CN107400047A - 离子液体催化甲醛缩合反应制备二羟基丙酮的方法 - Google Patents

离子液体催化甲醛缩合反应制备二羟基丙酮的方法 Download PDF

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CN107400047A
CN107400047A CN201710382150.7A CN201710382150A CN107400047A CN 107400047 A CN107400047 A CN 107400047A CN 201710382150 A CN201710382150 A CN 201710382150A CN 107400047 A CN107400047 A CN 107400047A
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catalyst
dihydroxyacetone
dha
formaldehyde
ionic liquid
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孙育成
姜玉婷
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Suzhou Shuanghu Chemical Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde
    • 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
    • B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form

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  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明公开了一种离子液体催化甲醛缩合反应制备二羟基丙酮的方法。采用离子液体为催化剂，在助催化剂协同作用下，甲醛在溶剂中缩合生成1,3‑二羟基丙酮。该方法采用甲醛作为反应原料，廉价易得，反应条件温和，反应过程简单易控。

Description

离子液体催化甲醛缩合反应制备二羟基丙酮的方法
技术领域
本发明涉及一种以离子液体为催化剂，甲醛缩合反应合成1,3-二羟基丙酮的方法。
背景技术
1,3-二羟基丙酮（1,3-dihydroxyacetone，简写为DHA）又称丙酮醇或二羟基丙酮，外观是白色或类白色粉末状结晶，具有甜、凉的味道，易吸湿。一般状态下是二聚体 (1,4-Dioxane) 的结晶，但经溶解或加热则变为单体，其单体易溶于水、乙醇、丙酮和乙醚等有机溶剂。二羟基丙酮是一种天然存在的水溶性酮糖，具有生物可降解性，对人体和环境无害，近年来广泛应用于制药、化妆品、食品添加剂、饲料等，同时，二羟基丙酮分子中含有三个官能团，化学性质活泼，广泛参与诸如聚合、缩合等各种化学反应，是一种重要的化工和生化原料。
目前，二羟基丙酮的生产方法主要有微生物发酵法和化学合成法。微生物法制备二羟基丙酮原理就是利用微生物代谢产生的甘油脱氢酶或二羟基丙酮合成酶的作用将甘油转化为二羟基丙酮。其中用于生产二羟基丙酮的微生物有醋酸杆菌（Acetobacter）(US4976589)，葡萄糖酸杆菌属（Gluconobacter）(US 5770411)等。但是，菌类的存在限制了甘油的浓度范围，使产物收率很难提高，生产效率低，副产物多，后处理工艺复杂，发酵周期长，生产成本高。化学法主要包括甘油催化氧化法和甲醛缩合法等。甘油催化氧化法主要是直接催化氧化甘油制备二羟基丙酮，当催化剂0.6%Bi~3%Pt负载在活性碳上时，在混合床反应器中甘油转化率为40%，二羟基丙酮的收率为3%（DE4228487）。该方法通常采用钯、铂等贵金属催化剂体系，具有催化剂昂贵，产物收率低，分离工艺复杂造成分离成本高等缺点。甲醛缩合法制备二羟基丙酮的报道较少，主要是在基本上无水的液体反应介质中进行甲醛的自缩合反应，生成二羟基丙酮或其二聚物或低聚物。北京旭阳化工技术研究院报道了一种固载化卡宾催化剂体系（CN 201510024406.8），140℃下反应2~4h，多聚甲醛转化率接近100%，二羟基丙酮选择性大于90%。固体催化剂表面易积碳而失活。
甲醛缩合法采用甲醛为反应原料，具有原料成本低，产物收率高等优势，是一条更为经济的制备路线，为此研究和开发一种高活性、高选择性、环境友好的催化剂体系及清洁工艺显得十分重要。
发明内容
本发明的目的在于提供一种离子液体催化甲醛缩合反应制备二羟基丙酮的方法。
一种离子液体催化甲醛缩合反应制备二羟基丙酮的方法，使用甲醛作为反应物，离子液体为催化剂，质子接受体化合物为助催化剂，所述催化剂的阳离子部分选自含氮杂环类阳离子，结构式为：
，
其中，R1为烷烃或者芳基；R2、R3为烷烃或者芳基，或R2, R3 = -(CH)4-。
所述催化剂的阴离子部分选自溴离子、氯离子、羧酸根。
所述的助催化剂选自咪唑、奎宁、吡啶、三乙胺、三辛胺或二乙醇胺。
所述的甲醛选自三聚甲醛、低聚甲醛或多聚甲醛。
采用极性溶剂为反应溶剂，包括乙醇、二甲亚砜、乙腈、1,4-二氧六烷、二甲基甲酰胺、水。
所述的极性溶剂优选为1,4-二氧六烷和乙醇。
所述的催化剂用量为甲醛投料量的0.5mol%~20mol%，优选1mol%~10mol%。
所述的助催化剂与催化剂的摩尔比为0.5:1~4:1，优选1:1~3:1mol/mol。
反应温度为40~160℃，优选80～120 ℃。
反应时间为0.5~10h，优选0.5～5 h。
本发明具有以下有益效果：
1）反应工艺简单，反应原料及溶剂无需除水，减低能耗；
2）反应原料均可来自煤化工，存在资源和价格优势，因而极具市场竞争力和发展前景；
3）离子液体催化剂具有腐蚀性低、环境友好、对设备无特殊要求；
4) 操作条件温和、容易操作、可控性强。
附图说明
图1为六种离子液体催化剂的结构式。
具体实施方式
本发明由离子液体催化合成二羟基丙酮的方法的化学反应方程式为：
反应过程使用甲醛为反应原料，离子液体作为催化剂，质子接受体类化合物作为助催化剂，催化剂的用量为甲醛投料量的0.5mol%~20mol%，助催化剂与催化剂的摩尔比为0.5:1~4:1，反应温度为40~160℃，反应时间为0.5~10h。
所述的离子液体阳离子部分选自含氮杂环类阳离子；离子液体阴离子部分选自溴离子、氯离子、羧酸根等。
本发明所述的离子液体阳离子的结构式为：
R1为烷烃或者芳基；R2、R3为烷烃或者芳基，或R2, R3 = -(CH)4-。图1示例性的图示了六种离子液体催化剂，但本领域技术人员应知，不仅限于此。
本发明所述的助催化剂为咪唑、奎宁、吡啶、三乙胺、三辛胺、二乙醇胺等。
本发明所用的甲醛源为三聚甲醛、低聚甲醛或多聚甲醛。
本发明所用的反应溶剂为极性溶剂，如乙醇、二甲亚砜、乙腈、1,4-二氧六烷、二甲基甲酰胺、水等，优选1,4-二氧六烷和乙醇。
本发明所述的催化剂用量优选为甲醛投料量的 1mol%~10mol%。
本发明所述的助催化剂与催化剂的摩尔比为优选1:1~3:1mol/mol。
本发明所述的反应温度优选80～120 ℃。
本发明所述的反应时间优选0.5～5 h。
实施例1
在100mL反应釜中依次加入4.5g多聚甲醛，1.7g 离子液体1，0.8g三乙胺，60mL乙醇，机械搅拌，30min内升温至90 oC，在氮气保护的条件下反应3h。反应结束后冷却，过滤除去催化剂，反应液采用气相色谱分析，外标法定量。二羟基丙酮收率为41.7%。
实施例2
同实施例1，使用离子液体4为催化剂，投料量为1.8g，二羟基丙酮收率为50.1%。
实施例3
同实施例1，使用离子液体6为催化剂，投料量为2.04g，二羟基丙酮收率为52.1%。
实施例4
在100mL反应釜中依次加入4.5g多聚甲醛，4.08g 离子液体6，1.6g三乙胺，60mL乙醇，机械搅拌，30min内升温至100 oC，在氮气保护的条件下反应3h。反应结束后冷却，过滤除去催化剂，反应液采用气相色谱分析，外标法定量。二羟基丙酮收率为63.5%。
实施例5
同实施例4，催化剂6的投料量为1.02g，助催化剂三乙胺的用量为0.4g，二羟基丙酮收率为15.5%。
实施例6
同实施例5，采用咪唑为助催化剂，二羟基丙酮收率为 19.5%。
实施例7
同实施例5，采用三辛胺为助催化剂，二羟基丙酮收率为 10.5%。
实施例8
同实施例3，在80 oC下反应1小时，二羟基丙酮收率为35.5%。
实施例9
同实施例3，在120 oC下反应1小时，二羟基丙酮收率为39.5%。
实施例10
同实施例4，采用三聚甲醛作为反应原料，二羟基丙酮收率为62.8%。

Claims (10)

1.一种离子液体催化甲醛缩合反应制备二羟基丙酮的方法，其特征在于：使用甲醛作为反应物，离子液体为催化剂，质子接受体化合物为助催化剂，所述催化剂的阳离子部分选自含氮杂环类阳离子，结构式为：
，
其中，R1为烷烃或者芳基；R2、R3为烷烃或者芳基，或R2, R3 = -(CH)4-。
2.如权利要求1的方法，其特征在于，所述催化剂的阴离子部分选自溴离子、氯离子、羧酸根。
3.如权利要求1的方法，其特征在于，所述的助催化剂选自咪唑、奎宁、吡啶、三乙胺、三辛胺或二乙醇胺。
4.如权利要求1的方法，其特征在于，所述的甲醛选自三聚甲醛、低聚甲醛或多聚甲醛。
5.如权利要求1的方法，其特征在于，采用极性溶剂为反应溶剂，包括乙醇、二甲亚砜、乙腈、1,4-二氧六烷、二甲基甲酰胺、水。
6.如权利要求5的方法，其特征在于，所述的极性溶剂优选为1,4-二氧六烷和乙醇。
7.如权利要求1的方法，其特征在于，所述的催化剂用量为甲醛投料量的0.5mol%~20mol%，优选1mol%~10mol%。
8.如权利要求1的方法，其特征在于，所述的助催化剂与催化剂的摩尔比为0.5:1~4:1，优选1:1~3:1mol/mol。
9.如权利要求1的方法，其特征在于，反应温度为40~160℃，优选80～120 ℃。
10.如权利要求1的方法，其特征在于，反应时间为0.5~10h，优选0.5～5 h。
CN201710382150.7A 2017-05-26 2017-05-26 离子液体催化甲醛缩合反应制备二羟基丙酮的方法 Pending CN107400047A (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049151A (zh) * 1989-07-26 1991-02-13 英国石油化学品有限公司 α-羟基酮类化合物的合成
US5166450A (en) * 1990-10-10 1992-11-24 Bp Chemicals Limited Production of hydroxyketones
US5410089A (en) * 1992-05-04 1995-04-25 Basf Aktiengesellschaft Preparation of dihydroxyacetone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049151A (zh) * 1989-07-26 1991-02-13 英国石油化学品有限公司 α-羟基酮类化合物的合成
US5166450A (en) * 1990-10-10 1992-11-24 Bp Chemicals Limited Production of hydroxyketones
US5410089A (en) * 1992-05-04 1995-04-25 Basf Aktiengesellschaft Preparation of dihydroxyacetone

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
TOSHIHIKO MATSUMOTO等: "Selective Formation of Triose from Formaldehyde Catalyzed by Thiazolium Salt", 《J. AM. CHEM. SOC.》 *
宋如等: "二羟基丙酮生产研究进展", 《化工技术与开发》 *
贾冰等: "甲醛聚糖生成DHA 反应研究进展等", 《现代化工》 *

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Application publication date: 20171128