CN101157669B - Hexafluoropropyl epoxide continuous production technique - Google Patents
Hexafluoropropyl epoxide continuous production technique Download PDFInfo
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- CN101157669B CN101157669B CN2007101142921A CN200710114292A CN101157669B CN 101157669 B CN101157669 B CN 101157669B CN 2007101142921 A CN2007101142921 A CN 2007101142921A CN 200710114292 A CN200710114292 A CN 200710114292A CN 101157669 B CN101157669 B CN 101157669B
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Abstract
The invention relates to a process for continuous production of hexafluoropropylene oxide. The materials are discharged when the reaction of hexafluoropropylene and oxygen is carried out fully, the hexafluoropropylene gas and the oxygen are mixed by proportion and then are introduced into the solvent in a reactor as a gas mixture, the oxygen and the hexafluoropropylene firstly pass through a solvent layer in the reactor and then are carried out the complete reaction in the solvent, the reactant is accumulated in a gas-phase space in the reactor continuously, the mixed gas containing the reactant in the gas phase can be controlled by pressure regulation, so as to discharge the materials to the outside of the reactor continuously, the discharging gas is condensed and reclaimed the containing solvent in the mixed gas by a condenser, the reactant gas after the condensation is sent to a processing system for further treatment and purification, finally the needed hexafluoropropylene oxide final product is obtained. The process flow is simple, the equipments are fewer, the operation is convenient and the equipment utilization ratio is high.
Description
Technical field
The invention belongs to fluorine-containing fine chemicals preparation field, relate in particular to a kind of method for preparing Propylene oxide hexafluoride with the R 1216 liquid-phase oxidation continuously.
Background technology
Propylene oxide hexafluoride (hexafluoropropylene oxide is called for short HFPO) claims perfluoro propene oxid again, is a kind of important organic fluoride intermediate.Because it has special chemically reactive, can be used for important fluorochemicalss such as synthetic perfluorinated sulfonic acid ion exchange resin, Meltability polytetrafluorethyletubular, fluorine ether oil, fluorochemical surfactant, viton, thereby be used widely in every field such as aerospace, electronics, nuclear power engineering, medicine.Nineteen fifty-nine is by synthetic first this compound of Dupont (DuPont) company.The said firm had delivered the patent by R 1216 (HFP) preparation HFPO in 1962.Henceforth, swift and violent the growing up of HFPO chemistry.In recent years, to deepening continuously that Propylene oxide hexafluoride is studied, the Application Areas of this product is constantly widened along with abroad.The fine chemical product that with HFPO is raw material emerges in an endless stream especially.Thereby HFPO has become an important intermediate in novel material research and the production.
Known oxidation R 1216 prepares the used oxygenant of Propylene oxide hexafluoride and mainly contains: and hydrogen peroxide (referring to US3358003,1967; US 3250808,1966; JP 63027487,1988); Hypochlorite (referring to US 4902810,1990); Organo-peroxide (referring to GB 1547493,1979); Carbonate (referring to US 4287128,1981); Molecular oxygen is (referring to US 3536733,1970; CN 1320598,2001; JP 9052886,1997) etc.Use hydrogen peroxide as oxygenant, because the price comparison of hydrogen peroxide own is expensive, transportation is stored all pretty troublesome, the production cost of Propylene oxide hexafluoride is raise, and can produce a large amount of waste water, causes environmental pollution.Have a large amount of waste water equally with hypochlorite and produce, unfavorable to environment.Organo-peroxide all is not suitable for industrial application from price and environmental consideration.Molecular oxygen is the oxygenant of most economical environmental protection in all oxygenants.
The method of having reported for preparing Propylene oxide hexafluoride with the liquid-phase oxidation of molecular oxygen R 1216 has in the presence of inert solvent (referring to GB 1034492,1966; US 3536733,1970; JP 2003040879,2003) or in the presence of initiator in inert solvent (referring to CN 1320598,2001) prepared in reaction Propylene oxide hexafluoride.In these methods, technology is all complicated, all can cause certain environmental problem with organic solvent or initiator.Transformation efficiency and selectivity are not high yet in addition, must be through complicated aftertreatment technologys such as separation, and production cost is than higher.
R 1216 and molecular oxygen can gas-phase reaction prepare Propylene oxide hexafluoride in the presence of solid catalyst.Preparing catalyzer used in the method for Propylene oxide hexafluoride at the molecular oxygen catalytic gas phase oxidation R 1216 of being reported has: 1. make catalyzer with barium compound, barium compound can be barium oxide, hydrated barta or barium salt, barium salt is that inorganic salt are better, as (referring to US 4288376,1981) such as barium fluoride, bariumchloride, barium sulfate, barium carbonate, nitrate of baryta.R 1216 and molecular oxygen are prepared Propylene oxide hexafluoride by fixed bed or the fluidized-bed reactor that barium compound is arranged.The transformation efficiency 24.2～34.1% of R 1216, the selectivity of corresponding Propylene oxide hexafluoride is 67.4～70.1%.2. silica gel or SiO
2Mixture is made catalyzer, and fixed bed or the fluidized-bed reactor by containing this activation rear catalyst with R 1216 and molecular oxygen carries out catalyzed oxidation and prepare Propylene oxide hexafluoride.The transformation efficiency of R 1216 is 10～40%, the selectivity about 80% of Propylene oxide hexafluoride (referring to US 3775438,1973, US 3775439,1973).It is very to have the Propylene oxide hexafluoride production method of development prospect that R 1216 and molecular oxygen catalytic gas phase oxidation prepare Propylene oxide hexafluoride, and its key is to prepare the catalyzer that has the Propylene oxide hexafluoride highly selective again under R 1216 high conversion prerequisite.Because of its production technique is simple relatively, safety, environmental protection, and the transformation efficiency height, at present, the method that countries in the world produce Propylene oxide hexafluoride substantially all adopts this method to produce.
The dioxygen oxidation R 1216 is produced the method for Propylene oxide hexafluoride, now is widely used.But production process is interrupter method production at present, promptly according to a certain percentage desired raw material is added in certain volumetrical reactor, and under certain temperature and pressure, oxygen and R 1216 reaction make Propylene oxide hexafluoride.The shortcoming of this method is that reactor can't use always in the reaction back discharging process, and the plant efficiency performance is not come out, and production capacity is low.In addition, this method only is applicable to small-scale production, if need extensive, produce in enormous quantities then need put very big of reactor or increase the quantity of onesize reactor, simultaneously every cover reactor needs the same same cover raw material auxiliary facility that is equipped with, the simple repetition, floor space is big, and personnel use many, very uneconomical.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of Propylene oxide hexafluoride quantity-produced technology, make Propylene oxide hexafluoride and the discharging of oxygen successive reaction, this method technical process is simple, and equipment is few, and is easy to operate; The plant factor height.
One of technical problem to be solved by this invention provides a kind of method that is applicable to successive reaction and discharging, R 1216 and oxygen is carried out with discharging simultaneously in abundant reaction, thereby maximally utilise reaction unit, makes the production capacity maximization.
Two of technical problem to be solved by this invention provides a kind of Propylene oxide hexafluoride continuous production device that is applicable to successive reaction and discharging.
Technical scheme of the present invention is as follows:
A kind of Propylene oxide hexafluoride quantity-produced method is characterized in that making the discharging simultaneously fully of R 1216 and oxygen reaction, and step is as follows:
R 1216 gas and oxygen are mixed in proportion the back with in the solvent in the gaseous mixture feeding reactor, oxygen and R 1216 pass through solvent layer earlier in reactor, fully reaction in solvent, reactant constantly accumulates in gas-phase space in the reactor, the mixed gas that contains reactant in the gas phase is regulated control by pressure, continuously discharging outside reactor, discharging gas is through condenser condenses and reclaim the solvent that mixed gas is carried secretly, condensed reactant gas is delivered to after-treatment system and is further processed and purifies, at last needed Propylene oxide hexafluoride finished product.
Above-mentioned condensed reactant gas aftertreatment gets final product by prior art with purification.
Preferably, in above-mentioned R 1216 and the oxygen mixture, R 1216 and oxygen quality are than 9.4～5: 1.
Preferably, above-mentioned R 1216 gasiform temperature is 85～100 ℃.
Preferably, constant pressure was at 1.0-1.6Mpa before the gas of oxygen and R 1216 mixed.
Preferably, 85～100 ℃ of the temperature in the aforesaid reaction vessel, pressure 1.3～1.4Mpa.
Preferably, the ratio of the total mass of the quality of above-mentioned solvent and reactant R 1216 and oxygen is 5～12: 1.
Method of the present invention is to belong to liquid phase reaction to prepare Propylene oxide hexafluoride, and above-mentioned solvent is the conventional solvent in this area, does not need to add any other auxiliary agents such as catalyzer.
The key of Propylene oxide hexafluoride quantity-produced method of the present invention is temperature and the pressure by the control reaction, and the material that enters reaction controls R 1216 with the amount of solvent layer than (being the time of material by solvent layer) and oxygen reaction fully reacts, and discharging simultaneously.
The present invention also provides a kind of device of implementing the method for the invention, it is characterized in that, described device comprises:
An oxygen channel is used for the conveying of high purity oxygen gas;
A R 1216 gas pipeline is used for the R 1216 transfer of gas;
A mixture conduit is used for carrying Propylene oxide hexafluoride and oxygen mixture to reactor;
Six gas regulating valve I-VI, wherein two adjustings when being used for oxygen delivery, two adjustings when being used for hexafluoro and carrying, the adjusting a during conveying that is used for oxygen and R 1216 mixed gas, the adjusting when being used for the reactor mixed gas delivery.
A R 1216 pressurestat, the constant voltage control when being used for the conveying of oxygen;
An oxygen pressurestat, the constant voltage control when being used for the conveying of oxygen;
A mixing tank is used for mixing of oxygen and two kinds of gases of R 1216;
A surge tank, the buffering that is used for the reactor air inlet is with stable;
A reactor is used to produce Propylene oxide hexafluoride;
A condenser is used for the recovery of mixed gas discharging entrapment solvent;
A discharging pipeline is used for the discharging of reaction mixture gas body.
The annexation of apparatus of the present invention each several part is as follows:
The gas regulating valve I of oxygen channel through the pressure-controlling table is arranged is communicated with the oxygen pressurestat, the gas regulating valve II of R 1216 gas pipeline through the pressure-controlling table is arranged is communicated with the R 1216 pressurestat, oxygen pressurestat and R 1216 pressurestat are communicated with mixing tank through gas regulating valve III, IV and mass rate indicating meter respectively, also are communicated with mass flow controller between oxygen pressurestat and the R 1216 pressurestat.Mixing tank is communicated with reactor through surge tank, gas regulating valve V, and the reactor bottom has discharge nozzle to be communicated with condenser through gas regulating valve VI, and the output tube of condenser is communicated with after-treatment system.
Compared with prior art, excellent results of the present invention has been to provide a kind of method that is applicable to successive reaction and discharging, R 1216 and oxygen are carried out with discharging simultaneously in abundant reaction, utilize the staged reaction principle, material is fully separated after the reaction in medium again, and then maximally utilise reaction unit, make the production capacity maximization.This technical process is simple, and equipment is few, and is easy to operate; The plant factor height.
Description of drawings
Fig. 1 is Propylene oxide hexafluoride of the present invention-oxygen successive reaction schema.Among the figure, 1 is the pipeline of oxygen; 2 is the R 1216 pipeline; 3 is with oxygen regulating valve I; 4 is R 1216 variable valve II; 5 is the oxygen pressurestat; 6 is the R 1216 pressurestat; 7 is oxygen pressurestat discharging variable valve III; 8 is R 1216 pressurestat discharging variable valve IV; 9 mass flow controllers; 10 is mixing tank; 11 is the comparison measurer of oxygen quality flow to the R 1216 mass rate. 12 is surge tank; 13 is mixed gas discharging variable valve V; 14 is the mixed gas pipeline; 15 are the reactor stirring; 16 is reactor; 17 is reactor gas discharge pipe; 18 is reactor gas discharging variable valve VI; 19 are discharging recovery condenser; 20 is the condenser discharge pipe.
PIC: pressure-controlling, MI: mass rate shows, MIC: mass rate control, MY: the oxygen quality flow is to the ratio of R 1216 mass rate.
Embodiment
Following embodiment will help the understanding of the present invention more, but not constitute the restriction to content of the present invention.
Embodiment: a kind of Propylene oxide hexafluoride quantity-produced method, make the discharging simultaneously fully of R 1216 and oxygen reaction, R 1216 gas and oxygen are mixed in proportion the back with in the solvent in the gaseous mixture feeding reactor, oxygen and R 1216 pass through solvent layer earlier in reactor, fully reaction in solvent, reactant constantly accumulates in gas-phase space in the reactor, the mixed gas that contains reactant in the gas phase is regulated control by pressure, continuously discharging outside reactor, discharging gas is through condenser condenses and reclaim the solvent that mixed gas is carried secretly, condensed reactant gas is delivered to after-treatment system and is further processed and purifies, at last needed Propylene oxide hexafluoride finished product.Successive reaction schema with reference to Fig. 1 is described in detail as follows:
The oxygen that transports by pipeline 1 with carry by pipeline 2 R 1216 of coming respectively through variable valve 3,4 in oxygen pressurestat 5 and R 1216 pressurestat 6; Control oxygen and R 1216 pressurestat constant pressure are at 1.0-1.6Mpa; Oxygen and R 1216 respectively through variable valve 7,8 and mass flowmeter by R 1216: the mass ratio of oxygen 1: 9.4～5 enters mixing tank 11, after mixing, two kinds of gases enter surge tank 12, enter reactor by variable valve 13 then, the ratio control of the total mass of the quality of reactor internal solvent and reactant R 1216 and oxygen is 5～12: 1.85～100 ℃ of temperature in the reactor, pressure 1.3～1.4Mpa, oxygen and R 1216 react under this temperature and pressure, make to contain hexafluoro cyclopropane gas mixture.Reaction mixture gas is by variable valve 18, through discharge pipe 17 to condenser 19, again through condenser discharge pipe 20 to after-treatment system.In reaction process, control surge tank 12 constant pressure 1.2-1.5Mpa, carrying out along with reaction, constantly consume the mixture in the surge tank, for guaranteeing the constant pressure of surge tank 12, oxygen pressurestat 5 outlet regulating valve opens, comparison measurer 11 calculates the mass rate of R 1216 automatically according to the mass rate of oxygen, thereby controls the aperture of R 1216 pressurestat outlet regulating valve automatically.In the reaction process, control reactor pressure-stabilisation is at 1.3-1.4Mpa, and its charging and discharging mainly realize by reactor pressure-controlling input and output material variable valve.
Claims (1)
1. Propylene oxide hexafluoride quantity-produced device, it is characterized in that the gas regulating valve I of oxygen channel through the pressure-controlling table is arranged is communicated with the oxygen pressurestat, the gas regulating valve II of R 1216 gas pipeline through the pressure-controlling table is arranged is communicated with the R 1216 pressurestat, oxygen pressurestat and R 1216 pressurestat are respectively through gas regulating valve III, IV and mass rate indicating meter are communicated with mixing tank, also be communicated with mass flow controller between oxygen pressurestat and the R 1216 pressurestat, mixing tank is through surge tank, gas regulating valve V is communicated with reactor, discharge nozzle is arranged at the reactor top, be communicated with condenser through gas regulating valve VI, the output tube of condenser is communicated with after-treatment system.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101142921A CN101157669B (en) | 2007-11-20 | 2007-11-20 | Hexafluoropropyl epoxide continuous production technique |
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| CN2007101142921A CN101157669B (en) | 2007-11-20 | 2007-11-20 | Hexafluoropropyl epoxide continuous production technique |
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| CN101157669B true CN101157669B (en) | 2010-11-10 |
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| CN101817728B (en) * | 2009-10-21 | 2013-06-26 | 山东华夏神舟新材料有限公司 | Method for producing hexafluoropropane oxide and coproducing perfluorovinyl ether |
| CN102676275B (en) * | 2012-05-07 | 2014-01-15 | 中国石油化工股份有限公司 | Lubricating oil additive as well as preparation method and application thereof |
| CN104672177B (en) * | 2013-12-03 | 2018-05-15 | 浙江化工院科技有限公司 | A kind of hexafluoropropylene oxide continuous production processes |
| CN105017467A (en) * | 2015-07-31 | 2015-11-04 | 苏州新区特氟龙塑料制品厂 | Preparation method of PFA soluble polytetrafluoroethylene |
| CN105439981B (en) * | 2015-12-31 | 2019-03-15 | 天津市长芦化工新材料有限公司 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure |
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