CN105439981B - The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure - Google Patents
The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure Download PDFInfo
- Publication number
- CN105439981B CN105439981B CN201511033514.8A CN201511033514A CN105439981B CN 105439981 B CN105439981 B CN 105439981B CN 201511033514 A CN201511033514 A CN 201511033514A CN 105439981 B CN105439981 B CN 105439981B
- Authority
- CN
- China
- Prior art keywords
- gas
- tube bundle
- liquid
- reactor
- hexafluoropropylene oxide
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses the device and methods that hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure；Preparation facilities includes premixer, peristaltic pump, gas storage tanks, U-tube bundle reactor, liquid knockout drum and gas collecting tank；The U-tube bundle reactor includes multi beam U-tube reactor, and the U-tube reactor is successively fastened and connected up and down by multiple U-tubes and is formed；Gas-liquid mixture occurs in U-tube bundle reactor after sufficiently reacting, and the liquid of generation is by triple valve influent knockout drum, the gas of generation enters gas collection tank by triple valve to get hexafluoropropylene oxide.Present invention employs liquid phase oxidation, continuous production at normal temperatures and pressures is realized, avoids the harsh conditions of high-temperature high-voltage reaction；Reaction does not generate acyl fluorides class by-product, and product is easily isolated, high conversion rate.
Description
Technical field
The present invention relates to technical field of chemistry, more particularly to continuously preparing hexafluoropropylene oxide under a kind of condition of normal pressure
Device and method.
Background technique
It is fluorine chemistry industry important component using hexafluoropropylene oxide as the fluoride-containing PMMA industrial chain in source, six
Fluorine propylene oxide is the important source material of a variety of fluoride-containing PMMAs, can derive a variety of downstreams from hexafluoropropylene oxide and produce
Product, including perfluoro-propionyl fluoride, perfluor sulfonyl base vinyl ethers, perfluoroalkyl vinyl ether, perfluoropolyether, Hexafluoro acetone etc., into
And perfluorosulfonic acid ion film can be prepared by these derivatives, soluble poly tetrafluoroethene, fluorine-containing surfactant is fluorine-containing
The products such as Medical anesthetic agent.The downstream product of hexafluoropropylene oxide is used in multiple industries, including chemical, aerospace,
Electronics, medicine, environmental protection, building, the fields such as fire-fighting.So the hexafluoropropylene oxide for how synthesizing high-quality is fluorine-containing fining
The important topic in product field.
E.I.Du Pont Company reports the synthetic method of hexafluoropropylene oxide in the sixties in last century for the first time, from there on, entirely
The world increases the demand of hexafluoropropylene oxide year by year, becomes fluorination for the research of the synthetic method of hexafluoropropylene oxide
The hot spot learned.The synthesis technology of most hexafluoropropylene oxide is to pass through epoxidation with hexafluoropropene (HFP) for raw material
Reaction preparation hexafluoropropylene oxide.Various documents are all to study different method for oxidation, currently, main method for oxidation includes
Liquid phase oxidation, dioxygen oxidation method.Liquid phase oxidation can be mainly divided into two oxidation systems of hydrogen peroxide and sodium hypochlorite, although
Liquid phase oxidation can generate a certain amount of waste water, but the gas-phase product that this method generates is more single, used oxidant
Mainly include hydrogen peroxide (GB904877, US3858003 and JP63027487) and sodium hypochlorite (EP2409970, US4902810,
US7405312 and CN102356072), the oxidation efficiency of liquid phase oxidation is high, and reaction rate is fast, and there is nothing in reaction process
Harmful acyl fluorine type gas generates.Dioxygen oxidation method can be divided into oxygen liquid phase oxidation (US3600409, JP9052886,
US3536733 and JP2003040879) and catalytic oxidation (US377438, US4288376 and CN1954911).Oxygen liquid phase
Oxidizing process has the method that hexafluoropropylene oxide is prepared under the participation of fluoride solvent in high temperature and pressure, although this method oxidant
Cost is very low, but needs to be added expensive fluoride solvent just and can control reaction and can generate the by-product of acyl fluorides class,
Purification process is more complicated.Catalytic oxidation is that hexafluoropropene and oxygen are prepared Hexafluoropropylene third by high temperature catalyst bed
The method of alkane, although this method realizes continuous production, catalyst preparation process is complicated and reaction temperature remains unchanged
At 100 DEG C or more, acyl fluorine type gas also can be generated inevitably, increase the difficulty of product purification.
The method for the most synthesis hexafluoropropylene oxide reported at present all carries out at high temperature under high pressure, and anti-
Answer mode in a manner of intermittent based on.So in a mild condition by the reaction of hexafluoropropylene oxide, being carried out using continuity method
Production is always the target pursued in fluorine chemistry industry.Chinese patent CN101157669 first reported one kind in reaction under high pressure
The technique of continuous production hexafluoropropylene oxide in kettle, although which realizes continuous production, but the technique is dangerous
Property, and heat of reaction is not easy to spread.Chinese patent CN201692802 and CN10651357 are reported in oxygen liquid phase oxidation
Under conditions of continuous production hexafluoropropylene oxide technique, above-mentioned two patents use tubular reactor produced Hexafluoropropylene third
Alkane, reaction achieves conversion ratio and selectivity higher than 80%, but reaction condition remains harshness, it is still desirable to 100
DEG C or more high temperature, carry out under the pressure of 1.5MPa or more.
Summary of the invention
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide continuously make under a kind of condition of normal pressure
The device and method of standby hexafluoropropylene oxide.
The technical solution adopted to achieve the purpose of the present invention is: continuously preparing Hexafluoropropylene third under a kind of condition of normal pressure
The device of alkane, it is characterised in that including premixer, peristaltic pump, gas storage tanks, U-tube bundle reactor, liquid knockout drum and
Gas collection tank；The material outlet of the premixer is connect with one end of the peristaltic pump；The other end of the peristaltic pump is logical
Triple valve is crossed to connect with the material inlet of the gas storage tanks and U-tube bundle reactor；The material of the U-tube bundle reactor
Outlet is connect by triple valve with the liquid knockout drum and gas collecting tank.
The U-tube bundle reactor includes multi beam U-tube reactor, the U-tube reactor be by multiple U-tubes successively
Be fastened and connected composition up and down.
Preferably, the U-tube bundle reactor includes 50-100 beam U-tube reactor.
The method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure, it is characterised in that the following steps are included:
(1) buffer system is added into liquor natrii hypochloritis and adds organic solvent after system to be buffered is completely dissolved,
Then it is stirred evenly in premixer, liquid reactants is made
(2) triple valve is opened, by the hexafluoropropene gas in the liquid reactants and the gas storage tanks in premixer
Body is passed through in U-tube bundle reactor simultaneously；
(3) gas-liquid mixture occurs in U-tube bundle reactor after sufficiently reacting, and the liquid of generation is flowed by triple valve
In liquid knockout drum, the gas of generation enters gas collection tank by triple valve to get hexafluoropropylene oxide.
Compared with prior art, the beneficial effects of the present invention are:
(1) continuous production hexafluoropropylene oxide at normal temperatures and pressures is realized, the harsh item of high-temperature high-voltage reaction is avoided
Part；
(2) liquid phase oxidation is used, the traditional advantage with liquid phase oxidation, reaction does not generate acyl fluorides class by-product,
Product is easily isolated.
(3) U-tube bundle reactor heat exchange area is big, and gas and liquid can be sufficiently mixed, and can sufficiently inhibit side reaction
Generation, the selectivity of reaction is good, high conversion rate.
Detailed description of the invention
Fig. 1 show the structural schematic diagram that the device of hexafluoropropylene oxide is continuously prepared under condition of normal pressure.
Fig. 2 show the structural schematic diagram of U-tube bundle reactor 5 in Fig. 1.
Specific embodiment
Below in conjunction with specific embodiment, invention is further described in detail.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
It is as shown in Figure 1 the device that hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure, including premixer 1, compacted
Dynamic pump 2, gas storage tanks 4, U-tube bundle reactor 5, liquid knockout drum 7 and gas collecting tank 8；The material of the premixer 1
Outlet is connect with one end of the peristaltic pump 2；The other end of the peristaltic pump 2 by triple valve 3 and the gas storage tanks 4 and
The material inlet of U-tube bundle reactor 5 connects；The material outlet of the U-tube bundle reactor 5 passes through triple valve 6 and the liquid
Body knockout drum 7 and gas collecting tank 8 connect.
Shown in Fig. 2, the U-tube bundle reactor 5 includes multi beam U-tube reactor, and the U-tube reactor is by multiple
U-tube is successively fastened and connected composition up and down.
Preferably, the U-tube bundle reactor 5 includes 50-100 beam U-tube reactor.
The method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure, comprising the following steps:
(1) buffer system is added into liquor natrii hypochloritis and adds organic solvent after system to be buffered is completely dissolved,
Then it is stirred evenly in premixer 1, liquid reactants is made
(2) triple valve 3 is opened, by the hexafluoropropene in the liquid reactants and the gas storage tanks 4 in premixer 1
Gas is passed through in U-tube bundle reactor 5 simultaneously；
(3) gas-liquid mixture occurs in U-tube bundle reactor 5 after sufficiently reacting, and liquid passes through 6 influent of triple valve
In knockout drum 7, the gas of generation enters gas collection tank 8 by triple valve 6 to get hexafluoropropylene oxide.
Infrared spectrum characterization is carried out by the gas reactant collected to gas collection tank 8, finally calculates the conversion of reaction
Rate and selectivity.
Embodiment 1:
4000g aqueous sodium hypochlorite solution (effective chlorine 3.8%) is added in reaction premixer 1, is added under stirring
Enter 500g borax and 50g sodium hydroxide, after all dissolutions, then 800g toluene and 15g tricaprylmethyl chlorination is added thereto
Ammonium (TOMAC) continues stirring 30 minutes, reaction solution is added to U by threeway 3 with the rate of 100g/min by peristaltic pump 2
In type pipe reactor 5, the switch of hexafluoropropene gas hold-up tank 4 is opened simultaneously, by a certain amount of hexafluoropropene (HFP) with 8g/
The rate of min is also added in U-tube reactor 5 by the other end of threeway 3, and gas-liquid mixture fills in U-tube reactor 5
Divide reaction, the gas and liquid after reaction are had respectively entered in liquid knockout drum 7 and gas collecting tank 8 by threeway 6.From gas
Sample is taken in collecting tank 8, is obtained by infrared spectroscopy calculating, the conversion ratio of the reaction is 80%, and selectivity is 87%.
Embodiment 2,3
Unlike as described in Example 1, embodiment 2,3 changes the additional amount of borax and sodium hydroxide.
Embodiment 4-9
As unlike embodiment 1, embodiment 4-9 changes the type of organic solvent
Embodiment 10
4000g aqueous sodium hypochlorite solution (effective chlorine 3.8%) is added in reaction premixer 1, is added under stirring
Enter 100g potassium carbonate and 30g saleratus, after all dissolutions, then 800g toluene and 15g tricaprylmethyl chlorine is added thereto
Change ammonium (TOMAC), continues stirring 30 minutes, be added to reaction solution by threeway 3 with the rate of 100g/min by peristaltic pump 2
In U-tube reactor 5, the switch of hexafluoropropene gas hold-up tank 4 is opened simultaneously, by a certain amount of hexafluoropropene (HFP) with 8g/
The rate of min is also added in U-tube reactor 5 by the other end of threeway 3, and gas-liquid mixture fills in U-tube reactor 5
Divide reaction, the gas and liquid after reaction are had respectively entered in liquid knockout drum 7 and gas collecting tank 8 by threeway 6.From gas
Sample is taken in collecting tank 8, is obtained by infrared spectroscopy calculating, the conversion ratio of the reaction is 75%, and selectivity is 83%.
Embodiment 11
4000g aqueous sodium hypochlorite solution (effective chlorine 3.8%) is added in reaction premixer 1, is added under stirring
Enter 500g borax and 50g sodium hydroxide, after all dissolutions, then 800g toluene and 15g tricaprylmethyl chlorination is added thereto
Ammonium (TOMAC) continues stirring 30 minutes, reaction solution is added to spiral shell by threeway 3 with the rate of 100g/min by peristaltic pump 2
In coil reactor 5, the switch of hexafluoropropene holding vessel 4 is opened simultaneously, by a certain amount of hexafluoropropene (HFP) with 5g/min's
Rate is also added in U-tube reactor by the other end of threeway 5, and gas-liquid mixture is sufficiently anti-in U-tube reactor 5
It answers, the gas and liquid after reaction are had respectively entered in liquid knockout drum 7 and gas collecting tank 8 by threeway 6.From gas collection
Sample is taken in tank 8, is obtained by infrared spectroscopy calculating, the conversion ratio of the reaction is 84%, and selectivity is 79%.
Embodiment 12-16
As unlike embodiment 11, embodiment 12-16 changes reaction solution and the rate of HFP.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (2)
1. a kind of method for continuously preparing the device preparation hexafluoropropylene oxide of hexafluoropropylene oxide under condition of normal pressure, feature exist
In, comprising the following steps: (1) buffer system is added into liquor natrii hypochloritis and has been added after system to be buffered is completely dissolved
Then solvent stirs evenly in premixer, liquid reactants (2) are made and open triple valve, by the liquid in premixer
Hexafluoropropene gas in precursor reactant object and the gas storage tanks is passed through in U-tube bundle reactor simultaneously；(3) gas-liquid mixture
After sufficiently reaction occurs in U-tube bundle reactor, the liquid of generation passes through in triple valve influent knockout drum, the gas of generation
Body enters gas collection tank by triple valve to get hexafluoropropylene oxide；
The device of hexafluoropropylene oxide, including the storage of premixer, peristaltic pump, gas are continuously prepared under the condition of normal pressure
Tank, U-tube bundle reactor, liquid knockout drum and gas collecting tank；The material outlet of the premixer and the peristaltic pump
One end connection；The other end of the peristaltic pump is entered by triple valve and the material of the gas storage tanks and U-tube bundle reactor
Mouth connection；The material outlet of the U-tube bundle reactor is connect by triple valve with the liquid knockout drum and gas collecting tank；
The U-tube bundle reactor includes multi beam U-tube reactor, and the U-tube reactor is successively fastened up and down by multiple U-tubes
Connection composition.
2. the device for continuously preparing hexafluoropropylene oxide under a kind of condition of normal pressure according to claim 1 prepares Hexafluoropropylene
The method of propane, which is characterized in that the U-tube bundle reactor includes 50-100 beam U-tube reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511033514.8A CN105439981B (en) | 2015-12-31 | 2015-12-31 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511033514.8A CN105439981B (en) | 2015-12-31 | 2015-12-31 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105439981A CN105439981A (en) | 2016-03-30 |
| CN105439981B true CN105439981B (en) | 2019-03-15 |
Family
ID=55550678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511033514.8A Active CN105439981B (en) | 2015-12-31 | 2015-12-31 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439981B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449106A (en) * | 2019-09-06 | 2019-11-15 | 铜仁学院 | A kind of highly effective continuous reaction unit of amino acid surfactant |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4925961A (en) * | 1981-05-06 | 1990-05-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the production of hexafluoropropylene oxide |
| CN1049661A (en) * | 1989-08-25 | 1991-03-06 | 纳幕尔杜邦公司 | The three-phase liquid phase epoxidation method of perfluoroolefine class |
| CN1954911A (en) * | 2005-10-24 | 2007-05-02 | 山东东岳神舟新材料有限公司 | Solid catalyst and its preparation and method of catalytic preparation epoxy propane hexafluoride |
| CN101157669A (en) * | 2007-11-20 | 2008-04-09 | 山东东岳神舟新材料有限公司 | Hexafluoropropyl epoxide continuous production technique |
| US20080091052A1 (en) * | 2006-10-16 | 2008-04-17 | Korea Research Institute Of Chemical Technology | Manufacturing method of hexafluoropropylene oxide with high yield |
| CN201692802U (en) * | 2010-06-08 | 2011-01-05 | 上海三爱富新材料股份有限公司 | Device for continuously producing hexafluoro propylene oxide |
| CN102356072A (en) * | 2009-03-17 | 2012-02-15 | 大金工业株式会社 | Method for producing hexafluoropropylene oxide |
-
2015
- 2015-12-31 CN CN201511033514.8A patent/CN105439981B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4925961A (en) * | 1981-05-06 | 1990-05-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the production of hexafluoropropylene oxide |
| CN1049661A (en) * | 1989-08-25 | 1991-03-06 | 纳幕尔杜邦公司 | The three-phase liquid phase epoxidation method of perfluoroolefine class |
| CN1954911A (en) * | 2005-10-24 | 2007-05-02 | 山东东岳神舟新材料有限公司 | Solid catalyst and its preparation and method of catalytic preparation epoxy propane hexafluoride |
| US20080091052A1 (en) * | 2006-10-16 | 2008-04-17 | Korea Research Institute Of Chemical Technology | Manufacturing method of hexafluoropropylene oxide with high yield |
| CN101157669A (en) * | 2007-11-20 | 2008-04-09 | 山东东岳神舟新材料有限公司 | Hexafluoropropyl epoxide continuous production technique |
| CN102356072A (en) * | 2009-03-17 | 2012-02-15 | 大金工业株式会社 | Method for producing hexafluoropropylene oxide |
| CN201692802U (en) * | 2010-06-08 | 2011-01-05 | 上海三爱富新材料股份有限公司 | Device for continuously producing hexafluoro propylene oxide |
Non-Patent Citations (1)
| Title |
|---|
| 六氟环氧丙烷的合成及主副反应机理研究;尹红等;《高校化学工程学报》;20150831;第29卷(第4期);参见第831页第14-22行，第835页第11-14行 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105439981A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817728B (en) | Method for producing hexafluoropropane oxide and coproducing perfluorovinyl ether | |
| CN108250176A (en) | A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate | |
| CN104169246A (en) | Production method for 2,3,3,3-tetra-fluoropropene | |
| US9169225B2 (en) | Method for producing hexafluoropropylene oxide | |
| CN104926597A (en) | Preparation method of pulmonic cavity ventilating liquid | |
| CN102553407A (en) | Thermochemical cycle reaction system for decomposing CO2And H2O method and device | |
| CN105439981B (en) | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure | |
| CN103709009B (en) | A kind of liquid phase reaction preparation method of fluorochemical | |
| CN105461663B (en) | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of temperate condition | |
| CN103482576B (en) | Method for efficiently preparing high-purity chlorine dioxide and special device thereof | |
| CN104672177B (en) | A kind of hexafluoropropylene oxide continuous production processes | |
| CN103288587B (en) | A kind of preparation method of perfluoro alkane | |
| CN205443135U (en) | Prepare hexafluoropropylene oxide's device under gentle condition in succession | |
| CN102502566A (en) | Technology for synthesizing lithium hexafluorophosphate | |
| CN205443134U (en) | Prepare hexafluoropropylene oxide's device under ordinary pressure condition in succession | |
| CN108610310B (en) | Preparation method of perfluorohexanone precursor hexafluoropropylene oxide | |
| CN208279314U (en) | A kind of chlorohydrination epoxides production hypochlorous acid preparation facilities | |
| CN108341399A (en) | A kind of production of chlorohydrination epoxides hypochlorous acid preparation facilities and its application method | |
| CN106076195B (en) | A kind of continuous technique and device for preparing alkyl ether carboxylic acid's salt surfactant | |
| CN108794307B (en) | Micro-reaction system and method for synthesizing 4-bromo-3-methylanisole by solvent method | |
| CN205965746U (en) | Prepare saline surface -activeagent's of alkyl ether carboxylic acid device in succession | |
| CN109134186A (en) | The raw materials for production and its continuous preparation method of liquid ventilation liquid and ophthalmologic operation material | |
| CN113943214B (en) | Process for producing sevoflurane | |
| CN206359448U (en) | A kind of serialization prepares the device of fatty alkyl LAO | |
| CN110229129A (en) | A kind of device and method thereof preparing 4- chloride anhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |