CN105037083A - 一种制备二醋酸丁烯二醇酯的方法 - Google Patents
一种制备二醋酸丁烯二醇酯的方法 Download PDFInfo
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- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- XXGZPUCDKOQDDL-UHFFFAOYSA-N acetic acid;butane-1,4-diol Chemical class CC(O)=O.OCCCCO XXGZPUCDKOQDDL-UHFFFAOYSA-N 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 229960004249 sodium acetate Drugs 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 abstract description 2
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- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- YXKKRBFPZPKVMH-UHFFFAOYSA-L disodium acetic acid sulfate Chemical compound [Na+].[Na+].CC(O)=O.[O-]S([O-])(=O)=O YXKKRBFPZPKVMH-UHFFFAOYSA-L 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010931 ester hydrolysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- NMTBZBPWKJALHU-UHFFFAOYSA-N O=C.C#C Chemical compound O=C.C#C NMTBZBPWKJALHU-UHFFFAOYSA-N 0.000 description 1
- HQNVSUZJHUXJAX-UHFFFAOYSA-N acetic acid;butane-1,4-diol Chemical compound CC(O)=O.CC(O)=O.OCCCCO HQNVSUZJHUXJAX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明公开了一种制备二醋酸丁烯二醇酯的方法，包括以下步骤，二醋酸丁烯二醇酯、水、催化剂催化水解，采用间歇式反应釜，其中二醋酸丁烯二醇酯与水的摩尔比1∶10-1∶32，反应过程中保持体系常温常压，持续搅拌，并缓慢通入微量氧气氮气混合气体，其中氧氮比为1∶10，通入速度30-60ml/min.m3，本发明采用混合制剂硫酸氢钠和醋酸钠，常温常压条件下，水解绿色合成丁烯二醇，反应废弃物少，且易于处理，聚合物少，一步合成，操作条件好，生产成本低廉，生产投资少，产物转化率高，具有较好的生产便捷性。
Description
技术领域
本发明涉及一种制备二醋酸丁烯二醇酯的方法。
背景技术
二醋酸丁烯二醇酯是生产1，4-丁二醇工业化生产的关键中间体，其直接加工的产品丁烯二醇可用于医药化工等多种技术领域。原有丁烯二醇常采用乙炔甲醛加成，采用选择性催化氢化，获得目标产物丁烯二醇。由于采用乙炔法生产加工，因此此生产路线环境污染大，废弃物多，越来越不利于中国现在绿色环境的需求，寻找一种便捷廉价，特别是环境友好的丁烯二醇的生产工业技术成为我们关注的焦点之一。
采用2-丁烯法生产加工1，4-丁二醇的生产技术方案，具有环境友好，生产技术可靠安全，投资成本低廉，原材料价格有竞争力，正在成为人们加快1，4-丁二醇工业产业结构调整，特别是开辟一条中国人自主开发的工业技术方案。
二醋酸丁烯二醇酯的来源主要是丁二烯与醋酸、氧气化合得到，国内外对二醋酸酯丁烯二醇的水解鲜有报道，这主要是由于二醋酸丁烯二醇酸性或水性条件水解都会存在一些聚合物或醚化产物，产物杂质较高，粗品后续精制难度较大，为解决这些问题，开发新的水解技术与水解方法，解决二醋酸丁烯二醇酯水解问题就显得尤为重要。
发明内容
本发明技术是为了解决背景技术的不足，提供一种改进的二醋酸丁烯二醇酯水解生产技术合成方法，以便彻底解决原有醋酸酯水解生产过程中出现的种种技术问题。
本发明的目的是以如下方式实现的：一种制备二醋酸丁烯二醇酯的方法，包括以下步骤：
A、用二醋酸丁烯二醇酯、水、催化剂催化水解，采用间歇式反应釜，其中二醋酸丁烯二醇酯与水的摩尔比1∶10-1∶32，反应过程中保持体系常温常压，持续搅拌，并缓慢通入微量氧气氮气混合气体，其中氧氮比为1∶10，通入速度30-60ml/min.m3；
B、步骤A中的催化合成体系为：硫酸氢钠与醋酸钠的混合固体，其中硫酸氢钠与醋酸钠摩尔比为1∶4-1∶8。
本发明的优点：本发明采用混合制剂硫酸氢钠和醋酸钠，常温常压条件下，水解绿色合成丁烯二醇，反应废弃物少，且易于处理，聚合物少，一步合成，操作条件好，生产成本低廉，生产投资少，产物转化率高，具有较好的生产便捷性。
具体实施方式：
一种制备二醋酸丁烯二醇酯的方法，包括以下步骤：
A、利用二醋酸丁烯二醇酯、水、催化剂催化水解，采用间歇式反应釜，其中二醋酸丁烯二醇酯与水的摩尔比1∶10-1∶32，反应过程中保持体系常温常压，持续搅拌，并缓慢通入微量氧气氮气混合气体，其中氧氮比为1∶10，通入速度30-60ml/min.m3；
B、步骤A中的催化合成体系为：硫酸氢钠与醋酸钠的混合固体，其中硫酸氢钠与醋酸钠摩尔比为1∶4-1∶8。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (1)
1.一种制备二醋酸丁烯二醇酯的方法，包括以下步骤：
A、用二醋酸丁烯二醇酯、水、催化剂催化水解，采用间歇式反应釜，其中二醋酸丁烯二醇酯与水的摩尔比1∶10-1∶32，反应过程中保持体系常温常压，持续搅拌，并缓慢通入微量氧气氮气混合气体，其中氧氮比为1∶10，通入速度30-60ml/min.m3；
B、步骤A中的催化合成体系为：硫酸氢钠与醋酸钠的混合固体，其中硫酸氢钠与醋酸钠摩尔比为1∶4-1∶8。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111167516A (zh) * | 2020-02-21 | 2020-05-19 | 浙江大学 | 一种多孔炭负载型单分子杂多酸催化剂及其制备方法和应用 |
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| CN111167516A (zh) * | 2020-02-21 | 2020-05-19 | 浙江大学 | 一种多孔炭负载型单分子杂多酸催化剂及其制备方法和应用 |
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