CN107056601A - A kind of preparation technology of trifluoroacetic acid - Google Patents
A kind of preparation technology of trifluoroacetic acid Download PDFInfo
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- CN107056601A CN107056601A CN201710336411.1A CN201710336411A CN107056601A CN 107056601 A CN107056601 A CN 107056601A CN 201710336411 A CN201710336411 A CN 201710336411A CN 107056601 A CN107056601 A CN 107056601A
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- Prior art keywords
- trifluoroacetic acid
- preparation technology
- fixed bed
- acid according
- nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthesis technique of trifluoroacetic acid, the preparation technology includes：Solid catalyst is put into fixed bed, then hydrogen peroxide is passed through with stabilized pressure pump, fixed temperature is increased to, then is passed through nitrogen and HFC-143a and hydroperoxidation, product trifluoroacetic acid is finally given.The preparation technology of the trifluoroacetic acid of the present invention uses HFC-143a for raw material, and preparation process is simple and product purity is high, product purity >=99%, conversion ratio >=95%, and catalyst can be used continuously in fixed bed, improve enterprise efficiency.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of preparation technology of trifluoroacetic acid.
Background technology
Trifluoroacetic acid is a kind of conventional organic acid, and it has very strong acidity and oxidisability, and it is to be only second to three at present
The strong oxidizing property organic acid of fluorine methanesulfonic acid.Trifluoroacetic acid can be as the catalysts and solvents reacted, its still protection well
Agent and deprotection agent, protection amino and hydroxyl are commonly used to as protective agent, as deprotection agent, are often used in de- Boc；In addition,
Trifluoroacetic acid can also be used to prepare synthesize some trifluoroacetic acid derivatives, such as TFAA, it is a kind of it is important in
Mesosome, has been widely used in the chemical syntheses such as medicine, agricultural chemicals, wide market.
The primary synthetic methods of trifluoroacetic acid have：1) classics Simons electrofluorination methods, acetylfluoride is perfluorinated, alkali fusion, acid
Change obtains trifluoroacetic acid.2) trifluorobichloroethane (HCFC-123) direct oxidation method, using trifluorobichloroethane as raw material, in catalysis
The lower direct oxidation of agent effect obtains trifluoro-acetyl chloride and trifluoroacetic acid.3) trifluorotrichloroethane (HCFC-113) oxidizing process, with three
Chlorofluoroethane be raw material under conventional Louis acid catalysis, obtain trifluoroacetic acid by rearrangement, oxidation, alkali fusion, acidifying.China
Research to trifluoroacetic acid is started in the 1980s, the mainly Simons electrofluorinations that industrial production now is used
Method, in recent years we have also been developed some synthetic methods of oneself, mainly with trifluorobichloroethane and trifluorotrichloroethane
For raw material, new catalyst is synthesized.
The content of the invention
Goal of the invention：The invention aims to solve deficiency of the prior art there is provided one kind to use HFC-143a
For raw material, by oxidation reaction finished product trifluoroacetic acid, its preparation technology is reasonable in design, and its absorptivity and total recovery are high, and
Energy consumption is low, and accessory substance is few, clean environment firendly, the synthesis and production process of safe and reliable trifluoroacetic acid.
Technical scheme：A kind of synthesis and production process of trifluoroacetic acid of the present invention, comprises the following steps：
(1) catalyst and quartz sand are mixed, puts into fixed bed reaction kettle, slowly carry out warming temperature；
(2) by hydrogen peroxide stabilized pressure pump, it is passed into fixed bed, and keeps pressure to be in stable state, temperature all the time
It is increased to fixed value；
(3) HFC-143a and nitrogen are passed into fixed bed simultaneously, anti-raw reaction is contacted with hydrogen peroxide；
(4) distillation operation is carried out to the material of generation, obtains trifluoroacetic acid；
(5) for catalyst can clean there is provided give step (1) reuse.
Further, the catalyst described in step (1) is Pd-SiW12/SiO2、Al2O3、HY、HB、SiW12/SiO2+
Pd/C、Fe/ZSM-5。
Further, temperature is increased to 50 DEG C -70 DEG C in step (1), and heating rate is 2 DEG C/min.
Further, temperature is increased to 50 DEG C -70 DEG C in step (2).
Further, the flow of hydrogen peroxide described in step (2) is 1.53ml/h-4.58ml/h.
Further, it is to play a part of diluting HFC-143a that nitrogen is added described in step (3), and the flow of nitrogen is
24ml/h-47ml/h。
Further, the flow of HFC-143a described in step (3) is 4.8ml/h-9.4ml/h.
Beneficial effect：The present invention draws trifluoroacetic acid, selectivity height, high conversion rate, production capacity using fixed bed production
High, product purity is high, easy to operate, energy consumption is low, and reagent is easy to get, and solid catalyst used is repeatable to be utilized, clean environment firendly, peace
It is complete reliable.
Brief description of the drawings
Fig. 1 is overall flow schematic diagram of the invention.
Embodiment
Present disclosure is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
Embodiment 1
A kind of preparation technology of trifluoroacetic acid as shown in Figure 1, comprises the following steps：
(1) catalyst and 2g quartz sands are mixed, puts into fixed bed reaction kettle, slowly carry out warming temperature；
(2) by hydrogen peroxide stabilized pressure pump, it is passed into fixed bed, and keeps pressure to be in stable state, temperature all the time
It is increased to fixed value；
(3) HFC-143a and nitrogen are passed into fixed bed simultaneously, anti-raw reaction is contacted with hydrogen peroxide；
(4) distillation operation is carried out to the material of generation, obtains trifluoroacetic acid；
(5) for catalyst can clean there is provided give step (1) reuse.
Further, the catalyst described in step (1) is that Fe/ZSM-5 mass is 0.5g.
Further, step (1) and step (2) heating, refer to increase the temperature to 50 DEG C, and heating rate is 2 DEG C/
min。
Further, what step (2) was described is 30% hydrogen peroxide, hydrogen peroxide：Nitrogen：HFC-143a mol ratio
1：5：2.
Further, the flow of step (2) described hydrogen peroxide is 1.53ml/h.
Further, the flow of step (3) described HFC-143a is 9.4ml/h, and the flow of nitrogen is 47ml/h.
Embodiment 2
A kind of preparation technology of trifluoroacetic acid as shown in Figure 1, comprises the following steps：
(1) catalyst and 2g quartz sands are mixed, puts into fixed bed reaction kettle, slowly carry out warming temperature；
(2) by hydrogen peroxide stabilized pressure pump, it is passed into fixed bed, and keeps pressure to be in stable state, temperature all the time
It is increased to fixed value；
(3) HFC-143a and nitrogen are passed into fixed bed simultaneously, anti-raw reaction is contacted with hydrogen peroxide；
(4) distillation operation is carried out to the material of generation, obtains trifluoroacetic acid；
(5) for catalyst can clean there is provided give step (1) reuse.
Further, the catalyst described in step (1) is Pd-SiW12/SiO2, quality is 1g.
Further, step (1) and step (2) heating, refer to increase the temperature to 70 DEG C, and heating rate is 2 DEG C/
min。
Further, what step (2) was described is 30% hydrogen peroxide, hydrogen peroxide：Nitrogen：HFC-143a mol ratio
2：5：4.
Further, the flow of step (2) described hydrogen peroxide is 3.53ml/h.
Further, the flow of step (3) described HFC-143a is 4.8ml/h, and the flow of nitrogen is 24ml/h.
Embodiment 3
A kind of preparation technology of trifluoroacetic acid as shown in Figure 1, comprises the following steps：
(1) catalyst and 2g quartz sands are mixed, puts into fixed bed reaction kettle, slowly carry out warming temperature；
(2) by hydrogen peroxide stabilized pressure pump, it is passed into fixed bed, and keeps pressure to be in stable state, temperature all the time
It is increased to fixed value；
(3) HFC-143a and nitrogen are passed into fixed bed simultaneously, anti-raw reaction is contacted with hydrogen peroxide；
(4) distillation operation is carried out to the material of generation, obtains trifluoroacetic acid；
(5) for catalyst can clean there is provided give step (1) reuse.
Further, the catalyst described in step (1) is porous level Fe/ZSM-5, and quality is 2g.
Further, step (1) and step (2) heating, refer to increase the temperature to 70 DEG C, and heating rate is 2 DEG C/
min。
Further, what step (2) was described is 30% hydrogen peroxide, hydrogen peroxide：Nitrogen：HFC-143a mol ratio
2：5：4.
Further, the flow of step (2) described hydrogen peroxide is 4.58ml/h.
Further, the flow of step (3) described HFC-143a is 4.8ml/h, and the flow of nitrogen is 24ml/h.
The present invention draws trifluoroacetic acid using fixed bed production, and selectivity height, high conversion rate, production capacity are high, product is pure
Spend high, easy to operate, energy consumption low, and reagent is easy to get, solid catalyst used is repeatable to be utilized, and clean environment firendly is safe and reliable.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit according to the present invention
Any simple modification, equivalent variations and the modification made to above example, in the range of still falling within technical solution of the present invention.
Claims (7)
1. a kind of preparation technology of trifluoroacetic acid, it is characterised in that comprise the following steps：
(1) catalyst and quartz sand are mixed, puts into fixed bed reaction kettle, slowly carry out warming temperature；
(2) by hydrogen peroxide stabilized pressure pump, it is passed into fixed bed, and keeps pressure to be in stable state, temperature rise all the time
To fixed value；
(3) HFC-143a and nitrogen are passed into fixed bed simultaneously, anti-raw reaction is contacted with hydrogen peroxide；
(4) distillation operation is carried out to the material of generation, obtains trifluoroacetic acid；
(5) for catalyst can clean there is provided give step (1) reuse.
2. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Urging described in step (1)
Agent is Pd-SiW12/SiO2、Al2O3、HY、HB、SiW12/SiO2+Pd/C、Fe/ZSM-5。
3. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Temperature is raised in step (1)
To 50 DEG C -70 DEG C, heating rate is 2 DEG C/min.
4. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Temperature is raised in step (2)
To 50 DEG C -70 DEG C.
5. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Peroxide described in step (2)
The flow for changing hydrogen is 1.53ml/h-4.58ml/h.
6. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Added described in step (3)
Nitrogen is to play a part of diluting HFC-143a, and the flow of nitrogen is 24ml/h-47ml/h.
7. a kind of preparation technology of trifluoroacetic acid according to claim 1, it is characterised in that：Trifluoro described in step (3)
The flow of ethane is 4.8ml/h-9.4ml/h.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710336411.1A CN107056601A (en) | 2017-05-13 | 2017-05-13 | A kind of preparation technology of trifluoroacetic acid |
| PCT/CN2017/099972 WO2018209842A1 (en) | 2017-05-13 | 2017-08-31 | Preparation process for trifluoroacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710336411.1A CN107056601A (en) | 2017-05-13 | 2017-05-13 | A kind of preparation technology of trifluoroacetic acid |
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|---|---|
| CN107056601A true CN107056601A (en) | 2017-08-18 |
Family
ID=59597820
Family Applications (1)
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|---|---|---|---|
| CN201710336411.1A Pending CN107056601A (en) | 2017-05-13 | 2017-05-13 | A kind of preparation technology of trifluoroacetic acid |
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| WO (1) | WO2018209842A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658751A (en) * | 2018-03-29 | 2018-10-16 | 浙江巨化技术中心有限公司 | A kind of preparation method of trifluoroacetic acid |
| WO2018209842A1 (en) * | 2017-05-13 | 2018-11-22 | 南通宝凯化工有限公司 | Preparation process for trifluoroacetic acid |
| CN111039771A (en) * | 2019-12-25 | 2020-04-21 | 湖南有色郴州氟化学有限公司 | Preparation method of 3,3, 3-trifluoropropionic acid |
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| US5736012A (en) * | 1996-09-10 | 1998-04-07 | Alliedsignal Inc. | Process for the preparation of a fluorinated acid |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| CN106349033A (en) * | 2016-08-23 | 2017-01-25 | 西安近代化学研究所 | Process for preparing trifluoroacetaldehyde hydrate from 1,1,1-halothane |
| CN106699540A (en) * | 2015-11-14 | 2017-05-24 | 宁夏际华环境安全科技有限公司 | Trifluoroacetic acid production technology |
Family Cites Families (5)
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| CN1049421C (en) * | 1997-06-11 | 2000-02-16 | 中国科学院上海有机化学研究所 | Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. |
| CA2907955A1 (en) * | 2013-05-13 | 2014-11-20 | Saudi Basic Industries Corporation | Methods for preparing acetic acid via ethane oxidation |
| CN103524325A (en) * | 2013-10-14 | 2014-01-22 | 常熟振氟新材料有限公司 | Preparation method of trifluoroacetic acid |
| CN106008199A (en) * | 2016-06-24 | 2016-10-12 | 湖北风绿科技股份有限公司 | Method for synthesizing trifluoroacetic acid with industrial waste gas |
| CN107056601A (en) * | 2017-05-13 | 2017-08-18 | 南通宝凯化工有限公司 | A kind of preparation technology of trifluoroacetic acid |
-
2017
- 2017-05-13 CN CN201710336411.1A patent/CN107056601A/en active Pending
- 2017-08-31 WO PCT/CN2017/099972 patent/WO2018209842A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5736012A (en) * | 1996-09-10 | 1998-04-07 | Alliedsignal Inc. | Process for the preparation of a fluorinated acid |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| CN106699540A (en) * | 2015-11-14 | 2017-05-24 | 宁夏际华环境安全科技有限公司 | Trifluoroacetic acid production technology |
| CN106349033A (en) * | 2016-08-23 | 2017-01-25 | 西安近代化学研究所 | Process for preparing trifluoroacetaldehyde hydrate from 1,1,1-halothane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018209842A1 (en) * | 2017-05-13 | 2018-11-22 | 南通宝凯化工有限公司 | Preparation process for trifluoroacetic acid |
| CN108658751A (en) * | 2018-03-29 | 2018-10-16 | 浙江巨化技术中心有限公司 | A kind of preparation method of trifluoroacetic acid |
| CN108658751B (en) * | 2018-03-29 | 2021-06-15 | 浙江巨化技术中心有限公司 | Preparation method of trifluoroacetic acid |
| CN111039771A (en) * | 2019-12-25 | 2020-04-21 | 湖南有色郴州氟化学有限公司 | Preparation method of 3,3, 3-trifluoropropionic acid |
| CN111039771B (en) * | 2019-12-25 | 2022-06-03 | 湖南有色郴州氟化学有限公司 | Preparation method of 3,3, 3-trifluoropropionic acid |
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| Publication number | Publication date |
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| WO2018209842A1 (en) | 2018-11-22 |
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| CB03 | Change of inventor or designer information |
Inventor after: Xu Maoqian Inventor after: Chun Fanli Inventor after: Zeng Xiaofei Inventor after: Gai Xikun Inventor after: Xing Chuang Inventor after: Yang Ruiqin Inventor after: Wu Shengjun Inventor after: Chen Caiyan Inventor before: Wu Shengjun Inventor before: Chen Caiyan Inventor before: Yang Ruiqin Inventor before: Xing Chuang Inventor before: Li Huaxin Inventor before: Zhang Linlin Inventor before: Zou Xueming Inventor before: Huang Kaihua |
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Application publication date: 20170818 |
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