CN101348565B - Purification process of oligo-ether containing heteropoly acid - Google Patents
Purification process of oligo-ether containing heteropoly acid Download PDFInfo
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- CN101348565B CN101348565B CN2008101224165A CN200810122416A CN101348565B CN 101348565 B CN101348565 B CN 101348565B CN 2008101224165 A CN2008101224165 A CN 2008101224165A CN 200810122416 A CN200810122416 A CN 200810122416A CN 101348565 B CN101348565 B CN 101348565B
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Abstract
The invention relates to a purification process for a low polyether containing heteropoly acid. Low polyether raw liquid containing heteropoly acid is passed through an inorganic membrane filter device for filtering and reaching the aim of purification. The inorganic membrane filter device is adopted to remove the heteropoly acid in the low polyether, and the content of the heteropoly acid in the purified low polyether is less than 50ppm, thereby having a good purification effect. In addition, the process has a simple operation and no pollution; the separated heteropoly acid can be recovered for reuse, thereby remarkably reducing production cost.
Description
Technical field
The present invention relates to a kind of purifying process that contains the oligo-ether of heteropolyacid.
Background technology
Since the thirties in 20th century, H.Meerwein found tetrahydrofuran polyreaction; Whether people have carried out deep research to this polyreaction, develop a series of catalystsystem, be homogeneous phase according to reaction system; Catalystsystem is divided into two types, i.e. homogeneous catalysis system and heterogeneous catalysis system.Wherein, homogeneous catalyst has positive oxygen ion, carbonium ion, acylium cation, protonic acid, super acid, silicon compound, carboxylic acid and acid anhydrides thereof; Heterogeneous catalyst has clay, composite oxides and solid super-strong acid etc.
The middle and later periods eighties 20th century finds that heteropolyacid (HPA) is the extraordinary catalyzer of ring-opening polymerization.One type of oxygenatedchemicals that heteropolyacid is made up of through oxygen atom ligand according to certain space structure heteroatoms (like P, Si, Co, As etc.) and polyatom (like Mo, W, V, Nb, Ta etc.).Its structure can be divided into once, secondary and three aggregated(particle) structures; The characteristics of its cage structure; Making the monomer molecule air tube of bamboo in granary shape structure of in catalytic process, can freely coming in and going out form false liquid phase state, is one type of protonic acid that strength of acid is also higher than sulfuric acid, and it is low not only to have a preparation of being easy to, Stability Analysis of Structures, corrodibility; Be soluble in the characteristics of most of organic solvents, what is more important HPA can reclaim and reuse.
Pure and mild outer village one youth in Qingdao has carried out more detailed research to this heteropoly acid catalysis system; Bednarek in 1989 etc. are with lower concentration H
3PMoO
42Be initiator, 25 ℃ of following polymerizations, making relative molecular weight through 500h is 10000～100000 polymkeric substance; Go up intermediate molecular weight (600～3000) THF polyethers commonly used for making industry; People such as Zhang Hongzhi use oxyethane, propylene oxide, epoxy chloropropane and trimethylene oxide to be promotor; With water or glycol is the relative molecular weight regulator; HPA catalysis THF ring-opening reaction is studied, under low HPA concentration (massfraction 2%), can be polymerize relative molecular weight at 600～3000 polytetramethylene ether diol (PTMEG).
Though heteropolyacid is a kind of extraordinary ring-opening polymerization catalyst,, after polyreaction,, be mixed among the PTMEG product if separate not exclusively, will produce pernicious influence to the performance of product P TMEG.Aoshima has reported the method for removing heteropolyacid in the PTMEG product: in reactant (Aethoxy Sklerol and THF mixture), add carbonatoms below 15, boiling point is higher than THF; And can not produce the alkane or the Organohalogen compounds of azeotrope; Like heptane, octane, nonane, chloro-octane, toluene(mono)chloride etc.; The PTMEG purity of the maximum that this method can reach does not reach the requirement of product application for containing heteropolyacid 500ppm; And this method only is applicable to heteropolyacid, and other assorted many salt are not then possessed separating effect.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome the deficiency of prior art, and a kind of purifying process that contains the oligo-ether of heteropolyacid is provided, and this purifying process has good purification effect, behind the purifying in the oligo-ether heteropolyacid content below 50ppm.
For solving above technical problem, the present invention takes following technical scheme:
A kind of purifying process that contains the oligo-ether of heteropolyacid, thus the oligo-ether stoste that will contain heteropolyacid is filtered through the inorganic membrane filtration device and is reached the purifying purpose.
A technical scheme of the present invention is: a kind of as in ceramic membrane, metallic membrane and the metal oxide film of the mineral membrane that the inorganic membrane filtration device uses, the mean pore size of mineral membrane is 0.01～0.2 μ m.
The content of heteropolyacid is 200～5000ppm in the above-mentioned oligo-ether stoste.
The further technical scheme of above-mentioned purifying process is: the oligo-ether stoste that will contain heteropolyacid is introduced stock chest; Add organic solvent; Pressurize through recycle pump; Constantly circulate in the loop that mixture is linked to be between stock chest and inorganic membrane filtration device and carry out purifying, collect oligo-ether solution at last, remove organic solvent and get the oligo-ether product.
Mixture is through the inorganic membrane filtration device time, and the temperature of oligo-ether solution is 30～90 ℃; The WP of recycle pump is 0.01～0.5MPa, and circular flow is at 0.2～10m
3Between/the h.
Organic solvent is aromatic solvent or ketones solvent.The mixture of one or more in the preferred benzene,toluene,xylene of aromatic solvent.A kind of in the preferred acetone of ketones solvent, the pimelinketone or the mixed solvent of the two.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
Take the inorganic membrane filtration device that the heteropolyacid in the oligo-ether is removed, heteropolyacid content is below 50ppm in the oligo-ether behind the purifying, and purification effect is good; And take that this technological operation heteropolyacid simple, pollution-free, after separating is recyclable to be utilized again, production cost is low.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 crosses in the cleaner liquid HPA content curve over time among the embodiment 4.
Embodiment
Mineral membrane is a kind of of solid film, and it is by inorganic materials, the semi-permeable membranes of processing like metal, MOX, pottery, sintered glass, zeolite, inorganic macromolecule material etc.Mineral membrane can be divided into dense film and porous-film two big classes, and dense film mainly contains various metals and alloy film thereof, like palladium metal film, metal silverskin and palladium-nickel, palladium-Jin, palladium-silver alloy film.
According to the standard that IUPAC formulates, inorganic porous membrane can be divided into three major types by pore size: the aperture is the gross porosity film greater than 50nm, and the aperture is referred to as filtering membrane between 2nm-50nm, and the aperture is referred to as microporous membrane less than 2nm.Industrialized at present mineral membrane gross porosity film and filtering membrane belong to micro-filtration and ultra-filtration technique.
Purifying process with the polytetramethylene ether diol that makes through heteropoly acid catalysis is an example below, in conjunction with accompanying drawing and concrete embodiment the present invention is carried out detailed explanation, and wherein the number-average molecular weight of polytetramethylene ether diol is between 300～6000.
Embodiment 1
In the mixture stock chest, adding heteropolyacid content earlier is the polytetramethylene ether diol stoste 10L of 400ppm, adds pimelinketone 10L again, behind the thorough mixing, starts recycle pump, circular flow 0.2m
3/ h, pump discharge pressure is controlled at 0.01MPa, and the mixture temperature is controlled at about 50 ℃; Circulate after 1 hour; Getting and leach clear liquid, is 10ppm through polyatom (like Mo, W, V, Nb, Ta etc.) content in the ICP detector detection clear liquid, and the heteropolyacid rejection reaches 97.5%.
Embodiment 2
In the mixture stock chest, adding heteropolyacid content earlier is the polytetramethylene ether diol stoste 10L of 4000ppm, adds acetone 10L again, behind the thorough mixing, starts recycle pump, circular flow 1m
3/ h, pump discharge pressure is controlled at 0.5MPa, and the mixture temperature is controlled at about 90 ℃; Circulate after 2 hours; Getting and leach clear liquid, is 45ppm through polyatom (like Mo, W, V, Nb, Ta etc.) content in the ICP detector detection clear liquid, and the heteropolyacid rejection reaches 99%.
Embodiment 3
In the mixture stock chest, adding heteropolyacid content earlier is the polytetramethylene ether diol stoste 10L of 1000ppm, adds toluene 10L again, behind the thorough mixing, starts recycle pump, circular flow 10m
3/ h, pump discharge pressure is controlled at 0.2MPa, and the mixture temperature is controlled at about 30 ℃; Circulate after 1 hour; Getting and leach clear liquid, is 5ppm through polyatom (like Mo, W, V, Nb, Ta etc.) content in the ICP detector detection clear liquid, and the heteropolyacid rejection reaches 99.5%.
Embodiment 4
The inorganic membrane filtration device is plug-in to the oligo-ether production line; Carry out continuous running experiment; Moved 258 hours altogether, HPA content in the cleaner liquid is crossed in sampling analysis in good time, every two hours writes down operating parameter (comprising temperature, film intake pressure, film top hole pressure, circular flow, filtration flux).The result sees Fig. 2.
As can be seen from Figure 2, cross that heteropolyacid content has fluctuation in the cleaner liquid, but basically between 0～50ppm, concentrate on below the 30ppm, and heteropolyacid content is all more than 500ppm in the reaction stoste, the heteropolyacid decreasing ratio is about 95%.This shows that mineral membrane is obvious to the HPA filter effect, and work-ing life is also longer.
From above instance, can find out, utilize the method among the present invention, can reduce heteropolyacid content in the polyether product (50ppm below) greatly, and pollution-free, long service life, the recyclable utilization of catalyzer.
Claims (7)
1. purifying process that contains the oligo-ether of heteropolyacid; Described oligo-ether is the polytetramethylene ether diol of number-average molecular weight between 300～6000; It is characterized in that: thus the oligo-ether stoste that will contain heteropolyacid is filtered through the inorganic membrane filtration device and is reached the purifying purpose; The temperature of described oligo-ether stoste is 30～90 ℃; A kind of as in ceramic membrane, metallic membrane and the metal oxide film of the mineral membrane that described inorganic membrane filtration device uses, the mean pore size of described mineral membrane is 0.01～0.2 μ m.
2. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 1 is characterized in that: the content of heteropolyacid is 200～5000ppm in the described oligo-ether stoste.
3. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 1; It is characterized in that: the oligo-ether stoste that will contain heteropolyacid is introduced stock chest continuously; Add organic solvent; Through recycle pump pressurization, constantly circulate in the loop that mixture is linked to be between stock chest and inorganic membrane filtration device and carry out purifying, collect oligo-ether solution at last, remove organic solvent and get the oligo-ether product.
4. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 3, it is characterized in that: the WP of described recycle pump is 0.01～0.5MPa, and circular flow is at 0.2～10m
3Between/the h.
5. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 3 is characterized in that: said organic solvent is aromatic solvent or ketones solvent.
6. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 3 is characterized in that: described aromatic solvent is one or more the mixture in the benzene,toluene,xylene.
7. a kind of purifying process that contains the oligo-ether of heteropolyacid according to claim 5 is characterized in that: described ketones solvent is a kind of in acetone, the pimelinketone or the mixture of the two.
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| CN101348565B true CN101348565B (en) | 2012-01-11 |
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| JP2011126774A (en) * | 2009-11-20 | 2011-06-30 | Sumitomo Chemical Co Ltd | Method for recovering polyoxoanion compound |
| CN103936950A (en) * | 2013-01-17 | 2014-07-23 | 珠海市吉林大学无机合成与制备化学重点实验室 | Polyether material purifying method |
| CN105061749B (en) * | 2015-07-30 | 2017-11-28 | 浙江皇马科技股份有限公司 | A kind of butantetraol polyethenoxy ether and its synthetic method |
| CN112724396A (en) * | 2020-12-28 | 2021-04-30 | 苏州欣影生物医药技术有限公司 | Purification method for improving molecular weight distribution of polyethylene glycol derivatives |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5097077A (en) * | 1989-10-06 | 1992-03-17 | Basf Aktiengesellschaft | Purification of heteropolyacid-containing polyalkylene ether glycols |
| CN1354044A (en) * | 2001-12-15 | 2002-06-19 | 大连理工大学 | Method for recovering heteropolyacid catalyst |
| CN1394672A (en) * | 2002-07-01 | 2003-02-05 | 南京工业大学 | Catalyst membrane separation method for heterogeneous suspension state nano catalytic reaction |
| CN1583687A (en) * | 2004-06-03 | 2005-02-23 | 南京工业大学 | Continuous recovery process of coupling catalyst for catalytic alkylation reaction |
-
2008
- 2008-05-30 CN CN2008101224165A patent/CN101348565B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5097077A (en) * | 1989-10-06 | 1992-03-17 | Basf Aktiengesellschaft | Purification of heteropolyacid-containing polyalkylene ether glycols |
| CN1354044A (en) * | 2001-12-15 | 2002-06-19 | 大连理工大学 | Method for recovering heteropolyacid catalyst |
| CN1394672A (en) * | 2002-07-01 | 2003-02-05 | 南京工业大学 | Catalyst membrane separation method for heterogeneous suspension state nano catalytic reaction |
| CN1583687A (en) * | 2004-06-03 | 2005-02-23 | 南京工业大学 | Continuous recovery process of coupling catalyst for catalytic alkylation reaction |
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Owner name: TAICANG ZHONGHUA ENVIRONMENTAL PROTECTION MEDICAL Free format text: FORMER OWNER: ZHONGHUA INTERNATIONAL (SUZHOU) NEW MATERIAL R + D CO., LTD. Effective date: 20120301 |
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Effective date of registration: 20120301 Address after: 215433 No. 18 South Binjiang Road, petrochemical District, Taicang Port Development Zone, Jiangsu, China Patentee after: Sinochem Taicang Environmental Protection Chemical Co., Ltd. Address before: 215433 No. 18 South Binjiang Road, petrochemical District, Taicang Port Development Zone, Jiangsu, China Patentee before: Sinochem International (Suzhou) New Material R&D Co., Ltd. |
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