CN111943858B - 一种阴离子含有羧基和巯基两种官能团的功能化离子液体及其制备方法和用途 - Google Patents
一种阴离子含有羧基和巯基两种官能团的功能化离子液体及其制备方法和用途 Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 69
- 150000001450 anions Chemical class 0.000 title claims abstract description 26
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims abstract description 21
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- 238000002360 preparation method Methods 0.000 title abstract description 5
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- 238000011069 regeneration method Methods 0.000 claims abstract description 6
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- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 5
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- AAUWHQKFMQZZRN-UHFFFAOYSA-M butyl(triethyl)azanium 2-sulfanylpropanoate Chemical compound SC(C(=O)[O-])C.C(C)[N+](CC)(CC)CCCC AAUWHQKFMQZZRN-UHFFFAOYSA-M 0.000 description 2
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- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- HGGLDADJQQPKKC-UHFFFAOYSA-N 2-butyl-1-methylimidazole Chemical group CCCCC1=NC=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-N 2-ethyl-1-methylimidazole Chemical group CCC1=NC=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
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- MPDDDPYHTMZBMG-UHFFFAOYSA-N butyl(triethyl)azanium Chemical compound CCCC[N+](CC)(CC)CC MPDDDPYHTMZBMG-UHFFFAOYSA-N 0.000 description 1
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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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
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
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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
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
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Abstract
本发明公开了一种阴离子含有羧基和巯基两种官能团的功能化离子液体及其制备方法和用途，该功能性离子液体的阳离子为四烷基季铵阳离子、四烷基季膦盐阳离子和二烷基咪唑阳离子，阴离子为同时含巯基和羧酸官能团的有机酸阴离子，如巯基丁二酸阴离子和2‑巯基丙酸阴离子等。本发明的阴离子含巯基羧酸官能团的离子液体用于捕集硫化氢时，设备条件简单、较高的吸收容量和易解吸再生等，可适用于工业烟道气及工业废气的脱硫处理。
Description
技术领域
本发明涉及一种阴离子含有羧基和巯基两种官能团的功能化离子液体及其制备方法和用途。
背景技术
硫化氢(H2S)是一种剧毒腐蚀性气体，其主要来源于煤的低温焦化、含硫石油和天然气的开采、染料、制革等工业过程中。H2S在化工方面主要用于制备硫磺，近年来硫磺的化工市场供不应求。天然气或合成气中常常含有少量H2S组分，若能将这部分H2S从气体中分离出来资源化利用，不仅能提高硫磺的原料供应，还能避免由于H2S存在造成的生产设备和管道腐蚀问题。
工业用于吸收硫化氢的方法有很多，主要分为干法和湿法两大类。干法脱硫技术通常存在过程复杂、吸附量小、吸附剂难再生等缺点。目前多采用湿法脱硫技术，该法应用广泛，技术成熟，脱硫量相对较高，其中吸收剂以弱碱性溶液包括醇胺溶液、氨水等应用最为普遍。通常使用的醇胺有：单乙醇胺(MEA)、二甘醇胺(DGA)、二乙醇胺(DEA)、N-甲基二乙醇胺(MDEA)、二异丙醇胺(DIPA)等。但使用有机胺溶液也存在许多缺陷，如：有机胺易挥发，会产生挥发性有机化合物而污染环境；有机胺易降解变质，对设备腐蚀严重；解吸能耗高而回收率低等。
离子液体(Ionic Liquid,IL)是一种在常温下由阴阳离子组成的有机熔融盐类，其作为一种新型的绿色溶剂，具有诸多优点，如熔点低、液程范围宽、不挥发、热稳定性好、可设计性等。离子液体可以通过改变阴阳离子的结构来改变其物理、化学性质，通过设计特定性质的离子液体可用于H2S气体的吸收，并且能克服传统脱硫技术的缺陷，可绿色高效吸收H2S。
目前，有越来越多离子液体用于捕捉酸性气体(如二氧化碳，二氧化硫)的研究，而对于捕集H2S的关注相对较少。中国专利CN101961598A报道了将烷基卤化铵等与己内酰铵按摩尔比为1：1～10混合生成的离子液体用于吸收硫化氢，但其吸收量较低。中国专利CN107115761A报道了一种碱性功能化离子液体与溶剂混合物做为吸收剂，虽然改善了离子液体对于H2S的溶解度，但其会造成溶剂损失，不利于节约资源。
发明内容
针对现有技术的不足，本发明的第一个目的是提供一种阴离子同时含有羧基和巯基的功能化离子液体；
本发明的第二个目的是提供一种阴离子同时含有羧基和巯基的功能化离子液体的制备方法；
本发明的第三个目的是提供一种阴离子同时含有羧基和巯基的功能化离子液体的用途。
本发明中的离子液体阳离子为季铵、季膦和咪唑类，具有碱性，阴离子为有机羧酸且引入巯基基团，化学吸收和物理吸收作用捕捉H2S。本发明提供的离子液体具有较低粘度、低热容、高H2S吸收容量，是一种高效节能的H2S吸收剂。
本发明的具体技术方案如下：
一种阴离子含有羧基和巯基的离子液体，其阳离子为四烷基季铵阳离子、四烷基季膦阳离子或N,N-二烷基咪唑阳离子；阴离子为含有巯基的有机羧酸阴离子。
优选的，所述离子液体中的阳离子结构选自式1-式3：
式中，R1为C1～C14的直链烷基，R2为C1～C14的直链烷基；R3为C1～C14的直链烷基，R4为C1～C14的直链烷基；R5为C1～C14的直链烷基。
优选的，所述的阳离子为三甲基丙基铵、三甲基丁基铵、三乙基丁基铵、四丁基季膦、N,N-甲基乙基咪唑、N,N-甲基丁基咪唑等阳离子。
优选的，所述的阴离子选自巯基丁二酸、2-巯基丙酸、半胱氨酸、4-巯基丁酸的酸根阴离子。
其中，所述阴离子原料的结构式如下：
巯基丁二酸
2-巯基丙酸
2-氨基-3-巯基丙酸
4-巯基丁酸
本发明还保护一种制备上述离子液体的方法，包括如下步骤：首先称取阳离子的卤化物，将阳离子的卤化物与氧化银反应或与OH-型阴离子树脂进行阴离子交换得到含目标阳离子的氢氧化物，最后与含巯基基团的羧酸中和得到相应的离子液体。
上述方法中，用作合成季铵阳离子的原料为溴化N，N，N-三乙基丁基铵。
优选的，采用季铵反应合成溴化N，N，N-三乙基丁基铵，使用的原料为溴代正丁烷和三乙胺，按摩尔比1:1进行投料反应。
上述方法中，用作合成季磷阳离子和咪唑阳离子的原料分别为四丁基溴化膦和1-丁基-3-甲基咪唑氢溴酸盐。
上述方法中，含巯基基团的羧酸选自巯基丁二酸、2-巯基丙酸、半胱氨酸、4-巯基丁酸中的任一种或多种。
本发明还保护上述离子液体在脱除H2S中的应用，包括如下步骤：在稳定的温度和压力下，用所制备的离子液体吸收H2S，再在加热或减压条件下将H2S解吸出来，达到吸收剂循环再生的目的。
上述方法中，离子液体吸收H2S的温度为20～70℃。
上述方法中，离子液体吸收H2S的分压为0～100kPa。
上述方法中，所述的离子液体再生方法包括水蒸汽汽提法、闪蒸法或空气氧化法。
上述方法中，所述的离子液体再生温度为70～80℃。
上述方法中，所述的离子液体再生压强为0～1kPa。
上述功能性离子液体在脱除H2S的方法，具体包括如下步骤：在温度20～70℃和压力1～100kPa条件下，用所制备的离子液体吸收H2S气体；再在温度70～80℃和压力0.001～1kPa条件下，解吸出H2S，使离子液体吸收剂再生。
有益效果
本申请提供的一种阴离子含有羧基和巯基两种官能团的功能化离子液体及其制备方法和用途，与现有技术相比，具有如下有益效果：(1)本发明的功能化离子液体对H2S的吸收容量较现有技术有明显提高，可达0.963molH2S/mol IL；(2)本发明的功能化离子液体由于巯基的吸电子作用，分散了阴离子上的电荷，降低了H2S的吸收能，使吸收的二氧化硫易脱吸，且本发明的离子液体在解吸过程中不会造成溶剂损失，使离子液体可循环利用。
具体实施方式
下面将结合具体实施例对本发明提供的离子液体吸收剂吸收H2S的方法做进一步详细的说明，但不限制本发明的实施范围。
实施例1
在250mL茄形瓶中加入0.5mol的三乙胺、0.5mol的溴代正丁烷和50mL的乙醇(溶剂)，在温度80℃下回流反应24h，反应结束后，通过旋蒸掉大部分溶剂，将所得混合物在60℃下真空干燥24h以去除剩余溶剂及未反应的原料，即可得溴化N，N，N-三乙基丁基铵。取0.05mol溴化N，N，N-三乙基丁基铵溶于10mL的50％(v/v)乙醇/水混合溶液，再取0.025mol的氧化银，分批加入，常温避光反应6h，然后过滤除去反应生成的溴化银，即可得到氢氧化N，N，N-三乙基丁基铵溶液。或者也可将溴化N，N，N-三乙基丁基铵水溶液通过IRN-78型OH-型阴离子交换树脂得到氢氧化N，N，N-三乙基丁基铵溶液。然后在氢氧化N，N，N-三乙基丁基铵溶液中分批加入0.05mol的巯基丁二酸(或者氢氧化N，N，N-三乙基丁基铵溶液与巯基丁二酸的摩尔比为2:1)中和，常温反应6h，反应结束后旋蒸除去大部分溶剂，再在80℃真空干燥箱内干燥48h即得阴离子含巯基和羧基官能团的离子液体N，N，N-三乙基丁基铵巯基丁二酸盐。其化学结构式为：
表征结果：1H NMR(300MHz,D2O)δ3.62–3.52(p,J＝7.2Hz,1H),3.23–3.05(m,J＝10.3,9.2Hz,8H),2.88–2.65(ddq,J＝38.8,16.1,8.9,8.5Hz,2H),1.57–1.53(hept,J＝7.8Hz,2H),1.34–1.16(dp,J＝31.5,7.5Hz,11H),0.90–0.81(dt,J＝14.5,7.3Hz,3H)ppm.13C NMR(75MHz,CD3OD)δ176.9,174.5,56.5,52.5,41.9,39.1,23.2,19.4,12.8,6.6ppm.
实施例2
用类似于实施例1的方法，先用0.5mol三乙胺和0.5mol溴代正丁烷合成溴化N，N，N-三乙基丁基铵，取0.05mol溴化N，N，N-三乙基丁基铵溶于10mL的50％(v/v)乙醇/水混合溶液，分批加入0.025mol的氧化银生成氢氧化N，N，N-三乙基丁基铵溶液，然后和0.05mol的2-巯基丙酸发生中和反应，即可得到离子液体N，N，N-三乙基丁基铵2-巯基丙酸盐。其化学结构式为：
表征结果：1H NMR(300MHz,D2O)δ3.19–3.12(q,J＝7.3Hz,6H),3.06–3.03(m,2H),1.59–1.48(m,2H),1.33–1.31(m,3H),1.28–1.22(t,J＝4.5Hz,3H),1.17–1.11(m,9H),0.86–0.81(t,J＝7.4Hz,3H)ppm.13C NMR(75MHz,CDCl3)δ177.4,56.7,53.0,52.1,40.2,23.6,19.7,13.6,7.6ppm.
实施例3：
用类似于实施例1的方法，将0.05mol四丁基溴化膦溶于10mL的50％(v/v)乙醇/水混合溶液，再和0.025mol的氧化银生成四丁基氢氧化膦溶液，然后和0.05mol巯基丁二酸发生中和反应，即可得到离子液体四丁基膦巯基丁二酸盐。其化学结构式为：
表征结果：1H NMR(300MHz,CDCl3)δ3.72–3.60(m,1H),2.93-2.71(d,J＝17.1Hz,2H),2.26–2.17(m,8H),1.56-1.50(s,16H),0.95-0.91(q,J＝9.0,7.8Hz,12H).13C NMR(75MHz,CDCl3)δ176.0,174.1,42.7,39.8,23.7,18.8,18.2,13.4.
实施例4：
用类似于实施例1的方法，将0.05mol四丁基溴化膦溶于10mL的50％(v/v)乙醇/水混合溶液，再和0.025mol的氧化银生成四丁基氢氧化膦溶液，然后和0.05mol的2-巯基丙酸发生中和反应，即可得到离子液体四丁基溴化膦2-巯基丙酸盐。其化学结构式为：
表征结果：1H NMR(300MHz,CDCl3)δ3.85(d,3H),3.44–3.42(m,1H),2.27-2.22(ddt,J＝16.6,8.3,4.0Hz,8H),1.44-1.42(tq,J＝7.6,3.3Hz,16H),0.89-0.88(h,J＝3.1Hz,12H)ppm.13C NMR(75MHz,CD3OD)δ176.0,53.8,52.0,23.6,18.8,18.1,13.4.
实施例5：
用类似于实施例1的方法，将0.05mol1-丁基-3-甲基咪唑氢溴酸盐溶于10mL的50％(v/v)乙醇/水混合溶液，再和0.025mol的氧化银生成氢氧化1-丁基-3-甲基咪唑溶液，然后和0.05mol巯基丁二酸发生中和反应，即可得到离子液体1-丁基-3-甲基咪唑巯基丁二酸盐。其化学结构式为：
实施例6
用类似于实施例1的方法，将0.05mol1-丁基-3-甲基咪唑氢溴酸盐溶于10mL的50％(v/v)乙醇/水混合溶液，再和0.025mol的氧化银生成氢氧化1-丁基-3-甲基咪唑溶液，然后和0.05mol的2-巯基丙酸发生中和反应，即可得到离子液体1-丁基-3-甲基咪唑2-巯基丙酸盐。其化学结构式为：
实施例7
准确称取实施例1中合成的N，N，N-三乙基丁基铵巯基丁二酸盐1g置于吸收池中，将吸收池抽真空，30℃恒温条件下，向吸收池内通入H2S进行吸收，若吸收池内压力保持30min平衡，表明离子液体吸收H2S已达饱和。经实验，当H2S分压为100kPa时，H2S的吸收量为0.378mol H2S/mol IL。
实施例8
准确称取实施例2中合成的N，N，N-三乙基丁基铵2-巯基丙酸盐1g置于吸收池中，将吸收池抽真空，30℃恒温条件下，向吸收池内通入H2S进行吸收，若吸收池内压力保持30min平衡，表明离子液体吸收H2S已达饱和。经实验，当H2S分压为100kPa时，H2S的吸收量为0.449mol H2S/mol IL。
实施例9
准确称取实施例4中合成的四丁基溴化膦2-巯基丙酸盐1g置于吸收池中，将吸收池抽真空，30℃恒温条件下，向吸收池内通入H2S进行吸收，若吸收池内压力保持30min平衡，表明离子液体吸收H2S已达饱和。经实验，当H2S分别为100kPa时，H2S的吸收量为0.963mol H2S/mol IL；吸收温度为40℃，其他条件相同时，当H2S分压为100kPa时，H2S的吸收量为0.850mol H2S/mol IL。
实施例10
将实施例5中吸收H2S达到平衡后的离子液体在80℃、压力为0.01kPa的条件下解吸1小时，分别再用解吸后的离子液体重复实施例5的操作，1h后再次达到吸收平衡，如此重复吸收、解吸5次，H2S吸收量并无明显下降。
对比例
中国专利CN101961598A报道了己内酰铵-烷基烷基卤化铵离子液体吸收H2S实施方案中，对H2S的吸收量为0.3mol H2S/mol IL；中国专利CN107115761A报道了将碱性功能化离子液体与溶剂乙二醇的混合液作为吸收剂吸收H2S，但有机溶剂在高温解吸时易造成溶剂损失；本发明的阴离子含巯基巯基羧酸官能团的离子液体对硫化氢的吸收量可达约0.963mol H2S/mol IL，且只有离子液体作为溶剂，不易挥发，解吸时不会造成溶剂损失。
Claims (6)
1.一种阴离子同时含有羧基和巯基两种官能团的功能化离子液体，其特征在于，阳离子为四丁基季膦，阴离子为2-巯基丙酸的酸根阴离子。
2.一种如权利要求1所述的阴离子同时含有羧基和巯基两种官能团的功能化离子液体的制备方法，其特征在于，包括如下步骤：首先称取目标阳离子的卤化物，目标阳离子的卤化物再与氧化银反应或与OH-型阴离子树脂进行阴离子交换得到含目标阳离子的氢氧化物，最后与含巯基基团的羧酸中和得到相应的离子液体。
3.根据权利要求2所述的制备方法，其特征在于，所述阳离子为季磷阳离子，原料为四丁基溴化膦。
4.根据权利要求2所述的一种阴离子同时含有羧基和巯基两种官能团的功能化离子液体的制备方法，其特征在于，所述含巯基基团的羧酸为2-巯基丙酸。
5. 权利要求1所述的功能性离子液体在脱除H2S的方法，其特征在于，具体包括如下步骤：在温度20～70℃和压力1～100kPa条件下，用所制备的离子液体吸收H2S气体；再在温度70～80℃和压力0.001～1kPa条件下，解吸出H2S，使离子液体吸收剂再生。
6.根据权利要求5所述的功能化离子液体在脱除H2S的方法，其特征在于，所述的离子液体再生方法包括水蒸汽汽提法、闪蒸法或空气氧化法。
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| CAS RN号为2425618-28-4等;STN;《Registry》;20200615;第1-88页 * |
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