CN106542997B - A kind of method that modified graphene catalyzes and synthesizes diethy-aceto oxalate - Google Patents
A kind of method that modified graphene catalyzes and synthesizes diethy-aceto oxalate Download PDFInfo
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- CN106542997B CN106542997B CN201610998045.1A CN201610998045A CN106542997B CN 106542997 B CN106542997 B CN 106542997B CN 201610998045 A CN201610998045 A CN 201610998045A CN 106542997 B CN106542997 B CN 106542997B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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Abstract
The present invention relates to a kind of methods that modified graphene catalyzes and synthesizes diethy-aceto oxalate, rich hydroxylating graphene oxide is added before reaction into synthesis of diethyl oxalate employing reactor, due to the physico-chemical property that rich hydroxylating graphene oxide is excellent, so that oxalic acid molecule reacts efficiently thorough with ethanol molecule on the surface of graphene, diethy-aceto oxalate yield is improved by 93.3% to 99% or more.This method is simple and practical, and rich hydroxylating graphene oxide can reuse, at low cost, is suitble to large-scale production.
Description
Technical field
The invention belongs to medicine intermediates to synthesize field, and in particular to a kind of modified graphene catalyzes and synthesizes diethy-aceto oxalate
Method.
Background technique
Diethy-aceto oxalate is one of basic organic of chemical industry.It is widely used in medicine, plastics, prints and dyes, has
Machine synthesis etc..There are mainly two types of the synthetic methods of industrial diethy-aceto oxalate: i.e. traditional esterification process and developing in recent years
The catalyzing carbon monoxide oxidative coupling method got up.Esterification process is the conventional method industrially continued to use always.This method is oxalic acid, ethyl alcohol
Carry out the method for reaction dehydration according to a certain ratio with toluene (benzene).But the production cycle is long, unit consumption is high, this directly influences production
The production efficiency of producer.
In view of the limitation and disadvantage of above-mentioned technique, the present invention provides a kind of improved synthetic process, based on modification
The unique physicochemical property of graphene oxide, it has high-specific surface area (2630m2/ g), good chemical stability, and in view of
Hydroxyl have good hydrophilic, oleophylic performance and modified graphene ultra-large aperture (200nm~240nm), pi-pi bond with
Aromatic group interaction.So that oxalic acid molecule adheres on the surface of graphene with ethanol molecule, when avoiding original process distillation,
The loss of ethyl alcohol and benzene, so that reaction is thoroughly efficient.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that modified graphene catalyzes and synthesizes diethy-aceto oxalate, utilize rich hydroxyl
The excellent physicochemical property of graphite alkene, greatly improves mass transfer rate when diethyl oxalate synthesis, and greatly improves reaction
Yield.
The technical solution adopted by the present invention to solve the technical problems is: a kind of modified graphene catalyzes and synthesizes oxalic acid diethyl
The method of ester, comprising the following steps:
1) 98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, successively
0.6g graphite powder, 3.6g sodium perchlorate is added；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；
2) oxalic acid, ethyl alcohol, dehydrating agent, rich hydroxylating graphene oxide, control reaction temperature are proportionally added into reactor
Degree terminates up to dehydration, distills 140 DEG C of removing solvent benzols, and cooling is separated by filtration diethy-aceto oxalate, rich hydroxylating graphene oxide.
Specifically, the step 2) mesoxalic acid: ethyl alcohol: dehydrating agent: rich hydroxylating graphene oxide feed ratio is 200:
220-250:19-22:0.9-3。
Specifically, dehydrating agent is benzene in the step 2).
Specifically, reaction temperature is controlled at 120 DEG C or less in the step 2).
The invention has the following advantages: making oxalic acid due to the high-adsorption-capacity characteristic of rich hydroxylating graphene oxide
The mixed solution of molecule and ethyl alcohol can be adsorbed on completely inside the aperture of graphene, keep reaction more thorough, by reaction yield
6 percentage points are improved, greatly reduces production cost, and number can be recycled in the rich hydroxylating graphene oxide being added
Not less than 45 times.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention
Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection scope within.
Embodiment 1
98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, successively plus
Enter 0.6g graphite powder, 3.6g sodium perchlorate；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；?
In 1000ml four-hole bottle, oxalic acid, ethyl alcohol, benzene, rich hydroxylating graphene oxide 200g, 230g, 22g, 2g, reaction temperature are put into respectively
Degree control, hereinafter, up to going out without moisture, is continuously heating to 140 DEG C at 120 DEG C, distills benzene, benzene is steamed.Cooling separation oxalic acid
Diethylester, rich hydroxylating graphene oxide, diethy-aceto oxalate yield 99.1%.
Embodiment 2
98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, successively plus
Enter 0.6g graphite powder, 3.6g sodium perchlorate；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；?
In 1000ml four-hole bottle, oxalic acid, ethyl alcohol, benzene, rich hydroxylating graphene oxide 200g, 240g, 19g, 3g, reaction temperature are put into respectively
Degree control, hereinafter, up to going out without moisture, is continuously heating to 140 DEG C at 120 DEG C, distills benzene, benzene is steamed.Cooling separation oxalic acid
Diethylester, rich hydroxylating graphene oxide, diethy-aceto oxalate yield 99.0%.
Embodiment 3
98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, successively plus
Enter 0.6g graphite powder, 3.6g sodium perchlorate；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；?
In 1000ml four-hole bottle, oxalic acid, ethyl alcohol, benzene, rich hydroxylating graphene oxide 200g, 250g, 21g, 0.9g, reaction are put into respectively
Temperature control, hereinafter, up to going out without moisture, is continuously heating to 140 DEG C at 120 DEG C, distills benzene, benzene is steamed.Cooling separation grass
Diethyl phthalate, rich hydroxylating graphene oxide, diethy-aceto oxalate yield 99.1%.
Embodiment 4
98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, successively plus
Enter 0.6g graphite powder, 3.6g sodium perchlorate；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；?
In 1000ml four-hole bottle, oxalic acid, ethyl alcohol, benzene, rich hydroxylating graphene oxide 200g, 220g, 20g, 1g, reaction temperature are put into respectively
Degree control, hereinafter, up to going out without moisture, is continuously heating to 140 DEG C at 120 DEG C, distills benzene, benzene is steamed.Cooling separation oxalic acid
Diethylester, rich hydroxylating graphene oxide, diethy-aceto oxalate yield 99.3%.
Comparative example
In 1000ml four-hole bottle, oxalic acid, ethyl alcohol, benzene 200g, 240g, 21g are put into respectively, and reaction temperature is controlled 120
DEG C hereinafter, be continuously heating to 140 DEG C until go out without moisture, benzene is distilled, benzene is steamed, diethy-aceto oxalate, oxalic acid diethyl are obtained
Ester yield is 93.3%.
Claims (3)
1. a kind of method that modified graphene catalyzes and synthesizes diethy-aceto oxalate, which comprises the following steps:
1) 98% sulfuric acid of 400ml is maintained the temperature at -2 DEG C, 30% hydrogen peroxide of 10ml is added, after keeping the temperature 30min, sequentially added
0.6g graphite powder, 3.6g sodium perchlorate；Then 20 DEG C of heat preservation 1-3h, centrifugation obtain rich hydroxylating graphene oxide；
2) it is proportionally added into oxalic acid, ethyl alcohol, dehydrating agent benzene, rich hydroxylating graphene oxide into reactor, controls reaction temperature
Until dehydration terminates, 140 DEG C of removing benzene are distilled, cooling is separated by filtration diethy-aceto oxalate, rich hydroxylating graphene oxide.
2. the method that modified graphene as described in claim 1 catalyzes and synthesizes diethy-aceto oxalate, which is characterized in that the step
2) mesoxalic acid: ethyl alcohol: dehydrating agent: rich hydroxylating graphene oxide feed ratio is 200:220-250:19-22:0.9-3.
3. the method that modified graphene as described in claim 1 catalyzes and synthesizes diethy-aceto oxalate, which is characterized in that the step
2) reaction temperature control is at 120 DEG C or less in.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158839A (en) * | 1996-10-31 | 1997-09-10 | 昆山制药总厂 | Dimethyl oxalate synthesizing technology |
| CN1165809A (en) * | 1997-06-04 | 1997-11-26 | 梅永泉 | Tech. for prodn. of dimethyl oxalate |
| US5976324A (en) * | 1996-10-14 | 1999-11-02 | Bayer Aktiengesellschaft | Removal of water from reaction mixtures |
| CN102911042A (en) * | 2012-10-29 | 2013-02-06 | 陕西联盟物流有限公司 | Preparation method of oxalic acid diisoamyl ester |
| CN105348092A (en) * | 2015-09-29 | 2016-02-24 | 西安嘉宏能源化工科技有限公司 | Oxalate preparation process and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764783B2 (en) * | 1988-02-26 | 1995-07-12 | 宇部興産株式会社 | Continuous production method of oxalic acid dimethyl ester |
-
2016
- 2016-11-14 CN CN201610998045.1A patent/CN106542997B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976324A (en) * | 1996-10-14 | 1999-11-02 | Bayer Aktiengesellschaft | Removal of water from reaction mixtures |
| CN1158839A (en) * | 1996-10-31 | 1997-09-10 | 昆山制药总厂 | Dimethyl oxalate synthesizing technology |
| CN1165809A (en) * | 1997-06-04 | 1997-11-26 | 梅永泉 | Tech. for prodn. of dimethyl oxalate |
| CN102911042A (en) * | 2012-10-29 | 2013-02-06 | 陕西联盟物流有限公司 | Preparation method of oxalic acid diisoamyl ester |
| CN105348092A (en) * | 2015-09-29 | 2016-02-24 | 西安嘉宏能源化工科技有限公司 | Oxalate preparation process and application thereof |
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Denomination of invention: A method for catalytic synthesis of Diethyl Oxalate with modified graphene Effective date of registration: 20211130 Granted publication date: 20190416 Pledgee: Dongying Hekou District sub branch of China Post Savings Bank Co.,Ltd. Pledgor: SHANDONG HUIHAI PHARMACEUTICAL& CHEMICAL Co.,Ltd. Registration number: Y2021980013568 |