chemical field common agents, can be commercially available.
Further, the water of 1~20 parts by weight is also may include in above-mentioned composite desulfurizing agent.Inventor is the study found that compound
Contain a certain amount of water in desulfurizing agent, desulfurization effect can be further increased.
Specifically, the water in composite desulfurizing agent, can be external adding water, i.e., it is individually added into when configuring composite desulfurizing agent
Water can also be the moisture carried in other components, for example would generally contain a certain amount of water in the chemical reagent bought,
It can also be the moisture etc. absorbed in operational process.
The present invention finally provides a kind of method carrying out deep desulfuration to sulfurous gas, including：Make sulfurous gas and above-mentioned
Composite desulfurizing agent enters from the lower part of fine de-sulfur tower and top respectively, and counter current contacting occurs for the two, and obtained processed gas is certainly smart
The top of desulfurizing tower is discharged, and sulfur-rich solvent is discharged from the bottom of fine de-sulfur tower,
Wherein, contain the organic sulfurs such as hydrogen sulfide and COS in sulfurous gas simultaneously, and the content of hydrogen sulfide is not higher than
3000mg/Nm3。
Specifically, above-mentioned sulfurous gas can be the product that the higher tail gas of sulfur content obtains after hydramine absorption processing,
Such as the product that tail gas of sulphur obtains after SCOT technique desulfurization process, wherein containing up to 300mg/Nm3Hydrogen sulfide and COS
Equal organic sulfurs, also contain a large amount of carbon dioxide.Certainly, above-mentioned sulfurous gas can also be the gas for coming from other processing units
Body.
The realization of above-mentioned process for deep desulphurization may not need and is transformed to original Sulphur tail gas desulfurization device.Specific
In production, a fine de-sulfur tower can be added in conventional desulfurizer, for example add essence on the basis of original SCOT flows and take off
Sulphur tower makes tail gas of sulphur reduction hydrogenated first and hydramine absorption processing, obtained sulfurous gas is then passed through fine de-sulfur tower
It is middle to implement above-mentioned deep desulfuration.Compared to traditional sulfur removal technology such as complexing iron process, ionic liquid technique and flue gas alkali cleaning, this hair
Process for deep desulphurization provided in bright has obviously advantage in terms of equipment construction investment and public work consumption.
Above-mentioned fine de-sulfur tower is to distinguish original desulfurizer, can be specifically desulfurizing tower commonly used in the art,
The mass transfer apparatus that can also be taken other form.In specific implementation process of the present invention, fine de-sulfur tower is packed tower, with theoretical tower
Plate meter, packed height are equivalent to 6~8 shelf theory column plates；The tower top pressure of fine de-sulfur tower can be controlled in 0~200kPa, enters
At 30~60 DEG C, the input material volume ratio of sulfurous gas and composite desulfurizing agent has the temperature control of the composite desulfurizing agent of fine de-sulfur tower
Body can (100~300)： 1(Nm3/h：m3/h)。
After deep desulfuration, the hydrogen sulfide content in processed gas is no more than 5mg/Nm3, organic sulfur content is no more than
20mg/Nm3(all in terms of sulphur), even up to arrive 10mg/Nm3Hereinafter, individual event sulfide content reaches discharge standard, and vulcanize
Object content summation converts into SO2Less than 50mg/Nm3, reached can direct emission standard, therefore be discharged at the top of the fine de-sulfur tower
Processed gas can directly carry out high altitude discharge, without conventional incineration technique etc., thus further reduce energy consumption,
Avoid environmental pollution.
Meanwhile the composite desulfurizing agent is relatively low to the absorptivity of carbon dioxide, therefore be not in conventional amine sulfur removal technology,
In deep removal H2Caused CO during S2The series of problems that suction rate increases altogether, sour gas quality reduces.
A large amount of sulfide is absorbed in composite desulfurizing agent, obtained sulfur-rich solvent can be obtained by further implementing to regenerate
To poor sulphur solvent, which, which may return in fine de-sulfur tower, recycles.
Sulfur-rich solvent is regenerated specifically, this field conventional means can be used, such as can be by desorption and regeneration, specifically
Can be desorption, heating desorption and these desorption and regenerations under negative pressure desorption, strippant (such as inert gas, vapor) effect
The joint of mode.Can generally mode of heating be taken to be parsed, avoid generating new pollutant, can specifically take bottom reboiler
Heating generates vapour phase mode and carries out parsing regeneration.
The regeneration of sulfur-rich solvent can be completed in conventional essence takes off regenerator, preferably valve tower.Specifically make sulfur-rich molten
Agent enters from the top of valve tower, and bottom reboiler heating generates vapour phase and enters from the lower part of valve tower, and the two is in valve tower
Counter current contacting, to make the sulfide in the sulfur-rich solvent of liquid phase constantly be transferred in gas phase, sulfide is dense in sulfur-rich solvent
Degree will continuously decrease from top to bottom, and obtained poor sulphur solvent is discharged from float valve tower bottom；In gas phase the concentration of sulfide then by
Lower and upper gradual increase, vapour phase are discharged at the top of valve tower, and condensed cooling finally obtains regeneration gas and withdrawing fluid.
Wherein, the tower tray number of plies of valve tower is 20~30, and tower top pressure is 50~100kPa, and tower top temperature is 90~110
DEG C, column bottom temperature is 120~165 DEG C, and the charge ratio of withdrawing fluid and sulfur-rich solvent is (50~100) kg：1t.
The entry position of above-mentioned sulfur-rich solvent can suitably be adjusted according to field working conditions, and the entrance of general sulfur-rich solvent can be arranged
At the 4th~6 layer of tower tray.
Due to the poor sulphur solvent that sulfur-rich solvent is obtained through desorption and regeneration, it is back to fine de-sulfur tower and is followed as composite desulfurizing agent
Ring uses, and can not only save cost of material, and entire depth sweetening process does not have " three wastes " generation, therefore, the depth is de-
The method of sulphur is a kind of desulfurization technology cleaned.
The present invention provides a kind of composite desulfurizing agents can be achieved at the same time sulfur-bearing by the reasonable disposition before each component
The deep removal of the organic sulfurs such as hydrogen sulfide and COS in gas, so as to get processed gas in hydrogen sulfide content be not higher than 5mg/
Nm3, COS contents are not higher than 20mg/Nm3, individual event sulfide content reaches discharge standard, and sulfide content summation converts into SO2
Less than 50mg/Nm3, it is far below《GB31570-2015 petroleum refining industry pollutant emission standards》Requirement, therefore can realize
The direct emission of processed gas.Also, the composite desulfurizing agent is relatively low to the lower absorptivity of carbon dioxide, and it is de- to avoid conventional amine
In sulphur technique, in deep removal H2Caused CO during S2The serial disadvantage that suction rate increases altogether, sour gas quality reduces
End.
The present invention also provides the methods for implementing deep desulfuration to sulfurous gas using above-mentioned composite desulfurizing agent, can not only
Hydrogen sulfide and organic sulfur in deep removal sulfurous gas simultaneously, and the method for entire depth desulfurization has investment for trnasforming urban land expense
Low, the operation energy consumption feature close with the de- technique of former amine, entire depth sweetening process not new " three wastes " generate, and belong to cleaning
Change desulfurization technology, is conducive to practical large-scale application and popularization.
Description of the drawings
Fig. 1 is that the technological process that deep desulfuration is carried out to sulfurous gas provided in the embodiment of the invention is illustrated
Figure.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Present embodiment provides a kind of method carrying out deep desulfuration to sulfurous gas, and process flow diagram can refer to
Fig. 1, wherein dotted portion representation sulphur tail gas carry out desulfurization through SOCT techniques；Bold portion represents real to obtained sulfurous gas
Apply deep desulfuration.The desulfurization of SOCT techniques and deep desulfuration specifically comprise the following steps：
Step 1：Tail gas of sulphur is sent into reheater and is heated to 250 DEG C or so.
Step 2：Gas from step 1 is mixed into hydrogenation reactor with hydrogen, under the action of hydrogenation catalyst,
Sulfur component SO therein2、COS、CS2Etc. being reduced into H2S obtains sulphur and hydrogen tail gas, general sulphur is added to add the H in hydrogen tail gas2S
Content is in 10000~30000mg/Nm3, organic sulfur content is 50~300mg/Nm3。
Step 3：The sulphur come out from hydrogenation reactor adds hydrogen tail gas to enter chilling tower after waste heat boiler recycles waste heat
Further cooling.
Step 4：In chilling tower, the sulphur after cooling adds hydrogen tail gas with water counter current contacting further to cool down, until being suitble to
H2The temperature that S absorbs, while liquid sulfur therein is removed with water from chilling bottom of tower.
Step 5：The sulphur being discharged after cooling down in chilling tower adds hydrogen tail gas to enter the de- tower of amine, and the de- tower of amine, which specifically can be used, to be filled out
Expect that tower, packed height are equivalent to 6~8 shelf theory plates, tower top pressure is 0~200kPa (G), and the temperature of alcohol amine solvent is 25~45
DEG C, gas liquid ratio is 100~300.
MDEA solution specifically can be used in alcohol amine solvent, to absorb the H added in hydrogen tail gas2S simultaneously inhales CO less as far as possible2, obtain
Sulfur-rich amine liquid takes off tower bottom discharge from amine, is regenerated through amine liquid regenerative system, and obtained poor thiamines liquid, which is made to take off in tower back to amine, to follow
Ring uses；And sulphur adds the sulfurous gas that hydrogen tail gas obtains after amine is de- to take off top of tower discharge, wherein H from amine2The content of S exists
300mg/Nm3Within, organic sulfur content is in 300mg/Nm3Within.
Step 6：Sulfurous gas enters from the lower part of fine de-sulfur tower, and composite desulfurizing agent enters from the top of fine de-sulfur tower, and two
Person's counter current contacting in fine de-sulfur tower realizes H remaining in sulfurous gas2The deep removal of S and organic sulfur.
Specifically, fine de-sulfur tower uses packed tower, height to be equivalent to 6~8 shelf theory plates, tower top pressure is 0~
The temperature of 200kPa, composite desulfurizing agent are 30~60 DEG C, and gas liquid ratio is 100~300 (Nm3/h： m3/h)。
From the processed gas that fine de-sulfur tower tower top obtains, H2S contents are less than 5mg/Nm3, organic sulfur content is less than 20mg/
Nm3, the toxic of the content's index is far smaller than 50mg/Nm3SO2Toxic, it is possible to direct high altitude discharge.
Step 7：The sulfur-rich solvent of fine de-sulfur tower bottom discharge is subsequently sent to the de- regenerator of essence, to reduce energy consumption, using adding
The method of thermal desorption is recycled with recycling design.
It is 20~30 that the de- regenerator of essence, which specifically uses valve tower, the tower tray number of plies, and sulfur-rich solvent enters tower mouth and is located at the 4th~6 layer,
Tower top pressure is 50~100kPa (G), and tower top temperature is 90~110 DEG C, and overhead condenser outlet temperature is 30~50 DEG C, bottom of tower
Temperature is 120~165 DEG C, and it is 50~100 (the kg vapor/sulfur-rich solvents of t), sulfur-rich solvent that reboiler, which heats vapor consumption,
Temperature into valve tower is 80~135 DEG C.
Step 8：The regeneration gas that the de- regeneration column overhead of essence obtains is sent into sulphur unit sulphur stove to recycle sulphur；Bottom of tower is discharged
Poor sulphur solvent back to recycling in fine de-sulfur tower.
Technical solution of the present invention is described in detail below in conjunction with specific embodiments and the drawings.
Embodiment 1
The present embodiment provides a kind of process for deep desulphurization for sulfurous gas, wherein sulfurous gas comes from tail gas of sulphur
Product after SCOT techniques carry out desulfurization.The detailed process of SCOT technique desulfurization is carried out according to above-mentioned steps 1 to step 5, deep
The detailed process for spending desulfurization is carried out according to above-mentioned steps 6 to step 8.
The specific process parameter of the desulfurization of SCOT techniques and deep desulfuration is referring to table 1.Wherein, compound desulfurization used in step 6
The weight percentages of components of agent is：Methyl sulfolane：30%, MDEA：20%, N- N-formyl morpholine N：30%, isopropanol：10%,
Water：10%.
The sulphur obtained in step 2 adds the sulfurous gas obtained in hydrogen tail gas, step 5 and sulfurous gas de- through depth
The component for the processed gas that sulphur obtains is as shown in table 2.
Table 1
Table 2
| Component | Sulphur adds hydrogen tail gas | Sulfurous gas | Processed gas |
| H2S% | 1.5~2 | 60mg/Nm3 | ＜ 1mg/Nm3 |
| CO2% | 25 | — | — |
| H2% | 2~5 | — | — |
| N2% | 68~71.5 | — | — |
| COS mg/Nm3 | ~100mg/Nm3 | 64~100 | ＜ 10mg/Nm3 |
| Total sulfur rolls over SO2mg/Nm3 | 20000~28000 | 240~320 | ＜ 20mg/Nm3 |
Note：Composition described above is molar ratio, and COS contents are in terms of sulphur.
According to table 2 it is found that by the above-mentioned deep desulfuration of sulfurous gas implementation, H in obtained processed gas2S and COS
Content all significantly reduce, wherein H2S content ＜ 1mg/Nm3, COS content ＜ 10mg/Nm3, individual event sulfide content reaches
Discharge standard, and total sulfur content converts into SO250mg/Nm is reached3Hereinafter, being far below《GB31570-2015 petroleum refining industries
Pollutant emission standard》Requirement, it is thus possible to by the direct high altitude discharge of processed gas.
Fine de-sulfur tower and the de- regenerator of the essence forward and backward energy consumption that comes into operation are compared, the results are shown in Table 3.
Table 3
According to table 3 it is recognized that while being additionally arranged fine de-sulfur tower and the de- regenerator of essence, but operation energy consumption takes off basic one with former amine
It causes.Therefore the process for deep desulphurization has the advantages that operating cost is low.
Experimental example 1
Composite desulfurizing agent used in embodiment 1 is existed with MDEA desulfurizing agents (the MDEA aqueous solutions that mass concentration is 30%)
Laboratory evaluation device carries out performance comparison, and specific comparison result is referring to table 4.
Table 4
Note：Data in table 4, which measure under the conditions of static absorption test, to be obtained.
4 comparison result of table shows that the depriving hydrogen sulphide effect of the composite desulfurizing agent is similar to MDEA desulfurizing agents, but for
The removal efficiency of COS is 4.9 times of MDEA desulfurizing agents；And with the extension of soak time, variation is little, illustrates to have very big
Sulfur capacity, carbon dioxide slippage rate ratio MDEA desulfurizing agents are 11.6 percentage points high.
Embodiment 2
The present embodiment provides a kind of process for deep desulphurization for sulfurous gas, wherein sulfurous gas comes from tail gas of sulphur
Product after SCOT techniques carry out desulfurization.The detailed process of SCOT technique desulfurization is carried out according to above-mentioned steps 1 to step 5, deep
The detailed process for spending desulfurization is carried out according to above-mentioned steps 6 to step 8.
The specific process parameter of the desulfurization of SCOT techniques and deep desulfuration is referring to table 5.Wherein, compound desulfurization used in step 6
The weight percentages of components of agent is：Sulfolane：20%, DIPA：20%, N-Methyl pyrrolidone：40%, 1,2- butanediol：
10%, water：10%.
The sulphur obtained in step 2 adds the sulfurous gas obtained in hydrogen tail gas, step 5 and sulfurous gas de- through depth
The component for the processed gas that sulphur obtains is as shown in table 6.
Table 5
Table 6
| Component | Sulphur adds hydrogen tail gas | Sulfurous gas | Processed gas |
| H2S% | 1.5~2 | 60mg/Nm3 | ＜ 1mg/Nm3 |
| CO2% | 5 | — | — |
| H2% | 2~5 | — | — |
| N2% | 88~91.5 | — | — |
| COS mg/Nm3 | ~80mg/Nm3 | 64~70 | ＜ 10mg/Nm3 |
| Total sulfur rolls over SO2mg/Nm3 | 20000~28000 | 128~268 | ＜ 20 |
Note：Composition described above is molar ratio, and COS contents are in terms of sulphur.
According to table 6 it is found that by the above-mentioned deep desulfuration of sulfurous gas implementation, H in obtained processed gas2S and COS
Content all significantly reduce, wherein H2S content ＜ 1mg/Nm3, COS content ＜ 10mg/Nm3, individual event sulfide content reaches
Discharge standard, and total sulfur content converts into SO220mg/Nm is reached3Hereinafter, being far below《GB31570-2015 petroleum refining industries
Pollutant emission standard》Requirement, it is thus possible to by the direct high altitude discharge of processed gas.
Embodiment 3
The present embodiment provides a kind of process for deep desulphurization for sulfurous gas, wherein sulfurous gas comes from tail gas of sulphur
Product after SCOT techniques carry out desulfurization.The detailed process of SCOT technique desulfurization is carried out according to above-mentioned steps 1 to step 5, deep
The detailed process for spending desulfurization is carried out according to above-mentioned steps 6 to step 8, and adds a compression between chilling tower and amine take off tower
Machine adds hydrogen tail gas to enter amine after compressor boosting and takes off tower from the vulcanization for the discharge that cools down in chilling tower.
The specific process parameter of the desulfurization of SCOT techniques and deep desulfuration is referring to table 7.Wherein, compound desulfurization used in step 6
The weight percentages of components of agent is：Sulfolane：30%, MDEA：20%, N-Methyl pyrrolidone：40%, water：10%.
The sulphur obtained in step 2 adds the sulfurous gas obtained in hydrogen tail gas, step 5 and sulfurous gas de- through depth
The component for the processed gas that sulphur obtains is as shown in table 8.
Table 7
Table 8
| Component | Sulphur adds hydrogen tail gas | Sulfurous gas | Processed gas |
| H2S% | 1.5~2 | ＜ 5mg/Nm3 | ＜ 1mg/Nm3 |
| CO2% | 25 | — | — |
| H2% | 2~5 | — | — |
| N2% | 68~71.5 | — | — |
| COS mg/Nm3 | ~100mg/Nm3 | 45~60 | ＜ 10mg/Nm3 |
| Total sulfur rolls over SO2mg/Nm3 | 20000~28000 | 90~150 | ＜ 20mg/Nm3 |
Note：Composition described above is molar ratio, and COS contents are in terms of sulphur.
According to table 8 it is found that by the above-mentioned deep desulfuration of sulfurous gas implementation, H in obtained processed gas2S's and COS
Content all significantly reduces, wherein H2S content ＜ 1mg/Nm3, COS content ＜ 10mg/Nm3, individual event sulfide content reaches row
Standard is put, and total sulfur content converts into SO220mg/Nm is reached3Hereinafter, being far below《GB31570-2015 petroleum refining industries are dirty
Contaminate object discharge standard》Requirement, it is thus possible to by the direct high altitude discharge of processed gas.
Fine de-sulfur tower and the de- regenerator of the essence forward and backward energy consumption that comes into operation are compared, the results are shown in Table 9.
Table 9
According to table 9 it is recognized that while being additionally arranged fine de-sulfur tower and the de- regenerator of essence, still, due to using boost operations, run
Energy consumption is more de- than former amine to be substantially reduced.Simultaneously as compressor boost operations are increased before de- amine, therefore electrisity consumption should mutually have
Increased.Therefore, which has the advantages that operating cost is low, and manufacturer can flexibly select according to actual demand
Whether the booster apparatus such as compressor are added.
Embodiment 4
The present embodiment provides a kind of process for deep desulphurization for sulfurous gas, wherein in sulfurous gas and embodiment 3
Sulfurous gas is consistent, and concrete component can be found in table 7；Deep desulfuration technique and used composite desulfurizing agent reference embodiment 2,
The specific process parameter of middle deep desulfuration can be found in table 5.
In the processed gas obtained by deep desulfuration, H2The content of S is less than 1mg/Nm3, the content of COS is less than 5mg/
Nm3, total sulfur content is (with SO2Meter) it is less than 15mg/Nm3。
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of composite desulfurizing agent, which is characterized in that include the component of following parts by weight：
Sulfone or sulfoxide：2~40 parts, organic amine desulfurizer：2~30 parts, the monohydric alcohol or dihydric alcohol of C3~C8：0~20 part, reinforcing
Agent：5~90 parts；
Wherein, the hardening agent is selected from N- N-formyl morpholine Ns, N-Methyl pyrrolidone, polyethylene glycol, triethylene glycol, tetraethylene glycol and carbonic acid
At least one of acrylic ester.
2. composite desulfurizing agent according to claim 1, which is characterized in that the sulfone be selected from sulfolane, methyl sulfolane and
At least one of oil sulfone；The sulfoxide is selected from dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide.
3. composite desulfurizing agent according to claim 1 or 2, which is characterized in that the sulfone or sulfoxide and the hardening agent
Quality sum accounts for the 40~90% of composite desulfurizing agent quality.
4. composite desulfurizing agent according to claim 1, which is characterized in that the organic amine desulfurizer is selected from isopropylamine, first
At least one of base diethanol amine, monoethanolamine, diisopropanolamine (DIPA), diethanol amine and diglycolamine.
5. composite desulfurizing agent according to claim 1, which is characterized in that the monohydric alcohol is branched-chain alcoho, the dihydric alcohol
For the dihydric alcohol of C4~C8.
6. according to claim 1-5 any one of them composite desulfurizing agents, which is characterized in that further include the water of 1~20 parts by weight.
7. a method of deep desulfuration is carried out to sulfurous gas, which is characterized in that including：Make sulfurous gas and claim 1-
6 any one of them composite desulfurizing agents enter from the lower part of fine de-sulfur tower and top respectively, and counter current contacting occurs for the two, obtains
Processed gas and sulfur-rich solvent are discharged from the top and bottom of fine de-sulfur tower respectively,
Wherein, hydrogen sulfide and organic sulfur are contained in the sulfurous gas, and the content of hydrogen sulfide is not higher than 3000mg/Nm3。
8. the method according to the description of claim 7 is characterized in that the sulfurous gas be sulfur-containing tail gas after hydramine absorbs
Product.
9. method according to claim 7 or 8, which is characterized in that the fine de-sulfur tower is packed tower, and packed height is
6~8 shelf theory column plates；
The tower top pressure of the fine de-sulfur tower is 0~200kPa, and the temperature of the composite desulfurizing agent is 30~60 DEG C, the sulfur-bearing
The input material volume ratio of gas and composite desulfurizing agent is (100~300) Nm3/h：1m3/h。
10. according to claim 7-9 any one of them methods, which is characterized in that further include：The sulfur-rich solvent is carried out again
It is raw, obtain poor sulphur solvent；
The poor sulphur solvent is back in fine de-sulfur tower and is recycled.
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| CN113082944A (en) * | 2021-03-26 | 2021-07-09 | 四川益能康生环保科技有限公司 | Composite absorbent for removing sulfur dioxide in tail gas and preparation method thereof |
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