CN113321590B - Binuclear quaternary ammonium salt ionic liquid compound and preparation method and application thereof - Google Patents
Binuclear quaternary ammonium salt ionic liquid compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of dual-core seasonAmmonium salt ionic liquid compounds having two quaternary ammonium cations and an acid anion selected from formate, acetate, propionate, butyrate, and ethoxyacetate. The application also discloses a preparation method of the ionic liquid and a method for preparing the ionic liquid in H 2 Application in S absorption and removal. The ionic liquid has a novel structure, is convenient to synthesize, and can effectively avoid the defects of large pollution, strong corrosivity, high energy consumption and the like of the traditional organic amine process. In addition, compared with common ionic liquid, the ionic liquid H provided by the invention 2 The S absorption capacity is higher, and the effect is obvious.
Description
Technical Field
The invention belongs to the technical field of ionic liquids, and particularly relates to a binuclear quaternary ammonium salt ionic liquid, a preparation method thereof and application thereof in hydrogen sulfide absorption.
Background
Natural gas is widely used in thousands of households due to its cleanness and convenience, and is considered to be one of the most promising alternative energy sources for human production and life at present. However, natural gas contains methane (CH) as the main component 4 ) In addition, there are many impurities such as hydrogen sulfide (H) 2 S), carbon dioxide (CO) 2 ) And the like, and hydrogen sulfide is a highly toxic corrosive gas. The removal of hydrogen sulphide is therefore of vital importance for the safe use of natural gas.
Hydrogen sulfide has weak acidity and reducibility, and its absorption method includes two methods, namely a dry method and a wet method. The dry desulfurization method has simple process and convenient operation, is relatively suitable for treating the gas with low sulfur content, and the common desulfurizing agents comprise active carbon, metal oxide and the like. However, since the preparation of high-purity activated carbon is expensive, the activated carbon is rarely used in large-scale production in factories. The wet desulfurization mainly comprises a liquid absorption method and an absorption oxidation method. The liquid absorption methods mainly include an alkanolamine method, a hot potassium carbonate method and the like, and the main problems of the methods are equipment corrosion, solvent degradation and absorption loss. The absorption oxidation method mainly comprises an arsenic-based process and a vanadium-based desulfurization process, and the methods have the main problems of high chemical consumption, poor quality of elemental sulfur, possibility of secondary pollution and the like.
The ionic liquid is a novel environment-friendly green solvent, is in a liquid state at room temperature or 100 ℃, and is organic molten salt consisting of organic anions and cations. Researches show that the ionic liquid has the advantages of extremely low vapor pressure, low melting point, strong dissolving capacity, high thermal stability, designable structure and the like, and particularly, the structure of the ionic liquid can be designed according to needs, and the ionic liquid is functionalized into task-specific ionic liquids (TSILs) to realize efficient and selective separation or reaction processes. In addition, the ionic liquid is almost non-volatile, and a plurality of environmental problems caused by gas-liquid cross contamination during absorption can be effectively avoided. And compared with the traditional water solvent, the specific heat capacity of the ionic liquid is lower, and latent heat cannot be consumed due to volatilization, so that the total energy consumption of the absorbent desorption regeneration process is relatively lower. In conclusion, the ionic liquid can be used as a novel gas absorbent with high efficiency, cleanness and energy conservation.
At present, the application research of the ionic liquid in the aspect of acid gas absorption focuses more on CO 2 Capture and flue gas desulfurization of 2 S removal has been less relevant to research. Jou et al report H at a temperature of 298- 2 S in ionic liquid [ bmim][PF 6 ]Solubility in (c). Organic amine type iron-based ionic liquid and ionic liquid-alcohol amine solution compound type solvent are developed in sequence for H 2 And (4) absorbing and separating S. Huang et al also synthesized [ N 2224 ][DMG]、[N 2224 ][IMA]And [ N 2224 ][NIA]Use of 3 quaternary ammonium salt Lewis basic ionic liquids for absorbing H 2 And S. However H 2 The solubility of S in these ionic liquids is still very low. Therefore, high H was developed 2 S absorption amount of ionic liquid for driving ionic liquid to remove H 2 S has important significance.
Disclosure of Invention
Invention (I)The purpose is as follows: aiming at the problems in the prior art, the application provides a class of binuclear quaternary ammonium salt ionic liquid compounds, a preparation method thereof and a method for absorbing H 2 And (5) application in S.
The technical scheme is as follows: the binuclear quaternary ammonium salt ionic liquid compound has two quaternary ammonium radical cations and an acid radical anion.
Preferably, the cation is
The cation is (N, N, N, N) 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene-diammonium radical, N, N 4 ,N 4 ,N 4 Bis- (triethyl) -butylene-diammonium radical, N, N 5 ,N 5 ,N 5 Bis- (triethyl) -pentylidene-diammonium radical, N, N 6 ,N 6 ,N 6 Bis- (triethyl) -hexamethylene-diammonium radical.
The anions are formate (For), acetate (Ac), propionate (Prop), butyrate (Buty) and ethoxyacetate (EOAc) in sequence
The application also discloses a preparation method of the binuclear quaternary ammonium salt ionic liquid compound, which comprises the following steps:
(1) firstly, obtaining halide containing target cations through quaternization;
(2) then reacting the halide containing the target cation with silver oxide to obtain hydroxide containing the target cation;
(3) finally neutralizing with acid radical anion to obtain the ionic liquid.
The application also discloses the application of the binuclear quaternary ammonium salt ionic liquid compound in H 2 Application in S absorption and removal. Wherein, the absorption and removal process operating conditions are as follows: h 2 The S partial pressure is 0-1bar and the temperature is 30-50 ℃. This application is through introducing two quaternary ammonium groups simultaneously in ionic liquid's cationic structure for ionic liquid has two acid radical anions, and acid radical anion can combine the proton of hydrogen sulfide, once improves ionic liquid and absorbs H 2 The ability of S.
Has the beneficial effects that: compared with the prior art, the application provides a brand-new binuclear quaternary ammonium salt ionic liquid compound, the ionic liquid has a novel structure and is convenient to synthesize, and the defects of high pollution, strong corrosivity, high energy consumption and the like of the traditional organic amine process can be effectively avoided. In addition, compared with common ionic liquid, the ionic liquid H provided by the invention 2 The S absorption capacity is higher, and the effect is obvious.
Detailed Description
The present application will be described in detail with reference to specific examples.
Example 1: binuclear quaternary ammonium ionic liquid C 3 (N 222 ) 2 ][For] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 3-dibromopropane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in sequence, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain a product, namely N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene dibromide salt (C) 3 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 3 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in the dark. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propyleneoxydiammonium (C) 3 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: 0.03mol of formic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the mixture by using a constant pressure dropping funnel 3 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl) -propylene-bis (bis-carboxylic acid) salt (C) 3 [N 222 ] 2 [For] 2 )。
And (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ4.49–3.63(m,4H),3.58–3.40(m,12H),2.47(td,J＝7.9,7.2,3.5Hz,1H),1.33(t,J＝7.3Hz,18H),1.15(t,J＝7.0Hz,1H). 13 C NMR(100MHz，CDCl 3 )δ167.34,59.52,53.02,22.52,7.57.
example 2: binuclear quaternary ammonium ionic liquid [ C 3 (N 222 ) 2 ][Ac] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 3-dibromopropane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in sequence, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain a product, namely N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene dibromide salt (C) 3 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 3 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propyleneoxydiammonium (C) 3 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a binuclear quaternary ammonium ionic liquid: 0.03mol of acetic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the mixture by using a constant pressure dropping funnel 3 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-acetic acid) salt (C) 3 [N 222 ] 2 [Ac] 2 ) The chemical structural formula is as follows:
and (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ7.28(s,1H),5.80–5.69(m,6H),3.62–3.48(m,12H),1.37–1.30(m,18H),1.17(t,J＝7.0Hz,2H). 13 C NMR(100MHz，CDCl 3 )δ176.17,59.32,52.51,24.05,15.68,7.28.
example 3: binuclear quaternary ammonium ionic liquid [ C ] 3 (N 222 ) 2 ][Prop] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 3-dibromopropane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in sequence, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain a product, namely N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene dibromide salt (C) 3 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 3 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl)Yl) -propylenediammonium hydroxide (C) 3 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: weighing 0.03mol of propionic acid, dissolving in 20ml of absolute ethyl alcohol, and dripping C into the solution by using a constant pressure dropping funnel 3 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-propionic acid) salt (C) 3 [N 222 ] 2 [Prop] 2 ) The chemical structural formula is as follows:
and (3) characterization results: nuclear magnetic hydrogen spectrum 1 H NMR(400MHz,CDCl 3 ) δ 7.28(s,1H),3.43(dd, J ═ 7.5,1.4Hz,4H),3.38(d, J ═ 7.3Hz,4H),2.23(q, J ═ 7.6Hz,12H), 1.38-1.34 (m,6H),1.17(t, J ═ 7.0Hz,2H),1.08(t, J ═ 7.6Hz,18H), nuclear magnetic carbon spectrum 13 C NMR(100MHz，CDCl 3 )δ179.55,59.55,52.87,30.23,15.03,10.60,7.53.
Example 4: binuclear quaternary ammonium ionic liquid [ C ] 3 (N 222 ) 2 ][Buty] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 3-dibromopropane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in turn, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum for 48 hours at the temperature of 60 ℃ to obtain a product, namely N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene dibromide salt (C) 3 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 3 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.0 batch by batch15mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propyleneoxydiammonium (C) 3 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: weighing 0.03mol of butyric acid, dissolving in 20ml of absolute ethyl alcohol, and dripping C into the solution by using a constant pressure dropping funnel 3 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-butyric acid) salt (C) 3 [N 222 ] 2 [Buty] 2 ) The chemical structural formula is as follows:
and (3) characterization results: nuclear magnetic hydrogen spectrum 1 H NMR(400MHz,CDCl 3 ) δ 5.97-5.89 (m,1H),4.01(d, J ═ 7.2Hz,2H),3.48(dd, J ═ 8.2,6.0Hz,6H),1.62(q, J ═ 7.5Hz,12H),1.37(s,4H),1.33(d, J ═ 2.4Hz,4H),1.17(t, J ═ 7.0Hz,2H),0.93(t, J ═ 7.4Hz,18H), nuclear magnetic carbon spectrum 13 C NMR(100MHz，CDCl 3 )δ178.57,59.67,52.98,38.70,19.39,15.96,14.13,7.60.
Example 5: binuclear quaternary ammonium ionic liquid [ C ] 3 (N 222 ) 2 ][EOAc] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 3-dibromopropane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in sequence, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain a product, namely N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene dibromide salt (C) 3 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: weighing 0.015mol C 3 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propyleneoxydiammonium (C) 3 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: 0.03mol of ethoxyacetic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the absolute ethyl alcohol by using a constant pressure dropping funnel 3 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-ethoxyacetic acid) salt (C) 3 [N 222 ] 2 [EOAc] 2 ) The chemical structural formula is as follows:
and (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ5.76–5.64(m,2H),3.54(q,J＝7.0Hz,12H),3.47(d,J＝3.9Hz,4H),3.42–3.39(m,4H),3.36(t,J＝7.3Hz,6H),1.35–1.31(m,4H),1.19(t,J＝7.0Hz,18H),1.14(s,1H). 13 C NMR(100MHz，CDCl 3 )δ174.42,76.95,66.08,59.44,52.82,22.39,14.92,7.41.
example 6: binuclear quaternary ammonium ionic liquid [ C ] 4 (N 222 ) 2 ][Ac] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: adding 0.05mol of triethylamine, 0.02mol of 1, 4-dibromobutane and 40mL of ethanol into a 250mL round-bottom flask with reflux magnetons in sequence, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain the product, N, N 4 ,N 4 ,N 4 -bis- (triethyl) -butylidenebromideSalt (C) 4 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 4 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 4 ,N 4 ,N 4 Bis- (triethyl) -butylidenediammonium hydroxide (C) 4 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: 0.03mol of acetic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the mixture by using a constant pressure dropping funnel 4 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 4 ,N 4 ,N 4 -bis- (triethyl) -butylidene-bis (bis-acetic acid) salt (C) 4 [N 222 ] 2 [Ac] 2 ) The chemical structural formula is as follows:
and (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ3.59(t,J＝7.5Hz,4H),3.45–3.29(m,12H),2.08–1.97(m,4H),1.92(s,8H),1.31(tt,J＝7.3,1.9Hz,18H). 13 C NMR(100MHz，CDCl 3 )δ176.17,56.55,52.64,24.35,18.81,7.42.
example 7: binuclear quaternary ammonium ionic liquid [ C ] 5 (N 222 ) 2 ][Ac] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: sequentially adding 0.05mol of triethylamine, 0.02mol of 1, 5-dibromopentane and 40mL of ethanol into a 250mL round-bottom flask with a reflux magneton, heating, stirring and refluxing, controlling the temperature to be 80 ℃, reacting for 48 hours, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ for 48 hours to obtain the product，N,N,N,N 5 ,N 5 ,N 5 Bis- (triethyl) -pentylidene dibromide salt (C) 5 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 5 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 5 ,N 5 ,N 5 Bis- (triethyl) -pentamethylenediammonium (C) 5 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: 0.03mol of acetic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the mixture by using a constant pressure dropping funnel 5 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 5 ,N 5 ,N 5 -bis- (triethyl) -pentamethylene-di (bis-acetic acid) salt (C) 5 [N 222 ] 2 [Ac] 2 ) The chemical structural formula is as follows:
and (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ3.59(t,J＝7.5Hz,4H),3.45–3.29(m,12H),2.08–1.97(m,4H),1.92(s,8H),1.31(tt,J＝7.3,1.9Hz,18H). 13 C NMR(100MHz，CDCl 3 )δ176.03,56.84,52.58,28.84,24.51,20.79,7.41.
example 8: binuclear quaternary ammonium ionic liquid [ C ] 6 (N 222 ) 2 ][Ac] 2 Preparation of
Preparing hydrophilic brominated ionic liquid: 0.05mol of triethylamine, 0.02mol of 1, 6-dibromohexane and 40mL of ethanol are sequentially added into a 250mL round-bottom flask provided with a reflux magneton, heated, stirred and refluxed, the temperature is controlled at 80 DEG CReacting for 48 hours, removing the solvent by rotary evaporation, and drying for 48 hours in vacuum at the temperature of 60 ℃ to obtain a product, N, N 6 ,N 6 ,N 6 Bis- (triethyl) -hexylidene dibromide salt (C) 6 [N 222 ] 2 [Br] 2 )。
Preparing the binuclear ionic liquid diammonium hydroxide: 0.015mol of C is weighed 6 [N 222 ] 2 [Br] 2 Dissolving in 10ml of 50% (v/v) ethanol water mixed solution, transferring into a 100ml round-bottom flask tightly wrapped with tinfoil, and adding 0.015mol Ag 2 And O, reacting for 6 hours at normal temperature in a dark place. Then filtering to remove silver bromide generated in the reaction to obtain N, N, N, N 6 ,N 6 ,N 6 Bis- (triethyl) -hexamethylenediammonium hydroxide (C) 6 [N 222 ] 2 [OH] 2 ) And (3) solution.
Preparing a dual-core quaternary ammonium ionic liquid: 0.03mol of acetic acid is weighed and dissolved in 20ml of absolute ethyl alcohol, and C is dripped into the mixture by using a constant pressure dropping funnel 6 [N 222 ] 2 [OH] 2 Reacting in the solution at normal temperature for 24 hours, removing most of the solvent by rotary evaporation, and drying in vacuum at 65 ℃ for 48 hours to obtain the product N, N, N, N 6 ,N 6 ,N 6 Bis- (triethyl) -hexamethylene-bis (bis-acetic acid) salt (C) 6 [N 222 ] 2 [Ac] 2 ) The chemical structural formula is as follows:
and (3) characterization results: 1 H NMR(400MHz,CDCl 3 )δ5.58(s,4H),3.47–3.31(m,12H),1.89(s,7H),1.36–1.25(m,18H). 13 C NMR(100MHz，CDCl 3 )δ180.52,56.26,52.43,28.35,25.21,22.86,6.57.
example 9: binuclear quaternary ammonium ionic liquid C 3 (N 222 ) 2 ][For] 2 Study of Hydrogen sulfide absorption
The N, N, N, N synthesized in example 1 was accurately weighed 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-carboxylic acid) salt (C) 3 (N 222 ) 2 ][For] 2 )1g of the solution is placed in an absorption tank, and H is introduced into the absorption tank at the temperature of 30 DEG C 2 S is absorbed, and the pressure tends to be balanced in 30 minutes, which shows that the ionic liquid absorbs H 2 S is already in equilibrium. Calculated at H 2 When the S partial pressures are respectively 1bar, H 2 The molar ratio of the absorbed amount of S to the ionic liquid was 0.78.
Example 10: binuclear quaternary ammonium ionic liquid [ C ] 3 (N 222 ) 2 ][Ac] 2 Study of Hydrogen sulfide absorption
The N, N, N, N synthesized in example 2 was accurately weighed 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-acetic acid) salt (C) 3 [N 222 ] 2 [Ac] 2 )1g of the solution is placed in an absorption tank, and H is introduced into the absorption tank at the temperature of 30 DEG C 2 S is absorbed, and the pressure is balanced in 30 minutes, which shows that the ionic liquid absorbs H 2 S is already in equilibrium. Calculated at H 2 When the S partial pressures are respectively 1bar, H 2 The molar ratio of the absorption amount of S to the ionic liquid was 1.31.
Example 11: binuclear quaternary ammonium ionic liquid [ C ] 3 (N 222 ) 2 ][Prop] 2 Study of Hydrogen sulfide absorption
The N, N, N, N synthesized in example 3 was accurately weighed 3 ,N 3 ,N 3 -bis- (triethyl) -propylene-bis (bis-propionic acid) salt (C) 3 [N 222 ] 2 [Prop] 2 )1g of the solution is placed in an absorption tank, and H is introduced into the absorption tank at the temperature of 30 DEG C 2 S is absorbed, and the pressure is balanced in 30 minutes, which shows that the ionic liquid absorbs H 2 S is already in equilibrium. Calculated at H 2 When the S partial pressures are respectively 1bar, H 2 The molar ratio of the absorbed amount of S to the ionic liquid was 1.04.
Example 12: binuclear quaternary ammonium ionic liquid C 3 [N 222 ] 2 [Buty] 2 Study of Hydrogen sulfide absorption
The N, N, N, N synthesized in example 4 was accurately weighed 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-butyric acid) salt (C) 3 [N 222 ] 2 [Buty] 2 )1g of the solution is placed in an absorption tank, and H is introduced into the absorption tank at the temperature of 30 DEG C 2 S is absorbed, and the pressure is balanced in 30 minutes, which shows that the ionic liquid absorbs H 2 S is already in equilibrium. Calculated at H 2 When the S partial pressures are respectively 1bar, H 2 The molar ratio of the absorbed amount of S to the ionic liquid was 1.07.
Example 13: binuclear quaternary ammonium ionic liquid C 3 [N 222 ] 2 [EOAc] 2 Study of Hydrogen sulfide absorption
The N, N, N, N synthesized in example 5 was accurately weighed 3 ,N 3 ,N 3 -bis- (triethyl) -propylidene-bis (bis-ethoxyacetic acid) salt (C) 3 [N 222 ] 2 [EOAc] 2 )1g of the solution is placed in an absorption tank, and H is introduced into the absorption tank at the temperature of 30 DEG C 2 S is absorbed, and the pressure is balanced in 30 minutes, which shows that the ionic liquid absorbs H 2 S is already in equilibrium. Calculated at H 2 When the S partial pressures are respectively 1bar, H 2 The molar ratio of the absorbed amount of S to the ionic liquid was 0.99.
Comparative example:
chinese patent CN101961598A reports that caprolactam-alkyl ammonium halide ionic liquid absorbs H 2 In the S embodiment, for H 2 The S absorption was 0.3mol H 2 S/mol IL; chinese patent CN107115761A reports that H is absorbed by using a mixed solution of alkaline functionalized ionic liquid and solvent ethylene glycol as an absorbent 2 S, but the organic solvent is easy to cause solvent loss when being desorbed at high temperature; the absorption capacity of the ionic liquid to the hydrogen sulfide can reach 1.31mol H at most 2 S/mol IL, the pure ionic liquid is adopted as an absorbent, so that the ionic liquid is not easy to volatilize, and the solvent loss is not caused during desorption.
Claims (3)
1. Binuclear quaternary ammonium salt ionic liquid compound in H 2 The application of S absorption and removal is characterized in that the binuclear quaternary ammonium salt ionic liquid compound has two quaternary ammonium radical cations and acid radical anions;
the cation is
(ii) a The anion is formate, acetate, propionate, butyrate or ethoxyacetate.
2. The binuclear quaternary ammonium salt ionic liquid compound according to claim 1 in H 2 The application of S absorption and removal is characterized in that the cation is N, N, N, N 3 ,N 3 ,N 3 Bis- (triethyl) -propylidene-diammonium radical, N, N 4 ,N 4 ,N 4 Bis- (triethyl) -butylene-diammonium radical, N, N 5 ,N 5 ,N 5 Bis- (triethyl) -pentylidene-diammonium radical, N, N 6 ,N 6 ,N 6 -bis- (triethyl) -hexylidene-diammonium radical.
3. The binuclear quaternary ammonium salt ionic liquid compound according to claim 1 in H 2 Use in S absorption removal, characterized in that H 2 The process operation conditions for S absorption and removal are as follows: h 2 The S partial pressure is 0-1bar and the temperature is 30-50 ℃.
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