CN1281424A - 制备γ-丁内酯、丁-1,4二醇和四氢呋喃的方法 - Google Patents
制备γ-丁内酯、丁-1,4二醇和四氢呋喃的方法 Download PDFInfo
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- CN1281424A CN1281424A CN98811036A CN98811036A CN1281424A CN 1281424 A CN1281424 A CN 1281424A CN 98811036 A CN98811036 A CN 98811036A CN 98811036 A CN98811036 A CN 98811036A CN 1281424 A CN1281424 A CN 1281424A
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- Prior art keywords
- maleic anhydride
- ester
- alkyl
- high boiling
- hydrogenation
- Prior art date
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract 6
- 238000002360 preparation method Methods 0.000 title description 2
- 150000002148 esters Chemical class 0.000 claims abstract description 63
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000009835 boiling Methods 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 alkyl dicarboxylic acids Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 13
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001530 fumaric acid Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 23
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical group COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims description 19
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 11
- 229940014772 dimethyl sebacate Drugs 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 241000282326 Felis catus Species 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 150000004702 methyl esters Chemical group 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 abstract 1
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005201 scrubbing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- ZSQCNVWYBBKUHS-UHFFFAOYSA-N (2,3-dimethylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C ZSQCNVWYBBKUHS-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- JQCVPZXMGXKNOD-UHFFFAOYSA-N 1,2-dibenzylbenzene Chemical compound C=1C=CC=C(CC=2C=CC=CC=2)C=1CC1=CC=CC=C1 JQCVPZXMGXKNOD-UHFFFAOYSA-N 0.000 description 1
- GGMPTLAAIUQMIE-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=CC=CC=C1 GGMPTLAAIUQMIE-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-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
- LWYAUHJRUCQFCX-UHFFFAOYSA-N 4-dodecoxy-4-oxobutanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCC(O)=O LWYAUHJRUCQFCX-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- ANSWCYTXKAIJOK-UHFFFAOYSA-N dibutyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1CCCCC1C(=O)OCCCC ANSWCYTXKAIJOK-UHFFFAOYSA-N 0.000 description 1
- HEJZJSIRBLOWPD-WCWDXBQESA-N didodecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCC HEJZJSIRBLOWPD-WCWDXBQESA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
本发明描述了一种生产丁-1,4-二醇、γ-丁内酯和/或四氢呋喃的方法。在吸收区,将包含马来酸酐、水和碳氧化物的蒸汽流与高沸点溶剂进行接触,形成马来酸酐在该高沸点酯中的溶液,该高沸点酯在大气压下的沸点至少比马来酸酐高约30℃,且选自包含最高13个碳原子的烷基二羧酸的二-(C1-C4烷基)酯、马来酸的、富马酸的、琥珀酸的单-和二-(C10-C18烷基)酯及其混合物、萘单羧酸的(C1-C4烷基)酯、芳族三羧酸的三-(C1-C4烷基)酯、以及间苯二甲酸的二-(C1-C4烷基)酯。使用包含氢气的气体流将溶液中的马来酸酐汽提,这样可形成包含氢气和马来酸酐的蒸汽流,将其在氢化区与多相氢化催化剂进行接触,将马来酸酐转化成选自丁-1,4-二醇、γ-丁内酯和四氢呋喃的至少一种C4化合物。
Description
本发明涉及丁-1,4-二醇、γ-丁内酯和四氢呋喃的生产。
丁-1,4-二醇与变化量的γ-丁内酯和四氢呋喃一起可通过马来酸酐的氢解而制成。丁-1,4-二醇主要用作塑料工业的原料,特别用于生产聚对苯二甲酸丁二醇酯。它还可用作生产γ-丁内酯以及重要溶剂四氢呋喃的中间体。
马来酸酐通常是在部分氧化催化剂的存在下,通过烃原料如苯、混合C4烯烃、或正丁烷的蒸汽相氧化而制成。在苯的部分氧化过程中,通常使用一种由MoO3和可能其它促进剂促进的五氧化二钒载体催化剂。反应温度为约400-455℃,反应压力为约1-3巴,同时使用约4倍理论量的空气以保持在爆炸极限之外。接触时间为约0.1秒。如果该原料是一种混合C4烯烃原料,即混合丁烯原料,那么部分氧化催化剂可以是承载在矾土上的五氧化二钒。典型的反应条件包括,采用约425-485℃的温度和约1.70-2.05巴的压力。空气与丁烯的体积比为约75∶1以保持在爆炸极限之下。另外,按照更现代的做法,可以设计出尽管空气与丁烯的加料混合物处于可燃限度内,但能够令人满意地进行安全操作的装置。如果正丁烷作为原料,该催化剂通常是五氧化二钒且反应条件包括使用约350-450℃的温度和约1-3巴的压力。空气∶正丁烷的体积比为约20∶1,即使这在可燃限度内。用于这种部分氧化反应的反应器的一种设计包括立式管,周围有熔融盐循环通过的夹套,这样可控制反应温度。
在每种情况下,将热蒸汽反应混合物从反应物的出口端取出,其中除了有机杂质如甲酸、乙酸、丙烯酸、和未转化烃原料,还包含马来酸酐蒸汽、水蒸气、碳氧化物、氧气、氮气、和其它惰性气体。
从该反应混合物中回收马来酸酐的一种方法是使用能产生蒸汽的液流将其冷却至约150℃,然后通过水冷却将其进一步冷却至约60℃,这样可冷凝部分马来酸酐,通常约30-60%的马来酸酐。然后用水洗涤剩余物流。
用水或水溶液与含水淤浆进行洗涤,例如描述于US-A-2638481。这种洗涤可形成马来酸的溶液,然后通过例如用二甲苯蒸馏来脱水,这样可去除水并重新形成酸酐。但该方法的一个缺点在于,不可接受比例的产物留在蒸汽相中。此外,某些马来酸不可避免地异构化成富马酸。副产物富马酸表示损失了有价值的马来酸酐且难以从工艺体系中回收,因为它往往形成结晶物质,造成工艺问题。
由于这种异构化问题,已经提出各种其它的无水洗涤液体。例如,GB-A-727828、GB-A-763339和GB-A-768551已经提出将邻苯二甲酸二丁酯作为洗涤液体。US-A-4118403提出,使用包含最高10%重量邻苯二甲酸酐的邻苯二甲酸二丁酯。US-A-3818680提出,使用通常为液体的分子内羧酸酐,如支链C12-15-链烯基取代的琥珀酸酐,从离开部分氧化反应器的反应混合物中吸收马来酸酐。为此目的,FR-A-1125014已经提出了磷酸三(甲苯)酯。JP-A-32-8408已经提出用于此目的的对苯二甲酸二甲酯,JP-A-35-7460提出了马来酸二丁酯。US-A-3040059提出将高分子量蜡作为洗涤溶剂,而US-A-2893924提出用五氯联苯进行洗涤。FR-A-2285386提出,在高于蒸汽反应混合物中水的露点的某个温度下,使用分子量150-400且沸点在140℃以上的芳族烃溶剂,例如二苄基苯。US-A-3850758描述,在从蒸汽部分氧化反应混合物中将马来酸酐吸收到二甲基二苯酮之后进行蒸馏。按照US-A-4071540,至少一部分包含至少3个甲基的多甲基二苯酮可用作马来酸酐的液体吸收剂。US-A-3891680提出,使用具有C4-C8烷基和在两个烷基中总共10-14个碳原子的邻苯二甲酸二烷基酯从反应混合物中吸收马来酸酐。ZA-A-80/1247提出将环脂族酸的酯如六氢邻苯二甲酸二丁酯作为马来酸酐的吸收溶剂。
还已提出,将离开部分氧化反应器的反应混合物中的马来酸酐进行直接冷凝。但这种方法因为在蒸汽相中留有不可接受比例的马来酸酐而低效。
然后按照US-A-5347021和EP-B-0373947所述,将冷凝之后或通过洗涤或吸收和蒸馏而回收的马来酸酐产物进行氢化,得到丁-1,4-二醇以及变化量的γ-丁内酯和四氢呋喃,在此将上述两篇文献作为参考并入本发明。
需要改进通过氢化反应由马来酸酐来生产丁-1,4-二醇、γ-丁内酯和四氢呋喃。特别需要降低组建这种装置的资金成本并降低其运行成本,这样可更容易制造丁-1,4-二醇、γ-丁内酯和四氢呋喃。
因此,本发明的一个目的是改进由马来酸酐来生产丁-1,4-二醇、γ-丁内酯和四氢呋喃。
按照本发明,提供了一种生产选自丁-1,4-二醇、γ-丁内酯和四氢呋喃的至少一种C4化合物的方法,包括在多相氢化催化剂的存在下,将马来酸酐在蒸汽相中进行氢化的步骤,该方法包括:
(a)在吸收区,将包含马来酸酐蒸汽、水蒸气和碳氧化物的蒸汽流与作为溶剂的高沸点酯进行接触,形成马来酸酐在高沸点酯中的溶液,所述高沸点酯在大气压下的沸点至少比马来酸酐高约30℃,且选自包含最高13个碳原子的烷基二羧酸的二-(C1-C4烷基)酯、马来酸的、富马酸的、琥珀酸的单-和二-(C10-C18烷基)酯及其混合物、萘单羧酸的(C1-C4烷基)酯、芳族三羧酸的三-(C1-C4烷基)酯、以及间苯二甲酸的二-(C1-C4烷基)酯;
(b)从吸收区中回收废气流;
(c)将马来酸酐在高沸点酯中的溶液与包含氢气的气流进行接触,这样可从中汽提掉马来酸酐,形成包含氢气和马来酸酐的蒸汽流;
(d)在氢化区,将步骤(c)蒸汽流中的物质在氢化条件下与多相氢化催化剂进行接触,这样可通过氢化将马来酸酐转化成选自丁-1,4-二醇、γ-丁内酯和四氢呋喃的至少一种C4化合物;和
(e)从氢化区中回收包含所述至少一种C4化合物的产物流。
本发明方法中步骤(a)的蒸汽流优选在部分氧化催化剂的存在下,通过使用分子氧气(通常是空气形式)部分氧化烃原料而制成。烃原料可以是苯、或混合C4烯烃流,但最优选正丁烷。使用正丁烷作为烃原料从成本角度来说是目前优选的,因为它是一种比苯或丁烯更廉价的原料。因此,在本发明方法中,用于生产步骤(a)中包含马来酸酐的蒸汽流的原料最优选正丁烷,且催化剂优选五氧化二钒。在这种情况下典型的部分氧化条件包括,使用约350-450℃的温度和约1-3巴的压力,空气与正丁烷的比率为约15∶1-50∶1,如约20∶1,且部分氧化催化剂包括五氧化二钒;接触时间通常为约0.01-0.5秒,如约0.1秒。
烃原料的部分氧化适合在这样一种反应器中进行,其中包括立式管,周围有熔融盐循环通过的夹套,这样可控制反应温度。来自部分氧化反应器的蒸汽流可随后通过外冷却由锅炉加料水冷却以产生蒸汽,而且还可通过进一步外冷却由冷却水冷却至约60-160℃。
在本发明工艺的步骤(a)中,蒸汽马来酸酐流优选与高沸点酯在约60-160℃,优选约80-120℃的温度以及约1-3巴的压力下进行接触,形成在高沸点酯中包含马来酸酐的溶液。接触可通过将蒸汽流吹泡通过高沸点酯而进行。另外,高沸点酯可喷雾到蒸汽流中。还可使用逆流接触设备,其中在气体-液体接触设备如填充涤气塔中或配有塔板的涤气塔,用高沸点酯的下降流与上升蒸汽流接触。在该步骤中,高沸点酯通常处于比蒸汽流要低的温度,这样可冷却后者。
在所得马来酸酐在高沸点酯中的溶液中,马来酸酐在高沸点酯中的浓度可以是约100-400克/升。
高沸点酯在大气压下的沸点至少比马来酸酐高约30℃,优选至少高约60℃-70℃。作为可从中选择合适高沸点酯的包含最高13个碳原子的烷基二羧酸酯的例子,可以提及辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、和十三烷二酸的二甲酯、二乙酯、二-正-或异-丙酯、二-正-、-仲-或异-丁酯。该酯的烷基部分优选衍生自与用于酯化步骤(c)的C1-C4烷醇相同的烷醇。这样,发生任何酯基转移反应都不会产生其它酯。因此,如果所用烷醇为甲醇且马来酸二烷基酯为马来酸二甲酯,用作高沸点酯的所有酯也优选二甲酯,如癸二酸二甲酯。
高沸点酯可另外选自一种C4烷基二羧酸,即马来酸、富马酸、和琥珀酸的单一和二-(C10-C18烷基)酯、及其混合物。这些酯的例子包括衍生自正癸醇、月桂醇、肉豆蔻醇、鲸蜡醇、硬脂醇和二十烷醇的酯及其混合物。
高沸点酯可另外选自萘单羧酸的(C1-C4烷基)酯如萘-2-甲酸甲酯、芳族三羧酸的三-(C1-C4烷基)酯如苯-1,2,4-三甲酸三甲酯、或间苯二甲酸的二-(C1-C4烷基)酯如间苯二甲酸二甲酯。
用于步骤(a)的高沸点酯适合包含来自氢气汽提步骤(c)的物质。
只要在步骤(a)中采用合适的条件,从本发明工艺步骤(b)中回收的气体流就基本上没有马来酸酐。
在本发明的工艺步骤(c)中,将包含氢气的气体流通过马来酸酐的溶液。
氢气汽提步骤优选基本上在氢化区入口压力或在稍高于氢化区入口压力的压力下进行。氢气汽提步骤类似地优选在基本上氢化区所需入口温度或稍低于该温度,例如低于该温度约5-20℃的温度下进行。然后通过另外混入热的含氢气气体将温度升至所需入口温度,该气体具有将蒸汽含酯流稀释的附加优点,这样可保证其温度在其露点之上,优选高于其露点至少约5℃。
氢化步骤有利地在蒸汽相中进行,其中使用多相氢化反应催化剂。典型的氢化反应催化剂包括促进的铜基催化剂,如有机化学杂志(J.Org.Chem.),150,第177-185页所述的那种类型Cu/Zn/Mg/Cr催化剂。
催化剂颗粒的粒径优选为约0.5-5毫米。颗粒可以是任何合适的形状,如球、粒、环或鞍状。如果使用固定床催化剂,反应器可以是管壳式反应器,可在基本上等温下操作;但优选绝热反应器。使用绝热反应器是有利的,因为其资金成本相对管壳式反应器较低,且一般更容易将所选催化剂加料到反应器中。
氢化是在高温如约150-300℃、更常见约180-280℃和约5-100巴、优选约10-70巴的压力下进行。
从氢化区回收氢化产物混合物,其中除了丁-1,4-二醇,还包含一些四氢呋喃和γ-丁内酯。即使需要的主要产物为丁-1,4-二醇,四氢呋喃和γ-丁内酯的存在并非缺点,因为这些化合物是商业上重要的化学品,因此将它们回收成纯净态是经济的。如果需要,可将γ-丁内酯循环到氢化区以另外生产丁-1,4-二醇。
关于蒸汽相氢化马来酸酐的其它细节可以参考G.L.Castiglioni等人在石油和煤-天然气-石油化学及燃料化学(Erdoel und Kohle-Erdgas-Petrochemie vereinigt mit Brennstoff-Chemie),Bd.48,Heft 4/5,1995年4月/五月第174-178页上的论文(在标题Wissenschaft & Technik(Science & Technology)之下)。所得粗氢化产物混合物的随后纯化可按照类似于US-A-4584419、WO-A-86/03189、WO-A-88/0937、US-A-4767869、US-A-4945173、US-A-4919765、US-A-5254758、US-A-5310954和WO-A-91/01960所述的方式进行。
为了清楚地理解本发明并便于将其实现为用于生产丁-1,4-二醇以及一些γ-丁内酯和四氢呋喃的装置,现在仅通过实施例并参考附图(所述装置的流程图)来描述使用按照本发明的一种优选工艺。
参考附图,将正丁烷在1-3巴的压力和400℃的温度下在线路1供料到部分氧化装置2(另外在线路3向其供给空气)。部分氧化装置2是常规设计,包括部分氧化反应器,其中包括填充有部分氧化催化剂的管,所述催化剂由填充到管中的五氧化二钒组成,该管配有夹套,熔融盐可循环通过该夹套以控制温度。该部分氧化反应器在20∶1的空气∶正丁烷加料比下操作。
通过用锅炉加料水外冷却,将热蒸汽部分氧化产物流冷却以产生蒸汽,然后用冷却水冷却,将其温度降至138℃。将其从装置2的线路4处回收。其中包含2.9%重量/重量的马来酸酐、5.8%重量/重量的水、1.3%重量/重量的二氧化碳、1.0%重量/重量的一氧化碳、0.01%重量/重量的乙酸、0.01%重量/重量的丙烯酸、15.7%重量/重量的氧气,余量基本上包含氮气和其它惰性气体。将其加料到涤气塔5的底部,向上与通过在约68℃下由线路6供料的癸二酸二甲酯的下流喷雾流逆流而行。包含0.03%重量/重量马来酸酐的该洗涤废气流在排气线路7离开涤气塔5的顶部,然后将其通入废气燃烧器。
从涤气塔5的底部回收线路8中的液体流,其中包含约15%重量/重量马来酸酐、0.1%乙酸和0.04%重量/重量丙烯酸在癸二酸二甲酯中的溶液。将其供料到在180℃的温度和580psia(40巴)的压力下操作的汽提塔9的顶部附近。在马来酸酐溶液注入塔9的位置之上,塔9具有许多蒸馏塔板,这样可降低癸二酸二甲酯在塔9塔顶流中的带出。马来酸酐在癸二酸二甲酯中的溶液逆着来自线路10的氢气上升流,向下流过汽提塔9。汽提的癸二酸二甲酯通过线路6从汽提塔9的底部回收到涤气塔5的顶部。从汽提塔9的顶部,在线路11中出现几乎饱和的蒸汽混合物流,其中包含在氢气中的马来酸酐,氢气∶马来酸酐的摩尔比为约400∶1。该蒸汽混合物流的温度为约180-200℃,且压力为约40巴。用来自线路12的其它热氢气(温度为约180-220℃)将其稀释,得到一种蒸汽流,其中氢气∶马来酸酐的摩尔比为约450∶1且至少比其露点高约5℃。
该蒸汽混合物在线路13中向前通入氢化装置14,其中包括填充有铜基催化剂(例如,促进的铜催化剂)且操作时的入口温度为180℃、入口压力为565psia(39巴)、和出口温度为200℃的绝热反应器。马来酸酐的加料速率对应于0.1/小时的液体时空速率。该装置还包括一纯化区,其中将粗氢化产物混合物在几个阶段进行蒸馏,在线路15中生成纯丁-1,4-二醇。用于单独回收γ-丁内酯和四氢呋喃的线路分别标为16和17。新鲜癸二酸二甲酯溶剂可通过线路18加入,而循环的溶剂流的清洗流可在线路19中取出。
用作溶剂的癸二酸二甲酯可,例如由萘-2-甲酸甲酯、苯-1,2,4-三甲酸三甲酯或间苯二甲酸二甲酯替代。另外,作为高沸点酯癸二酸二甲酯可由马来酸二-(C10-C18烷基)酯、富马酸二-(C10-C18烷基)酯、或琥珀酸二-(C10-C18烷基)酯、或其两种或多种的混合物的替代,它们视需要可以与相应的马来酸单-(C10-C18烷基)酯、富马酸单-(C10-C18烷基)酯、或琥珀酸单-(C10-C18烷基)酯、或其两种或多种的混合物、和/或与相应的游离酸或酸混合物,即马来酸、富马酸、和/或琥珀酸进行混合。通常,在这种情况下的高沸点酯主要包含二酯或二酯混合物,不超过少量(通常各低于约5%摩尔)的相应单酯或单酯混合物和/或相应酸或酸混合物。作为这种高沸点酯的一个例子,可以提及马来酸二月桂基酯,它可包含最高约10%摩尔的琥珀酸二月桂基酯以及少量,优选分别低于约5%摩尔,更优选分别低于约1%摩尔,甚至更优选分别低于约0.25%摩尔的富马酸二月桂基酯、马来酸单月桂基酯、富马酸单月桂基酯和琥珀酸单月桂基酯的一种或多种。此外,线路6中的循环流可包含少量,通常分别低于约10%摩尔,甚至更优选分别低于约5%摩尔的马来酸酐、马来酸、富马酸、和/或琥珀酸。
Claims (15)
1.一种生产选自丁-1,4-二醇、γ-丁内酯和四氢呋喃的至少一种C4化合物的方法,包括在多相氢化催化剂的存在下,在马来酸酐蒸汽相中进行氢化的步骤,该方法包括:
(a)在吸收区,将包含马来酸酐蒸汽、水蒸气和碳氧化物的蒸汽流与作为溶剂的高沸点酯进行接触,形成马来酸酐在高沸点酯中的溶液,所述高沸点酯在大气压下的沸点至少比马来酸酐高约30℃,且选自包含最高13个碳原子的烷基二羧酸的二-(C1-C4烷基)酯、马来酸的、富马酸的、琥珀酸的单-和二-(C10-C18烷基)酯及其混合物、萘单羧酸的(C1-C4烷基)酯、芳族三羧酸的三-(C1-C4烷基)酯、以及间苯二甲酸的二-(C1-C4烷基)酯;
(b)从吸收区中回收废气流;
(c)将马来酸酐在高沸点酯中的溶液与包含氢气的气流进行接触,这样可从中汽提掉马来酸酐,形成包含氢气和马来酸酐的蒸汽流;
(d)在氢化区,将步骤(c)蒸汽流中的物质在氢化条件下与多相氢化催化剂进行接触,这样可通过氢化将马来酸酐转化成选自丁-1,4-二醇、γ-丁内酯和四氢呋喃的至少一种C4化合物;和
(e)从氢化区中回收包含所述至少一种C4化合物的产物流。
2.根据权利要求1的方法,其中步骤(a)的所述蒸汽流是在部分氧化催化剂的存在下使用分子氧气部分氧化烃原料而得到的。
3.根据权利要求2的方法,其中所述烃原料是正丁烷。
4.根据权利要求3的方法,其中所述部分氧化催化剂包括五氧化二钒,且其中所述部分氧化条件包括使用约350-450℃的温度和约1-3巴的压力,空气与正丁烷的比率为约15∶1-50∶1,且接触时间为约0.01-0.5秒。
5.根据权利要求1-4中任何一项的方法,其中在步骤(a)中,将所述蒸汽马来酸酐流与高沸点溶剂在约60-160℃的温度和约1-3巴的压力进行接触,形成在高沸点酯中包含马来酸酐的溶液。
6.根据权利要求5的方法,其中所述接触步骤是在逆流接触设备中进行的,其中在气体一液体接触设备中,将下降的高沸点酯流与上升蒸汽流接触。
7.根据权利要求1-6中任何一项的方法,其中所述高沸点酯为甲酯。
8.根据权利要求7的方法,其中所述高沸点酯为癸二酸二甲酯。
9.根据权利要求1-8中任何一项的方法,其中用于步骤(a)的所述高沸点酯包括来自氢气汽提步骤(c)的循环物质。
10.根据权利要求1-9中任何一项的方法,其中所述氢气汽提步骤是基本上在氢化区入口压力下进行的。
11.根据权利要求1-10中任何一项的方法,其中所述氢气汽提步骤是在氢化区入口温度至低于氢化区入口温度约20℃的某个温度下进行的。
12.根据权利要求1-11中任何一项的方法,其中所述氢化步骤在蒸汽相中,在约150-300℃的温度和约5-100巴的压力下,使用促进的铜催化剂来进行。
13.根据权利要求1-12中任何一项的方法,其中从氢化区回收一种氢化产物混合物,其中包含丁-1,4-二醇、以及四氢呋喃和γ-丁内酯。
14.根据权利要求13的方法,其中所述氢化产物混合物通过在一个或多个阶段中进行蒸馏而纯化,这些阶段包括在“轻馏分”塔中进行蒸馏,从塔顶分离出该混合物的各种挥发性组分,包括四氢呋喃和正丁醇。
15.根据权利要求14的方法,其中将来自所述“轻馏分”塔的底部产物在一个或多个阶段中进行蒸馏,这样可进一步纯化得到纯的丁-1,4-二醇。
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US9718798B2 (en) | 2013-03-14 | 2017-08-01 | Micromidas, Inc. | Solid forms of 5-(halomethyl)furfural and methods for preparing thereof |
US10011577B2 (en) | 2013-09-20 | 2018-07-03 | Micromidas, Inc. | Methods for producing 5-(halomethyl)furfural |
US10093638B2 (en) | 2011-06-09 | 2018-10-09 | Micromidas, Inc. | Utilizing a multiphase reactor for the conversion of biomass to produce substituted furans |
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GB0421928D0 (en) * | 2004-10-01 | 2004-11-03 | Davy Process Techn Ltd | Process |
MX2015005251A (es) | 2012-10-26 | 2015-10-29 | Micromidas Inc | Metodos para producir 5-(halometil)furfural. |
KR102604948B1 (ko) * | 2021-06-25 | 2023-11-23 | 씨제이제일제당(주) | 테트라하이드로퓨란, 감마부티로락톤 또는 1,4-부탄디올의 제조 방법 |
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US9718798B2 (en) | 2013-03-14 | 2017-08-01 | Micromidas, Inc. | Solid forms of 5-(halomethyl)furfural and methods for preparing thereof |
US10053441B2 (en) | 2013-03-14 | 2018-08-21 | Micromidas, Inc. | Methods for purifying 5-(halomethyl)furfural |
CN105189471B (zh) * | 2013-03-14 | 2018-10-26 | 微麦德斯公司 | 5-(卤代甲基)糠醛的提纯方法 |
CN109020930A (zh) * | 2013-03-14 | 2018-12-18 | 微麦德斯公司 | 5-(卤代甲基)糠醛的提纯方法 |
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US10011577B2 (en) | 2013-09-20 | 2018-07-03 | Micromidas, Inc. | Methods for producing 5-(halomethyl)furfural |
US10710970B2 (en) | 2013-09-20 | 2020-07-14 | Micromidas, Inc. | Methods for producing 5-(halomethyl)furfural |
US11299468B2 (en) | 2013-09-20 | 2022-04-12 | Origin Materials Operating, Inc. | Methods for producing 5-(halomethyl)furfural |
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JP2001523656A (ja) | 2001-11-27 |
AU9753398A (en) | 1999-06-07 |
SA99191004B1 (ar) | 2006-10-04 |
BR9814141A (pt) | 2000-10-03 |
MXPA00004661A (es) | 2003-08-20 |
WO1999025675A1 (en) | 1999-05-27 |
ZA989584B (en) | 1999-08-25 |
AU761294B2 (en) | 2003-05-29 |
JP4268335B2 (ja) | 2009-05-27 |
CA2309992A1 (en) | 1999-05-27 |
DE69812429T2 (de) | 2003-08-14 |
US6204395B1 (en) | 2001-03-20 |
EP1049657A1 (en) | 2000-11-08 |
KR20010032013A (ko) | 2001-04-16 |
ID26660A (id) | 2001-01-25 |
NO20002472D0 (no) | 2000-05-12 |
AR017612A1 (es) | 2001-09-12 |
CN1132805C (zh) | 2003-12-31 |
NO20002472L (no) | 2000-05-12 |
GB9724195D0 (en) | 1998-01-14 |
DE69812429D1 (de) | 2003-04-24 |
MY118197A (en) | 2004-09-30 |
EP1049657B1 (en) | 2003-03-19 |
KR100530781B1 (ko) | 2005-11-23 |
TW460444B (en) | 2001-10-21 |
ES2195406T3 (es) | 2003-12-01 |
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