WO2006040065A1 - Verfahren zur herstellung und entwässerung von zyklischen formalen - Google Patents
Verfahren zur herstellung und entwässerung von zyklischen formalen Download PDFInfo
- Publication number
- WO2006040065A1 WO2006040065A1 PCT/EP2005/010761 EP2005010761W WO2006040065A1 WO 2006040065 A1 WO2006040065 A1 WO 2006040065A1 EP 2005010761 W EP2005010761 W EP 2005010761W WO 2006040065 A1 WO2006040065 A1 WO 2006040065A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- water
- cyclic
- cyclic formal
- mixture
- Prior art date
Links
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000012466 permeate Substances 0.000 claims abstract description 23
- 239000012465 retentate Substances 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 25
- 238000005373 pervaporation Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- -1 3-dioxoIan Chemical compound 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- ULAGGPJVDRGWTI-UHFFFAOYSA-N 1,3,5-trioxepane Chemical compound C1COCOCO1 ULAGGPJVDRGWTI-UHFFFAOYSA-N 0.000 claims description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 claims description 2
- INCCMBMMWVKEGJ-UHFFFAOYSA-N 4-methyl-1,3-dioxane Chemical compound CC1CCOCO1 INCCMBMMWVKEGJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 3
- 229920001477 hydrophilic polymer Polymers 0.000 claims 3
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims 1
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000000895 extractive distillation Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
Definitions
- the invention relates to a process for the preparation of anhydrous cyclic formals.
- Cyclic formals can be prepared by acid-catalyzed reaction of dihydric alcohols (di-alcohols) and formaldehyde.
- the technically most important cyclic formal is 1, 3-dioxolane (dioxolane). It is produced industrially by the acid-catalyzed reaction of aqueous formaldehyde with ethylene glycol. From the reaction mixture dioxolane can be separated by distillation, but it is always accompanied by water, because both components form an azeotrope with about 93 wt .-% dioxolane. Many methods have been proposed for solving this separation problem, and most of them use extraction or extractive rectification to overcome the azeotropic point of the water / dioxolane mixture.
- US 5,690,793 and US 5,695,615 disclose processes for the purification of cyclic formals in which water is removed in an extractive distillation with polar, low-volatility solvents.
- No. 5,456,805 describes the separation of dioxolane and water from the reaction of formaldehyde with ethylene glycol by extractive distillation with n-pentane.
- BE 669 480 discloses a process for the extraction of dioxolane from aqueous mixtures with chlorinated hydrocarbons and subsequent alkaline scrubbing of the crude dioxolane.
- JP 07 285 958 teaches a method according to which the azeotrope of water and dioxolane is extracted in the liquid phase with hydrocarbons and then the organic phase is distilled to pure dioxolane.
- the processes according to the prior art need to be improved because they introduce a third substance as extraction or entrainment agent into the process in addition to water and cyclic formal.
- This third substance must normally be purified in a separate material cycle in order to be able to be used again. If this is not completely successful, a partial disposal of the third substance leads to expensive subsequent purification or pollution of the environment. In any case, the additional separation operations require additional energy for their operation.
- the invention therefore provides a process for the separation of cyclic formals, in particular of 1,3-dioxolane, from mixtures with water, characterized in that a) the cyclic formal and water-containing mixture with a ⁇ ßriq selective
- Another object of the invention is a process for the separation of cyclic
- Formal, in particular 1,3-dioxolane, from mixtures with water characterized in that a) a mixture of cyclic formal and water accumulates to near the azeotrope concentration, b) a cyclic formal enriched, liquid mixture from step a ) from an aqueous selective pervaporation membrane, c) from the pervaporation a liquid retentate with a higher content of cyclic formal and a vaporous, water-rich permeate wins.
- the membrane separation is not carried out as pervaporation with liquid feed, but as vapor permeation with a vaporous starting mixture of the cyclic formal with water.
- the invention therefore further provides a process for the separation of dioxolane or other cyclic formals from mixtures with water, characterized in that a) a mixture of cyclic formal and water in the vicinity of
- Cyclic formals are obtained in a cyclization reaction of di-alcohols and formaldehyde.
- Typical representatives are 1,3-dioxolane (from ethylene glycol), 1,3-dioxepane (from 1,4-butanediol), diethylene glycol formal, 4-methyl-1,3-dioxolane (from 1, 2-propanediol), 1, 3 Dioxane (from 1,3-propanediol), 4-methyl-1,3-dioxane (from 1,3-butanediol) and 1,3,5-trioxepan (from ethylene glycol and two molecules of formaldehyde). Preference is given to 1,3-dioxolane.
- Suitable catalytically active acids are, for example, mineral acids such as sulfuric acid, phosphoric acid or aliphatic or aromatic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid or even strongly acidic ion exchange resins or heteropolyacids such as polyphosphoric acid, tungstophosphoric acid or molybdophosphoric acid.
- the reaction can be performed according to the prior art in a stirred tank reactor with attached distillation column or as a reactive distillation.
- the mixture of cyclic formal and water obtained at the top of this column already contains more than 30% by weight, preferably more than 40% by weight and more preferably more than 50% by weight of cyclic formal.
- the mixture may contain, in addition to the cyclic formal and water, other components of the reaction mixture such as di-alcohol or formaldehyde in small concentrations.
- the feed mixture consisting essentially of cyclic formal and water as distillate or Brüdendampf from the
- the invention therefore provides a process for the preparation of cyclic formals from di-alcohols and formaldehyde, characterized in that a) the di-alcohol and the formaldehyde with catalysis of a suitable acid for
- step B) from the reaction vessel, a vaporous mixture is released, which contains substantially the cyclic formal and water, c) the mixture of cyclic formal obtained in step b) accumulates to near the azeotrope concentration, d) a cyclic formal enriched , liquid mixture from step c) an aqueous selective pervaporation membrane, e) from the pervaporation, a liquid retentate with a higher content of cyclic formal and a vaporous, water-rich permeate wins.
- the vaporous mixture from step b) is not condensed, but instead fed to it as vapor of an aqueous-selective vapor permeation membrane.
- This procedure is particularly advantageous in terms of the evaporation energy to be applied because it uses the energy content of the vapor from the reaction vessel.
- the invention therefore further provides a process for the preparation of cyclic formals from di-alcohols and formaldehyde, characterized in that a) the di-alcohol and the formaldehyde are reacted by catalysis of a suitable acid, b) a vaporous form from the reaction vessel Relaxed mixture containing essentially the cyclic formal and water, c) the mixture of cyclic formal obtained in step b) to near the
- Azeotrop concentration increases, d) a cyclic formal enriched, steam mixture from step c) an aqueous selective Dampfpermeationsmembran supplies, e) from the vapor permeation a vaporous retentate with a higher content of cyclic formal and a vaporous, water-rich permeate with higher wins
- the accumulation of the mixture of cyclic formal and water up to the azeotrope concentration can be carried out by conventional rectification, wherein a water flow is formed in addition to the enriched mixture.
- the enrichment of the cyclic formal to the azeotrope in a membrane separation is carried out with an organically selective membrane.
- the cyclic formal is enriched to more than 80%, preferably more than 90%, of the azeotrope concentration before it is fed to the membrane process according to the invention in step d).
- the concentration in the feed of the membrane is preferably above 80% by weight and more preferably above 90% by weight.
- membranes are used which preferably allow water to permeate before organic components.
- Suitable membranes for the process according to the invention can likewise be used in the process of pervaporation with liquid membrane feed and in the process of vapor permeation.
- the separation-active layer of the membrane is in a preferred embodiment of poly (vinyl alcohol) (PVOH), which is obtained by more or less complete hydrolysis of poly (Vi nylacetat).
- PVH poly (vinyl alcohol)
- Such membranes are commercially available.
- the separation-active layer of the membrane has a thickness of 1 to 200 ⁇ m, preferably 2 to 50 ⁇ m and particularly preferably 4 to 10 ⁇ m.
- the separation factor ⁇ of the membrane process depends on the selectivity of the membrane and the pressure ratio across the membrane.
- the separation factor ⁇ of the membrane process can be determined experimentally as follows:
- the permeation rate of the membrane depends on the one hand on the structure of the membrane, such as - within certain limits - on the thickness of the separation-active layer; on the other hand, however, also from the operating conditions of the membrane process:
- the permeation rate decreases with increasing concentration of the cyclic formal in the feed, on the other hand increases with increasing temperature of the feed and increases with increasing pressure ratio across the membrane.
- the permeation rate through the membrane is between 0.1 kg / m 2 / h and 50 kg / m 2 / h, preferably between 0.5 kg / m 2 / h and 25 kg / m 2 / h and particularly preferably between 1 kg / m 2 / h and 10 kg / m 2 / h.
- a pressure difference is applied across the membrane. This is typically done by applying a negative pressure to the permeate side of the membrane. However, the pressure difference can also be increased by increasing the partial pressure of the water on the feed side of the membrane.
- the pressure ratio across the membrane is between 2 and 500, preferably between 5 and 50.
- a particular advantage of the method is that you can still achieve good separation performance with a heated inlet.
- the skilled person is aware that
- Pervaporation membrane can be swollen at elevated temperatures of polar, aprotic solvents such as cyclic formals and lose their selectivity.
- separation factors of ⁇ > 10, preferably ⁇ > 20 are achieved even at feed temperatures of T> 40 ° C.
- the feed to the pervaporation or vapor permeation membrane to T> 40 is achieved even at feed temperatures of T> 40 ° C.
- the retentate has a cyclic formal content of more than 99% by weight, more preferably more than 99.5% by weight.
- the cyclic formal thus obtained can be worked up to the desired purity in further separation steps become.
- composition of the aqueous permeate in a preferred embodiment of the invention is more than 70% by weight of water and more preferably more than 90% by weight.
- a pervaporation test cell is recirculated to a mixture of 50% by weight of dioxolane and 50% by weight of water, which was heated to 75 ° C.
- Example 1 was repeated identically, but with 85 wt .-% dioxolane in the feed.
- Permeation rate was 4.2 kg / m 2 / h. and the dioxolane concentration in the permeate was 3.9
- Example 1 was repeated identically, but with 98 wt .-% dioxolane in the feed.
- Example 1 was repeated identically, but the inlet temperature was 55 0 C.
- the permeation rate dropped to 2 kg / m 2 / h and the dioxolane concentration was 3.5 wt .-%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007535087A JP4970270B2 (ja) | 2004-10-08 | 2005-10-06 | 環状ホルマールの製造及び脱水法 |
US11/665,047 US20090200153A1 (en) | 2004-10-08 | 2005-10-06 | Method for producing and dehydrating cyclic formals |
CN2005800391907A CN101060913B (zh) | 2004-10-08 | 2005-10-06 | 环状缩甲醛的制备和脱除水的方法 |
HK08104550.6A HK1114576A1 (en) | 2004-10-08 | 2008-04-24 | Method for producing and dehydrating cyclic formals |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004049056A DE102004049056A1 (de) | 2004-10-08 | 2004-10-08 | Verfahren zur Herstellung und Reinigung von zyklischen Formalen |
DE102004049056.2 | 2004-10-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006040065A1 true WO2006040065A1 (de) | 2006-04-20 |
Family
ID=35185117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/010761 WO2006040065A1 (de) | 2004-10-08 | 2005-10-06 | Verfahren zur herstellung und entwässerung von zyklischen formalen |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090200153A1 (de) |
JP (1) | JP4970270B2 (de) |
CN (1) | CN101060913B (de) |
DE (1) | DE102004049056A1 (de) |
HK (1) | HK1114576A1 (de) |
WO (1) | WO2006040065A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012116920A (ja) * | 2010-11-30 | 2012-06-21 | Polyplastics Co | ポリオキシメチレン樹脂の製造方法 |
JP5762809B2 (ja) * | 2011-04-20 | 2015-08-12 | 旭化成ケミカルズ株式会社 | 環状ホルマールの精製方法 |
JP2013053106A (ja) * | 2011-09-05 | 2013-03-21 | Asahi Kasei Chemicals Corp | 環状ホルマール化合物の製造方法 |
CN113543869A (zh) * | 2019-01-09 | 2021-10-22 | 沙特基础工业全球技术公司 | 使用优化的渗透蒸发法进行的具有高水含量的含二醇混合物的脱水 |
CN111978284A (zh) * | 2020-08-14 | 2020-11-24 | 中化学科学技术研究有限公司 | 一种二氧五环制备工艺及制备系统 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0096339A2 (de) * | 1982-06-01 | 1983-12-21 | Deutsche Carbone AG | Mehrschichtige Membran und ihre Verwendung zur Trennung von Flüssigkeitsgemischen nach dem Pervaporationsverfahren |
WO1999005137A1 (de) * | 1997-07-26 | 1999-02-04 | Basf Aktiengesellschaft | Verfahren zur abtrennung von trioxan |
EP1167333A2 (de) * | 2000-06-26 | 2002-01-02 | F. Hoffmann-La Roche Ag | Verfahren und Vorrichtung zur Herstellung von Acetalen und Ketalen |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL171534C (nl) * | 1970-06-16 | 1983-04-18 | Monsanto Co | Werkwijze voor het afscheiden van water uit mengsels die water en formaldehyd bevatten. |
JPS59203602A (ja) * | 1983-05-02 | 1984-11-17 | Asahi Chem Ind Co Ltd | 複合膜 |
JPS59203607A (ja) * | 1983-05-06 | 1984-11-17 | Asahi Chem Ind Co Ltd | 異方性親水性膜及びその製造方法 |
JPS6316007A (ja) * | 1986-07-08 | 1988-01-23 | Agency Of Ind Science & Technol | 液体混合物の分離法 |
US4798674A (en) * | 1988-03-10 | 1989-01-17 | Texaco Inc. | Separation of organic liquids |
DE3939867A1 (de) * | 1989-12-01 | 1991-06-06 | Gft Ges Fuer Trenntechnik | Composite-membran zur abtrennung von wasser aus organische komponenten enthaltenden fluiden mittels pervaporation |
SG49998A1 (en) * | 1992-10-31 | 1998-06-15 | Hoechst Ag | Process for separating trioxane from an aqueous mixture |
JPH0733762A (ja) * | 1993-07-20 | 1995-02-03 | Asahi Chem Ind Co Ltd | トリオキサンの製造方法 |
US5616736A (en) * | 1994-02-04 | 1997-04-01 | Hoechst Celanese Corporation | Method of preparing cyclic formals |
US5720895A (en) * | 1994-08-11 | 1998-02-24 | Kao Corporation | Polyol ether derivatives and production methods therefor |
US6528025B1 (en) * | 2000-06-26 | 2003-03-04 | Roche Vitamins Inc. | Process of manufacturing equipment for preparing acetals and ketals |
WO2002055513A1 (fr) * | 2001-01-15 | 2002-07-18 | Asahi Kasei Kabushiki Kaisha | Procede de production de methylal cyclique |
-
2004
- 2004-10-08 DE DE102004049056A patent/DE102004049056A1/de not_active Withdrawn
-
2005
- 2005-10-06 CN CN2005800391907A patent/CN101060913B/zh not_active Expired - Fee Related
- 2005-10-06 JP JP2007535087A patent/JP4970270B2/ja not_active Expired - Fee Related
- 2005-10-06 WO PCT/EP2005/010761 patent/WO2006040065A1/de active Application Filing
- 2005-10-06 US US11/665,047 patent/US20090200153A1/en not_active Abandoned
-
2008
- 2008-04-24 HK HK08104550.6A patent/HK1114576A1/xx not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0096339A2 (de) * | 1982-06-01 | 1983-12-21 | Deutsche Carbone AG | Mehrschichtige Membran und ihre Verwendung zur Trennung von Flüssigkeitsgemischen nach dem Pervaporationsverfahren |
WO1999005137A1 (de) * | 1997-07-26 | 1999-02-04 | Basf Aktiengesellschaft | Verfahren zur abtrennung von trioxan |
EP1167333A2 (de) * | 2000-06-26 | 2002-01-02 | F. Hoffmann-La Roche Ag | Verfahren und Vorrichtung zur Herstellung von Acetalen und Ketalen |
Non-Patent Citations (2)
Title |
---|
LIPNIZKI, F. ET AL.: "Hydrophobic pervaporation of binary and ternary solutions: evaluation of fluxes, selectivities, and coupling effects.", SEPARATION SCIENCE AND TECHNOLOGY, vol. 39, no. 10, 2004, pages 2235 - 2259, XP009056531 * |
WESSLEIN M ET AL: "PERVAPORATION OF LIQUID MIXTURES THROUGH POLY (VINYL ALCOHOL) (PVA)MEMBRANES. I. STUDY OF WATER CONTAINING VINARY SYSTEMS WITH COMPLETE AND PARTIAL MISCIBILITY", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER SCIENTIFIC PUBL.COMPANY. AMSTERDAM, NL, vol. 51, no. 1/2, 15 July 1990 (1990-07-15), pages 169 - 179, XP000541760, ISSN: 0376-7388 * |
Also Published As
Publication number | Publication date |
---|---|
CN101060913B (zh) | 2013-03-06 |
JP4970270B2 (ja) | 2012-07-04 |
CN101060913A (zh) | 2007-10-24 |
JP2008515837A (ja) | 2008-05-15 |
DE102004049056A1 (de) | 2006-04-13 |
HK1114576A1 (en) | 2008-11-07 |
US20090200153A1 (en) | 2009-08-13 |
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