TWI405748B - 製備烷二醇之方法 - Google Patents
製備烷二醇之方法 Download PDFInfo
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- TWI405748B TWI405748B TW096133629A TW96133629A TWI405748B TW I405748 B TWI405748 B TW I405748B TW 096133629 A TW096133629 A TW 096133629A TW 96133629 A TW96133629 A TW 96133629A TW I405748 B TWI405748 B TW I405748B
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- Prior art keywords
- catalyst
- alkylene
- solid support
- water
- diester
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 36
- -1 alkylene glycol Chemical compound 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 27
- 239000003456 ion exchange resin Substances 0.000 claims description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 125000005587 carbonate group Chemical group 0.000 claims description 5
- 125000005496 phosphonium group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 14
- 150000005690 diesters Chemical class 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000001030 gas--liquid chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- HFSKWPUHEMGYMQ-UHFFFAOYSA-N 1,3-dioxolan-2-one Chemical compound O=C1OCCO1.O=C1OCCO1 HFSKWPUHEMGYMQ-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- 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
- C07D317/32—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本發明係關於藉由相應碳酸伸烷二酯催化水解而製備烷二醇之方法。
烷二醇(尤其單烷二醇)具有確定的商業利潤。舉例而言，單烷二醇在防凍組合物中用作溶劑並在聚對苯二甲酸伸烷基酯(例如，用於纖維或瓶子者)之生產中用作基本材料。
藉由環氧烷液相水解生產烷二醇已為人們熟知。水解通常藉由添加大量過量水來進行，例如，20至25莫耳水/莫耳環氧烷。該反應可視為親核取代反應，由此打開環氧烷環，水充當親核劑。由於最初形成之單烷二醇亦可充當親核劑，所以通常形成單烷二醇、二烷二醇及更高烷二醇之混合物。為增加對單烷二醇之選擇性，需要抑制初始產物與環氧烷間之副反應，該反應與環氧烷水解相競爭。
一種抑制副反應之有效方法係增加存在於反應混合物中之水的相對量。儘管此措施可提高對單烷二醇生產之選擇性，但却造成需清除大量水來回收產物之問題。
人們已做出大量努力來尋找用於增加反應選擇性而不需使用大量過量水之替代方法。環氧烷朝向烷二醇之水解反應可在一催化系統中使用少量過量水來進行。因此，此等努力通常著重於更具活性之水解觸媒的選擇，且文獻中已揭示多種觸媒。
此外，自環氧烷生產烷二醇之方法(包括兩步驟式方法)已在此項技術中有所描述。此等方法包括在觸媒存在下環氧烷與二氧化碳之反應，隨後所得碳酸伸烷二酯接著發生熱水解或催化水解。此等兩步驟式方法之實例包括描述於日本專利第JP－A－57106631號、日本專利第JP－A－59013741號及美國專利第US－B－6080897號中者。
適於碳酸伸烷二酯水解之觸媒描述於美國專利第US－A－4283580號，該專利係關於呈金屬或化合物形式之鉬或鎢在藉由經取代或未經取代碳酸伸乙二酯與水反應生產經取代或未經取代之乙二醇中作為觸媒的用途。
儘管碳酸伸烷二酯水解已取得進步，業內仍需能使期望產物容易純化之觸媒系統。
我們現在驚奇地發現碳酸伸烷二酯至相應烷二醇之水解(用水催化轉化碳酸伸烷二酯)可藉由固定於固體載體上之碳酸氫根來有效催化。因此本發明提供一種用於製備烷二醇之方法，該方法包括在觸媒存在下使相應碳酸伸烷二酯與水反應，其中該觸媒包括固定於具有一或多個正電性位點之固體載體上之碳酸氫根作為活性相。
此非均相系統使期望產物容易地自催化組合物中分離出。此分離不需在催化組合物之存在下在純化烷二醇通常所需之高溫下蒸餾該產物即可實現。進一步之優點係在相同反應器體積下觸媒之濃度更高。使用碳酸氫根作為活性相之優點係可自催化劑浸出之產物僅係二氧化碳及水且有反應副產物或試劑。因此產物流中無陌生的分子。
在本發明方法中用作起始材料之碳酸伸烷二酯具有其習知定義，即，在其分子中具有碳酸根基之化合物。
尤其適合者係具有通式(I)五員碳酸伸烷二酯環(1,3－二氧戊環－2－酮)之碳酸伸烷二酯，
其中R1
至R4
各獨立代表氫原子或具有1至6個碳原子之視情況經取代之烷基。R1
、R2
、R3
及/或R4
所代表之任一烷基較佳具有1至3個碳原子。對於取代基，可存在非活性部分(如羥基)。較佳地，R1
、R2
及R3
代表氫原子且R4
代表未經取代之C1
－C3
－烷基，且更佳地，R1
、R2
、R3
及R4
皆代表氫原子。
因此，適合之碳酸伸烷二酯之實例包括碳酸伸乙二酯、碳酸伸丙二酯、碳酸1,2－伸丁二酯及碳酸2,3－伸丁二酯。本發明中，通式(II)之最佳碳酸伸烷二酯係碳酸伸乙二酯，其中R1
、R2
、R3
及R4
皆代表氫原子。
碳酸伸烷二酯之製備已為熟習此項技術者所熟知。其可藉由包括在觸媒存在下使相應環氧烷接觸二氧化碳之方法來製備。
尤其適合者係具有如下通式(II)之環氧烷，
其中R1
至R4
對應於相應碳酸伸烷二酯之R1
至R4
。因此，適合之環氧烷包括環氧乙烷、環氧丙烷、1,2－環氧丁烷及2,3－環氧丁烷。本發明中，通式(II)之最佳環氧烷係環氧乙烷，其中R1
、R2
、R3
及R4
皆代表氫原子。
環氧烷之製備已為熟習此項技術者所熟知。在環氧乙烷之情況下，其可藉由熟知之乙烯直接氧化而製備，即利用基於銀之觸媒且通常亦使用有機減速劑(例如有機鹵化物)藉由空氣或氧氣氧化而製備(參見例如Kirk Othmer's Encyclopedia of Chemical Technology，第4版，第9卷，第923－940頁)。
本發明之觸媒包括固定於具有一或多個正電性位點之固體載體上之碳酸氫根作為活性相。就觸媒之活性而言，不需以作為活性相之碳酸氫根開始。亦可以羥基或以固定於固體載體上之碳酸根基開始。此等基團可視為作為此反應活性相之碳酸氫根的前體。在催化反應起始階段期間，由於在碳酸伸烷二酯轉化時所形成之大量CO2
及水或醇的存在，碳酸根基轉化為碳酸氫根活性相。
本發明之方法中所用之碳酸氫根之量適宜地介於0.0001至0.5莫耳/莫耳碳酸伸烷二酯間。較佳地，該碳酸氫根以介於0.001至0.1莫耳/莫耳碳酸伸烷二酯間之量存在。
固體載體係具有一或多個正電性位點之載體。適合之具有一或多個正電性位點之固體載體包括彼等具有無機性質者，例如碳、二氧化矽、二氧化矽－氧化鋁、沸石、玻璃及黏土(例如水滑石)。此等固體載體可藉由吸附、反應或接枝與陽離子結合。另外，經固定錯合大環(例如冠醚)亦可視為本發明之具有一或多個正電性位點之固體載體，此乃因此等材料能結合陽離子。較佳地，該固體載體包括四級銨、四級鏻、四級砷鎓、四級銻鎓或三級鋶陽離子或錯合大環。更佳地，該陽離子係四級銨或四級鏻離子。
有利地，本發明使用一種含有強鹼性離子交換樹脂之固體載體，其中該陽離子連接至聚合物骨架。該聚合物骨架可包含高分子量聚合物及共聚物，其包括聚伸烷基、聚酯、聚碳酸酯、聚胺基甲酸酯、甲醛樹脂等。適合之市售離子交換樹脂包括彼等含有聚丙烯酸酯或苯乙烯－二乙烯基苯共聚物作為聚合物骨架者。亦可使用具有基於二氧化矽之聚合物骨架(例如聚矽氧烷)之樹脂及在其聚合物骨架中納入乙烯基吡啶單體之樹脂。適於本發明方法之市售離子交換樹脂包括(但不限於)Lewatit 500 KR(Lewatit係商標名)、Amberlite IRA－900、Amberlite IRA－458(Amberlite係商標名)、Amberjet 4200、Amberjet 4400(Amberjet係商標名)、DOWEX 1x16(DOWEX係商標名)、Reillex HPQ(Reillex係商標名)、Marathon－A、Marathon－MSA(Marathon係商標名)及DELOXAN AMP(DELOXAN係商標名)。其他適合之離子交換樹脂包括彼等根據Nishikubo等人於J.Polym.Sci.,Part A：Polym.Chem.,
(1993)31,939－947中所述方法製備者。此等樹脂具有所謂的間隔基團，其含有將聚合物骨架連接至陽離子之化學結構。適合間隔基團包含一視情況插入一或多個氧原子之伸烷基。
碳酸氫根或其前體羥基或碳酸根基之一可藉由熟習此項技術者所熟知之任何技術固定於固體載體上。此等技術包括孔體積浸漬、浸漬、沉澱及離子交換。較佳地，碳酸氫根或其前體之一係通過離子交換固定於固體載體上。離子交換包括使固體載體接觸溶液。在固定碳酸氫根之較佳情況下，該溶液可含有過量碳酸氫鈉或其可係經CO2
飽和之水。當使用經CO2
飽和之水溶液時，重複交換反應直至流出物之pH類似於經CO2
飽和之溶液之pH。此步驟後緊接著為一水洗步驟。較佳地，離子交換在介於0℃至100℃間之溫度下發生，更佳在介於20℃至90℃間。較佳地，離子交換在常壓下發生。
本發明之方法可於任何適用於水解製程之反應系統中實施。
本發明方法中所用之碳酸伸烷二酯可包括經純化碳酸伸烷二酯或其他任何適合之碳酸伸烷二酯。碳酸伸烷二酯亦可係來自碳酸伸烷二酯生產單元之粗產物，在該生產單元中相應環氧烷在觸媒存在下與二氧化碳接觸。此觸媒可能仍存在於該粗產物中。
較佳地，供應至反應器之水的總量係至少0.5莫耳/莫耳碳酸伸烷二酯、較佳至少1莫耳/莫耳碳酸伸烷二酯之量。供應至反應器之水的總量較佳係至多20莫耳/莫耳碳酸伸烷二酯之量，更佳係至多5莫耳/莫耳碳酸伸烷二酯之量，甚至更佳係至多2莫耳/莫耳碳酸伸烷二酯。
本發明之方法可以間歇作業實施。然而，尤其對於大規模實施例而言，較佳連續實施此方法。
此連續方法可於以升流式或降流式運行之固定床反應器中實施。其他反應器選擇包括泡罩塔反應器及流化床反應器。
本發明之反應器可維持在等溫、絕熱或混合條件下。等溫反應器通常係殼式及管式反應器(大多數為多管型)，其中該等管包含觸媒且冷卻劑在管外流動。絕熱反應器不會冷卻，且離開其的產物液流可在一單獨熱交換器中冷卻。
本發明之方法可有利地使一部分反應器輸出循環至同一反應器至少一個入口，此乃因其能將可能在反應器頂部與底部間產生之任何溫差最小化。因此，與習用反應器相比其需要較少的外部溫度控制以維持反應溫度。當絕熱條件較佳時此尤其有利。欲循環之反應器輸出部分可在該反應器輸出離開該反應器後方便地與不欲循環部分分離；或者欲循環之反應器輸出部分可經由該反應器一與自其去除不欲循環之反應器輸出部分之出口不同的出口方便地自反應器中取出。欲循環之反應器輸出混合物之量可根據所採用之其他反應參數而改變以獲得最優性能。
在一些使用含有如上所提及四級或三級基團之觸媒的方法中偶爾可能出現之問題係產物液流中存在少量雜質。舉例而言，當強鹼性陰離子交換樹脂(其中該等鹼性基團包括四級銨或鏻基團)用作催化基團之固體載體時，已發現在作業期間少量胺或膦易於自樹脂浸出至產物液流中。產物液流中之其他雜質可包括源自腐蝕抑制劑(其可添加於本方法所用之水中)之胺。儘管該等污染物到達終產物之量通常極少，但其可影響終產物品質，因此期望將該等量降至盡可能低以不影響產物品質。舉例而言，三甲胺(TMA)及/或二甲胺(DMA)可以多至10 ppm之量到達終產物，而TMA之魚腥味在低至1 ppb之量時即可檢測到。
去除此等污染物之有效措施係使用後反應器床，其含有酸性物質、尤其係強酸性離子交換樹脂，可有效捕獲污染物。強酸性離子交換樹脂可係磺酸型樹脂。市售實例為彼等以商標名AMBERLYST 15、AMBERJET 1500H、AMBERJET 1200H、DOWEX MSC－1、DOWEX 50W、DIANON SK1B、LEWATIT VP OC 1812、LEWATIT S 100 MB及LEWATIT S 100 G1為人們所知者。此等強酸性離子交換樹脂可以H＋
形式及以鹽形式(例如Na＋
形式)使用。當後反應器保護床中僅使用H＋
形式強酸性樹脂時，則產物液流流經其後可變為酸性。使用呈H＋
形式與鹽形式之強酸性離子交換樹脂之混合物具有產物液流之pH仍接近中性之優點。
此後反應器床可定位於在其中實施本反應方法之水解反應床之後。將該強酸性後反應器床定位於其中碳酸伸烷二酯經受水解形成相應烷二醇之反應器床後之附加優點係將任何可能仍存在於產物烷二醇產物液流中之殘餘碳酸伸烷二酯水解為烷二醇。
為使作業期間強酸性離子交換樹脂耗盡及置換或再生，較佳在兩個或以上單獨容器內運行該後反應器床以允許此處理在此兩個容器間轉換，從而維持連續作業。
耗盡的強酸性離子交換樹脂可藉由用酸(例如HCl及H2
SO4
)處理再生。已證明0.1至2 N之熱硫酸係有效的。
為適應作業期間可能仍出現之任何觸媒膨脹，反應器體積可有利地大於其中觸媒所佔體積，較佳大於10－70體積%。
本發明碳酸伸烷二酯催化水解之適宜反應溫度通常介於20至200℃間；溫度介於60至130℃較佳。
反應壓力通常經選擇介於100至500千帕之間、較佳200至3000千帕之間、最佳介於200至1500千帕之間。
下述實例用於闡述本發明。
於填充水之玻璃管中將150毫升呈氯化物形式之四級銨型濕離子交換樹脂(Amberjet 4200,ex Rohm & Haas,交換能力1.3 meq/毫升)製漿。藉由用碳酸氫鈉溶液(溶於2500克水中10倍莫耳過量)處理約5小時來交換該氯化物陰離子(液時空速為4公升/公升小時)。接著，用1200毫升水洗滌交換的樹脂約2小時(液時空速為4公升/公升小時)。在所得觸媒中，來自Amberjet 4200之氯化物陰離子幾乎完全與預期碳酸氫根陰離子交換，最終氯化物含量低於100 ppm。
該實驗在120毫升玻璃高壓釜中實施。向反應器中加入35克碳酸伸乙二酯及21.5克水。以足以提供4.1毫莫耳觸媒之量添加水解觸媒。用CO2
次掃反應器並且用4.5巴(450千帕)之CO2
氣氛加壓。將反應器內容物加熱至110℃，同時將壓力維持在4.5巴。以30分鐘之固定時間間隔取出樣品並藉由氣液色譜法(GLC)分析。結果顯示於表I中。
於固定床栓流反應器中在連續流條件下測試製備的Amberjet 4200/碳酸氫根催化劑(IER能力為1.3 meq/毫升)達2000小時以上。在兩個不同實驗中以0.51及0.75公升/公升小時之兩種液時空速(LHSV)測試觸媒之性能。
藉由將20毫升觸媒放置於一65公分長0.5英吋寬設置有使用熱油系統之加熱夾套的Hoke管中測試觸媒性能。在溫度為90℃左右且壓力為1000千帕下於催化劑床上使用HPLC泵將含有17.5重量% EC之碳酸伸乙二酯(EC)/水混合物降流抽送達至少2000小時。藉由熱油系統之溫度來控制反應溫度。在觸媒床中心放置一熱電偶套管，用熱電偶量測床溫。將反應器流出物冷卻並收集於產物容器中，自其中取出樣品用於GLC分析。結果總結於表II中。
如表II中所示之結果明顯表明經過一長時期後觸媒仍有活性。
Claims (8)
- 一種用於製備烷二醇之方法，該方法包括在觸媒存在下使相應碳酸伸烷二酯與水反應，其中該觸媒包括固定於具有一或多個正電性位點之固體載體上之碳酸氫根作為活性相。
- 如請求項1之方法，其中該固體載體係強鹼性離子交換樹脂，其中陽離子連接至聚合物骨架。
- 如請求項1或請求項2之方法，其中該固體載體包括四級銨、四級鏻、四級砷鎓、四級銻鎓或三級鋶陽離子。
- 如請求項3之方法，其中該固體載體包括四級銨或四級鏻陽離子。
- 如請求項1或2之方法，其中該觸媒最初包括固定於該固體載體上之碳酸根基、碳酸氫根基或羥基。
- 如請求項1或2之方法，其中該方法係在介於40至200℃間之溫度及介於100至5000千帕間之壓力下實施。
- 如請求項1或2之方法，其中該碳酸伸烷二酯係碳酸伸乙二酯。
- 一種用於製備烷二醇之方法，其包含以下步驟：- 藉由在觸媒存在下使相應環氧烷接觸二氧化碳來製備碳酸伸烷二酯。- 然後藉由請求項1至7中任一項之方法使該碳酸伸烷二酯與水及/或醇反應。
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| US20070213545A1 (en) * | 2005-12-22 | 2007-09-13 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
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| US20070203349A1 (en) * | 2005-12-22 | 2007-08-30 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
| US20070197808A1 (en) * | 2005-12-22 | 2007-08-23 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
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2007
- 2007-09-05 US US11/850,544 patent/US7462748B2/en not_active Expired - Fee Related
- 2007-09-07 CA CA002662824A patent/CA2662824A1/en not_active Abandoned
- 2007-09-07 TW TW096133629A patent/TWI405748B/zh not_active IP Right Cessation
- 2007-09-07 CN CN200780039278.8A patent/CN101528649B/zh not_active Expired - Fee Related
- 2007-09-07 JP JP2009527146A patent/JP2010502677A/ja not_active Withdrawn
- 2007-09-07 AR ARP070103962A patent/AR062705A1/es not_active Application Discontinuation
- 2007-09-07 EP EP07820058A patent/EP2069274A1/en not_active Withdrawn
- 2007-09-07 WO PCT/EP2007/059385 patent/WO2008028953A1/en active Application Filing
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| US3629343A (en) * | 1968-10-11 | 1971-12-21 | Vnii Neftekhim Protsessov | Process for the production of alkylene glycols |
| US4691041A (en) * | 1986-01-03 | 1987-09-01 | Texaco Inc. | Process for production of ethylene glycol and dimethyl carbonate |
| WO2002098828A1 (en) * | 2001-05-31 | 2002-12-12 | Dow Global Technologies Inc. | Process for the preparation of alkylene glycols |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200827328A (en) | 2008-07-01 |
| CA2662824A1 (en) | 2008-03-13 |
| US20080064881A1 (en) | 2008-03-13 |
| EP2069274A1 (en) | 2009-06-17 |
| WO2008028953A1 (en) | 2008-03-13 |
| CN101528649B (zh) | 2013-05-29 |
| JP2010502677A (ja) | 2010-01-28 |
| CN101528649A (zh) | 2009-09-09 |
| AR062705A1 (es) | 2008-11-26 |
| US7462748B2 (en) | 2008-12-09 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |