CN116407927A - Absorbent for deep sweetening of refinery fuel gas and preparation method and application thereof - Google Patents
Absorbent for deep sweetening of refinery fuel gas and preparation method and application thereof Download PDFInfo
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- CN116407927A CN116407927A CN202111681467.3A CN202111681467A CN116407927A CN 116407927 A CN116407927 A CN 116407927A CN 202111681467 A CN202111681467 A CN 202111681467A CN 116407927 A CN116407927 A CN 116407927A
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- absorbent
- percent
- fuel gas
- gas
- absorption
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- 239000002250 absorbent Substances 0.000 title claims abstract description 89
- 230000002745 absorbent Effects 0.000 title claims abstract description 89
- 239000002737 fuel gas Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- -1 alcohol amine Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 26
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 13
- 239000003637 basic solution Substances 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 10
- 229940043276 diisopropanolamine Drugs 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution 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
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 50
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 32
- 229910052717 sulfur Inorganic materials 0.000 description 32
- 239000011593 sulfur Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- AHXXIYFEJGGBMG-UHFFFAOYSA-N 1-[2-(tert-butylamino)ethoxy]ethanol Chemical compound CC(O)OCCNC(C)(C)C AHXXIYFEJGGBMG-UHFFFAOYSA-N 0.000 description 2
- HUHGPYXAVBJSJV-UHFFFAOYSA-N 2-[3,5-bis(2-hydroxyethyl)-1,3,5-triazinan-1-yl]ethanol Chemical compound OCCN1CN(CCO)CN(CCO)C1 HUHGPYXAVBJSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
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
- B01D53/1487—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
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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- 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
The invention discloses an absorbent for deep sweetening of refinery fuel gas, a preparation method and application thereof, wherein the absorbent comprises the following components in percentage by mass: 1.0 to 10.0 percent of organic alcohol amine, 0.5 to 20.0 percent of organic solvent, 2.0 to 30.0 percent of oxidation solvent, 0.2 to 1.0 percent of inorganic salt and the balance of water. The absorption method is a method for deeply removing organic mercaptan in fuel gas by using the absorbent under a hypergravity field, and the hypergravity absorption equipment has the advantages of simple operation, small occupied area, small absorbent consumption, strong impact resistance and low investment and operation cost. The absorbent provided by the invention is composed of organic alcohol amine, organic solvent, oxidation solvent, inorganic salt and water, and the absorbent has the advantages of wide raw material sources, low price, no toxicity and harm, simple preparation, safe transportation and storage, and can realize physical absorption and chemical absorption at the same time, and the components are mutually cooperated and promoted, so that the absorption efficiency of organic mercaptan can be obviously improved.
Description
Technical Field
The invention belongs to the field of fuel gas purification of refineries in the field of petrochemical industry, and particularly relates to an absorbent for deep sweetening of the refinery fuel gas, and a preparation method and application thereof.
Background
Crude oil can be subjected to atmospheric and vacuum distillation, catalytic cracking, catalytic reforming, hydrocracking, delayed coking and other treatment processes to obtain a large amount of byproduct gaseous hydrocarbon, which is called as refinery gas, and most of the refinery gas is used as fuel gas for a heating furnace after gas separation and alcohol amine desulfurization. The sulfur content of the fuel gas is generally 20 to 100mg/Nm 3 Hydrogen sulfide, methyl mercaptan, ethyl mercaptan, carbonyl sulfide and the like are used as main sulfur-containing substances. When the fuel gas is burnt in the heating furnace, sulfide is oxidized to generate SO 2 ，SO 2 Some of them are further oxidized to form SO 3 ，SO 3 Generating sulfuric acid steam when meeting water vapor. When the temperature of the flue gas is reduced to the sulfuric acid dew point, sulfuric acid steam is condensed on the metal surfaces of the heating furnace body and the heating furnace air preheater, and sulfuric acid dew point corrosion is formed. The acid dew point of the flue gas is related to the excess air factor of the combustion, the water vapor content, and the sulfur content in the fuel gas, which is the most critical contributor.
In order to improve the heat efficiency of the heating furnace, the large-scale heating furnace is provided with an air preheater, and the temperature of the flue gas is reduced and the heat of the flue gas is recovered while the air is preheated through heat exchange between fresh air and the flue gas. The temperature of the flue gas is reduced, the recovered heat is increased, and the efficiency of the heating furnace is improved. Too low a flue gas temperature has acid dew point corrosion problems, and therefore the flue gas temperature design value must be at least 15 ℃ above the flue gas dew point temperature. At present, the exhaust gas temperature of a heating furnace in a refinery is generally controlled to be 120-160 ℃, and the thermal efficiency of the heating furnace is 91-93%.
The sulfur content in the fuel gas is reduced, so that the sulfuric acid steam content in the flue gas is reduced, the acid dew point temperature of the flue gas is reduced, and the method is one of effective means for reducing the exhaust gas temperature and improving the efficiency of the heating furnace.
The supergravity technology is a novel chemical process strengthening technology developed in recent years, and can improve the gas-liquid mass transfer efficiency by 1-3 orders of magnitude under the supergravity field condition, so that the scale of a treatment device can be greatly reduced, and meanwhile, the production efficiency and the capacity of the device are improved. The supergravity device has the characteristics of quick starting, simple operation, strong adaptability and the like, and has been well applied to the treatment of flue gas, tail gas and waste gas. Aiming at the requirement of further deeply purifying and removing sulfides in fuel gas of an oil refinery, the supergravity technology has good research and application prospects.
CN112023662 a discloses a composite absorbent for petroleum and natural gas purification, which contains absorbent tert-butylaminoethoxyethanol TBEE, 1,3, 5-tris (2-hydroxyethyl) -hexahydro s-triazine and oxazolidine compound, synergist N-methylpyrrolidone, polyethylene glycol dimethyl ether and N-methylmorpholine, penetrating agent, defoamer and antioxidant. Can make the removal rate of sulfur in natural gas reach 95%, and the total sulfur content in purified gas is not more than 30mg/m 3 Reaching the index of natural gas. The absorbent has obvious absorption effect on high-concentration sulfide in natural gas, especially on hydrogen sulfide gas, but the total sulfur content in purified gas is still higher, and the absorbent is not suitable for deep removal of low-concentration sulfide in fuel gas.
CN 112708488A discloses a liquefied petroleum gas sweetening compound solvent, which comprises 5-30wt% of inorganic strong base, 2.5-20wt% of alcohol auxiliary agent, 0.2-2.0wt% of alcohol amine auxiliary agent, 1-5wt% of ether auxiliary agent, and the balance of water. In practice, sodium mercaptide is generated by utilizing the reaction of strong alkali and mercaptan, the to-be-regenerated composite solvent containing sodium mercaptide is subjected to oxidation reaction in an extraction section and is contacted with oxygen to generate disulfide, and the like, then the mixed product generated by regeneration is extracted and separated by using reverse extraction oil, the disulfide enters an oil phase, and the water phase product is regenerated composite liquid. The use of alkali liquor, namely the discharge of alkali slag/waste alkali liquor; the solubility of the alcohol, the alcohol amine and the ether auxiliary agent in alkali liquor is greatly reduced compared with the solubility in water; the activity of sodium mercaptide in the oxygen contact oxidation spent composite solvent is limited, and sodium mercaptide which is not oxidized is repeatedly accumulated in a circulating system, so that the alkali liquor efficiency is greatly reduced; the process flow is long and complex.
CN 105695018A discloses an additive for liquefied gas sweetening and its application method, specifically, inorganic strong base such as sodium hydroxide, potassium hydroxide, etc. are used as main agent, alcohol amine and polyalcohol compound are used as cosolvent, metal ruthenium-containing salt is used as oxygen carrier, and phthalocyanine metal salt is used as catalyst. Dissolving mercaptan in liquefied gas into additive, and neutralizing with inorganic alkali to produce sodium mercaptan, which is reacted in the presence of catalyst, oxygen carrier and O 2 Disulfide formation occurs under the action of the catalyst. The process is complex and the flow is long; alkali liquor is used, and alkali slag is discharged; the catalyst has the common problems of poor solubility or low activity, influences the absorption efficiency, and brings in metallic cobalt and ruthenium.
CN104785296 a discloses a liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas sweetening, which consists of active components of tetra-beta-p-sulfophenoxy cobalt phthalocyanine, one or a compound of stabilizer propylene glycol dimethyl ether, N-methyl diethanolamine or triethanolamine, emulsifier octadecyl dimethyl benzyl ammonium chloride and NaOH solution. Although the solubility of the active component tetra-beta-p-sulfophenoxy cobalt phthalocyanine in water and alkali liquor is improved, the principle and flow of mercaptan removal are acid-base reaction with NaOH to generate sodium mercaptide, the sodium mercaptide is oxidized into disulfide under the action of a catalyst and air, waste alkali slag is generated by using the alkali liquor, and the absorption process is complex.
The sweetening absorbent and the absorption method in the prior art have better absorption effect on components such as hydrogen sulfide in waste gas, but have insignificant removal effect on low-concentration thiol-containing waste gas, especially low-concentration organic thiol, and the conventional absorption process is relatively complex, and the mass transfer effect needs to be improved.
Disclosure of Invention
Aiming at the urgent need of improving the heat efficiency of a heating furnace in a refinery and the defects existing in the prior art, the invention provides an absorbent for deep sweetening of refinery fuel gas, and a preparation method and application thereof. The absorbent provided by the invention is composed of organic alcohol amine, organic solvent, oxidation solvent, inorganic salt and water, the raw materials of the absorbent are wide in sources, low in cost, nontoxic and harmless, simple to prepare, safe to transport and store, physical absorption and chemical absorption can be realized at the same time, the components are mutually cooperated and promoted, and the absorption efficiency of organic mercaptan can be obviously improved.
In order to achieve the purpose, the invention provides an absorbent for deep sweetening of refinery fuel gas, which comprises the following components in percentage by mass:
1.0 to 10.0 percent of organic alcohol amine,
0.5 to 20.0 percent of organic solvent,
2.0 to 30.0 percent of oxidation solvent,
inorganic salt 0.2-1.0%
The balance of water.
The absorbent of the present invention, wherein the organic alcohol amine is preferably selected from one or more of N-Methyldiethanolamine (MDEA), triethanolamine (TEA), dimethylethanolamine (DMEA), diethylethanolamine (DEEA), isobutylamine (AMP), monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIPA), and methylmonoethanolamine (MMEA).
The absorbent of the invention is preferably that the organic solvent is at least one selected from tributyl phosphate, dimethylformamide, sulfolane, dimethyl sulfoxide, N-methyl pyrrolidone and polyethylene glycol dimethyl ether, wherein the polyethylene glycol dimethyl ether is polyethylene glycol dimethyl ether with a carbon chain length of 3-8.
The absorbent of the invention is characterized in that the oxidation solvent is preferably selected from one or more of sodium chlorate, potassium hypochlorite, potassium chlorate, sodium hypochlorite, hydrogen peroxide and potassium permanganate.
The absorbent of the present invention is preferably one in which the inorganic salt is at least one selected from sodium carbonate and potassium carbonate.
Preferably, the absorbent consists of the following components in percentage by mass:
1.0 to 8.0 percent of organic alcohol amine,
0.5 to 20.0 percent of organic solvent,
2.0 to 28.0 percent of oxidation solvent,
0.2 to 1.0 percent of inorganic salt,
the balance of water.
The absorbent of the present invention, wherein preferably, the organic alcohol amine is selected from one or more of N-methyldiethanolamine MDEA, isobutolamine AMP, monoethanolamine MEA, diethanolamine DEA, diisopropanolamine DIPA.
The absorbent of the invention is characterized in that the organic solvent is preferably at least one selected from tributyl phosphate, dimethylformamide, N-methylpyrrolidone and polyethylene glycol dimethyl ether, wherein the polyethylene glycol dimethyl ether is polyethylene glycol dimethyl ether with a carbon chain length of 3-8.
The absorbent is characterized in that the oxidation solvent is preferably one or more selected from sodium hypochlorite, sodium chlorate, potassium hypochlorite, potassium chlorate, hydrogen peroxide and potassium permanganate.
The absorbent of the present invention is preferably one in which the inorganic salt is at least one selected from sodium carbonate and potassium carbonate.
The invention also provides a preparation method of the absorbent for deeply removing the mercaptan from the refinery fuel gas, which comprises the following steps: under the stirring state, firstly adding inorganic salt into water to form a basic solution, then sequentially adding organic alcohol amine and organic solvent, uniformly mixing to form a mixed solution, and finally adding an oxidation solvent and uniformly mixing.
The preparation method of the invention, wherein preferably, the stirring is low-speed stirring, the rotating speed is 100-200r/min, and the preparation method comprises the following conditions: the temperature is 10 to 35 ℃, preferably 20 to 30 ℃.
Specifically, the preparation method of the absorbent for deep sweetening of refinery fuel gas provided by the invention comprises the following steps:
(1) Adding inorganic salt into water, stirring and dissolving to form a base solution.
(2) Adding organic alcohol amine into the basic solution in the step (1), stirring for 5-10 min, and uniformly mixing.
(3) Adding an organic solvent into the mixed solution obtained in the step (2), stirring for 10-20 min, and uniformly mixing.
(4) Adding an oxidizing solvent into the mixed solution in the step (3), stirring for 10-30 min, fully dissolving, and uniformly mixing to form the deep mercaptan removal absorbent.
The invention also provides a method for deeply removing mercaptan in refinery fuel gas, which comprises the following steps:
(1) The fuel gas enters the hypergravity machine through the fan, passes through the filler from the outer cavity to enter the inner cavity under the pressure effect, and is discharged from the gas outlet pipe in the center;
(2) Meanwhile, the absorbent enters the supergravity machine, is uniformly sprayed on a packed bed layer through a liquid distributor after passing through the inner cavity of a drum of the supergravity machine, flows outwards along the radial direction under the action of centrifugal force generated by high-speed rotation, falls down after touching a static outer cavity wall, and is discharged from a liquid outlet at the bottom;
(3) The fuel gas and the absorbent are in reverse contact in the packing layer to carry out mass transfer, mercaptan molecules in the fuel gas are dissolved and absorbed by the absorbent, and the absorbent is recycled.
The method of the invention is characterized in that preferably, the supergravity machine is filled with regular stainless steel wire mesh filler or stainless steel corrugated plate filler, further preferably regular stainless steel wire mesh filler, and the specific surface area of the filler is 900-1200 m 2 /m 3 More preferably 1000 to 1200m 2 /m 3 。
The method of the invention, whereinOptionally, the conditions of the reverse contact are: the hypergravity factor is 30-150, the operating pressure is 0.1-0.8 MPa, and the liquid-gas ratio is 2.0-20.0L/m 3 。
The principle of the absorption method for deep desulfurization of fuel gas is as follows: the sulfur content is 20 to 100mg/Nm 3 The fuel gas is introduced into the hypergravity machine through the fan, the absorbent is dispersed into a liquid film, liquid wires or small liquid drops under the action of a high-speed rotating packed bed, a huge interphase contact area is formed, and meanwhile, the updating rate of a phase interface is very fast, so that the gas-liquid mass transfer efficiency (the mass transfer efficiency is improved by 1-3 orders of magnitude compared with that under the conventional gravity condition) can be greatly improved, and the mercaptan in the fuel gas is dissolved and absorbed by the absorbent. The absorbent can be recycled, and meanwhile, the metering pump supplements fresh absorption liquid with a certain proportion to the absorption liquid tank, so that the absorption liquid in the supergravity device is kept to have stable absorption capacity and absorption effect.
By scientific design, the absorption of thiols by the absorbent is a result of the interaction of chemical and physical absorption. The organic alcohol amine has the advantages of large absorption capacity, high selectivity and low energy consumption on acid gas in fuel gas, has structures of amino, hydroxyl and the like, interacts with mercaptan and promotes the dissolution of the mercaptan in the absorbent. The addition of the organic solvent can promote the dissolution of each component in the absorbent, increase the dissolution of the organic mercaptan component in the absorbent and greatly improve the absorption and dissolution effects of the organic mercaptan. The oxidizing solvent may oxidize the organic thiol molecules absorbed and dissolved in the absorbent directly into stable sulfonates and the like. The inorganic salt provides an alkaline environment, increases the disturbance in the fluid, increases the mass transfer driving force, reduces the thickness of a mass transfer liquid film and the liquid film resistance, further promotes the mass transfer of gas phase and liquid phase, and improves the absorption and purification efficiency. The components of the absorbent are mutually cooperated and promoted, and the absorption efficiency of the absorbent on the mercaptan component in the fuel gas is improved.
In summary, the beneficial effects of the invention are as follows:
(1) The absorbent provided by the invention mainly comprises organic alcohol amine, organic solvent, oxidation solvent, inorganic salt and water, and has the advantages of wide sources, low price, no toxicity and harm, simple preparation and safe transportation and storage.
(2) Aiming at low-concentration thiolates (mainly hydrogen sulfide, methyl mercaptan and ethanethiol) in refinery fuel gas, the absorbent provided by the invention realizes physical absorption and chemical absorption at the same time, and all components are mutually cooperated and mutually promoted, so that the absorption efficiency of organic mercaptan can be obviously improved.
(3) The super-gravity absorption device provided by the invention has the advantages of small occupied area, small consumption of the absorbent, low investment and operation cost, high mass transfer efficiency, simple absorption process operation and stronger shock resistance.
(4) The adsorbent of the invention is combined with a supergravity absorption device, and after the deep desulfurization treatment is carried out on the low-concentration sulfur-containing fuel gas of the oil refinery, the total sulfur content of the inlet gas is 20-100 mg/Nm 3 The removal rate of mercaptan is more than or equal to 98 percent, and the sulfur content is reduced to 4mg/Nm 3 The temperature of the exhaust gas of the heating furnace is reduced, the heat efficiency of the heating furnace is improved, and the circulation amount and the energy consumption of the absorption liquid are greatly reduced.
Drawings
Fig. 1 is a schematic structural view of an embodiment of a supergravity machine according to the present invention.
Wherein, the reference numerals:
1. gas inlet, 2, liquid inlet, 3, gas outlet, 4, liquid outlet.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Raw material or equipment source: distribution, supplied by Dalianda gas limited, supplied by North university in the equipment hypergravity machine.
Evaluation analysis method: determination of sulfide by gas analysis sulfur chemiluminescence gas chromatography GB/T33318-2016.
Example 1
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.1kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.8kg of N-methyldiethanolamine, 0.5kg of polyethylene glycol dimethyl ether and 0.6kg of sodium hypochlorite are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 8% of N-Methyldiethanolamine (MDEA), 5% of polyethylene glycol dimethyl ether, 6% of sodium hypochlorite, 1% of sodium carbonate and 80% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 40, and the liquid-gas ratio is 6L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 80-100 mg/Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 2
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.05kg of potassium carbonate is dissolved in water to prepare a basic solution, then 0.2kg of diethanolamine, 0.2kg of dimethylamide and 0.5kg of potassium hypochlorite are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: diethanolamine (DEA) 2%, dimethylformamide 2%, potassium hypochlorite 5%, potassium carbonate 0.5% and water 90.5%.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 60-80/Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 3
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.02kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.1kg of isobutylamine (AMP), 0.3kg of tributyl phosphate and 1kg of hydrogen peroxide are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 1% of isobutylamine (AMP), 3% of tributyl phosphate, 10% of hydrogen peroxide, 0.2% of sodium carbonate and 85.8% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 30-50 Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 4
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.06kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.2kg of N-methyldiethanolamine, 0.4kg of monoethanolamine, 0.5kg of N-methylpyrrolidone and 1.4kg of sodium hypochlorite are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 2% of N-Methyldiethanolamine (MDEA), 4% of Monoethanolamine (MEA), 5% of N-methylpyrrolidone, 14% of sodium hypochlorite, 0.6% of sodium carbonate and 74.4% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 30-50 Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 5
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.1kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.2kg of Diisopropanolamine (DIPA), 0.3kg of diethanolamine, 0.4kg of dimethylformamide, 0.2kg of sodium hypochlorite and 0.6kg of potassium hypochlorite are sequentially added, and each step is fully stirred until uniform mixing is achieved, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 2% of Diisopropanolamine (DIPA), 3% of diethanolamine (MEA), 4% of dimethylformamide, 2% of sodium hypochlorite, 6% of potassium hypochlorite, 1% of sodium carbonate and 82% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 80-100 Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 6
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.08kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.2kg of triethanolamine, 0.3kg of diethanolamine, 0.2kg of sulfolane and 0.6kg of potassium permanganate are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 2% of Triethanolamine (TEA), 3% of diethanolamine (MEA), 2% of sulfolane, 6% of potassium permanganate, 0.8% of sodium carbonate and 86.2% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the supergravity deviceThe filler of (2) is stainless steel wire mesh with specific surface area of 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 50-80 Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Example 7
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.02kg of sodium carbonate is dissolved in water to prepare a basic solution, then 1kg of N-methyldiethanolamine, 0.05kg of dimethyl sulfoxide and 0.2kg of sodium chlorate are sequentially added, each step is fully stirred until the mixture is uniformly mixed, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 10% of N-Methyldiethanolamine (MDEA), 0.5% of dimethyl sulfoxide, 2.0% of sodium chlorate, 0.2% of sodium carbonate and 87.3% of water.
The absorbent is used in the technical process of deep purification and mercaptan removal of fuel gas, and the specific operation process is as follows: in the test site, the filler of the supergravity device is stainless steel wire mesh, and the specific surface area is 1200m 2 /m 3 The hypergravity factor is 60, and the liquid-gas ratio is 12L/m 3 The temperature of the absorption liquid is 20-35 ℃. After the device runs stably, the total sulfur content of the air inlet is 50-60 Nm 3 Taking out a gas sample at a gas port according to the standard HJ 732-2014, and analyzing by a gas chromatography, wherein the removal rate of the mercaptan is more than or equal to 98 percent, and the total sulfur content is 4mg/Nm 3 The following is given.
Comparative example 1
The comparative example adopts a conventional desulfurizing agent, and the desulfurizing agent comprises the following components in percentage by mass: 25% of tert-butylaminoethoxyethanol TBEE, 25% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 15% of oxazolidine compound, 5% of N-methylpyrrolidone, 4% of polyethylene glycol dimethyl ether, 5% of N-methylmorpholine, 2% of sodium succinate sulfonate, 0.5% of polyether modified silicone oil, 0.5% of p-hydroxyanisole and the balance of deionized water.
The fuel gas is reversed with absorbent in a conventional gravity absorption towerAnd carrying out absorption mass transfer to the contact. The total sulfur content of the air inlet is 80-100 mg/Nm 3 After the absorption treatment, the removal rate of mercaptans was 64.1% and the total sulfur content was 28.7 mg/Nm 3 。
Comparative example 2
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.06kg of sodium carbonate is dissolved in water to prepare a basic solution, then 0.2kg of N-methyldiethanolamine, 0.4kg of monoethanolamine, 0.5kg of N-methylpyrrolidone and 0.4kg of sodium hypochlorite are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 2% of N-Methyldiethanolamine (MDEA), 4% of Monoethanolamine (MEA), 5% of N-methylpyrrolidone, 4% of sodium hypochlorite, 0.6% of sodium carbonate and 84.4% of water.
The fuel gas is reversely contacted with the absorbent in a conventional gravity absorption tower to carry out absorption mass transfer. The total sulfur content of the air inlet is 30-50 mg/Nm 3 After the absorption treatment, the removal rate of mercaptans was 88.1% and the total sulfur content was 12.7 mg/Nm 3 。
Comparative example 3
10kg of absorbent is prepared, and the specific preparation process is as follows: under the stirring state, 0.2kg of sodium carbonate is dissolved in water to prepare a basic solution, then 1.2kg of N-methyldiethanolamine and 0.6kg of monoethanolamine are sequentially added, each step is fully stirred until the mixture is uniform, and finally a stable solution is formed for standby. The absorbent solution comprises the following components in percentage by mass: 12.0% of N-Methyldiethanolamine (MDEA), 6.0% of Monoethanolamine (MEA), 2.0% of sodium carbonate and 80.0% of water.
The fuel gas is reversely contacted with the absorbent in a conventional gravity absorption tower to carry out absorption mass transfer. The total sulfur content of the air inlet is 50-60 mg/Nm 3 After the absorption treatment, the removal rate of mercaptans was 58.2% and the total sulfur content was 22.6 mg/Nm 3 。
As can be seen from the results of examples 1-7 and comparative examples 1-3, the absorbent formula and the absorption method for deep sweetening of refinery fuel gas provided by the invention have the advantages that the components and the contents are mutually cooperated and promoted, and the finally obtained absorbent has excellent sweetening effect.
The above embodiments are only for illustrating the technical concept and features of the present invention, and it is intended to enable those skilled in the art to understand the present invention and implement the same, and all modifications made according to the spirit of the main technical solution of the present invention shall be covered in the protection scope of the present invention.
Claims (11)
1. An absorbent for deep sweetening of refinery fuel gas, which is characterized by comprising the following components in percentage by mass:
1.0 to 10.0 percent of organic alcohol amine,
0.5 to 20.0 percent of organic solvent,
2.0 to 30.0 percent of oxidation solvent,
inorganic salt 0.2-1.0%
The balance of water.
2. The absorbent according to claim 1, characterized in that it consists of the following components in mass percent:
1.0 to 8.0 percent of organic alcohol amine,
0.5 to 20.0 percent of organic solvent,
2.0 to 28.0 percent of oxidation solvent,
0.2 to 1.0 percent of inorganic salt,
the balance of water.
3. The absorbent according to claim 1, wherein the organic alcohol amine is selected from one or more of N-methyldiethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, isobutanolamine, monoethanolamine, diglycolamine, diethanolamine, diisopropanolamine, and methylmonoethanolamine.
4. The absorbent according to claim 3, wherein the organic alcohol amine is one or more selected from the group consisting of N-methyldiethanolamine, isobutolamine, monoethanolamine, diethanolamine, diisopropanolamine.
5. The absorbent according to claim 1, wherein the organic solvent is at least one selected from tributyl phosphate, dimethylformamide, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone and polyethylene glycol dimethyl ether.
6. The absorbent according to claim 1, wherein the oxidizing solvent is selected from one or more of sodium chlorate, potassium hypochlorite, potassium chlorate, sodium hypochlorite, hydrogen peroxide, potassium permanganate.
7. The absorbent according to claim 1, wherein the inorganic salt is at least one selected from sodium carbonate and potassium carbonate.
8. A process for the preparation of an absorbent for deep sweetening of refinery fuel gas according to any one of claims 1-7, comprising the steps of: under the stirring state, firstly adding inorganic salt into water to form a basic solution, then sequentially adding organic alcohol amine and organic solvent, uniformly mixing to form a mixed solution, and finally adding an oxidation solvent and uniformly mixing.
9. The method according to claim 8, wherein the stirring is performed at a low speed at a rotational speed of 100-200r/min, and the method comprises the following steps: the temperature is 10 to 35 ℃, preferably 20 to 30 ℃.
10. A method for deeply removing mercaptans in refinery fuel gas, comprising the steps of:
(1) The fuel gas enters the hypergravity machine through the fan, passes through the filler from the outer cavity to enter the inner cavity under the pressure effect, and is discharged from the gas outlet pipe in the center;
(2) Simultaneously, the absorbent according to any one of claims 1-7 enters the hypergravity machine, is uniformly sprayed on a filler bed layer through a liquid distributor after entering from the inner cavity of a rotating drum of the hypergravity machine, flows outwards along the radial direction under the action of centrifugal force generated by high-speed rotation, falls down after touching a static outer cavity wall, and is discharged from a liquid outlet at the bottom;
(3) The fuel gas and the absorbent are in reverse contact in the packing layer to carry out mass transfer, mercaptan molecules in the fuel gas are dissolved and absorbed by the absorbent, and the absorbent is recycled.
11. The method of claim 10, wherein the conditions of the reverse contact are: the hypergravity factor is 30-150, the operating pressure is 0.1-0.8 MPa, and the liquid-gas ratio is 2.0-20.0L/m 3 。
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