CN104209086B - Can be used to separate the adsorption separating agent and separation method of hexafluoropropene and HFPO mixed gas - Google Patents
Can be used to separate the adsorption separating agent and separation method of hexafluoropropene and HFPO mixed gas Download PDFInfo
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- CN104209086B CN104209086B CN201410261826.3A CN201410261826A CN104209086B CN 104209086 B CN104209086 B CN 104209086B CN 201410261826 A CN201410261826 A CN 201410261826A CN 104209086 B CN104209086 B CN 104209086B
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- hexafluoropropene
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Abstract
The adsorption separating agent that one kind can be used to separate hexafluoropropene (HFP) and HFPO (HFPO) mixed gas is solid absorption release agent, the adsorption separating agent is made up of silicate mineral and metallic compound, it is characterized in that the appropriate proportioning of silicate mineral and metallic compound, obtained adsorption separating agent is efficiently separated hexafluoropropene and HFPO mixed gas after calcining.In pipe separator, separation temperature is room temperature, pressure 1 × 10‑3~3MPa, HFP the and HFPO mixed gas of hexafluoropropene concentration 50~60% initially only have HFP by prepared release agent bed in exit gas, HFPO is concentrated on solid absorbent.After the operation of adsorbing separation, molar fraction be 0.98 HFP yields up to 16%.The adsorption separating agent is reusable after decompression pumping.Adsorption separating agent of the invention can be used for pressure-variable adsorption and separate HFP and HFPO mixed gas, be the separation of HFP and HFPO mixed gas, find brand-new and energy-conserving and environment-protective a separating technology route.
Description
Technical field
The present invention relates to the adsorbing separation that one kind separates hexafluoropropene (HFP) and HFPO (HFPO) mixed gas
Agent and environmental protection separation method, the adsorption separating agent are directed to the mixed gas of HFP and HFPO, adsorbed in separator,
Can be separated after desorption.On the adsorption separating agent said mixture should be kept completely separate with pressure-variable adsorption.
Background technology
HFPO (HFPO) is important perfluor epoxide, is important intermediate in Organic fluoride industry.
Due to its distinctive three-membered ring, it is set to be polymerized under anion initiation；Can be reacted with various nucleopilic reagents, produced all kinds of
Perfluoroalkyl vinyl ether, the latter is widely used in synthesis fluorubber, meltbility fluororesin and the fluoropolymer containing functional groups；Also
For synthesizing, PSVE, PPVE, bisphenol AF etc. be various in style, high added value fine chemicals.
The main method for preparing HFPO has：Nucleophilic oxidizing process, electrochemical process, the photochemical catalysis oxidizing process of molecular oxygen and put
Penetrate several process routes such as chemical oxidization method, catalytic gas phase oxidation method, liquid-phase oxidation of molecular oxygen method.It is now industrial frequently with
It is the liquid phase direct oxidation method with hexafluoropropene (HFP) as raw material.In patent 1320598, JP9052886,2003040879 etc.,
Report and HFPO is prepared in different inert solvent, HFP conversion ratios are that 72~78%, HFPO is selectively 60~77%.
Be in contact for the organic phase and oxygen containing oxidant water that contain hexafluoropropene (HFP) in organic solvent by CN101528719A,
CN101367778A carries out liquid phase oxidation reaction preparation HFPO in using the reaction dissolvent for adding auxiliary agent with oxygen.
It is still HFP is reacted in reactor internal solvent with oxygen in CN101157669A reports, condensed reactant gas are rear
HFPO is continuously produced after processing system treatment and purification.As can be seen here, all there is unreacted unstripped gas HFP in product, to obtain
High-purity HFPO is obtained, HFPO and HFP mixed gas must be separated.And unreacted raw material HFP can also be reused.
Both HFP and HFPO boiling points are respectively：- 29.4 DEG C and -27.4 DEG C, closely, thus it is difficult using conventional method
To separate.The separation method to HFP and HFPO mixed gas has chemical method and physical method at present.Chemical method mainly has：
Bromination method, high-temperature oxidation, with element fluorine (F2) catalytic oxidation etc..HFP loss amounts are big in bromination method, while in separation process
In can produce substantial amounts of waste water and waste residue.High-temperature oxidation is to make HFP that oxidation reaction occur with oxygen again in a solvent, also needs water
Wash, alkali cleaning etc., process route is long.Element fluorine (F2) catalytic oxidation be using fluorine gas trigger and decompose unreacted HFP, point
From high cost and operational danger is big.Physical method to the purification of HFP and HFPO mixed gas separations mainly has：Extraction, directly
The way of distillation and extraction fractional distillation etc..JP09020765 is separated HFPO by extraction from mixture, then to containing HFP
Mixture heated to reclaim the unstripped gas HFP that is evaporated.Japanese Asahi Glass house journals report, using straight
The way of distillation is connect to separate the gaseous mixture of HFPO and HFP.Evaporation does not need extractant and in the absence of chemical reaction, does not produce useless
Gurry, non-environmental-pollution has the disadvantage to need the number of plates many, and cannot simultaneously obtain high-purity HFPO and HFP.In current industrial production
Mainly use extraction fractional distillation.US4358348, US3326780 are reported in the presence of solvent, HFP and HFPO mixtures are entered
Row extracting rectifying, can obtain fine separating effect；It is extractant that US4134796 then uses composite inert liquid, minimizes tower.
CN101455908A reports in 2009, selection epoxychloropropane makees extractant, obtains HFPO of the purity more than 99%；HFP with
Extractant is pressed into recovery tower again, and tower top isolates HFP.Patent CN102356073A will be by formula C within 2012nHaFbRepresented
At least a kind fluorine-containing saturated compounds makees solvent extraction distillation, and the mixture comprising HFPO and HFP is separated into comprising HFPO the
1 cut and the 2nd cut comprising HFP Yu solvent.For the separation of this mixture, the separation method that can be found at present is little.Have
Not in above-mentioned separation method, the method that HFPO-HFP mixtures are separate is made we have proposed by adsorbing separation.
The content of the invention
The present invention passes through hexafluoropropene (HFP) and HFPO (HFPO) mixture by adsorption separating method
Absorption is separated, and can directly obtain a pure component.
The present invention have found a kind of solid absorption release agent for separating HFPO-HFP mixed gas.The adsorption separating agent
It is made up of silicate mineral and metallic compound.Specifically preparation method is：Silicate mineral is carried out into constituent analysis first, is ground
Mill, 100~500 targeted fine powders of screening, are added in the metal compound solution or suspension for preparing after washing, add water and fully stir
Mixing makes to form uniform slurries, is then dried at 80~120 DEG C 1~12 hour, then small in 300~1200 DEG C of calcinings 5~12
When, the solid after calcining is crushed, take 10~100 mesh particles.
Using the solid release agent for preparing, in pipe separator, separation temperature is room temperature, 1 × 10- of pressure3 ~3MPa,
Make HFP the and HFPO mixed gas of HFP concentration 50~60% by prepared release agent bed, pipe separator length 0.5
~70 meters, in first separation operation, detection exit gas initially only has HFP, and HFPO is concentrated in solid phase.HFP rubs in gas phase
When your fraction is 0.98, molar fraction is 0.98 HFP yields highest 16%.Decompression evacuate after be passed through again HFP concentration 50~
60% HFP and HFPO mixed gas, molar fraction is 0.98 HFP yields 9%.It is follow-up to reuse adsorption separating agent effect
It is identical with second.If the adsorption separating agent that will be prepared is used for pressure-variable adsorption separates said mixture, can be complete by two components
Separate.
Compared with existing separation method, the present invention can using pressure swing adsorption method separate HFP and HFPO mixed gas, with
Lower advantage：
(1) adsorption separating agent preparing raw material is easy to get, and low cost, preparation method is simple.
(2) separation method is without the use of solvent, environment will not be polluted, environmental protection.
(3) new approaches of HFPO-HFP mixtures separation are proposed --- pressure-variable adsorption is separated, open one it is brand-new
And the separating technology route of energy-conserving and environment-protective.
Brief description of the drawings
Fig. 1 is the breakthrough curve of hexafluoropropene on the adsorption separating agent 1 of the preparation of embodiment 1.
Fig. 2 is the breakthrough curve of hexafluoropropene when adsorption separating agent 1 prepared by embodiment 1 is reused for the first time.
Fig. 3 is the breakthrough curve of hexafluoropropene when adsorption separating agent 1 prepared by embodiment 1 is reused for the 5th time.
Fig. 4 is the breakthrough curve of hexafluoropropene on the adsorption separating agent 2 of the preparation of embodiment 2.
Fig. 5 is the breakthrough curve of hexafluoropropene on the adsorption separating agent 3 of the preparation of embodiment 3.
Specific embodiment
Embodiment 1
Silicate mineral is carried out into composition detection.Its main component is：SiO261%, A12O333%.After crushing, particle diameter is taken
100~500 mesh 250g, impurity is removed to clarifying with distillation water washing, and 120 DEG C of drying are then calcined 5 hours at 1000 DEG C, will
Solid after calcining is crushed, and takes 40~80 mesh particles, is fitted into stainless steel tube used by adsorbing separation, and quartz is sequentially filled in pipe
Cotton, release agent, silica wool.HFP the and HFPO mixed gas of HFP concentration 50~60% are passed through separating pipe with certain flow rate,
Pipe exports timing sampling, and sample is through GC9800 type chromatographics.HFP concentration (y is made by analysis resultHFP) with the time
The breakthrough curve of change such as Fig. 1 shows.Initially there was only HFP in exit gas, when HFP molar fractions are 0.98 in gas phase, determine
HFPO concentration is 0.69 on solid absorbent, and molar fraction is 0.98 HFP yields 14%.Decompression is passed through HFP again after evacuating
HFP the and HFPO mixed gas of concentration 50~60%, molar fraction is 0.98 HFP yields 9%.Kinetic penetration curve is determined,
As Fig. 2 shows.Reuse effect for 5th time same with second, breakthrough curve such as Fig. 3 shows.If by the HFP of HFP concentration 81% and
HFPO mixed gas are passed through separating pipe, then can be concentrated to 91% by HFPO on solid absorbent.
Embodiment 2
Silicate mineral is carried out into composition detection.Its main component is：SiO256%, A12O337%.After crushing, particle diameter is taken
100~500 mesh 250g, impurity is removed to clarifying with distillation water washing, is subsequently adding SiO2 ：Na2The sodium silicate solution of O=1
50ml, stirs, 120 DEG C of drying, and subsequent operation is with example 1.Kinetic penetration curve is determined, such as Fig. 4 shows.Molar fraction is
0.98 HFP yields 16%.
Embodiment 3
Silicate mineral is carried out into composition detection.Its main component is：SiO259%, A12O335%.After crushing, particle diameter is taken
100~500 mesh 250g, impurity is removed to clarifying with distillation water washing, is subsequently adding the calcium carbonate suspension 50ml of 0.5mol/L,
Stir, 120 DEG C of drying, subsequent operation is with example 1.Kinetic penetration curve is determined, such as Fig. 5 shows.Molar fraction is 0.98
HFP yields 6%.
Claims (2)
1. a kind of method that adsorption separating agent separates hexafluoropropene and HFPO mixed gas, it is characterised in that：The suction
Attached release agent is made up of silicate mineral and metallic compound, and specific preparation method is：Silicate mineral is carried out into composition first
Analysis, grinding, 100~500 targeted fine powders of screening, is added in the metal compound solution or suspension for preparing after washing, plus
Water is sufficiently stirred for making to form uniform slurries, is then dried at 80~120 DEG C 1~12 hour, then in 300~1200 DEG C of calcinings
5~12 hours, the solid after calcining is crushed, take 10~100 mesh particles；The metallic compound is alkali metal, alkaline-earth metal
Or the compound of transition metal；In pipe separator, separation temperature is room temperature, pressure 1 × 10-3~3MPa, allows hexafluoropropene
The hexafluoropropene and HFPO mixed gas of concentration 50~60% are by prepared adsorption separating agent bed, tubular type point
0.5~70 meter from device length, in first separation operation, detection exit gas initially only has hexafluoropropene, Hexafluoropropylene in solid phase
Propane is concentrated.
2. a kind of the method for claim 1, it is characterised in that：Depressurized after first separation operation and be evacuated, then be passed through hexafluoro
Density of propylene is 50~60% hexafluoropropene and HFPO gaseous mixture, initially still there was only hexafluoro third in exit gas
Alkene, adsorption separating agent is reusable, and the release agent can be used for pressure-variable adsorption and separate hexafluoropropene and HFPO mixing
Gas, finally can be kept completely separate hexafluoropropene and HFPO mixed gas.
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| CN201410261826.3A CN104209086B (en) | 2014-06-13 | 2014-06-13 | Can be used to separate the adsorption separating agent and separation method of hexafluoropropene and HFPO mixed gas |
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| CN107694509B (en) * | 2017-10-24 | 2020-09-04 | 苏州金宏气体股份有限公司 | Adsorbent for removing hexafluoropropylene in octafluorocyclobutane and preparation method thereof |
| CN111170835B (en) * | 2020-02-23 | 2022-06-24 | 郑州大学 | Method for catalytically removing perfluoro isopropyl vinyl ether in perfluoro n-propyl vinyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3107967A1 (en) * | 1981-03-03 | 1982-09-16 | Hoechst Ag, 6000 Frankfurt | "METHOD FOR PRODUCING PURE HEXAFLUORPROPYLENOXIDE" |
| CN1119288C (en) * | 2001-12-28 | 2003-08-27 | 湖北名流累托石科技股份有限公司 | Rectorite adsorbent for treating waste water and its preparing process |
| CN101455908B (en) * | 2008-12-19 | 2011-06-08 | 山东东岳神舟新材料有限公司 | High pure hexafluoropropylene oxide preparation method using extraction rectification |
| US8877017B2 (en) * | 2009-03-18 | 2014-11-04 | Daikin Industries, Ltd. | Method for separating hexafluoropropylene oxide from hexafluoropropylene |
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