CN115282770A - Method for removing hydrogen sulfide gas by novel guanidyl magnetic ionic liquid - Google Patents
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 143
- 239000007789 gas Substances 0.000 title claims abstract description 53
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 36
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 claims abstract description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 38
- 230000023556 desulfurization Effects 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 claims description 181
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 229910052717 sulfur Inorganic materials 0.000 claims description 36
- 239000011593 sulfur Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 abstract description 14
- 230000002745 absorbent Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 150000003839 salts Chemical group 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
-
- 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
- B01D2252/30—Ionic liquids and zwitter-ions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/65—Catalysts not containing noble metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for removing hydrogen sulfide gas by using a novel guanidino magnetic ionic liquid. The invention provides a guanidyl magnetic ionic liquid which has an amino group, small molecular weight and low viscosity and is used as a desulfurizing agent, and H 2 S is absorbed and oxidized into elemental sulfur to realize the desulfurization and purification of the gas. After the elemental sulfur is recovered, air or oxygen is introduced into the reacted ionic liquid to enable the ionic liquid to be regenerated and recycled. Compared with the traditional desulfurization method, the desulfurization process hardly causes the loss of the absorbent and has larger H 2 S solubility and stronger H 2 S oxidation ability, no side reaction in the absorption process, small secondary pollution and overcoming the defects of the prior artThe desulfurization process has the problems of more secondary salt, easy pollution and the like, and has good development prospect in the field of industrial gas purification.
Description
Technical Field
The invention relates to the technical field of gas purification, relates to preparation of a novel guanidino magnetic ionic liquid and application of the novel guanidino magnetic ionic liquid in removal of hydrogen sulfide in gas, and particularly relates to a method for removing hydrogen sulfide gas by using the novel guanidino ionic liquid. In the desulfurization method, the ionic liquid desulfurizer has amino groups, and is enhanced to be acidic H 2 The affinity of S, small molecular weight, low viscosity, better mass transfer effect, low conveying power consumption, no pollution, no side reaction, high desulfurization rate and recycling after regeneration, and is a novel green and environment-friendly hydrogen sulfide removal process.
Technical Field
Due to the enforcement of regulations on environmental pollution of exhaust gases such as SOx and NOx to the atmosphere, deep desulfurization of fuel products such as diesel oil and gasoline has attracted increasing attention. The catalytic process requires high temperature, high pressure, high energy cost, and limited ability to effectively eliminate refractory sulfides in fuels. Hydrogen sulfide is a gas produced by the decomposition of sulfur-containing organic compounds or the reaction of metal sulfides with acids. Colorless, smelly eggs, is volatile, can generate blue flame when being burnt, and is a byproduct in a plurality of industrial production processes. The hydrogen sulfide poisoning happens all over the world, and in China, the hydrogen sulfide poisoning accounts for the second place of occupational acute poisoning and is only second to carbon monoxide poisoning. Hydrogen sulfide gas seriously threatens the life safety of workers and needs to be paid high attention.
Over the past several decades, alternative fuel desulfurization technologies have been developed, such as oxidation, extraction, adsorption, biological desulfurization, and the like. The oxidation desulfurization has high desulfurization efficiency and wide prospect, but the used oxidant can also oxidize hydrocarbon and organic sulfur-containing compounds in the fuel oil, thereby greatly reducing the quality of the fuel oil. The extraction method is more and more concerned due to mild and simple operation conditions, but the extraction method cannot change the chemical structure of compounds in the fuel oil, so that the extraction method has little influence on the quality of the fuel oil. In addition, some of the organic solvents used pose further environmental and safety concerns due to their flammability and volatility.
The ionic liquid is an ionic compound consisting of anions and cations, is a liquid which is not easy to volatilize at room temperature, and the anions and cations can be inorganic ions and organic ions, and has the characteristics of outstanding designability, super-solubility, wide electrochemical window and high thermochemical stability. The non-aqueous phase ionic liquid wet oxidation desulfurization process constructed based on good oxidability, redox reversibility and stability of metal-based ionic liquid and super-solubility in organic solvent is rapidly developed and is used for energy spectrum analysis of fuel oil. Many aromatic ionic liquids exhibit low selectivity between aromatic sulfur components and toluene due to their similar pi-pi interactions, and are partially dissolved in fuel, thereby changing the composition of the fuel and contaminating the fuel. Therefore, a novel room-temperature ionic liquid which has high desulfurization efficiency, good selectivity, small pollution to grease and good recyclability is urgently needed to be found. The magnetic ionic liquid not only has the excellent performance of the traditional ionic liquid, but also has strong response to an additional magnet, and is easy to separate and reuse.
Chinese patent No. CN202110747808.6, named as a reproducible complex ionic liquid desulfurizer, and a preparation method and application thereof, provides a desulfurizer which has good removal effect on organic sulfur such as carbonyl sulfur, carbon disulfide, mercaptan and the like, desorbs the adsorbed organic sulfur by heating after saturated adsorption, and can be repeatedly regenerated and reused. The Chinese patent No. CN202110292619.4, named as iron-copper ionic liquid desulfurizer, preparation method and desulfurization method, provides a preparation method of a novel iron-copper ionic liquid with high sulfur capacity, good desulfurization effect and stable regeneration performance, and can be directly used as industrial sulfur. Chinese patent No. CN201210088605.1 entitled "preparation method and application of ionic liquid desulfurizer with bimetal reaction active center" provides ionic liquid with bimetal reaction active center consisting of organic complex Co or Fe cation and complex Fe anion, and is suitable for removing mercaptanOrganic sulfur and inorganic H such as thioether and thiophene 2 S, the organic sulfur removal rate reaches 90-100wt%, and H 2 The S desulfurization efficiency reaches 95 to 100 weight percent. Chinese patent No. CN202011355696.1, entitled "a method and equipment for desulfurizing sulfur-containing gas by using ionic liquid" provides a method and equipment for desulfurizing sulfur-containing gas by using ionic liquid, and effectively avoids the problems of pipeline blockage, scaling, difficult sulfur separation, slow ionic liquid regeneration and the like in the process of transporting and regenerating rich liquid.
[TMG]The Cl/xFeCl3 novel guanidino magnetic ionic liquid desulfurization technology is characterized in that the absorbent is nontoxic and can absorb H in one step 2 Conversion of S to the elements S, H 2 The removal rate of S can reach more than 99%. Compared to other ionic liquids, and [ TMG]The Cl/xFeCl3 novel guanidino magnetic ionic liquid has no pollution to model oil and shows good extraction performance. Since the solubility difference is related to the toluene component, the pi interaction between pi-toluene and imidazole rings plays a key role in enhancing the mutual solubility, and therefore, [ TMG]The Cl/xFeCl3 novel guanidino magnetic ionic liquid has much less pollution to fuel oil than imidazole-based ionic liquid. Furthermore, [ TMG ]]The Cl/xFeCl3 novel guanidino magnetic ionic liquid has small viscosity, good stability and high mass transfer speed in extraction experiments. Thus, this patent proposes [ TMG]Cl/xFeCl3 novel guanidyl magnetic ionic liquid and is applied to gas desulfurization.
Disclosure of Invention
The invention aims to provide a method for removing hydrogen sulfide by catalytic oxidation by using a novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid as a liquid-phase absorption system, which comprises the steps of mixing anhydrous FeCl3 and [ TMG ] Cl in equal molar ratio to form a liquid mixture in an N2 environment, filtering, drying in vacuum to obtain [ TMG ] [ FeCl4], and adding a certain amount of FeCl3 to obtain the [ TMG ] Cl4]. In the desulfurization method, the ionic liquid desulfurizer has amino groups, enhances the affinity with acidic H2S, has small molecular weight, low viscosity, better mass transfer effect, low transmission power consumption, no pollution, no side reaction, high desulfurization rate and recycling after regeneration.
[ TMG ] of the present invention]Cl/xFeCl 3 Novel guanidyl magnetic ionic liquid contains cationsAnd an anion, the cation being [ TMG ]] + The anion is Cl/xFeCl 3 - Wherein the cation [ TMG ]] + With anions Cl/xFeCl 3 - Is 1:1.
It is preferable that: said [ TMG ]]The magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 - 6 emu/g。
The second purpose of the invention is to provide a preparation method of the novel guanidino magnetic ionic liquid of [ TMG ] Cl/xFeCl3. The steps of the synthesis and preparation process of the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid are as follows:
(1) 0.1mol of 1,1,3,3-tetramethylguanidine was added to 25ml of acetonitrile with vigorous stirring. Then, a small excess of hydrochloric acid was added dropwise over 2 hours, followed by continuous stirring for 4 hours. After the reaction is finished, the solvent is removed, and the intermediate product [ TMG ]]Cl was dried at 60 ℃ for 2 hours under low pressure. In N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
(2) The FeCl 3 Is anhydrous FeCl 3 The purity is 99 percent;
(3) 1,1,3,3-tetramethylguanidine, acetonitrile, hydrochloric acid purity of 99%;
(5) Said [ TMG ]]Raw material [ TMG ] of Cl/xFeCl3 novel guanidyl magnetic ionic liquid][FeCl 4 ]And FeCl 3 The purity of (A) is more than 99%;
(6) Said [ TMG ]]The preparation process of the Cl/xFeCl3 novel guanidino magnetic ionic liquid is carried out in N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Mixing Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 Thus obtaining the product;
the third purpose of the invention is to provide a method for removing hydrogen sulfide gas by [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid, which comprises the following steps:
(1) At N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]；
(2)[TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl3 novel guanidino magnetic ionic liquid;
(3)[TMG]the magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 -6 emu/g；
(4) Introducing hydrogen sulfide gas into the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid to perform catalytic oxidation reaction so as to absorb and remove hydrogen sulfide;
(5) And (3) regenerating and recycling the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid after the desulfurization reaction is finished.
Preferably, said [ TMG]In the raw material of Cl/xFeCl3 novel guanidino magnetic ionic liquid, the FeCl 3 Is anhydrous FeCl 3 The purity is 99 percent; the 1,1,3,3-tetramethylguanidine, acetonitrile and hydrochloric acid have the purity of 99 percent.
Preferably, said [ TMG ]]The preparation method of the Cl/xFeCl3 novel guanidino magnetic ionic liquid comprises the following steps: 0.1mol of 1,1,3,3-tetramethylguanidine was added to 25ml of acetonitrile with vigorous stirring. Then, a small excess of hydrochloric acid was added dropwise over 2 hours, followed by continuous stirring for 4 hours. After the reaction is finished, the solvent is removed, and the intermediate product [ TMG ]]Cl was dried at 60 ℃ for 2 hours under low pressure. In N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
Preferably, the [ TMG ] is prepared]Raw material [ TMG ] of Cl/xFeCl3 novel guanidyl magnetic ionic liquid][FeCl 4 ]And FeCl 3 The purity of (A) is 99% or more.
Preferably, said [ TMG]The preparation process of the Cl/xFeCl3 novel guanidino magnetic ionic liquid is carried out in N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Cl mixed to form a liquidThe mixture is filtered and dried in vacuum to obtain [ TMG ]][FeCl 4 ]Adding a certain amount of FeCl 3 Thus obtaining the product.
Preferably, said [ TMG]The magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 - 6 emu/g。
Preferably, said [ TMG ]]Cl/xFeCl3 novel guanidino magnetic ionic liquid serving as both catalyst and oxidant, wherein Fe 3+ The ions are an oxidizing agent to convert hydrogen sulfide to elemental sulfur.
Preferably, the elemental sulfur is insoluble in a desulfurizer system, and sulfur particles are separated by a method of centrifugation, sedimentation and filtration, so that the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid can be regenerated and recycled.
Preferably, air or oxygen is introduced into the novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid after the desulfurization reaction, and the pressure is reduced and the novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid is heated at the same time, so that the novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid after the desulfurization reaction is regenerated and recycled.
The invention constructs a desulfurization system with [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid as an absorbent. Compared with other ionic liquids, the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid has no pollution to model oil and shows good extraction performance. In addition, the novel [ TMG ] Cl/xFeCl3 guanidyl magnetic ionic liquid has small viscosity, better stability and high mass transfer speed in extraction experiments.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention aims to provide a method for removing hydrogen sulfide by catalytic oxidation by using a novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid as a liquid-phase absorption system, which comprises the steps of mixing anhydrous FeCl3 and [ TMG ] Cl in equal molar ratio to form a liquid mixture in an N2 environment, filtering, drying in vacuum to obtain [ TMG ] [ FeCl4], and adding a certain amount of FeCl3 to obtain the [ TMG ] Cl4]. In the desulfurization method, the ionic liquid desulfurizer has amino groups, enhances the affinity with acidic H2S, has small molecular weight, low viscosity, better mass transfer effect, low transmission power consumption, no pollution, no side reaction, high desulfurization rate and recycling after regeneration.
[ TMG ] of the present invention]Cl/xFeCl 3 The novel guanidyl magnetic ionic liquid comprises cations and anions, wherein the cations are [ TMG ]] + The anion is Cl/xFeCl 3 - Wherein the cation [ TMG ]] + With anions Cl/xFeCl 3 - Is 1:1.
It is preferable that: said [ TMG ]]The magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 - 6 emu/g。
The second purpose of the invention is to provide a preparation method of the novel guanidino magnetic ionic liquid of [ TMG ] Cl/xFeCl3. The steps of the synthesis and preparation process of the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid are as follows:
(1) 0.1mol of 1,1,3,3-tetramethylguanidine was added to 25ml of acetonitrile with vigorous stirring. Then, a small amount of excess hydrochloric acid was added dropwise over 2 hours, followed by continuous stirring for 4 hours. After the reaction is finished, the solvent is removed, and the intermediate product [ TMG ]]Cl was dried at 60 ℃ for 2 hours under low pressure. At N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
(2) The FeCl 3 Is anhydrous FeCl 3 The purity is 99 percent;
(3) 1,1,3,3-tetramethylguanidine, acetonitrile, hydrochloric acid purity of 99%;
(5) Said [ TMG ]]Raw material of Cl/xFeCl3 novel guanidyl magnetic ionic liquid [ TMG][FeCl 4 ]And FeCl 3 The purity of (A) is more than 99%;
(6) Said [ TMG ]]ClThe preparation process of the/xFeCl 3 novel guanidino magnetic ionic liquid is carried out in N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 Thus obtaining the product;
the third purpose of the invention is to provide a method for removing hydrogen sulfide gas from [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid, which comprises the following steps:
(1) In N 2 Under the environment, the anhydrous FeCl with equal molar ratio is added 3 And [ TMG ]]Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]；
(2)[TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl3 novel guanidino magnetic ionic liquid;
(3)[TMG]the magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 -6 emu/g；
(4) Introducing hydrogen sulfide gas into the [ TMG ] Cl/xFeCl3 novel guanidyl magnetic ionic liquid to perform catalytic oxidation reaction so as to absorb and remove hydrogen sulfide;
(5) And (3) regenerating and recycling the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid after the desulfurization reaction is finished.
Preferably, said [ TMG ]]In the raw material of Cl/xFeCl3 novel guanidyl magnetic ionic liquid, the FeCl 3 Is anhydrous FeCl 3 The purity is 99 percent; the 1,1,3,3-tetramethyl guanidine, acetonitrile and hydrochloric acid have the purity of 99 percent.
Preferably, said [ TMG]The preparation method of the Cl/xFeCl3 novel guanidino magnetic ionic liquid comprises the following steps: 0.1mol of 1,1,3,3-tetramethylguanidine was added to 25ml of acetonitrile with vigorous stirring. Then, a small excess of hydrochloric acid was added dropwise over 2 hours, followed by continuous stirring for 4 hours. After the reaction is finished, the solvent is removed, and the intermediate product [ TMG ]]Cl was dried at 60 ℃ for 2 hours under low pressure. In N 2 Under the environment, the anhydrous FeCl with equal molar ratio is added 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
Preferably, the [ TMG ] is prepared]Raw material [ TMG ] of Cl/xFeCl3 novel guanidyl magnetic ionic liquid][FeCl 4 ]And FeCl 3 The purity of (A) is 99% or more.
Preferably, said [ TMG]The preparation process of the Cl/xFeCl3 novel guanidino magnetic ionic liquid is carried out in N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Mixing Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 Thus obtaining the product.
Preferably, said [ TMG]The magnetic susceptibility of Cl/xFeCl3 novel guanidyl magnetic ionic liquid is 59.1 multiplied by 10 - 6 emu/g。
Preferably, said [ TMG]Cl/xFeCl3 novel guanidino magnetic ionic liquid serving as both catalyst and oxidant, wherein Fe 3+ The ions are an oxidizing agent to convert hydrogen sulfide to elemental sulfur.
Preferably, the elemental sulfur is insoluble in a desulfurizer system, and sulfur particles are separated by centrifugation, sedimentation and filtration, so that the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid can be recycled.
Preferably, air or oxygen is introduced into the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid after the desulfurization reaction, and the pressure is reduced and the ionic liquid is heated at the same time, so that the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid after the desulfurization reaction is regenerated and recycled.
The method for removing hydrogen sulfide from the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid comprises the following steps:
adding 100-200mL of the novel guanidino magnetic ionic liquid of [ TMG ] Cl/xFeCl3 into a reactor, and controlling the reaction temperature at 20-80 ℃. 0.1-1% hydrogen sulfide standard gas with the gas velocity of 10-30mL/min is introduced from the lower end of the reactor (0.1-0.3 mL/min of gas is introduced into each mL of ionic liquid), and the gas passes through a novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid desulfurization system in the form of small bubbles from the bottom end of the reactor after being introduced. And extracting tail gas every 5min, detecting whether hydrogen sulfide is contained in the tail gas, recording the reaction time when the concentration of the hydrogen sulfide in the extracted tail gas is detected to be more than 10ppm, and calculating the sulfur capacity corresponding to the experiment. The sulfur capacity calculation formula is as follows:
in the formula, S is sulfur capacity, g/L, Q is gas flow, mL/min, and V is ionic liquid volume, mL.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 5-20min under the condition of 1000-5000 r/min. The obtained sulfur is precipitated, filtered, washed by deionized water for 4 to 5 times, and then dried in vacuum for 2 to 5 hours at the temperature of between 60 and 85 ℃, and finally light yellow sulfur particles are obtained. And (4) carrying out infrared spectrum analysis on the ionic liquid which has absorbed the hydrogen sulfide to judge whether byproducts such as sulfate, thiosulfate and sulfite are generated.
It is a fourth object of the present invention to provide said [ TMG]A method for regenerating Cl/xFeCl3 novel guanidino magnetic ionic liquid, and the [ TMG]In the regeneration process of the Cl/xFeCl3 novel guanidino magnetic ionic liquid, the load is that the flow of air or oxygen introduced into each mL of the ionic liquid is 0.02-0.2mL/min, the temperature is 35-55 ℃, and when Fe is contained in the ionic liquid 2+ Regeneration is completed when the concentration is zero.
The regeneration of the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid desulfurizer comprises the following steps:
introducing air or pure oxygen into the recovered sulfur [ TMG ] in a mode of entering from bottom to top at normal pressure]In the Cl/xFeCl3 novel guanidino magnetic ionic liquid absorbent, the regeneration temperature is controlled to be 35-55 ℃, and the gas inlet flow is 10-25mL/min (the flow of air or oxygen introduced into each mL of ionic liquid is 0.02-0.2 mL/min). Measuring 0.5mL regenerated absorbent every 5-30 minutes to determine Fe therein 2+ Concentration, fe was not detected in the absorbent taken 3 times in succession 2+ Is present, the regeneration of the absorbent is considered complete.
The invention constructs a desulfurization system with [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid as an absorbent. Compared with other ionic liquids, the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid has no pollution to model oil and shows good extraction performance. In addition, the novel [ TMG ] Cl/xFeCl3 guanidino magnetic ionic liquid has low viscosity, good stability and high mass transfer speed in extraction experiments.
The specific implementation mode of the method for removing hydrogen sulfide gas by using the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid is detailed below.
Example 1
1,1,3,3-tetramethylguanidine (0.1 mol, 99% purity) and acetonitrile (25 mL, 99% purity) are sequentially placed into a 250mL round bottom flask with a condensing reflux device, a small amount of excess hydrochloric acid is added dropwise within 2h of constant-temperature mechanical stirring at a constant reaction temperature, continuous stirring is carried out for 4h, after the reaction is finished, the product is washed for 3 times to remove the solvent, and the intermediate product [ TMG ] Cl is dried for 2h at a low pressure of 60 ℃.
Under the N2 environment, anhydrous FeCl with equal molar ratio is added 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG ]][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
The reactor was charged with 100mL of a novel guanidino magnetic ionic liquid of [ TMG ] Cl/xFeCl3, and the reaction temperature was controlled at 30 ℃. 0.1% hydrogen sulfide standard gas with the gas velocity of 10mL/min is introduced from the lower end of the reactor under constant pressure (0.1 mL/min of gas is introduced into each mL of ionic liquid), and the gas passes through a novel guanidino magnetic ionic liquid desulfurization system of [ TMG ] Cl/xFeCl3 in the form of small bubbles from the bottom end of the reactor after introduction. And extracting tail gas every 5min, detecting whether hydrogen sulfide is contained in the tail gas, recording the reaction time when the concentration of the hydrogen sulfide in the extracted tail gas is detected to be more than 10ppm, and calculating the sulfur capacity corresponding to the experiment.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 20min at the condition of 1000 r/min. Precipitating the obtained sulfur, filtering, washing with deionized water for 4 times, and vacuum drying at 65 deg.C for 3h to obtain yellowish sulfur granules. And (4) carrying out infrared spectrum analysis on the ionic liquid which has absorbed the hydrogen sulfide to judge whether byproducts such as sulfate, thiosulfate and sulfite are generated.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 20min at the condition of 5000 r/min. The obtained sulfur precipitate was washed with deionized water 4 times and then vacuum dried at 85 ℃ for 3 hours to obtain 0.7453g of pale yellow sulfur.
Introducing air or pure oxygen into the recovered sulfur [ TMG ] in a mode of entering from bottom to top at normal pressure]Cl/xFeCl 3 In the novel guanidyl magnetic ionic liquid absorbent, the regeneration temperature is controlled to be 45 ℃, and the inlet gas flow is 10mL/min (the flow of air or oxygen introduced into each mL of ionic liquid is 0.02 mL/min). Measuring 0.5mL of regenerated absorbent every 10 minutes to determine Fe therein 2+ Concentration, fe could not be detected in the taken ionic liquid for 3 times 2+ Is present.
Example 2
1,1,3,3-tetramethylguanidine (0.2 mol, 99% purity) and acetonitrile (50 mL, 99% purity) are placed in sequence in a 250mL round bottom flask with a condensing reflux unit, a small amount of excess hydrochloric acid is added dropwise over 4 hours of constant mechanical stirring at a constant reaction temperature, continuous stirring is carried out for 8 hours, after the reaction is finished, the solvent is removed, and the intermediate product [ TMG ] Cl is dried at a low pressure of 60 ℃ for 3 hours.
In N 2 Under the environment, the anhydrous FeCl with equal molar ratio is added 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG ]][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
150mL of a novel guanidino magnetic ionic liquid of [ TMG ] Cl/xFeCl3 is added into the reactor, and the reaction temperature is controlled at 40 ℃. 0.5 percent hydrogen sulfide standard gas with the gas velocity of 25mL/min under constant pressure is introduced from the lower end of the reactor (0.2 mL/min of gas is introduced into each mL of ionic liquid), and the gas passes through a novel guanidino magnetic ionic liquid desulfurization system of [ TMG ] Cl/xFeCl3 in the form of small bubbles from the bottom end of the reactor after being introduced. And extracting tail gas every 5min, detecting whether hydrogen sulfide is contained in the tail gas, recording the reaction time when the concentration of the hydrogen sulfide in the extracted tail gas is detected to be more than 10ppm, and calculating the sulfur capacity corresponding to the experiment.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 10min at 3000 r/min. The obtained sulfur precipitate is filtered, washed with deionized water for 5 times, and vacuum dried at 75 deg.C for 4h to obtain light yellow sulfur granules. And (4) carrying out infrared spectrum analysis on the ionic liquid which has absorbed the hydrogen sulfide to judge whether byproducts such as sulfate, thiosulfate and sulfite are generated.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 20min at the condition of 5000 r/min. The obtained sulfur precipitate was washed with deionized water for 5 times and then vacuum-dried at 85 ℃ for 3 hours to obtain 1.2396g of pale yellow sulfur.
Introducing air or pure oxygen into the recovered sulfur [ TMG ] in a mode of entering from bottom to top under normal pressure]In the Cl/xFeCl3 novel guanidino magnetic ionic liquid absorbent, the regeneration temperature is controlled to be 45 ℃, and the air inlet flow rate is 20mL/min (the air or oxygen flow rate per mL of ionic liquid is 0.15 mL/min). Measuring 0.5mL of regenerated absorbent every 20 minutes to determine Fe therein 2+ Concentration, fe could not be detected in the taken ionic liquid for 3 times 2+ Is present.
Example 3
1,1,3,3-tetramethylguanidine (0.1 mol, purity 99%) and acetonitrile (20 mL, purity 99%) are placed in sequence in a 250mL round bottom flask with a condensing reflux device, a small amount of excess hydrochloric acid is added dropwise within 1.5h of constant-temperature mechanical stirring at a constant reaction temperature, stirring is continued for 3h, after the reaction is finished, the solvent is removed, and the intermediate product [ TMG ] Cl is dried for 2h at a low pressure of 60 ℃.
Equal molar proportions of anhydrous FeCl3 and [ TMG ] Cl were mixed under N2 to form a liquid mixture. The mixture was filtered and dried under vacuum to give [ TMG ] [ FeCl4]. Finally, a certain amount of FeCl3 is added into the [ TMG ] [ FeCl4] to obtain [ TMG ] Cl/xFeCl3.
The reactor was charged with 150mL of the novel guanidino magnetic ionic liquid of [ 2 ], [ TMG ] Cl/xFeCl3, the reaction temperature was controlled at 60 ℃. 0.7 percent hydrogen sulfide standard gas with the gas velocity of 20mL/min under constant pressure is introduced from the lower end of the reactor (0.25 mL/min of gas is introduced into each mL of ionic liquid), and the gas passes through a novel guanidino magnetic ionic liquid desulfurization system of [ TMG ] Cl/xFeCl3 in the form of small bubbles from the bottom end of the reactor after being introduced. Extracting tail gas every 10min and detecting whether the tail gas contains hydrogen sulfide, recording reaction time when the concentration of the hydrogen sulfide in the extracted tail gas is detected to be more than 10ppm, and calculating the sulfur capacity corresponding to the experiment.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 10min at 4000 r/min. The obtained sulfur precipitates, is filtered, washed by deionized water for 4 times and dried in vacuum at 70 ℃ for 4 hours, and finally light yellow sulfur particles are obtained. And (4) carrying out infrared spectrum analysis on the ionic liquid which absorbs the hydrogen sulfide to judge whether byproducts such as sulfate, thiosulfate and sulfite are generated.
And centrifuging the ionic liquid absorbing the hydrogen sulfide for 25min under the condition of 4000 r/min. The obtained sulfur precipitate was washed with deionized water 4 times and then vacuum dried at 85 ℃ for 2.5h to obtain pale yellow sulfur 0.6508g.
Introducing air or pure oxygen into the recovered sulfur [ TMG ] in a mode of entering from bottom to top at normal pressure]Cl/xFeCl 3 In the novel guanidyl magnetic ionic liquid absorbent, the regeneration temperature is controlled to be 50 ℃, and the inlet gas flow is 20mL/min (the flow of air or oxygen introduced into each mL of ionic liquid is 0.18 mL/min). Measuring 0.5mL regenerated absorbent every 25 minutes to determine Fe 2+ Concentration, fe could not be detected in the taken ionic liquid for 3 times 2+ Is present.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The above embodiments of the present application are described in detail, and specific examples are applied in the present application to explain the principles and implementations of the present application, and the description of the above embodiments is only used to help understand the technical solutions and core ideas of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (9)
1. A method for removing hydrogen sulfide gas by using novel guanidino magnetic ionic liquid is characterized by comprising the following steps:
and (3) synthesizing and characterizing the magnetic ionic liquid. Adding 1,1,3,3-tetramethylguanidine to acetonitrile under vigorous stirring, adding a small molar excess of hydrochloric acid dropwise to the solution after reaction, continuously stirring the mixture again, removing the solvent after reaction, and adding the intermediate [ TMG ] under reduced pressure]And drying the Cl. Next, anhydrous FeCl3 and [ TMG ] were mixed in an equimolar ratio under N2 atmosphere]Cl to form a liquid mixture. The mixture was filtered and dried under vacuum to obtain [ TMG ]][FeCl4]. Finally, an additional amount of FeCl3 is added to [ TMG ]][FeCl4]To obtain [ TMG ]]Cl/xFeCl 3 Novel guanidyl magnetic ionic liquid.
(1) Fully mixing 1,1,3,3-tetramethylguanidine and acetonitrile, stirring, dropwise adding a small amount of hydrochloric acid into the solution, and continuously stirring for full reaction to prepare [ TMG ] Cl;
(2) In N 2 Anhydrous FeCl is added under the environment 3 And [ TMG ]]Cl is mixed well to obtain [ TMG][FeCl 4 ]Excess FeCl 3 And [ TMG ]][FeCl 4 ]Mixing to obtain [ TMG]Cl/xFeCl 3 Novel guanidino magnetic ionic liquids;
(3) Introducing hydrogen sulfide gas into the [ TMG ]]Cl/xFeCl 3 In the novel guanidyl magnetic ionic liquid, catalytic oxidation reaction is carried out so as to absorb and remove hydrogen sulfide;
(4) The [ TMG ] after completion of desulfurization reaction]Cl/xFeCl 3 And the novel guanidyl magnetic ionic liquid is regenerated and recycled.
2. The method of claim 1, wherein the [ TMG ] is]Cl/xFeCl 3 The raw material of the novel guanidyl magnetic ionic liquid contains cations and anions, wherein the cations are [ TMG ]] + The anion is Cl/xFeCl 3 - Wherein the cation [ TMG ]] + With anions Cl/xFeCl 3 - Is 1:1.
The FeCl 3 Is anhydrous FeCl 3 The purity is 99 percent;
the 1,1,3,3-tetramethylguanidine, acetonitrile and hydrochloric acid have the purity of 99 percent.
3. The method of claim 1, wherein [ TMG ] is]The preparation method of the Cl/xFeCl3 novel guanidino magnetic ionic liquid comprises the following steps: 0.1mol of 1,1,3,3-tetramethylguanidine was added to 25ml of acetonitrile with vigorous stirring. Then, a small excess of hydrochloric acid was added dropwise over 2 hours, followed by continuous stirring for 4 hours. After the reaction is finished, the solvent is removed, and the intermediate product [ TMG ]]Cl was dried at 60 ℃ for 2 hours under low pressure. In N 2 Under the environment, the anhydrous FeCl with equal molar ratio is added 3 And [ TMG ]]The Cl is mixed to form a liquid mixture. The mixture was filtered and dried in vacuo to give [ TMG ]][FeCl 4 ]. Finally, in [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 To obtain [ TMG ]]Cl/xFeCl 3 。
4. The method of claim 3, wherein said [ TMG ] is prepared]Raw material of Cl/xFeCl3 novel guanidyl magnetic ionic liquid [ TMG][FeCl 4 ]And FeCl 3 The purity of (A) is 99% or more.
5. The method of claim 1, wherein the [ TMG ] is]The preparation process of the Cl/xFeCl3 novel guanidino magnetic ionic liquid is carried out in N 2 Under the environment, anhydrous FeCl with equal molar ratio 3 And [ TMG ]]Cl to form a liquid mixture, filtering and vacuum drying to obtain [ TMG][FeCl 4 ]Adding a certain amount of FeCl 3 Thus obtaining the product.
6. The method of claim 1, wherein the [ TMG ] is]The magnetic susceptibility of Cl/xFeCl3 novel guanidino magnetic ionic liquid is 59.1 multiplied by 10 -6 emu/g。
7. The method of claim 1, wherein the [ TMG ] is]Cl/xFeCl3 novel guanidino magnetic ionic liquid serving as both catalyst and oxidant, wherein Fe 3+ Ions as oxidizing agents for the sulfurThe hydrogen hydride is converted to elemental sulfur.
8. The method of claim 1, wherein the elemental sulfur is insoluble in a desulfurizing agent system, and sulfur particles are separated by centrifugation, sedimentation and filtration, so that the [ TMG ] Cl/xFeCl3 novel guanidino magnetic ionic liquid can be recycled.
9. The method of claim 1, wherein air or oxygen is introduced into the novel guanidino magnetic [ TMG ] Cl/xFeCl3 ionic liquid after the desulfurization reaction, and the pressure is reduced and the novel guanidino magnetic [ TMG ] Cl/xFeCl3 ionic liquid after the desulfurization reaction is heated, so that the novel guanidino magnetic [ TMG ] Cl/xFeCl3 ionic liquid after the desulfurization reaction is regenerated and recycled.
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