CN116943408B - Hindered amine composite desulfurizing agent and preparation method thereof - Google Patents
Hindered amine composite desulfurizing agent and preparation method thereof Download PDFInfo
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- CN116943408B CN116943408B CN202310787049.5A CN202310787049A CN116943408B CN 116943408 B CN116943408 B CN 116943408B CN 202310787049 A CN202310787049 A CN 202310787049A CN 116943408 B CN116943408 B CN 116943408B
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- 150000001412 amines Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims description 29
- 230000003009 desulfurizing effect Effects 0.000 title claims description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 41
- 230000023556 desulfurization Effects 0.000 claims abstract description 41
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 25
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 amine compound Chemical class 0.000 claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000013530 defoamer Substances 0.000 claims abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- AHXXIYFEJGGBMG-UHFFFAOYSA-N 1-[2-(tert-butylamino)ethoxy]ethanol Chemical compound CC(O)OCCNC(C)(C)C AHXXIYFEJGGBMG-UHFFFAOYSA-N 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- GPTXCAZYUMDUMN-UHFFFAOYSA-N tert-butyl n-(2-hydroxyethyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCO GPTXCAZYUMDUMN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- HDFZSPPOXSAVRI-UHFFFAOYSA-N n,n,n',n'-tetramethylethane-1,2-diamine;hydrochloride Chemical compound Cl.CN(C)CCN(C)C HDFZSPPOXSAVRI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- ICBMTPLNKKNYEX-UHFFFAOYSA-N 1,3-bis(tert-butylamino)propan-2-ol Chemical compound CC(C)(C)NCC(O)CNC(C)(C)C ICBMTPLNKKNYEX-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- MMAJXKGUZYDTHV-UHFFFAOYSA-N 1-benzhydrylazetidin-3-ol Chemical compound C1C(O)CN1C(C=1C=CC=CC=1)C1=CC=CC=C1 MMAJXKGUZYDTHV-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000003345 natural gas Substances 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 8
- 229940083037 simethicone Drugs 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012992 electron transfer agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a sterically hindered amine compound desulfurizer and a preparation method thereof, which belong to the technical field of petrochemical gas desulfurization in natural gas, coal chemical industry and the like, and the sterically hindered amine compound desulfurizer comprises the following components in mass fraction: 32-48% of hindered amine, 0-1% of corrosion inhibitor, 0.1-1.5% of defoamer, 14-20% of stabilizer, 8-15% of desulfurization auxiliary agent and the balance of solvent, wherein the desulfurization auxiliary agent comprises an aminated modified product of terpyridyl phenylboronic acid; the invention improves the absorption selectivity and the removal rate of the system to the hydrogen sulfide by adding the desulfurization auxiliary agent on the basis of the sterically hindered amine alkaline absorbent.
Description
Technical Field
The invention relates to the technical field of petrochemical gas desulfurization in natural gas, coal chemical industry and the like, in particular to a sterically hindered amine composite desulfurizer and a preparation method thereof.
Background
The mixed gas comprises natural gas, petroleum refinery gas, synthetic gas, liquefied petroleum gas and other gases. Hydrogen sulfide (H) is commonly contained in industrial gases such as natural gas, synthesis gas, and petroleum refinery gas 2 S) and organic sulfides, wherein the organic sulfides mainly comprise carbonyl sulfide, carbon disulfide, mercaptan, thioether and the like with different carbon numbers, and various existing organic/inorganic sulfide components are easy to cause corrosion of equipment and pipelines in the processes of exploitation, treatment, transportation and use, and can bring about environmental pollution when used as fuel and also cause serious harm to human health. Therefore, the mixed gas must be subjected to a purification treatment to meet the subsequent utilization requirements before further processing and utilization.
At present, there are many methods for desulfurizing mixed gas at home and abroad, and desulfurization is classified into dry desulfurization and wet desulfurization according to its weak acidity and strong reducibility. The dry desulfurization is to utilize the reducibility and the combustibility of hydrogen sulfide, and uses a solid oxidant and an adsorbent to desulfurize or directly burn, and the wet desulfurization is to carry out adsorption desulfurization firstly and then analysis recovery by a liquid desulfurizing agent according to a physical chemistry principle; the wet desulfurization mainly adopts organic amine liquid (alcohol amine) and mainly adopts Monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA), diisopropanolamine (DlPA), triethanolamine (TEA) and N-Methyldiethanolamine (MDEA) as desulfurizing agents of main agents, and the wet desulfurization of alcohol amine is a common method for removing hydrogen sulfide in natural gas and refinery gas. The prior alcohol amine is N-methyl diethanol amine (MDEA) or a mixture thereof with steric hindrance effect, and the desulfurizing agent has the effect on H 2 S/CO 2 Is removed from (a)Has certain selectivity, but poor removal selectivity, and simultaneously removes a large amount of carbon dioxide while removing hydrogen sulfide, and has high CO content 2 /H 2 The removal selectivity of the mixed gas with the S ratio still needs to be improved, the lower removal selectivity can cause the increase of the treatment capacity of a subsequent device, the circulation quantity of the amine liquid is required to be large, the production energy consumption is increased, and the energy consumption of the device is high.
Disclosure of Invention
Aiming at the problems, the invention provides a sterically hindered amine composite desulfurizer and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
a sterically hindered amine composite desulfurizer has the following composition by mass percent: 32-48% of hindered amine, 0-1% of corrosion inhibitor, 0.1-1.5% of defoamer, 14-20% of stabilizer, 8-15% of desulfurization auxiliary agent and the balance of solvent, wherein the desulfurization auxiliary agent comprises an amination product of terpyridyl phenylboronic acid, and the preparation method comprises the following steps:
weighing 4'- (4-boric acid phenyl) -2,2',6',2' -terpyridine (CAS number: 381218-96-8), adding chloroform, performing ultrasonic dispersion for 0.5-2h, centrifuging after dispersion is completed, collecting precipitate, dissolving the collected precipitate in deionized water, adding tetramethyl ethylenediamine hydrochloride (CAS number: 75804-28-3), fully stirring and mixing, heating the mixed system to 50-100 ℃ and performing heat preservation reflux for 1-2h, cooling to room temperature after reaction is completed, performing reduced pressure distillation to remove solvent, adding chloroform, performing ultrasonic dispersion for 0.5-2h, centrifuging, collecting precipitate, washing the collected precipitate with chloroform, and drying to obtain the aminated product of terpyridine phenylboronic acid.
In some preferred embodiments of the present invention, the sterically hindered amine is one or more of N-benzhydryl azetidin-3-ol, tert-butylaminoethoxyethanol, 1, 3-di-tert-butylamino-2-propanol, 1-cyclohexyl-3-aziridine alcohol.
In some preferred embodiments of the present invention, the corrosion inhibitor is one or more of imidazolyl dithiourea, 2-amino-imidazolidinone, bis (propargyloxymethyl) isopropyl benzyl ammonium chloride, bis (propargyloxymethyl) butyl benzyl ammonium chloride.
In some preferred embodiments of the present invention, the defoaming agent is a silicone oil, and the silicone oil is one or more of dimethyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil and polyether modified silicone oil.
In some preferred embodiments of the present invention, the stabilizer is one or more of N- (t-butoxycarbonyl) ethanolamine, morpholine, piperazine.
In some preferred embodiments of the present invention, the solvent is a mixed solvent of deionized water and a glycol, which is propylene glycol, 1, 4-butanediol, or 1, 5-pentanediol.
In some preferred embodiments of the invention, the mass ratio of the 4' - (4-boronylphenyl) -2,2',6',2 "-terpyridine to the tetramethylethylenediamine hydrochloride is 1: (0.53-0.55).
In some preferred embodiments of the present invention, the desulfurization aid comprises a modified product of 4,4' -bipyridine, the method of making comprising the steps of:
respectively weighing 4,4 '-bipyridine and alpha-chloro-3, 5-dichloro acetophenone, dissolving in anhydrous N, N-dimethylformamide solvent, fully mixing and stirring uniformly, stirring and refluxing for 12-24h at 100-120 ℃, cooling to room temperature after the reaction is finished, centrifugally separating and precipitating, washing the precipitate sequentially with anhydrous N, N-dimethylformamide and acetone, drying to obtain a substituted product, adding the substituted product into an aqueous solution of 2- (ethylamino) ethanol, fully stirring and refluxing for 12-24h at 100-120 ℃ under a protective atmosphere, cooling to room temperature after the reaction is finished, adding chloroform after steaming and removing the solvent under reduced pressure, ultrasonically dispersing for 0.5-2h, centrifugally collecting the precipitate, washing the collected precipitate with chloroform, and drying to obtain the modified product of the 4,4' -bipyridine.
In some preferred embodiments of the present invention, the mass ratio of the 4,4' -bipyridine and the α -chloro-3, 5-dichloroacetophenone, the 2- (ethylamino) ethanol is 1: (3.5-3.6): (6.3-6.5).
The invention also provides a preparation method of the sterically hindered amine composite desulfurizer, which comprises the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the stabilizer, then adding the solvent, stirring for 10-60min, then adding the corrosion inhibitor, the defoamer and the desulfurization auxiliary agent, and circularly stirring and refluxing for 30-60min to obtain the hindered amine composite desulfurizer.
The beneficial effects of the invention are as follows:
aiming at the problem that the existing alcohol amine desulfurizer is poor in hydrogen sulfide removal selectivity, the invention provides a sterically hindered amine composite desulfurizer which has good absorption selectivity and removal rate for hydrogen sulfide, is especially suitable for hydrogen sulfide removal in the processes of natural gas, coal chemical industry and petrochemical industry, has stable product performance and good water solubility, can prolong the application period of the desulfurizing amine liquid, and reduces the consumption of the desulfurizing amine liquid; specifically, the invention improves the removal rate of hydrogen sulfide by adding a desulfurization auxiliary agent on the basis of the existing sterically hindered amine alkaline absorbent, wherein the desulfurization auxiliary agent comprises an aminated product of terpyridyl phenylboronic acid, and the removal rate of the desulfurization agent system to hydrogen sulfide is effectively promoted based on terpyridyl and a polymethyl aminated boric acid group; furthermore, the invention further improves the removal selectivity of the desulfurizer system to hydrogen sulfide by compounding the modified product of the 4,4' -bipyridine, and particularly, the inner salt type substituted 4,4' -bipyridine has multiple oxidation-reduction states and electron accepting characteristics, is an electron transfer agent based on photo/thermal induction, takes the substituted 4,4' -bipyridine as a receptor, and takes N, N-diethylaniline as a donor, promotes the electron transfer of the modified product under photo/thermal induction, so that the hydrogen sulfide with higher reduction-oxidation activity has better affinity with the desulfurizer system, further improves the removal selectivity of the system to hydrogen sulfide in the mixed gas containing high carbon dioxide proportion, and increases the adsorption of the hydrogen sulfide; the invention improves the use concentration of the desulfurizing agent system by adding the defoaming agent, reduces amine running, reduces the circulating quantity of amine liquid, effectively reduces energy consumption and simultaneously reduces corrosion to devices.
Description of the embodiments
The invention will be further described with reference to the following examples.
Example 1
A sterically hindered amine composite desulfurizer has the following composition by mass percent: 37% of hindered amine, 0.1% of 2-amino-imidazolone, 0.5% of simethicone, 16% of N- (tert-butoxycarbonyl) ethanolamine, 10% of desulfurization auxiliary agent and 36.4% of solvent, wherein:
the hindered amine is tert-butylaminoethoxyethanol and 1, 3-di-tert-butylamine-2-propanol, wherein the mass ratio of the tert-butylaminoethoxyethanol to the 1:1, a mixture of two or more of the above-mentioned materials;
the desulfurization auxiliary agent is an amination product of terpyridyl phenylboronic acid, and the preparation method comprises the following steps:
weighing 4'- (4-boric acid phenyl) -2,2',6',2' -terpyridine (CAS number: 381218-96-8), adding chloroform, performing ultrasonic dispersion for 1h, centrifuging after dispersion is completed, collecting precipitate, dissolving the collected precipitate in deionized water, adding tetramethyl ethylenediamine hydrochloride (CAS number: 75804-28-3), fully stirring and mixing, heating the mixed system to 80 ℃ and keeping the temperature for reflux for 1.5h, cooling to room temperature after reaction is completed, concentrating under reduced pressure, adding chloroform, performing ultrasonic dispersion for 1h, centrifuging, collecting precipitate, washing the collected precipitate with chloroform, and drying to obtain an aminated product of terpyridine phenylboronic acid; the mass ratio of the 4'- (4-boranylphenyl) -2,2',6',2' -terpyridine to the tetramethyl ethylenediamine hydrochloride is 1:0.54;
the solvent is a mixed solvent of deionized water and 1, 4-butanediol (v/v=5:1);
the preparation method of the sterically hindered amine composite desulfurizer comprises the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the N- (tert-butoxycarbonyl) ethanolamine, then adding the solvent, stirring for 30min, then adding the 2-amino-imidazolone, the simethicone and the desulfurization auxiliary agent, and circularly stirring and refluxing for 30min to obtain the hindered amine composite desulfurizing agent.
Example 2
A sterically hindered amine composite desulfurizer has the following composition by mass percent: 37% of hindered amine, 0.1% of 2-amino-imidazolone, 0.5% of simethicone, 16% of N- (tert-butoxycarbonyl) ethanolamine, 10% of desulfurization auxiliary agent and 36.4% of solvent, wherein:
the hindered amine is tert-butylaminoethoxyethanol and 1, 3-di-tert-butylamine-2-propanol, wherein the mass ratio of the tert-butylaminoethoxyethanol to the 1:1, a mixture of two or more of the above-mentioned materials;
the desulfurization auxiliary agent is a modified product of 4,4' -bipyridine, and the preparation method comprises the following steps:
respectively weighing 4,4 '-bipyridine and alpha-chloro-3, 5-dichloroacetophenone, dissolving in an anhydrous N, N-dimethylformamide solvent, fully mixing and stirring uniformly, stirring and refluxing at 100 ℃ for 16 hours, cooling to room temperature after the reaction is finished, centrifugally separating and precipitating, washing the precipitate with anhydrous N, N-dimethylformamide and acetone in sequence, drying to obtain a substituted product, adding the substituted product into an aqueous solution (34 wt%) of 2- (ethylamino) ethanol, fully stirring and refluxing for 12 hours at 110 ℃ under a nitrogen protective atmosphere, cooling to room temperature after the reaction is finished, concentrating under reduced pressure, adding chloroform, performing ultrasonic dispersion for 11 hours, centrifugally collecting the precipitate, washing the collected precipitate with chloroform, and drying to obtain a modified product of the 4,4' -bipyridine; the mass ratio of the 4,4' -bipyridine to the alpha-chloro-3, 5-dichloroacetophenone to the 2- (ethylamino) ethanol is 1:3.53:6.4;
the solvent is a mixed solvent of deionized water and 1, 4-butanediol (v/v=5:1);
the preparation method of the sterically hindered amine composite desulfurizer comprises the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the N- (tert-butoxycarbonyl) ethanolamine, then adding the solvent, stirring for 30min, then adding the 2-amino-imidazolone, the simethicone and the desulfurization auxiliary agent, and circularly stirring and refluxing for 30min to obtain the hindered amine composite desulfurizing agent.
Example 3
A sterically hindered amine composite desulfurizer has the following composition by mass percent: 37% of hindered amine, 0.1% of 2-amino-imidazolone, 0.5% of simethicone, 16% of N- (tert-butoxycarbonyl) ethanolamine, 10% of desulfurization auxiliary agent and 36.4% of solvent, wherein:
the hindered amine is tert-butylaminoethoxyethanol and 1, 3-di-tert-butylamine-2-propanol, wherein the mass ratio of the tert-butylaminoethoxyethanol to the 1:1, a mixture of two or more of the above-mentioned materials;
the desulfurization auxiliary agent is a mixture of an aminated product of terpyridyl phenylboronic acid and a modified product of 4,4' -bipyridine, and the mass ratio of the desulfurization auxiliary agent to the modified product of the terpyridyl phenylboronic acid is 5:3, a step of;
the preparation method of the aminated product of terpyridyl phenylboronic acid is the same as that of example 1;
the preparation method of the modified product of 4,4' -bipyridine is the same as in example 2;
the solvent is a mixed solvent of deionized water and 1, 4-butanediol (v/v=5:1);
the preparation method of the sterically hindered amine composite desulfurizer comprises the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the N- (tert-butoxycarbonyl) ethanolamine, then adding the solvent, stirring for 30min, then adding the 2-amino-imidazolone, the simethicone and the desulfurization auxiliary agent, and circularly stirring and refluxing for 30min to obtain the hindered amine composite desulfurizing agent.
Example 4
A sterically hindered amine composite desulfurizer has the following composition by mass percent: 37% of sterically hindered amine, 0.1% of 2-amino-imidazolone, 0.5% of simethicone, 16% of N- (tert-butoxycarbonyl) ethanolamine and 46.4% of solvent, wherein:
the hindered amine is tert-butylaminoethoxyethanol and 1, 3-di-tert-butylamine-2-propanol, wherein the mass ratio of the tert-butylaminoethoxyethanol to the 1:1, a mixture of two or more of the above-mentioned materials;
the solvent is a mixed solvent of deionized water and 1, 4-butanediol (v/v=5:1);
the preparation method of the sterically hindered amine composite desulfurizer comprises the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the N- (tert-butoxycarbonyl) ethanolamine, then adding the solvent, stirring for 30min, then adding the 2-amino-imidazolone and the simethicone, and circularly stirring and refluxing for 30min to obtain the hindered amine composite desulfurizing agent.
Experimental example
The performance test of the composite desulfurizing agent of the embodiment 1-4 is carried out by using a simulated absorption device, specifically, the mixed gas containing nitrogen, hydrogen sulfide and carbon dioxide with a certain proportion is introduced into an absorption container filled with the composite desulfurizing agent (1L) of the embodiment 1-4 at a certain flow (100 mL/min) at room temperature for bubbling absorption, the component analysis is carried out on the tail gas at the outlet of the absorption container after the absorption for a certain time (30 min), the content of the hydrogen sulfide and the content of the carbon dioxide are measured by a gas chromatography, and the measurement results are shown in the following table:
finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A sterically hindered amine composite desulfurizing agent, characterized by the following composition in mass fraction: 32-48% of hindered amine, 0-1% of corrosion inhibitor, 0.1-1.5% of defoamer, 14-20% of stabilizer, 8-15% of desulfurization auxiliary agent and the balance of solvent, wherein the desulfurization auxiliary agent comprises an amination product of terpyridyl phenylboronic acid, and the preparation method comprises the following steps:
weighing 4'- (4-boric acid phenyl) -2,2',6',2' -terpyridine, adding chloroform, performing ultrasonic dispersion for 0.5-2h, centrifuging to collect precipitate after dispersion is completed, dissolving the collected precipitate in deionized water, adding tetramethyl ethylenediamine hydrochloride, fully stirring and mixing, heating the mixed system to 50-100 ℃, keeping the temperature and refluxing for 1-2h, cooling to room temperature after reaction is completed, performing reduced pressure evaporation to remove a solvent, adding chloroform, performing ultrasonic dispersion for 0.5-2h, centrifuging to collect precipitate, washing the collected precipitate with chloroform, and drying to obtain an aminated product of terpyridine phenylboronic acid;
the desulfurization auxiliary agent comprises a modified product of 4,4' -bipyridine, and the preparation method comprises the following steps:
respectively weighing 4,4 '-bipyridine and alpha-chloro-3, 5-dichloro acetophenone, dissolving in anhydrous N, N-dimethylformamide solvent, fully mixing and stirring uniformly, stirring and refluxing for 12-24h at 100-120 ℃, cooling to room temperature after the reaction is finished, centrifugally separating and precipitating, washing the precipitate sequentially with anhydrous N, N-dimethylformamide and acetone, drying to obtain a substituted product, adding the substituted product into an aqueous solution of 2- (ethylamino) ethanol, fully stirring and refluxing for 12-24h at 100-120 ℃ under a protective atmosphere, cooling to room temperature after the reaction is finished, adding chloroform after steaming under reduced pressure, ultrasonically dispersing for 0.5-2h, centrifugally collecting and precipitating, washing the collected precipitate with chloroform, and drying to obtain a modified product of the 4,4' -bipyridine;
the mass ratio of the 4,4' -bipyridine to the alpha-chloro-3, 5-dichloroacetophenone to the 2- (ethylamino) ethanol is 1: (3.5-3.6): (6.3-6.5).
2. The hindered amine composite desulfurizing agent according to claim 1, wherein the hindered amine is one or more of N-benzhydryl azetidin-3-ol, tert-butylaminoethoxyethanol, 1, 3-di-tert-butylamino-2-propanol, 1-cyclohexyl-3-aziridine alcohol.
3. The sterically hindered amine composite desulfurizer as claimed in claim 1, wherein the corrosion inhibitor is one or more of imidazolyl dithiourea, 2-amino-imidazolone, di (propynyloxymethyl) isopropyl benzyl ammonium chloride and di (propynyloxymethyl) butyl benzyl ammonium chloride.
4. The sterically hindered amine composite desulfurizer as claimed in claim 1, wherein the defoamer is organic silicone oil, and the organic silicone oil is one or more of dimethyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil and polyether modified silicone oil.
5. The hindered amine composite desulfurizing agent of claim 1, wherein the stabilizing agent is one or more of N- (tert-butoxycarbonyl) ethanolamine, morpholine and piperazine.
6. The hindered amine composite desulfurizing agent of claim 1, wherein the solvent is a mixed solvent of deionized water and a glycol, and the glycol is propylene glycol, 1, 4-butanediol or 1, 5-pentanediol.
7. A hindered amine complex desulfurization agent according to claim 1, wherein the mass ratio of 4' - (4-boronylphenyl) -2,2',6',2 "-terpyridine to tetramethylethylenediamine hydrochloride is 1: (0.53-0.55).
8. A process for the preparation of a sterically hindered amine complex desulfurizer as claimed in any one of claims 1 to 7, characterized by the following steps:
(1) Preparing the desulfurization auxiliary agent for later use;
(2) Firstly mixing the hindered amine and the stabilizer, then adding the solvent, stirring for 20-30min, then adding the corrosion inhibitor, the defoamer and the desulfurization auxiliary agent, and circularly stirring and refluxing for 40-60min to obtain the hindered amine composite desulfurizer.
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