TWI660936B - 從糖製備乙二醇的方法 - Google Patents
從糖製備乙二醇的方法 Download PDFInfo
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- TWI660936B TWI660936B TW104121106A TW104121106A TWI660936B TW I660936 B TWI660936 B TW I660936B TW 104121106 A TW104121106 A TW 104121106A TW 104121106 A TW104121106 A TW 104121106A TW I660936 B TWI660936 B TW I660936B
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- ethylene glycol
- glycol
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- product composition
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 48
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- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- 238000000197 pyrolysis Methods 0.000 claims description 44
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 3
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 2
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
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- 238000000926 separation method Methods 0.000 description 6
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- 150000002431 hydrogen Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 230000037361 pathway Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229940120731 pyruvaldehyde Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OSNSWKAZFASRNG-WNFIKIDCSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol;hydrate Chemical compound O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O OSNSWKAZFASRNG-WNFIKIDCSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- ATFVTAOSZBVGHC-UHFFFAOYSA-N Glycolaldehyde dimer Chemical compound OC1COC(O)CO1 ATFVTAOSZBVGHC-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 229930182830 galactose Natural products 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
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- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/205—1,3-Propanediol; 1,2-Propanediol
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- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
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- C07C47/127—Glyoxal
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- C07C49/185—Saturated compounds containing keto groups bound to acyclic carbon atoms containing —CHO groups
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- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本發明提供一種用於製備乙二醇之方法,其包含以下步驟:在催化劑及溶劑存在下使單醣熱解且使產物組成物氫化,其中氫化反應之壓力為40巴或大於40巴。
Description
本發明關於一種用於製備乙二醇之方法。
乙二醇可藉由多種途徑,包括從單醣,例如糖,經由醱酵及氫解方法或藉由氫甲醯化來製備。
醱酵途徑為五步驟方法,其中葡萄糖醱酵成乙醇及二氧化碳,繼而乙醇轉化成乙烯,乙烯轉化成環氧乙烷且環氧乙烷轉化成乙二醇。此方法之一個缺點為每莫耳醱酵的葡萄糖,兩莫耳二氧化碳與兩莫耳乙醇一起產生;此具有葡萄糖中所存在之理論最多67%之碳可轉化成乙醇的作用。
氫解途徑為兩步驟方法,其中葡萄糖還原成山梨糖醇,繼而山梨糖醇氫解成乙二醇,如US 6,297,409 B1及US 2008/0228014 A1所說明。相比於乙二醇,顯著量之丙二醇經由氫解方法形成。另外,所使用之催化劑之量為顯著的且似乎難以在使用後再活化。此外,所形成之副產物,尤其丁二醇,難以與所需產物分離。特定言之,出於分離(純化)目的之工業上有利的蒸餾方法極其難以應用,因為副產物具有與最終產物極其類似的沸點,且所需產物可能進一步反應,如US2014/0039224 A1及US 5,393,542
B1中所說明。
氫甲醯化途徑為兩步驟途徑,其中乙二醇醛係由甲醛、一氧化碳及氫製備,繼而使乙二醇醛氫化成乙二醇,如US 4,496,781 B1中所說明。似乎存在若干提取步驟以將甲醛與乙二醇醛分離且繼續進行氫化反應。
因此需要提供從糖製備乙二醇之替代、改良、高產且工業上可行的方法。額外優勢將為使用大於67%之最終產物或有商業價值的副產物中所存在的糖碳原子。
可設想,乙二醇可經由包含兩個步驟之方法製備;諸如從糖製備乙二醇醛及其後續氫化成二醇。所提出之方法之兩個步驟似乎為獨立成功的,如以下段落中所說明。
已知糖可熱解以獲得熱解產物組成物,其包含含氧化合物,諸如乙二醇醛,US 7,094,932 B2;熱解產物組成物包含C1-C3含氧化合物,包括甲醛、乙二醇醛、乙二醛、丙酮醛及丙酮醇。此反應之主要產物為乙二醇醛(US 7,094,932 B2)。水為反應溶劑。
亦已知純乙二醇醛可氫化成乙二醇。US 4,200,765 B1揭示在惡劣條件下乙二醇醛之氫化:在高壓[3000psi(約345巴)]、高溫[150℃]下,用有機溶劑[N-甲基吡咯啶]及鈀/碳[Pd/C]催化劑,持續延長的時間段[5h]。US 4,321,414 B1及US 4,317,946 B1揭示使用均相釕催化劑之乙二醇醛之氫化,且US 4,496,781 B1揭示在低壓[500psi(約35巴)]下,在高溫[160℃]下,用釕/碳催化劑[Ru/C],在作為溶劑之乙二醇及痕量乙腈中的連續流氫化。
如所說明,葡萄糖熱解獲得尤其乙二醇醛及純乙二醇醛之氫
化之兩個步驟似乎為獨立可能的。然而,為了使熱解產物組成物氫化,必須採用費力的分離方法以自熱解產物組成物中移除甲醛,因為甲醛為氫化催化劑之已知毒物,US 5,210,337 B1。US 5,393,542 B1揭示一種例示性純化方法,其包含多個蒸餾步驟,繼而溶劑誘導沈澱以獲得乙二醇醛。因此,不可能直接使熱解步驟之產物(熱解產物組成物)氫化,因為甲醛以顯著量存在於組成物中。
除移除甲醛之需求(其將增加所需的方法步驟之數目)外,使用例如水之無毒溶劑在工業上將亦為極大的優勢。因此,能夠在甲醛存在下使用無毒溶劑且在前述(熱解)反應之溶劑中進行氫化步驟將為顯著優勢。
關於乙二醇醛之氫化,儘管提供適合的反應條件以在有機溶劑中獲得高產率,但水作為溶劑之反應似乎不太成功。US 5,393,542 B1揭示當經受90℃或高於90℃之溫度時且在水為溶劑之情況下,乙二醇醛(2-羥乙醛)熱降解。
EP 0 002 908 B1揭示在110℃下在水溶液中使用各種催化劑之乙二醇醛反應物之氫化的產率(轉化率及選擇率)變化:阮尼鎳(Raney Nickel)[100%轉化率 49.4%選擇率],10% Pd/C[62%轉化率,61%選擇率]及10% Pt/C[100%轉化率,73%選擇率]。液態水中所使用之催化劑之額外缺點為催化劑上之應變。特定言之,在高溫(>160℃)下許多載體為不穩定的且將溶解、降解或表面積降低;Energy & Fuels 2006,20,2337-2343。因此,需要特定催化劑,且長期催化劑效能常常為成問題的,因此,必須頻繁更換催化劑(約3至6個月)。因此,溫和的反應條件是有利的以確保催化劑
在工業規模上及工業條件中之長壽命。
另外,當在催化劑存在下時,催化劑之選擇可能影響乙二醇醛之分解;US 5,210,337 B1揭示乙二醇醛『解鏈』形成甲醛且因此毒化氫化催化劑之問題。亦有可能的是,乙二醇醛可自縮合或與另一C1-C3含氧化合物縮合,亦說明於5,210,337 B1中。另外,催化劑之選擇及二醇產物之穩定性可能影響乙二醇醛之還原程度。有可能的是,催化劑可使乙二醇醛還原成乙醇或乙烷,亦即,過度還原乙二醇醛。
另外,已知溫度升高、基質濃度及所存在之催化劑之量及特性影響乙二醇醛之氫化反應之產率(轉化率及選擇率)。有機合成之非均相催化氫化手冊(Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis),Shigeo Nishimura,ISBN:978-0-471-39698-7,2001年4月。
如所表明,經由糖熱解及後續氫化從糖製備乙二醇之工業規模方法從兩個方面受阻。第一方面為需要自熱解產物組成物中移除甲醛以實現成功的氫化。第二方面為提供高產之溫和反應條件。此外,為提供工業上及商業上可行的方法,需要提供一種高產兩步驟方法,其利用無毒溶劑且產生極少量使用工業上可行的技術可與乙二醇產物分離的副產物。分離副產物與乙二醇產物之能力使得乙二醇能夠用於諸如聚合物生產之方法中。聚合物生產需要基質呈高純度形式。
現已發現,可從糖熱解獲得之熱解產物組成物可以較高產率、在溫和條件中、在極少副產物之情況下且直接由包含甲醛之熱解產物組成物氫化。
已發現,有可能在氫化反應之前使可從糖熱解獲得之熱解產物組成物經受氫化條件,且在溫和反應條件中且在具有極少副產物且不移除甲醛(亦即C1含氧化合物)之情況下獲得較高產率(較高轉化率及較高選擇率)。此外,已發現,乙二醇在較高壓力及溫度下為較穩定的且產生較少量副產物1,2-丁二醇。
本發明提供一種用於製備包含乙二醇之組成物之方法,其包含以下步驟:
a.使糖熱解以獲得熱解產物組成物;及
b.在催化劑、氫及溶劑存在下使步驟a.之熱解產物組成物氫化以獲得(經氫化的)產物組成物。
c.視情況分離(純化)乙二醇與步驟b.中所獲得之(經氫化的)產物組成物。
本發明之一態樣為步驟a.中C1含氧物之存在。步驟a.可理解為:使糖熱解以獲得包含C1含氧物之熱解產物組成物。或者,步驟a.可理解為:使糖熱解以獲得包含甲醛之熱解產物組成物。
本發明之產物可為包含乙二醇之步驟b.之(經氫化的)產物組成物。(經氫化的)產物組成物意謂包含乙二醇之步驟b.之產物。步驟b.之(經氫化的)產物組成物可進一步包含未反應之基質。或者,本發明之產物可為已經純化之步驟b.之產物,亦即,步驟c.之產物。
糖意謂一或多種選自由以下組成之群的糖:單醣及雙醣;較佳地,糖意謂一或多種選自由以下組成之群的糖:葡萄糖、蔗糖、果糖、
木糖、甘露糖、阿拉伯糖及半乳糖。較佳地,糖為單醣且為葡萄糖。糖可呈溶液形式,其中糖溶液包含糖及溶劑。
糖溶液之溶劑為選自由以下組成之群的溶劑:水或水與醇。醇意謂一或多種選自由甲醇及乙醇組成之群的醇。舉例而言,糖溶液可以水性糖溶液形式存在,較佳為水性葡萄糖溶液。
步驟b.之溶劑為選自由以下組成之群的溶劑:水;醇或水與醇。醇意謂一或多種選自由以下組成之群的醇:甲醇、乙醇、乙二醇及丙二醇。
步驟b.之溶劑可為水與醇之混合物。在該溶劑為水與醇之情況下,水與醇之比率等於或大於95:5、90:10、80:20、70:30、60:40、50:50、40:60及30:70。
步驟a.之熱解產物組成物亦可稱為粗熱解產物組成物。熱解產物組成物包含含氧化合物,諸如乙二醇醛,且可根據US 7,094,932 B2製備。熱解產物組成物包含C1-C3含氧化合物。C1-C3含氧化合物意謂包含具有一個、兩個或三個碳原子之碳鏈長度之含氧化合物。舉例而言,C1含氧化合物包含具有一個碳原子之碳鏈長度,諸如甲醛及甲酸;C2含氧化合物包含具有兩個碳原子之碳鏈長度,諸如乙二醇醛、乙二醛及乙酸;C3含氧化合物包含具有三個碳原子之碳鏈長度,諸如丙酮醛及丙酮醇。C1-C3含氧化合物組成物意謂包含一或多種選自由以下組成之群的化合物的組成物:甲醛、乙二醇醛、乙二醛、丙酮醛及丙酮醇。較佳地,熱解產物組成物包含C2含氧化合物。典型地,包含C1-C3含氧化合物之組成物之C2含氧化合物組分為例如10wt%或大於10wt%,30wt%或大於30wt%。在步驟a.之熱解產
物組成物包含甲醛及乙二醇醛之情況下,步驟a.之熱解產物組成物中所存在之甲醛與乙二醇醛之wt/wt比率為1:7至1:14:1:8至1:12;1:9至1:10。
步驟b.之氫化在包含催化劑金屬組分(諸如釕、釕合金、鈀、鉑或鎳)之催化劑存在下進行。催化劑金屬組分藉由諸如碳之載體支撐。已知催化劑包括釕/碳載體。舉例而言,步驟b.之氫化可在諸如釕/碳載體催化劑之催化劑存在下進行。舉例而言,步驟b.之氫化可在諸如5%或10%釕/碳載體催化劑之催化劑存在下進行。包含0.5%至2%釕之釕合金催化劑之實例揭示於WO 2014/066052 A1中。
步驟b.之催化劑可以1:1至15:1,1:1至11:1,1:1至10:1,1:1至7:1,1:1至5:1,3.0:1至15:1,3.1:1至15:1,3.2:1至15:1之甲醛:催化劑金屬組分之wt/wt比率存在於反應溶液中。
步驟b.之氫化可在約30巴至90巴,30巴至120巴,40巴至120巴,40巴至140巴,約90巴至150巴,較佳50巴至150巴之壓力下進行。壓力意謂氫分壓。
步驟b.之氫化可在40℃至160℃,50℃至140℃,60℃至130℃,較佳80℃至120℃之溫度下進行。
來自步驟a.之熱解產物之C2含氧化合物之乙二醇的產率(轉化率及選擇率)大於40%,大於50%,大於70%。
步驟a.之熱解產物組成物之C2含氧化合物至乙二醇(步驟b.)之轉化率為70%或大於70%,80%或大於80%。
轉化意謂熱解產物組成物之C2含氧化合物轉化成其他一或多種化合物。
步驟a.之熱解產物組成物之C2含氧物至乙二醇之選擇率為75%或大於75%,85%或大於85%,較佳95%或大於95%。
選擇性意謂熱解產物組成物之C2含氧化合物轉化成乙二醇而非諸如乙醇或乙烷之其他化合物。
步驟b.之產物包含等於或小於0.01:1、0.005:1、0.004:1、0.003:1之1,2-丁二醇(1,2-BDO):乙二醇wt/wt比率。
本發明之方法為兩個步驟。『兩步驟』方法意謂經由兩個化學轉化使糖轉化成乙二醇:糖之熱解及可由葡萄糖之熱解獲得之乙二醇醛之氫化。本發明之另一具體實例為兩步驟方法,其中步驟a.之熱解產物組成物直接於步驟b.中經氫化。舉例而言,包含C1-C3含氧化合物之步驟a.之熱解產物組成物用作氫化步驟(步驟b.)之起始組成物。舉例而言,步驟a.之產物經氫化。
純化意謂分離步驟b.之(經氫化的)產物組成物之特定化學產物,例如分離乙二醇、丙二醇及其他組分。例示性分離方法揭示於US 8,177,980 B2及US 2014/0039224 A1中。此類分離(純化)方法可為層析及蒸餾。
根據本發明製備之乙二醇可用作化學製品。舉例而言,乙二醇可在製備包括聚對苯二甲酸乙二酯(PET)之聚合物、聚酯樹脂、纖維及膜時用作單體。乙二醇亦可用作除冰劑、冷卻劑(尤其在冷藏器具中)、防凍劑或溶劑。如http://www.dow.com/ethyleneglycol/prod/meg.htm上所描述。
實施例:
實施例1:
藉由10wt%水性葡萄糖(D-葡萄糖單水合物;Sigma Aldrich)溶液之熱解獲得包含C1-C3含氧化合物之熱解產物組成物,如US 7,094,932 B2中所描述。在表1中給出熱解產物組成物之組成。
實施例2至實施例4:
將實施例1及表1中所描述之熱解產物組成物(15.5g)與5% Ru/碳催化劑(Sigma Aldrich,0.20g)一起裝載至高壓釜中。高壓釜用氫淨化3次,且隨後用氫加壓至表2中給出之各別壓力。歷經15分鐘之時程將混合物自室溫加熱至80℃,且攪拌6小時。隨後使高壓釜冷卻至室溫,且注意氫壓之下降。
藉由過濾將氫化產物混合物與催化劑分離,且藉由HPLC及GC進行分析。
乙二醇之最大理論產率係基於乙二醛及乙二醇醛兩者至乙二醇之氫化。
實施例2至實施例4說明隨著反應壓力升高,乙二醇之產率明顯提高。另外,實施例4表明相比於經由如US 20080228014 A1所說明之氫解途徑之乙二醇製備[1,2-BDO:乙二醇比率為0.08],藉由本發明之方法產生之1,2-BDO之產率較低。
實施例5至實施例8:
在30巴或90之壓力、120℃或140℃之溫度及3小時之反應持續時間之情況下,使用乙二醇或丙二醇作為基質[實施例1之熱解產物組成物]重複如實施例2至實施例4中所描述之方法。結果提供於表3中。
表3展示在氫化反應條件下隨著壓力升高,乙二醇及丙二醇之穩定性提高。
實施例9:
使乙二醇醛二聚體(1.0g)溶解於去礦物質水(14.5g)中。將溶液與5% Ru/碳催化劑(Sigma Aldrich,0.20g)一起裝載至高壓釜中。高壓釜用氫淨化3次,且隨後用氫加壓至表2中給出之各別壓力。在15分鐘期間將混合物自室溫加熱至80℃,且攪拌3小時。隨後使高壓釜冷卻至室溫,且注意氫壓之下降。
藉由過濾將產物混合物與催化劑分離,且藉由HPLC及GC進行分析。
實施例10:
在90巴之壓力下重複實施例9之方法。
實施例11:
在100℃之溫度下重複實施例9之方法。
實施例9至實施例11之結果提供於表4中。提供與乙二醇相關之所存在之1,2-丁二醇(1,2-BDO)之量。可見,反應之壓力升高導致所形成的1,2-丁二醇(1,2-BDO)減少,使得更溫和條件中之乙二醇產物之純度提高。
Claims (17)
- 一種用於製備乙二醇之方法,其包含以下步驟:a.使糖熱解以獲得包含甲醛的熱解產物組成物;及b.在催化劑及溶劑存在下使步驟a.之該熱解產物組成物氫化,其中步驟b.之反應之壓力為40巴或大於40巴。
- 如申請專利範圍第1項之方法,其中該方法為兩步驟方法,且步驟a.之該熱解產物組成物直接於步驟b.中經氫化。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之該產物經純化。
- 如申請專利範圍第1項或第2項之方法,其中步驟a.之該糖包含一或多種選自由以下組成之群的糖:葡萄糖、蔗糖、果糖、木糖、甘露糖、阿拉伯糖及半乳糖。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之該溶劑係選自由以下組成之群:水、醇與水及醇。
- 如申請專利範圍第5項之方法,其中該醇係選自由以下組成之群中之一或多者:甲醇、乙醇、乙二醇及丙二醇。
- 如申請專利範圍第1項或第2項之方法,其中該熱解產物組成物包含一或多種選自由以下組成之群的C2-3含氧化合物:乙二醇醛、乙二醛、丙酮醛及丙酮醇。
- 如申請專利範圍第1項或第2項之方法,其中該熱解產物組成物包含一或多種選自由以下組成之群的C2含氧化合物:乙二醇醛、乙二醛及乙酸。
- 如申請專利範圍第8項之方法,其中該包含C1-C3含氧化合物之組成物之C2含氧化合物組分為10wt%或大於10wt%。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之該催化劑包含選自由以下組成之群的金屬組分:釕、釕合金、鈀、鉑及鎳。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之該催化劑包含金屬組分且該催化劑金屬組分係以1:1至1:15之甲醛:催化劑金屬組分之wt/wt比率存在。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.在40巴至120巴之壓力下進行。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.在40℃至160℃之溫度下進行。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之C2含氧化合物至乙二醇之轉化率為至少70%。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之C2含氧化合物至乙二醇之選擇率為至少75%。
- 如申請專利範圍第1項或第2項之方法,其中步驟a.之該熱解產物組成物以1:7至1:14之甲醛:乙二醇醛之wt/wt比率包含甲醛。
- 如申請專利範圍第1項或第2項之方法,其中步驟b.之該產物包含等於或小於0.01:1之wt/wt比率之1,2-丁二醇:乙二醇。
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TW201634433A (zh) | 2016-10-01 |
US10077222B2 (en) | 2018-09-18 |
BR112016030694A2 (pt) | 2018-07-17 |
AU2015282666A1 (en) | 2017-01-12 |
ZA201608381B (en) | 2020-05-27 |
EP3160928A1 (en) | 2017-05-03 |
JP2017519792A (ja) | 2017-07-20 |
KR20170027778A (ko) | 2017-03-10 |
JP6861032B2 (ja) | 2021-04-21 |
PL3160928T3 (pl) | 2024-03-04 |
AU2015282666B2 (en) | 2019-04-18 |
CN106795079A (zh) | 2017-05-31 |
ES2962507T3 (es) | 2024-03-19 |
KR102044453B1 (ko) | 2019-11-13 |
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US20170137354A1 (en) | 2017-05-18 |
MX2016017154A (es) | 2017-05-03 |
CA2952535C (en) | 2019-03-19 |
BR112016030694B1 (pt) | 2020-12-15 |
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WO2016001169A1 (en) | 2016-01-07 |
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