CN1192727A - Syntheis of glycol ethers - Google Patents
Syntheis of glycol ethers Download PDFInfo
- Publication number
- CN1192727A CN1192727A CN96196232A CN96196232A CN1192727A CN 1192727 A CN1192727 A CN 1192727A CN 96196232 A CN96196232 A CN 96196232A CN 96196232 A CN96196232 A CN 96196232A CN 1192727 A CN1192727 A CN 1192727A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- clay
- anionic
- glycol ether
- ldh
- 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.)
- Pending
Links
- -1 glycol ethers Chemical class 0.000 title claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004927 clay Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 13
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 239000011229 interlayer Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- 238000006213 oxygenation reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910003023 Mg-Al Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- PRBXPAHXMGDVNQ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]acetic acid Chemical compound OCCOCCOCC(O)=O PRBXPAHXMGDVNQ-UHFFFAOYSA-N 0.000 description 1
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000008232 de-aerated water Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical class O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical class C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
- C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
This invention relates to a process for making glycol ethers by reacting an olefin oxide with an alcohol over a catalyst comprising a layered double hydroxide (LDH) clay with its layered structure intact and having interlamellar anions at least some of which are metal anions or (poly)oxometallate anions. In the LDH clays, the interlamellar anions present are inorganic metal anions, oxometallate or polyoxometallate anions and include inter alia one or more of the following anions: chromium, vanadium, molybdenum and phosphorus, and (poly)oxoanions thereof. A copper-chromium hydrotalcite anionic clay or a magnesium-aluminium hydrotalcite anionic clay exchanged with (poly)oxometallate anions are preferred.
Description
The present invention relates to the method for synthesizing glycol ether in the presence of metal oxide that embeds and oxyhydroxide.
Glycol ether is a kind of multi-usage molecule that combines the optimal dissolution feature of ethanol and ether.Glycol ether has miscibility and solvency power to a series of organic solvents and glassware for drinking water.Because these reasons, glycol ether is presented at the strong solvent that is used as resin in the industry of (i) topcoating highlightedly, (ii) be used as solvent in the braking fluid industry, (iii) be used as the frostproofer of various petroleum based fuels in the petroleum industry, (iv) be used as antifreezing agent and (the v) specialty products that use of family in the automotive industry.As everyone knows, can in the presence of acidity or basic catalyst, generate this glycol ether with ethanol and olefin oxide reaction.
One of inorganic materials that broad research is crossed its catalytic activity is a cationic clay.These clays comprise the negative charge metal silicate thin slice that embeds hydrated cation, for example terre verte.
Known another kind of clay is an anionic clay, metal oxide and the oxyhydroxide, particularly multi-layer type double-hydroxide (hereinafter referred to as " LDHs ") of this clay for embedding.These anionic clays are different from common cationic clay, wherein contain to have embedded anionic positively charged double-hydroxide thin slice, just form a newly-increased class material like this concerning common cationic clay.This compound is at for example Reichle, WT, and " anionic clay mineral substance " Wen Zhongyou that delivers " Chemtec, " in January, 1986 describes, and the formula that sees service:
[(M
2+)
1-x(M
3+)
x(OH)
2]
X+[(A
M-)
X/mNH
2O]
X-This compounds is made of metal oxide with positive charge that has embedded negatively charged ion and water molecules and oxyhydroxide thin slice.Positively charged layer is class brucite [Mg (OH)
2], have tervalent positively charged ion and on the octahedron point position of oxyhydroxide thin slice, replaced divalent cation.The anionic adsorption of hydration makes structure be electric neutrality.
A series ofly contain various divalent cation M
2+(Mg for example
2+, Zn
2+, Cu
2+, Ni
2+, Fe
2+, Co
2+Deng) and Tricationic M
3+(Al for example
3+, Cr
3+, Fe
3+Deng) and negatively charged ion A
M-(halogen for example, oxygenation anion, this class LDHs of combination organic anion etc.) can pass through directly with its crystallization in the solution from water, or by the anionresin of pre-crystallization LDH clay synthesize (referring to K.J.Martin and T.J.Pinnavaia " J.Am Chem Soc; " 108, p.541 (1986)).
This type of contains Mg
2+, Al
3+Or CO
3 2-The ionic natural mineral matter is called as hydrotalcite [Mg
6Al
2(OH)
16] CO
34H
2O, and be the foundation of main name that has " houghite " compound of same structure in the document.
Many documents disclose burnt LDHs and have catalytic activity.For example, the open catalyzer by the preparation of calcining houghite compound of US-A-4458026 can be used for the condensation of 3-acetaldol.JP-A-54111047 has described with burnt LDHs and has prepared alkylene glycol ether acetic ester.Similarly, EP-A-339426 discloses with burnt hydrotalcite the compound that contains active hydrogen atom has been carried out ethoxylation and/or propoxylation.Naturally occurring LDH clay is main carbonate containing in its interlayer farmland.This material only has low activity when being used as the catalyzer for preparing glycol ether usually, it is believed that calcining can improve its activity.
The calcining of LDHs can be at a broad, for example carry out in 200～600 ℃ the temperature range, this depends on their structure and composition, and causes reversibility avalanche (Reactivity of Solidds such as Sato, 2 of its multilayered structure usually, pp253-260 (1986) and Sato etc., Ind.Eng.Chem., Prod.Res.Dev., 25, pp89-92 (1986)), the result forms spinel M
2+M
2 3+O
4, together with free M is arranged
2+O forms.Above-mentioned all documents require LDHs with the incinerating form as catalyzer, promptly with the multilayered structure form of avalanche.
We the previous EP-A-0515636 that announces has described this double-hydroxide clay of not calcining form, contain magnesium and aluminium in its skeleton, be used for pure and mild olefin oxide reaction is generated glycol ether, during reaction, in its clay seam space, combine the negatively charged ion of reactant alcohol.Be used for this clay of synthetic and have anion, carbonate usually, but by ion exchange technique commonly used, it will exchange with the negatively charged ion of reactant alcohol in its interlayer space.
JP-A-H1-304043 has disclosed the houghite compound that is loaded with cupric ion, wherein the hydroxide ion catalysis aromatic halides vapor phase hydrolysis that exists at anionresin point.
This compounds of another family of describing among US-A-4774212 and the US-A-4843168, wherein contain magnesium and aluminium atom in the LDH clay skeleton, in its interlayer space, be combined with muriate, vitriol, nitrate, carbonate, the oxide compound of the negatively charged ion of terephthalate and vanadium and/or molybdenum (so-called " post ").The compound of describing in these files is different from the compound among the EP-A-0515636, because they relate to pillared clays, and contrast EP-A-0515636, it does not relate to pillared clays.These United States Patent (USP)s described the synthetic of these pillared clays and some organic reaction for example in the dehydrogenation of hydrocarbon, particularly aromatic hydrocarbon or the oxidative ammonolysis used as catalyzer.
Find at present, can produce the hydrotalcite anionic clay of the oxyhydroxide that in its skeleton structure, contains copper and chromium, be used for the object of the invention, this class clay also can be described as the LDH clay, and can be by the bigger negatively charged ion of combination in its interlayer space, particularly anionic metal and (gathering) oxometallic acid salt anionic are converted into pillared clays.In addition, also find in its skeleton, to contain magnesium, aluminium, the oxyhydroxide of copper and/or chromium, containing the anionic this hydrotalcite clay of anionic metal or (gathering) oxometallate in its interlayer space, particularly with its incinerating form not, is the useful catalyzer of producing glycol ether.
Therefore, the present invention relates to prepare a kind of method of glycol ether, this method is included in the catalyzer that contains LDH and exists and to carry out olefin oxide down and react with alcohol, this LDH multilayered structure be complete and the negatively charged ion of interlayer in to small part be anionic metal or (gathering) oxometallic acid salt anionic.
As the olefin oxide of reactant oxyethane, propylene and/or butylene suitably.
The alcohol that is used to react is aliphatics suitably, alicyclic or aromatic pure and mild can be single-, two-or polyvalent alcohol.Unit alcohol is preferred.The object lesson of alcohol comprises the alcohol of C1～C6, especially, and methyl alcohol, ethanol, Virahol and isopropylcarbinol.If the final product that requires is a monoethylene glycol ether, then the alcohol that uses suitably is molar excess.Usually, alcohol is 2: 1 with the mol ratio of olefin oxide suitably at least, and preferable range is 4: 1～15: 1, and most preferred range is 5: 1～12: 1.
The surprising feature of the present invention is the validity of not burnt LDHs as this catalysts, and this is different with above-mentioned record early.Therefore, in LDHs, the negatively charged ion that interlayer exists is the inorganic metal negatively charged ion, oxometallate or poly-oxometallic acid salt anionic and suitably particularly including one or more following negatively charged ion: chromium, vanadium, molybdenum and phosphorus and their (gathering) oxygenation anion.It is to comprise that oxygenation anion and oxometallic acid salt anionic the two and polyoxy thereof close derivative that term (gathering) oxygenation anion and (gather) oxometallic acid salt anionic look like.For example, copper-chromium hydrotalcite anionic clay when with (gathering) oxometallate anionresin, produces the improved greatly material of selectivity, as alcohol and olefin oxide catalyst for reaction.Can be by common technology at a kind of precursor for example chloride precursor (be easy to by co-precipitation synthetic), carry out this ion-exchange on terephthalate precursor or the lauryl sulfate precursor.
The method for preparing the hydrotalcite anionic clay is known technology.A kind of like this method has been described in US-A-4458026.Usually, for example sodium hydroxide and/or sodium carbonate solution mix with alkali in the pH value of control or PH scope with the solution of divalence or trivalent metal soluble salt.At room temperature with the mixed solution vigorous stirring up to forming slurries, suitably it is optionally heated for a moment then at 50～200 ℃, occur up to enough crystal, form LDH.Then synthetic LDH is filtered, washing and dry, and muriate or carbonate are arranged usually as interlayer anion.Containing other ionic material can or adopt the synthetic method preparation by ion-exchange, makes the ion that requires be bonded in the interlayer farmland.
Other synthetic method of the double-hydroxide LDHs that has magnesium and aluminium in this skeleton has been described in US-A-4774212 and US-A-4843168, as mentioned above, wherein anionic metal or (gathering) oxometallic acid salt anionic can be used as " post " and are bonded in the interlayer space.
The inventive method is carried out in liquid phase suitably.The peak optimization reaction temperature will depend on the reactant of use, but generally arrive about 250 ℃ in envrionment temperature, suitably at 50～150 ℃.Reaction can be carried out under pressure, its scope from environmental stress to about 50bar (5000KPa).
The inventive method can be used for for example fourth-1-alcohol and one or more ethylene oxide unit reaction, preparation butyl-monoethylene glycol ether (BMGE), diethylene glycol ether (BDGE), triethylene glycol ether etc.When preparation monoethylene glycol ether, be reflected under the very high selectivity and especially successfully carry out.
Reference is routine down, and the invention will be further described:
Embodiment 1:
A. the preparation of chloride precursor:
Mol ratio is 2: 1 1M Cu (NO
3)
23H
2The CrCl of O and 1M
36H
2The mixture 40ml of O joins respectively with constant flow velocity (4ml/hr) in the beaker of the interior dress 100ml 2M KCl aqueous solution.At fixed PH5.5,, copper-chromium muriate LDH is precipitated out by in high degree of agitation, in KCl solution, adding 2M NaOH aqueous solution 40ml with transit mixer under the room temperature.Finish reinforced in 10 hours and mother liquor under similarity condition aging 14 hours.In 1 hour under 4000rpm centrifuging operational condition, with the new distillatory of 250ml and the water continuous washing three times of removing carbonic acid.In ventilated drying oven, that the gel that reclaims is slowly dry down at 60 ℃.Then the dry material of crossing in the baking oven is pulverized, sieved, collect the particle of granularity in 0.5～1.0mm scope.The X-ray diffraction image of this material shows it is hydrotalcite, and δ (003) lattice is 7.7 .
B. the preparation of chromic acid salt face:
The material (1g) of preparation among above-mentioned 1 (a) is suspended in (CrO
4)
-2In the anionic aqueous solution (0.1M, 100ml).Under the room temperature, in 3 hours, the PH of this solution is remained on 8.5 with the 1M NaOH aqueous solution.In order to obtain the granule that granularity is about 0.5～1.0mm, then as described in 1 (a), with products therefrom 60 ℃ of washings and dry down.The XRD figure case is typical hydrotalcite anionic clay, and δ (003) lattice is 8.42 .
C. the preparation of dichromic acid salt face:
(0.1M 100ml) repeats above-mentioned 1 (b) step, and this solution makes pH value remain on 4.5 by adding 1M nitric acid with the dichromate anion solutions.Chromic acid salt face among XRD figure case and above-mentioned 1 (b) is quite similar, and its δ (003) lattice is 8.95 .
D. the preparation of pyrovanadic acid salt face:
The material (1g) of preparation among above-mentioned 1 (a) is suspended in the vanadic acid sodium aqueous solution (0.1M, 100ml).In order to embed pyrovanadic acid negatively charged ion, (V
2O
7)
4-, by high degree of agitation at room temperature, add the 1M sodium hydroxide solution in 3 hours, make solution PH remain on 10.Washing of adopting and granulation step are as hereinbefore.The XRD figure case of this product shows that δ (003) lattice is 7.62 .
E. the preparation of decavanadate phase:
The material (1g) of preparation among above-mentioned 1 (a) is suspended in 0.1M terephthalic acid (100ml) aqueous solution.High degree of agitation under the room temperature made PH remain on 7.5 with 2M NaOH in 5 hours.The XRD figure case of the decavanadate phase that obtains like this shows that δ (003) lattice is 13.95 .Promoted the anionic embedding of most of decavanadate like this.
In order to obtain the decavanadate phase, terephthalic acid salt face (1g) is suspended in the 0.1M sodium metavanadate aqueous solution (100ml), by at room temperature, add rare nitric acid in 3 hours, make solution PH remain on 4.5.Subsequent washing and drying treatment are to carry out with the middle identical method of describing of above-mentioned 1 (d).Products therefrom is crystallization well not, and XRD figure shows that mutually δ (003) lattice is 11.61 .
F. the preparation of seven molybdic acid salt faces:
The terephthalic acid salt face (1g) of preparation among above-mentioned 1 (e) is suspended in Na
2MoO
42H
2The O aqueous solution (0.1M, 100ml) in.For seven molybdate anions that keep forming thus in the solution, [Mo
7O
24]
6-,, make solution PH remain on 4.5 by adding rare nitric acid in following 3 hours of the room temperature.Subsequent washing and drying treatment with above-mentioned 1 (d) in the identical method described carry out.The XRD figure case of products therefrom shows that δ (003) lattice is 12.77 .
G. use the Preparation of Catalyst glycol ether of above-mentioned 1 (a)-1 (f):
Be equipped with in the stainless steel reactor (internal diameter is 0.9mm) of thermowell one, test the ability that above-mentioned catalyzer promotes the epoxidation of alcohol.The catalytic bed volume that uses in each test is 5cm
3Be used in and add the mixed solution charging that contains fourth-1-alcohol (6 moles) and oxyethane (1 mole) of depressing preparation and react.Oxyethane is co-fed to be kept in the liquid phase in the feed pot of (1000KPa) nitrogen pressure head that has 10barg.Reactor is at first at room temperature with mixing the reinforced 3000KPa (30barg) that is pressurized to.When the pressure of reactor reached and stablizes, liquid is reinforced to be 10cm with speed
3/ hour (LHSV=2) pumps into reactor.In 2 hours, temperature of reactor is raised to 120 ℃ (1 ℃ of about per minute) lentamente then.(be equivalent to running in 0 hour) after this temperature and pressure is issued to stable state, reaction mixture is the equivalent sampling analysis in the fixed interval.With being furnished with WCOT fused silica capillary column (50m, internal diameter 0.25mm, CP-Sil-5) pye-Unicam 4500 gas-chromatographies, (kept 10 minutes for 80 ℃ with program control temperature, raising speed be 6 ℃/minute up to 250 ℃) analytic sample, with monoethylene glycol ether, senior glycol ether and the by product relative quantity of determining to form.At arbitrary test period, mass balance normally 98% or higher.Detected result is listed in the following table.Table 1.
| Catalyzer | Oxyethane transformation efficiency (%w/w) | Glycol ether selectivity (%w/w) | By product (%w/w) | |
| ????a | ????45 | ???BMGE ????94 | Other ether 6 | ????0.2 |
| ????b | ????48 | ????95 | ????5 | ????0.2 |
| ????c | ????80 | ????95 | ????5 | ????0.3 |
| ????d | ????29 | ????100 | ????0 | ????0.1 |
| ????e | ????46 | ????100 | ????0 | ????0.1 |
| ????f | ????46 | ????100 | ????0 | ????0.1 |
The above results shows that present method has obtained extraordinary transformation efficiency and the selectivity to monoethylene glycol ether.In addition, in the extraordinary while of catalyzer operability with two chromic acid salt faces, catalyzer selectivity under the situation of the poly-oxometallic acid salt face with vanadate or molybdate type is increased to 100%.
H. the preparation of decavanadate column Mg-Al LDH
(company limited obtains from Kyowa chemical industry, KW-2100, MgO/Al with 20g incinerating hydrotalcite
2O
3=4.33, by weight) stirring joins and is dissolved in 1 liter of vanadic acid sodium (13.9g) solution in the distilled water.Initial PH is 9.25, by added 2M hydrochloric acid in 3 hours PH is adjusted to 4.5.After the filtration, that jonquilleous solid is with about 1 liter of distilled water wash, following dry 16 hours at 80 ℃ then.
I. the preparation of two vanadate column Mg-Al LDH
Under the nitrogen atmosphere Kyowa KW-2100LDH was calcined 18 hours at 450 ℃, place moisture eliminator to vacuumize cooling then.20g incinerating material was sized mixing 1 hour in degassing distilled water (cool off under nitrogen blanket obtain with boiling distillated water), guaranteed maximum dispersion.Mixture remains under the nitrogen atmosphere, to avoid by the pollution of Carbon Dioxide in Air.The suspension (0.25M) that will contain the 30.5g vanadic acid sodium in 1 liter of de aerated water further outgased 1/2 hour at 65 ℃ of logical nitrogen.Add 2MNaOH then, make the PH of solution bring up to 10, just obtain limpid colourless solution.This solution mixes with the LDH water slurry then, and mixture is high degree of agitation under 65 ℃ of nitrogen atmosphere.After filtration and with after 2 liters of hot washes that outgas, the light yellow product of generation places the moisture eliminator drying of bleeding.The X-ray powder diffraction pattern of last white powder shows and has generated houghite compound that δ (003) lattice is 7.8 .
J.[Mg-Al-Fe (III) (CN)
6The preparation of]-six cyano group ferrate (III) column LDH
The burnt Kyowa-2100LDH of 20g and 1 liter of degassing distilled water were sized mixing 1 hour, and to guarantee maximum dispersion, mixture remains under the nitrogen atmosphere, to avoid by the pollution of Carbon Dioxide in Air.To in 1 liter of degassing distilled water, contain 32.93gK
3(Fe[CN]
6) solution (0.1M) in the further degassing 0.5 hour of the logical nitrogen of room temperature, join under the high degree of agitation in the LDH slip.With jade-green sedimentation and filtration, with 2 liters of degassing hot washes, and dry in moisture eliminator.
K. the preparation (controlled trial) of rehydrated calcining Mg-Al-LDH
Kyowa-2100 calcining LDH further calcined 14 hours under nitrogen gas stream at 450 ℃.41.9g adding through nitrogen gas stream, this material purifies in the 500ml distilled water of the degassing.The gained slip is heated to 80 ℃, stirs 48 hours under nitrogen atmosphere.In 80 ℃ rotatory evaporator, dewater, then dry under 80 ℃, obtain final product.The X-ray powder diagram has shown the material of height crystallization, and δ (003) lattice is 7.7 .
L. prepare glycol ether with above-mentioned catalyzer h-k
Add catalyzer (8g) (all being screened under each situation＜150 μ m) in the propyl carbinol (978.6g) in 2 liters of stirring-type batch autoclave.After nitrogen purge, add about 116g oxyethane (propyl carbinol/oxyethane=5.0 mol ratios) then, sealing autoclave rises to 120 ℃.By applying the nitrogen top pressure pressure is risen to 3000KPa (30barg) then, keep reaction conditions to run out of until oxyethane.Product liquid gas chromatographic analysis, analytical results are listed in down tabulation 2.Table 2.
| Catalyzer | Selectivity (%w/w) to glycol ether | By product (%w/w) | |
| ????BMGE | Other ether | ||
| ????h | ????91.6 | ????7.8 | ????0.6 |
| ????h(a) | ????91.7 | ????7.8 | ????0.5 |
| ????i | ????83.6 | ????15.6 | ????0.6 |
| ????j | ????88.4 | ????11.6 | ????0 |
| ????k(b) | ????80.4 | ????19.3 | ????0.3 |
| ????m(b) | ????76.1 | ????23.8 | ????0.1 |
(a) the 7.1g catalyzer that reclaims from aforesaid operations is reused.
(b) oppose than test (not according to the present invention) with the 0.11g Potassium ethanoate.
Embodiment (h) to (j) shows, can obtain than the higher BMGE selectivity of commercial Potassium ethanoate catalyzer (routine m) with column LDH clay catalyst.Comparative Examples (k) has been used non-column Mg-Al LDH clay, shows if without column form object, and then the BMGE selectivity reduces.Under reaction conditions, non-cylindrical catalyst has also been lost material integrity and degree of crystallinity (by X-ray diffraction).Use columnar material, post catalyst reaction is easy to reclaim, and can recycle, and not lose MBGE selectivity (routine h (a)).
Claims (15)
1. the method for preparing glycol ether, this method comprises, in the presence of the catalyzer that comprises the LDH clay, with olefin oxide and alcohol reaction, the multilayered structure of this catalyzer is complete and contains interlayer anion, wherein to small part be anionic metal or (gathering) oxometallic acid salt anionic.
2. according to the process of claim 1 wherein that the olefin oxide as reagent is oxyethane, propylene and/or butylene.
3. according to the method for claim 1 or 2, the alcohol that wherein is used to react is aliphatics, and alicyclic or aromatic alcohols, this alcohol can be unit alcohol, double base alcohol or polyvalent alcohol.
4. according to the method for claim 3, wherein said alcohol is unit C1-C6 alcohol.
5. according to the method for claim 3 or 4, wherein said alcohol is selected from methyl alcohol, ethanol, Virahol and isopropylcarbinol.
6. according to each method in the aforementioned claim, wherein alcohol uses with the mole excess, and to obtain final product, this product is a monoethylene glycol ether.
7. according to the method for claim 6, wherein alcohol is 2: 1 with the mol ratio of olefin oxide at least.
8. according to each method in the aforementioned claim, wherein the interlayer anion that exists in the LDH clay is the inorganic metal negatively charged ion, oxometallic acid salt anionic or poly-oxometallic acid salt anionic and comprise especially one or more following negatively charged ion: chromium, vanadium, molybdenum and phosphorus and their (gathering) oxygenation anion.
9. method according to Claim 8 wherein (is gathered) polyoxy that oxygenation anion and (gathering) oxometallic acid salt anionic comprise oxygenation anion and oxometallic acid salt anionic the two and they and is closed derivative.
10. according to the method for claim 9, wherein catalyzer comprises the copper-chromium hydrotalcite anionic clay of usefulness (gathering) oxometallate anionresin.
11. according to the method for claim 9, wherein catalyzer comprises the magnesium-aluminum hydrotalcite anionic clay of usefulness (gathering) oxometallate anionresin.
12. according to each method in the aforementioned claim, wherein the alkene that takes place in the presence of the LDH clay catalyst is to carry out in liquid phase with the reaction of alcohol.
13. according to each method in the aforementioned claim, wherein the reaction at the alkene that takes place in the presence of the LDH clay catalyst and alcohol is to carry out to about 250 ℃ of scopes in envrionment temperature.
14. according to each method in the aforementioned claim, wherein alkene carries out to about 50bar (5000KPa) pressure range at barometric point with the reaction of alcohol.
15., when this method is used for fourth-1-alcohol with one or more ethylene oxide unit(s)s reaction, produce one or more butyl-monoethylene glycol ether (BMGE), two-glycol ether (BDGE), three-glycol ether according to each method in the aforementioned claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9512727.0 | 1995-06-22 | ||
| GBGB9512727.0A GB9512727D0 (en) | 1995-06-22 | 1995-06-22 | Synthesis of glycol ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1192727A true CN1192727A (en) | 1998-09-09 |
Family
ID=10776504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96196232A Pending CN1192727A (en) | 1995-06-22 | 1996-06-17 | Syntheis of glycol ethers |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0846093A1 (en) |
| JP (1) | JPH11507940A (en) |
| KR (1) | KR19990028313A (en) |
| CN (1) | CN1192727A (en) |
| AU (1) | AU6131296A (en) |
| CA (1) | CA2225399A1 (en) |
| GB (1) | GB9512727D0 (en) |
| WO (1) | WO1997000842A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005002724A1 (en) * | 2003-07-01 | 2005-01-13 | Beijing University Of Chemical Technology | The nitrate radical-type hidrotalcite with photochronism and the process for preparing it |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004012336A1 (en) * | 2004-03-11 | 2005-09-22 | Basf Ag | Process for the preparation of monoalkylene glycol monoethers |
| DE102008002091A1 (en) | 2007-05-31 | 2008-12-11 | Basf Se | Monoalkylene glycol monoether production involves reacting alcohol with alkylene oxide in presence of heterogeneous catalyst in liquid phase |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3843713A1 (en) * | 1988-04-25 | 1989-11-02 | Henkel Kgaa | USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION |
| GB9027632D0 (en) * | 1990-12-20 | 1991-02-13 | British Petroleum Co Plc | Process for the preparation of glycol ethers |
| AU660318B2 (en) * | 1991-08-23 | 1995-06-22 | Union Carbide Chemicals & Plastics Technology Corporation | Highly selective monoalkylene glycol catalysts |
-
1995
- 1995-06-22 GB GBGB9512727.0A patent/GB9512727D0/en active Pending
-
1996
- 1996-06-17 JP JP9503659A patent/JPH11507940A/en active Pending
- 1996-06-17 CN CN96196232A patent/CN1192727A/en active Pending
- 1996-06-17 EP EP96918757A patent/EP0846093A1/en not_active Ceased
- 1996-06-17 CA CA002225399A patent/CA2225399A1/en not_active Abandoned
- 1996-06-17 WO PCT/GB1996/001462 patent/WO1997000842A1/en not_active Application Discontinuation
- 1996-06-17 KR KR1019970709628A patent/KR19990028313A/en not_active Application Discontinuation
- 1996-06-17 AU AU61312/96A patent/AU6131296A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005002724A1 (en) * | 2003-07-01 | 2005-01-13 | Beijing University Of Chemical Technology | The nitrate radical-type hidrotalcite with photochronism and the process for preparing it |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0846093A1 (en) | 1998-06-10 |
| KR19990028313A (en) | 1999-04-15 |
| AU6131296A (en) | 1997-01-22 |
| CA2225399A1 (en) | 1997-01-09 |
| GB9512727D0 (en) | 1995-08-23 |
| JPH11507940A (en) | 1999-07-13 |
| WO1997000842A1 (en) | 1997-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0536879B1 (en) | Simplified preparation of hydrotalcite-type clays | |
| EP0318099A2 (en) | Monoalkylene glycol production using mixed metal framework compositions | |
| JPH09503750A (en) | Process for the preparation of alkoxylated products in the presence of mixed hydroxides modified with additives | |
| EP1204589B1 (en) | PROCESS FOR PRODUCING Mg-CONTAINING NON-Al ANIONIC CLAY | |
| CN101189065B (en) | Method of making mixed metal oxide containing sulfur | |
| US6800578B2 (en) | Process for producing anionic clay using boehmite which has been peptized with an acid | |
| US6652828B2 (en) | Process for producing Mg-containing non-Al anionic clay | |
| CN1192727A (en) | Syntheis of glycol ethers | |
| AU9096691A (en) | Process for the preparation of glycol ethers | |
| US6124506A (en) | Synthesis of glycol ethers | |
| JPH05200299A (en) | Monoalkylene glycol catalyst having high selectivity | |
| NZ235442A (en) | Preparation of catalytically active material: calcining an anionic double hydroxide clay, rehydrating with dissolved ion-free water and then recalcining | |
| Zulkifli et al. | A short review on the influence of the preparation method on the physicochemical properties of Mg/Al hydrotalcite for glucose isomerization | |
| CN101193700B (en) | Process for alcohol production by selective ether decomposition | |
| WO2008147596A1 (en) | Isopropyl alcohol from propylene using zirconium based mixed metal oxides | |
| CA2026116A1 (en) | Process for the preparation of glycol ethers | |
| CN1187303C (en) | Solid alkali catalyst for synthesizing propanediol ether | |
| CN1199925C (en) | Method for preparing propanediol ether | |
| US5364980A (en) | Process for the production of unsymmetrical tert-dialkyl ethers | |
| JP2001129397A (en) | Carbonate esterification catalyst and method for preparing cyclic carbonate | |
| CN1199926C (en) | Solid alkali catalyst for preparing propanediol ether | |
| Li et al. | Hydrolysis of Dimethyl Ether over Heteropoly Acids Catalyst | |
| JP2003055306A (en) | Method for dialkyl carbonate production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |