CN110354897A - 一种酸性聚合离子液体树脂催化剂的制备方法和应用 - Google Patents
一种酸性聚合离子液体树脂催化剂的制备方法和应用 Download PDFInfo
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Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
本发明涉及一种酸性聚合离子液体树脂催化剂的制备方法和应用。所述制备方法包括:将季铵盐和磺酸内酯按照1:1‑1:5(摩尔比)比例混合,在60‑120℃下反应4‑8h,得白色固体;将白色固体和羟基磺酸按照1:1‑1:8(摩尔比)的比例混合,在60‑120℃下反应4‑8h,得离子液体单体;将离子液体单体和甲醛按照1:1‑10(摩尔比)比例混合,在60‑120℃下反应4‑8h,得淡黄色固体即为酸性聚合离子液体树脂催化剂。该催化剂,机械强度高,形状可控,酸性不流失,对于酯化、缩合、烷基化、酯交换化等有很高的催化活性。催化剂可重复多次使用,效果没有明显下降。且没有废酸排放,没有二次污染。
Description
技术领域
本发明属于化工领域,特别涉及一种酸性聚合离子液体树脂催化剂的制备方法和应用。
背景技术
化工产业中酸催化剂是必不可少的,广泛应用于酯化、烷基化、醚化、硝化等各种反应中,目前使用的大多为盐酸、硫酸之类的液体无机酸催化剂。因为无机酸催化剂价廉易得,催化效果好,还是目前大型化工产品生产的首要催化剂。但无机酸在使用时会产生大量废酸,严重腐蚀设备,且不易与产物分离,难以循环使用,只能被丢弃,不仅使生产成本上升,还对环境造成了严重的污染。随着工业化的发展,环保要求日益严格。寻求替代传统硫酸催化剂的研究迫在眉睫。
固体酸催化剂是一种不易腐蚀设备、无毒,易分离且可循环使用的绿色环保型新型催化剂。有关固体酸催化剂的研究较多,固体酸包括分子筛,SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/SnO2、SO4 2-/Al2O3和固载的杂多酸,在许多化学反应上取得了一定的进展。但是固体酸催化剂存在活性稳定性差、易失活、寿命短等缺点。六十年末美国杜帮公司开发了一种带磺酸基的全氟磺型脂的超强酸Nafion树脂,近年来,已开始用于许多合成反应中,表现出超好的催化效果。但是Nafion全氟磺酸树脂制备存在成本太高、负载制备难控制等缺点,限制了其工业化推广和应用。
中国专利,名称:一种酸性聚合离子液体及其制备方法和应用;申请号:201710187273.5;申请公布号: 106916237A;申请人: 中国科学院过程工程研究所;发明人: 赵国英 王傲运 张锁江 张海涛;摘要:本发明涉及酸性聚合离子液体催化烷基化技术领域,具体为一种基于一种路易斯酸的酸性聚合离子液体催化剂制备烷基化油的方法。该方法采用路易斯酸酸化的聚合离子液体为催化剂,在20-200℃,采用固定床反应器,连续催化液相丁烷/丁烯烷基化反应。该专利是采用的带双键的离子液体单体聚合的方式制备的聚合离子液体,因为酸性易流失,转化率不是很高。
基于以上原因,本发明考虑制备一种酸性不易流失的酸性聚合离子液体树脂催化剂。
发明内容
本发明的目的是合成一种不同于已有专利的聚合离子液体树脂催化剂,具有价格低廉,酸性不易流失,可以多次重复使用的优点。其制备方法包括以下步骤:
以季铵盐、磺酸内酯和带羟基磺酸生成离子液体单体,然后和甲醛进行聚合反应生成酸性聚合离子液体树脂催化剂。其具体包括以下步骤:
步骤S1:将季铵盐、磺酸内酯及溶剂在一定温度下混合,反应一定时间,去除溶剂,得白色固体;
步骤S2:向白色固体中加入羟基磺酸,在一定温度下,反应一定时间,得到离子液体单体;
步骤S3:将离子液体单体与甲醛溶液混合,在一定温度下,反应一定时间,脱水,得到淡橘黄色固体,即酸性聚合离子液体树脂催化剂。
其中,所述季铵盐选自咪唑、吡啶或三乙胺。
其中,所述羟基磺酸选自对羟基苯磺酸、磺基水杨酸或甲酚磺酸。
其中,所述溶剂选自乙醇、丙酮或乙酸乙酯。
其中,反应温度介于60-100℃。
其中,反应时间介于5-12h。
其中,所述步骤S1中,季铵盐与磺酸内酯的摩尔比介于1:1-1:5。
其中,所述步骤S2中,白色固体与羟基磺酸的摩尔比介于1:1-1:8。
其中,所述步骤S3中,离子液体单体与甲醛溶液的摩尔比介于1:1-1:10。
本发明另外提供一种上述制备方法的应用,其用于催化酯化反应、烷基化反应或酯交换反应。本发明与现有技术相比,具有以下有益效果 :
(1)回收简便,可通过简单过滤分离。
(2)催化效果好,对一般的酸催化反应如 :酯化、缩合、烷基化、酯交换化等有很高的催化活性。
(3)催化剂可重复多次使用,效果没有明显下降。
(4)没有废酸排放,没有二次污染。
以下将通过具体的实施例对本发明做进一步的阐述 :
具体实施方式:
为了更好地理解本发明,下面结合实施案例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施案例,也不应视为对本发明的限制。
一、制备实施案例
实施案例1:
将三乙胺0.1mol、1,3-丙烷磺酸内酯0.105mol及溶剂乙醇混合反应,反应条件为80℃、8小时。旋蒸除去溶剂,得到白色固体,石油醚洗涤三次,80℃真空干燥5小时。
加入0.1mol的对羟基苯磺酸,85℃反应4个小时。得到离子液体单体。按照单体与甲醛摩尔比1:1的比例加入甲醛。85℃反应两个小时。得到的溶液用五氧化二磷真空干燥,在5小时得到淡橘黄色聚合离子液体树脂催化剂。
实施案例2
将咪唑0.1mol、1,3-丙烷磺酸内酯0.105mol及溶剂乙醇混合反应,反应条件80为摄氏度、10小时。旋蒸除去溶剂,得到白色固体,石油醚洗涤三次,80摄氏度真空干燥5小时。加入0.1mol的磺基水杨酸,85摄氏度反应5个小时。得到离子液体单体。
按照单体与甲醛摩尔比1:2的比例加入甲醛。85摄氏度反应两个小时。得到的溶液用五氧化二磷真空干燥,在5小时得到淡橘黄色聚合离子液体树脂催化剂。
实施案例3
将吡啶0.1mol、1,3丙烷磺酸内酯0.105mol及溶剂乙醇混合反应,反应条件为80℃、12小时。旋蒸除去溶剂,得到白色固体,石油醚洗涤三次,80℃真空干燥3小时。加入0.1mol的甲酚磺酸,85℃反应6个小时。得到离子液体单体。
按照单体与甲醛摩尔比1:3的比例加入甲醛。85℃反应两个小时。得到的溶液用五氧化二磷真空干燥,在3小时得到淡橘黄色聚合离子液体树脂催化剂。
二、应用实施案例
将实施例1制备的酸性聚合离子液体树脂催化剂,用于催化酯化反应、烷基化反应、酯交换反应,得以下实施例。
实施案例4、催化酯化反应
在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入0.1mol乙酸、0.125mol 正丁醇进行加热搅拌,然后加入 0.5g 的催化剂,进行加热回流搅拌,使反应产生的水从分水器分出,反应3h,计算收率为 97.2%。
重复试验:反应结束后,催化剂进行过滤回收,用乙醇洗涤后,置于80℃烘箱中干燥。在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入0.1mol乙酸、0.125mol 正丁醇进行加热搅拌,然后加入第一次反应完回收干燥后的催化剂0.5g,进行加热回流搅拌,使反应产生的水从分水器分出,反应3h,计算收率为 97.1%。催化剂共回收5次,同上述步骤重复5次反应试验,相同条件下,收率分别为97.3%、97.2%、97.1%、97.0%。收率没有明显下降。
对比实验: 在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入0.1mol乙酸、0.125mol 正丁醇进行加热搅拌,然后加入浓硫酸0.5g,进行加热回流搅拌,使反应产生的水从分水器分出,反应3h,计算收率为 98%,重复上述实验5次,收率一直保持在97%左右,没有降低。
实施案例5、催化烷基化化反应
首先将10g催化剂加入高压反应釜,将丁烯和异丁烷按照摩尔比1:10的比例混合,反应釜氮气加压至0.4-0.6MPa,通入混合液100ml,温度控制在30-40℃,反应10-15min,泄压,取样检测,记算转化率,丁烯转化率为80%。
重复实验:反应完成以后,催化剂过滤,乙醇洗涤,置于80℃烘箱中干燥。将干燥后的催化剂10g加入高压反应釜,将丁烯和异丁烷按照摩尔比1:10的比例混合,反应釜氮气加压至0.4-0.6MPa,通入混合液100ml,温度控制在30-40℃,反应10-15min,泄压,取样检测,记算转化率,丁烯转化率为81%。重复试验步骤反应5次,丁烯转化率分别为81%、80%、80.5%、81%。转化率没有明显下降。
对比实验:将10g浓硫酸加入高压反应釜,将丁烯和异丁烷按照摩尔比1:10的比例混合,反应釜氮气加压至0.4-0.6MPa,通入混合液100ml,温度控制在30-40℃,反应10-15min,泄压,取样检测,记算转化率,丁烯转化率为85%,重复上述实验5次,转化率一直保持在85%左右,没有降低。
实施案例6、催化酯交换化化反应
在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入地沟油8.71g、甲醇3.84g及催化剂1.74g反应,反应温度60-80℃,反应10-12小时,转化率100%。
重复实验:反应结束后,采用过滤的方式回收催化剂,醇洗涤,置于80℃烘箱中干燥。在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入地沟油8.71g、甲醇3.84g及干燥后的催化剂1.74g反应,反应温度60-80℃,反应10-12小时,转化率100%。重复上述实验5次,转化率均为100%。
对比实验:在备有电磁搅拌、温度计、回流冷凝管及分水器的100mL三颈瓶中加入地沟油8.71g、甲醇3.84g及浓硫酸1.74g反应,反应温度60-80℃,反应10-12小时,转化率100%,重复上述实验5次,转化率没有降低。
通过应用实施案例和对比试验案例比较,本发明制备的催化剂催化效果和传统的浓硫酸催化剂效果相当。但是本发明制备的催化剂为固体催化剂,与反应物和产物易于分离回收,可以应用于固定床反应器。而且重复5次,催化效果没有明显下降,说明此催化剂酸性不流失,而且没有二次污染。
申请人声明,以上实施案例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施案例对本发明进行了详细说明,本领域的技术人员可以理解,可以对本发明的技术方案进行修改或者等同替换,而不脱硫本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围中。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种你简单变型,这些简单变型均属于本发明的保护范围。
Claims (10)
1.一种酸性聚合离子液体树脂催化剂的制备方法,其特征在于:以季铵盐、磺酸内酯和羟基磺酸生成离子液体单体,然后和甲醛进行聚合反应生成酸性聚合离子液体树脂催化剂。
2.如权利要求1所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,包括以下步骤:
步骤S1:将季铵盐、磺酸内酯及溶剂在一定温度下混合,反应一定时间,去除溶剂,得白色固体;
步骤S2:向白色固体中加入羟基磺酸,在一定温度下,反应一定时间,得到离子液体单体;
步骤S3:将离子液体单体与甲醛溶液混合,在一定温度下,反应一定时间,脱水,得到淡橘黄色固体,即酸性聚合离子液体树脂催化剂。
3.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,所述季铵盐选自咪唑、吡啶或三乙胺。
4.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,所述羟基磺酸选自对羟基苯磺酸、磺基水杨酸或甲酚磺酸。
5.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,步骤S2中反应温度介于60-100℃,步骤S3中反应温度介于80-120℃。
6.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,步骤S2和步骤S3中反应时间均介于5-12h。
7.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,所述步骤S1中,季铵盐与磺酸内酯的摩尔比介于1:1-1:5。
8.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,所述步骤S2中,白色固体与羟基磺酸的摩尔比介于1:1-1:8。
9.如权利要求2所述的酸性聚合离子液体树脂催化剂的制备方法,其特征在于,所述步骤S3中,离子液体单体与甲醛溶液的摩尔比介于1:1-1:10。
10.如权利要求1-9中任一项所述的制备方法的应用,其特征在于:用于催化酯化反应、烷基化反应或酯交换反应。
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