CN108503507A - A kind of production technology of difluoroethanol - Google Patents
A kind of production technology of difluoroethanol Download PDFInfo
- Publication number
- CN108503507A CN108503507A CN201810125801.9A CN201810125801A CN108503507A CN 108503507 A CN108503507 A CN 108503507A CN 201810125801 A CN201810125801 A CN 201810125801A CN 108503507 A CN108503507 A CN 108503507A
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- difluoroethanol
- bed reactors
- method described
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- VUYQBMXVCZBVHP-UHFFFAOYSA-N 1,1-difluoroethanol Chemical compound CC(O)(F)F VUYQBMXVCZBVHP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- PBWZKZYHONABLN-UHFFFAOYSA-M difluoroacetate Chemical compound [O-]C(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-M 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000012856 packing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 6
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical group CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 6
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of production technologies of difluoroethanol, and the present invention is using difluoro acetate as raw material, by Catalyst packing in fixed bed reactors, it is passed through the replacement fixed bed interior air of nitrogen, then it is passed through hydrogen into fixed bed, raises simultaneously temperature, finally obtains product difluoroethanol.Catalytic conversion of the present invention is high, selectivity is good, at low cost, can realize continuous production, has good market promotion prospect.
Description
Technical field
The invention belongs to fluorine-containing field of fine chemical, and in particular to a kind of production technology of difluoroethanol.
Background technology
Fluorinated organic compound is due to its unique physics, chemical property and physiological activity by the extensive pass of researcher
Note, its synthetic route and physiological activity also have become the hot spot studied now.Difluoroethanol is that a kind of important aliphatic contains
Fluorine organic synthesis intermediate makes its chemical property be different from other alcohols due to the special construction containing difluoromethyl, can be with
It participates in a variety of organic synthesis, is widely used in the synthesis of insecticide and herbicide etc..
Difluoroethanol can be made using the following method at present：Metal hydride reduction method.Liquid phase catalytic hydrogenation reduction method.Gas
Phase catalytic hydrogenating reduction method.Base-catalyzed transesterification method.
Hydroxy compounds is restored by reducing agents such as metal cyanide methods and obtains difluoroethanol, and method is simple.But due to reduction
Agent is expensive, and reduction is violent, dangerous, and the separation of product and reducing agent and solvent is difficult, product last handling process it is complicated and
The three wastes are more, are not suitable for mass producing.Liquid phase catalytic hydrogenation method is current most widely used synthetic method, due to reactant with
Catalyst exposure level is greatly reduced compared with vapor phase method, therefore the reaction time is generally longer, is unfavorable for continuous production.Gas phase catalysis
Hydrogenating reduction method be a little it is simple for process, the reaction time is short, catalyst and product are easily separated, can continuous production, be suitble to big rule
Mould industrialized production, shortcoming reaction temperature is higher, and side reaction easily occurs.The key point and difficult point of the technique are that exploitation is high
Effect, catalyst with long service life.The high income of ester catalysis ester-interchange method generally speaking difluoroethanol, but reaction step is more,
Controllability is looked into, and causes total recovery not high.
Invention content
Goal of the invention：The purpose of the present invention is to solve deficiencies in the prior art, provide a kind of using difluoroacetic acid
Ethyl ester or methyl difluoroacetate are as raw material, and preparation process is simple and product purity is high, and catalyst palladium carbon connects in fixed bed
It is continuous to be not apparent from decline using catalytic efficiency, improve the performance of enterprises.
Technical solution is as follows：
Palladium carbon series catalysts are packed into fixed bed reactors by step 1.
Step 2 is passed through nitrogen into fixed bed reactors, until the air in fixed bed reactors is emptied, then rises
High-temperature is to 200-250 DEG C.
Step 3 is passed through difluoro acetate and hydrogen into fixed bed reactors, and the reaction time is 8-10 hours, is made two
Fluoroethanol.
Further, the Pd/C that is added in step 1 and step 3, difluoro acetate, hydrogen mass ratio be 0.5-1：5-
10：50-150.
Further, it when step 2 is passed through nitrogen emptying air, to replace 3 times or more.
Further, the raw material that step 3 uses is ethyl difluoro or methyl difluoroacetate.
Further, step 3 with nitrogen it is replacement fixed bed in air at least 3 times or more.
Further, difluoro acetate and hydrogen are continuously passed through in being reacted described in step 3, and pressure liter when reacting
Height arrives 1-2MPa, reacts 8-10 hours.
Advantageous effect：The preparation process of the difluoroethanol of the present invention uses ethyl difluoro or methyl difluoroacetate for original
Material, catalyst palladium carbon is filled into fixed bed reactors,；The air being passed through into fixed bed in nitrogen emptying reactor, will
Fixed bed is heated to 200-250 DEG C；It is passed through ethyl difluoro or methyl difluoroacetate and hydrogen into the fixed bed, makes
Pd/C, difluoro acetate, hydrogen mass ratio be 0.5-1：5-10：50-150 reacts 8-10 hours.Preparation process letter of the present invention
List and product purity height, efficiency is not apparent from decline to palladium carbon in use, improves the performance of enterprises.
Description of the drawings
Fig. 1 is the integrated artistic flow diagram of the present invention
Specific implementation mode
Present disclosure is further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
Palladium carbon series catalysts are packed into fixed bed reactors；Nitrogen is passed through into fixed bed reactors, until will consolidate
Air in fixed bed reactor empties, at least replace 3 times or more, then increase the temperature to 200 DEG C；Lead into fixed bed reactors
Enter difluoro acetate and hydrogen, make Pd/C, difluoro acetate, hydrogen mass ratio be 0.5：5：50；Reaction time is 8 hours,
Obtain sample.The content of difluoroethanol in sampling analysis product.
Embodiment 2
Palladium carbon series catalysts are packed into fixed bed reactors；Nitrogen is passed through into fixed bed reactors, until will consolidate
Air in fixed bed reactor empties, at least replace 3 times or more, then increase the temperature to 210 DEG C；Lead into fixed bed reactors
Enter difluoro acetate and hydrogen, make Pd/C, difluoro acetate, hydrogen mass ratio be 0.6：6：70；Reaction time is 8 hours,
Obtain sample.The content of difluoroethanol in sampling analysis product.
Embodiment 3
Palladium carbon series catalysts are packed into fixed bed reactors；Nitrogen is passed through into fixed bed reactors, until will consolidate
Air in fixed bed reactor empties, at least replace 3 times or more, then increase the temperature to 220 DEG C；Lead into fixed bed reactors
Enter difluoro acetate and hydrogen, make Pd/C, difluoro acetate, hydrogen mass ratio be 0.7：7：90；Reaction time is 9 hours,
Obtain sample.The content of difluoroethanol in sampling analysis product.
Embodiment 4
Palladium carbon series catalysts are packed into fixed bed reactors；Nitrogen is passed through into fixed bed reactors, until will consolidate
Air in fixed bed reactor empties, at least replace 3 times or more, then increase the temperature to 220 DEG C；Lead into fixed bed reactors
Enter difluoro acetate and hydrogen, make Pd/C, difluoro acetate, hydrogen mass ratio be 0.7：7：90；Reaction time is 10 hours,
Obtain sample.The content of difluoroethanol in sampling analysis product.
Embodiment 5
Palladium carbon series catalysts are packed into fixed bed reactors；Nitrogen is passed through into fixed bed reactors, until will consolidate
Air in fixed bed reactor empties, at least replace 3 times or more, then increase the temperature to 220 DEG C；Lead into fixed bed reactors
Enter difluoro acetate and hydrogen, make Pd/C, difluoro acetate, hydrogen mass ratio be 1：10：150；Reaction time is 10 hours,
Obtain sample.The content of difluoroethanol in sampling analysis product.
Claims (8)
1. a kind of production technology of difluoroethanol, feature include the following steps：
(1) Catalyst packing is entered in fixed bed reactors；
(2) and then into fixed bed reactors it is passed through nitrogen, until the air in fixed bed reactors is emptied, then increases temperature
Degree；
(3) difluoro acetate and hydrogen reaction are passed through into fixed bed reactors again；
(4) in sampling analysis product difluoroethanol content.
2. according to the method described in claim 1, it is characterized in that：Catalyst is palladium carbon series catalysts.
3. according to the method described in claim 1, it is characterized in that：The Pd/C, difluoro acetate, hydrogen mass ratio be
0.5-1：5-10：50-150.
4. according to the method described in claim 1, it is characterized in that：Raw material is ethyl difluoro or methyl difluoroacetate.
5. according to the method described in claim 1, it is characterized in that：Raising temperature described in step (2) is to be increased to 200-250
℃。
6. according to the method described in claim 1, it is characterized in that：Described in step (2) with nitrogen it is replacement fixed bed in sky
Gas at least 3 times or more.
7. according to the method described in claim 1, it is characterized in that：Pressurized with hydrogen is passed through to 1.0- described in step (3)
2.0MPa。
8. according to the method described in claim 1, it is characterized in that：Reaction described in step (3) is successive reaction, is being reacted
Hydrogen and ethyl difluoro or methyl difluoroacetate are continually fed into journey.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810125801.9A CN108503507A (en) | 2018-02-08 | 2018-02-08 | A kind of production technology of difluoroethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810125801.9A CN108503507A (en) | 2018-02-08 | 2018-02-08 | A kind of production technology of difluoroethanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108503507A true CN108503507A (en) | 2018-09-07 |
Family
ID=63375631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810125801.9A Pending CN108503507A (en) | 2018-02-08 | 2018-02-08 | A kind of production technology of difluoroethanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108503507A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524306A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing difluoroethanol by gas phase catalytic hydrogenation |
| CN106316795A (en) * | 2016-06-21 | 2017-01-11 | 浙江科技学院 | Method for preparing difluoroethanol through catalytic hydrogenation |
-
2018
- 2018-02-08 CN CN201810125801.9A patent/CN108503507A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524306A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing difluoroethanol by gas phase catalytic hydrogenation |
| CN106316795A (en) * | 2016-06-21 | 2017-01-11 | 浙江科技学院 | Method for preparing difluoroethanol through catalytic hydrogenation |
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| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180907 |