CN114349595A - Method for recycling by-product of BDO (methanol to ethane) prepared by allyl alcohol method - Google Patents
Method for recycling by-product of BDO (methanol to ethane) prepared by allyl alcohol method Download PDFInfo
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- CN114349595A CN114349595A CN202210016136.6A CN202210016136A CN114349595A CN 114349595 A CN114349595 A CN 114349595A CN 202210016136 A CN202210016136 A CN 202210016136A CN 114349595 A CN114349595 A CN 114349595A
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- Prior art keywords
- reaction
- autoclave
- formaldehyde
- catalyst
- propionaldehyde
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Links
- 238000000034 method Methods 0.000 title claims abstract description 63
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000006227 byproduct Substances 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 69
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- CBIFNLUPCWCNQT-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-2-methylpropanal Chemical compound OCC(C)(CO)C=O CBIFNLUPCWCNQT-UHFFFAOYSA-N 0.000 claims abstract description 38
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 claims abstract description 37
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009833 condensation Methods 0.000 claims abstract description 13
- 230000005494 condensation Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 93
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007868 Raney catalyst Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 8
- 229940073608 benzyl chloride Drugs 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- 125000005265 dialkylamine group Chemical group 0.000 claims description 3
- -1 dialkylamine organic base Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- 229940059936 lithium bromide Drugs 0.000 claims description 2
- 229940073577 lithium chloride Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 2
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 72
- 239000002994 raw material Substances 0.000 description 33
- 239000012071 phase Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 29
- 239000008346 aqueous phase Substances 0.000 description 22
- 238000005070 sampling Methods 0.000 description 21
- 238000007789 sealing Methods 0.000 description 20
- 239000012295 chemical reaction liquid Substances 0.000 description 19
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 208000012839 conversion disease Diseases 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 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 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 2
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for recycling a BDO byproduct by an allyl alcohol method. The method comprises the following steps: carrying out base-catalyzed condensation on the 2-hydroxymethyl propionaldehyde serving as a byproduct of the BDO of the allyl alcohol method and formaldehyde to obtain a 2, 2-dihydroxymethyl propionaldehyde intermediate; hydrogenating 2, 2-dimethylolpropionaldehyde to obtain trimethylolethane. The invention has novel synthetic route, successfully utilizes the by-product which is originally treated by burning, reduces the three wastes generated by BDO production and also improves the overall economy of the project. And secondly, the catalytic effect of the invention is superior to that of the prior common alkali catalyst, no pungent smell exists, the operation is convenient for personnel, the recycling process is greatly simplified, the operation is simple and convenient, and the yield is high.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a method for recycling a BDO byproduct by an allyl alcohol method.
Background
Trimethylolethane, also known as 2, 2-dimethylolpropanol and 2-hydroxymethyl-2-methyl-1, 3-propanediol, TME for short, is an odorless, white crystalline solid with a melting point of 199-. The trimethylolethane has three primary hydroxyl groups in the molecular structure, can react with different polybasic acids to obtain polyester resins with different structures, and the polyester resins can be crosslinked with functional materials such as isocyanate, amino resin and the like or modified with epoxy resin, organic silicon resin and the like, so that a series of resin products with good high temperature resistance, oxidation resistance and gloss retention are obtained. In addition, trimethylolethane is also used for synthesizing alkyd resin, the corresponding alkyd resin can be used in special paint products, and the paint has high baking resistance, stain resistance and excellent color durability and is widely welcomed by people.
The production of trimethylolethane basically uses propionaldehyde and formaldehyde as starting materials, and the process route can be divided into a Cannizzaro process and a hydrogenation process according to different reduction methods. The Cannizzaro process route adopts excessive formaldehyde as a reaction raw material, and propionaldehyde and 2 molecules of formaldehyde are subjected to condensation reaction to obtain a dimethylolpropionaldehyde intermediate; then under the action of catalyst, the dimethylolpropionaldehyde and formaldehyde produce disproportionation reaction to obtain trimethylolethane and formic acid.
The hydrogenation process adopts slightly excessive formaldehyde, firstly, the propionaldehyde and 2 molecules of formaldehyde are subjected to condensation reaction to obtain dimethylolpropionaldehyde, and then the dimethylolpropionaldehyde is separated and hydrogenated to obtain the trimethylolethane product (CN106278817, CN105669371 and CN 105669370). Because the byproduct formic acid of the Cannizzaro process has poor product purity, the prior trimethylolethane device at home and abroad mainly adopts a hydrogenation process.
In the allyl alcohol method BDO process, a certain amount of branched hydroformylation product 2-hydroxymethyl propionaldehyde is inevitably obtained in the allyl alcohol hydroformylation reaction, the direct application value of the byproduct is very low, 2-methyl propylene glycol can be obtained by hydrogenation, but the market consumption of the 2-methyl propylene glycol is relatively low, so the byproduct can only be incinerated in the form of waste liquid at present. Therefore, in the process of preparing BDO by using the allyl alcohol method, the development and the reuse of the byproduct 2-hydroxymethyl propionaldehyde become a difficult problem, and the economical efficiency of the project is restricted.
In conclusion, at present, a new method and a new scheme for utilizing the 2-hydroxymethyl propionaldehyde as the byproduct are urgently needed to be developed, the 2-hydroxymethyl propionaldehyde as the byproduct of the BDO prepared by the allyl alcohol method is reasonably utilized, waste is changed into valuable, and the overall economy of the project is improved. When developing the related utilization process, the method preferably has the advantages of concise process flow, mild reaction conditions, small device investment and the like so as to facilitate the amplification and implementation of the related scheme.
Disclosure of Invention
The invention aims to provide a method for recycling 2-hydroxymethyl propionaldehyde which is a byproduct of BDO (methanol to ethanol) in an allyl alcohol method. The method takes a share of byproducts as raw materials, has simple process route, mild reaction conditions and good practical value.
In order to achieve the purpose and achieve the technical effect, the invention adopts the following technical scheme:
a method for recycling a BDO byproduct in an allyl alcohol method comprises the following steps:
s1: carrying out base-catalyzed condensation on the 2-hydroxymethyl propionaldehyde serving as a byproduct of the BDO of the allyl alcohol method and formaldehyde to obtain a 2, 2-dihydroxymethyl propionaldehyde intermediate;
s2: hydrogenating 2, 2-dimethylolpropionaldehyde to obtain trimethylolethane.
The reaction scheme is schematically as follows:
in the invention, the base catalyst in S1 is a long-chain dialkylamine organic base, preferably one or more of N, N-dimethyl-N-dodecylamine, N-dimethyl-N-tetradecylamine, N-diethyl-N-tetradecylamine, N-dimethyl-N-hexadecylamine, N-diethyl-N-hexadecylamine and N, N-dimethyl-N-octadecylamine; preferably, the dosage of the alkali catalyst is 2.0-10.0% of the molar weight of the 3-hydroxy-2-methylpropionaldehyde.
In the invention, an alkylating agent alkyl halide is added into S1 to react with a long-chain dialkyl amino organic base in situ to partially quaternize the alkyl halide, wherein the alkyl halide is preferably one or more of methyl bromide, ethyl bromide, 1-bromopropane, 1-bromobutane, methyl iodide, ethyl iodide, 1-iodopropane, benzyl chloride and benzyl bromide; preferably, the alkyl halide is used in an amount of 10 to 20% by mole of the long chain dialkylamine.
In the invention, Lewis acid, preferably one or more of lithium chloride, lithium bromide, zinc chloride, zinc bromide and zinc sulfate is added into S1; preferably, the lewis acid is 1 to 10% of the molar amount of base catalyst.
In the invention, the feeding molar ratio of the condensation of the 3-hydroxy-2-methylpropionaldehyde and formaldehyde in the S1 is 1: 1.5-1: 3.
In the invention, the S1 is fed in the form of one or more of formaldehyde gas, paraformaldehyde and aqueous formaldehyde solution, preferably aqueous formaldehyde solution; preferably, the concentration of formaldehyde in the aqueous formaldehyde solution is from 37 to 50 wt%.
In the present invention, the S1 is carried out in the presence or absence of a solvent, and preferably, the two materials are directly mixed and reacted without using a solvent.
In the present invention, if a solvent is added to S1, the solvent is one or more of water, methanol, ethanol, benzene, toluene, xylene, n-hexane, n-heptane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, acetone, ethyl acetate, dichloromethane, and dichloroethane.
In the present invention, the S1 is a batch reaction or a continuous reaction; preferably, a batch reaction is adopted, and the reaction time is 2-5 hours.
In the invention, the reaction temperature of S1 is 40-80 ℃, and the reaction pressure is normal pressure.
In the invention, the S2 uses a hydrogenation catalyst; preferably, the hydrogenation catalyst is one or more of palladium carbon, palladium alumina, palladium silica, ruthenium carbon, raney nickel and raney cobalt, preferably raney nickel and/or raney cobalt; preferably, the dosage of the hydrogenation catalyst is 0.5-3.0% of the mass of the 2, 2-dimethylolpropionaldehyde.
In the present invention, S2 uses a co-catalyst; preferably, the cocatalyst is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide; preferably, the using amount of the cocatalyst is 1-100 ppm of the mass of the 2, 2-dimethylolpropionaldehyde.
In the present invention, the S2 reaction is carried out in a batch or continuous manner in an autoclave.
In the invention, a solvent is added in the S2 reaction; preferably, the solvent of S2 is one or more of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, n-butanol, t-butanol, acetone, and tetrahydrofuran, preferably water and/or methanol.
In the invention, hydrogen in the reaction kettle is kept stable in the S2 reaction process; preferably, the hydrogen pressure is 0.5 to 3.0 MPa.
In the invention, the reaction temperature in the S2 is 50-100 ℃.
Another object of the present invention is to provide a trimethylolethane product prepared by the above method.
The trimethylolethane product is prepared by condensing and hydrogenating 2-hydroxymethyl propionaldehyde which is a byproduct of BDO (methanol to ethanol) method and formaldehyde.
All pressures described herein are absolute pressures unless otherwise specified.
Compared with the prior art, the invention has the following positive effects:
1. one of the main raw materials of the method is derived from a byproduct of BDO (methanol to ethane) method, and formaldehyde is a bulk chemical and is simple and easy to obtain; the synthesis route is short, the yield is high, three wastes are hardly generated, and the method has a good cost advantage compared with the existing method.
2. The invention adopts alkylation reagents such as bromoethane, benzyl chloride and the like to react with long-chain dialkyl amido organic alkali in situ, so that quaternary ammonium at one end of the catalyst is salinized, the catalyst is favorable for moving to a water-oil interface, and the catalytic reaction efficiency is greatly improved.
3. After one end of the organic base catalyst with high boiling point is quaternized, the method has the advantages of liquid state, high boiling point, no bad smell and the like, and is convenient for personnel to operate; and after simple phase separation, the separation of the catalyst and the product can be realized, and the recycling process of the catalyst is greatly simplified. The organic base and the medium strong acid are used for concerted catalysis condensation reaction, and the reaction yield and selectivity are higher than those of the prior art.
4. In the hydrogenation reaction, a trace amount of alkali auxiliary agent is added, so that the high hydrogenation reaction activity of the catalyst can be effectively maintained, and the service life of the catalyst is prolonged.
Detailed Description
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
The main raw material information is as follows:
2-hydroxymethylpropanal, wanhua chemical, purity 91 wt% (main impurities are allyl alcohol, n-propanol, 4-hydroxybutanal); formaldehyde aqueous solution (37%) and Chinese medicine. Lithium chloride, lithium bromide, zinc chloride, zinc acetate, AR, a Chinese medicine reagent.
N, N-dimethyl N-octadecylamine, N-dimethyl N-hexadecylamine, N-dimethyl N-tetradecylamine, N-dimethyl N-decaamine, purity 99%, and an alatin reagent; tributylamine and carbofuran reagent with purity of 99%; sodium hydroxide, potassium hydroxide, meclin, AR. Methyl iodide, benzyl chloride, benzyl bromide, AR, purity 99%, Inokay.
Raney nickel, raney cobalt, euphoniaceae reagent;
methanol, n-hexane, julonga reagent, AR.
The gas chromatography test conditions of the present invention are as follows:
the instrument model is as follows: agilent 7890B; a chromatographic column: capillary column HP-Innowax (50 m.times.0.32 mm. times.0.4 μm); the initial temperature of the column box is 60 ℃, and the temperature is increased to 120 ℃ at the speed of 5 ℃/min; then the temperature is increased to 280 ℃ at the speed of 10 ℃/min and kept for 5 min. The temperature of the gasification chamber is 200 ℃. The carrier gas is high-purity nitrogen, the split ratio is 40:1, and the split flow is 45 mL/min. Carrier gas saving: 20mL/min, start wait time 2 min. The sample injection temperature is 280 ℃, the detector is FID, the detector temperature is 240 ℃, the air flow is 350mL/min, the hydrogen flow is 30mL/min, the tail gas flow is 30mL/min, and the sample injection amount is 0.2 muL.
Example 1
N, N-dimethyl N-octadecylamine catalyzes the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde.
And (3) cleaning a 2L stainless steel high-pressure kettle at room temperature, sealing, filling 0.5MPa of nitrogen, maintaining the pressure for 30min, and ensuring that the pressure in the high-pressure kettle is not reduced, thereby indicating that the equipment has good sealing property. Nitrogen is discharged, the autoclave is opened, catalysts N, N-dimethyl N-octadecylamine (7.74g,0.026mol) and methyl iodide (0.74g,0.0052mol) are added firstly, the autoclave is sealed again, then nitrogen is discharged for 3 times, 0.3MPa is charged each time, the air in the autoclave is replaced thoroughly, and finally the pressure in the autoclave is reduced to normal pressure. The autoclave is started to stir and the jacket is started to accompany heat, and the stirring speed is 800r/min for the full mixing and reaction of the amine and the methyl iodide. After the temperature in the autoclave is raised to 50 ℃ (the temperature raising process is carried out for 25 minutes), raw materials of 2-hydroxymethyl propionaldehyde (125.86g,1.3mol, content 91%), 37 wt% formaldehyde aqueous solution (158.25g,1.95mol) and lithium chloride (0.11g,2.6mmol) are sequentially added into the autoclave, reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the constant temperature at 50 ℃ for reaction for 1h, then raising the temperature of the reaction kettle to 80 ℃, and continuing to rapidly stir for reaction for 1h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the aqueous phase into a methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product 2, 2-dihydroxymethyl propionaldehyde is 97 percent.
Example 2
N, N-dimethyl-N-tetradecylamine is used for catalyzing the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde.
And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Nitrogen is discharged, the high-pressure kettle is opened, catalysts N, N-dimethyl N-tetradecylamine (31.39g,0.13mol) and iodomethane (3.69g,0.026mol) are added firstly, the high-pressure kettle is sealed again, then nitrogen is charged and discharged for 3 times, 0.3MPa is carried out each time, air in the high-pressure kettle is replaced thoroughly, and finally the pressure in the high-pressure kettle is reduced to normal pressure. The autoclave is started to stir and the jacket is externally accompanied by heat, and the stirring speed is 800r/min for fully mixing and reacting the amine and the methyl iodide. After the temperature in the autoclave is raised to 50 ℃ (the temperature raising process is carried out for 25 minutes), raw materials of 2-hydroxymethyl propionaldehyde (125.86g,1.3mol, content 91%), 37 wt% formaldehyde aqueous solution (210.99g,2.6mol) and lithium chloride (0.55g,13.0mmol) are sequentially added into the autoclave, reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the constant temperature at 50 ℃ for reaction for 1h, then raising the temperature of the reaction kettle to 80 ℃, and continuing to rapidly stir for reaction for 1h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the small amount of aqueous phase into a certain amount of methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product, namely the 2, 2-dihydroxymethyl propionaldehyde is 96 percent.
Example 3
N, N-dimethyl-N-hexadecylamine is used for catalyzing the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde.
And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Evacuating nitrogen, opening the autoclave, adding catalysts N, N-dimethyl-N-hexadecylamine (17.52g,0.065mol) and methyl iodide (0.92g,0.0065mol), resealing the autoclave, then inflating and deflating nitrogen for 3 times, each time under 0.3MPa, completely replacing the air in the autoclave, and finally reducing the pressure in the autoclave to normal pressure. The autoclave is started to stir and the jacket is externally accompanied by heat, and the stirring speed is 800r/min for fully mixing and reacting the amine and the methyl iodide. After the temperature in the autoclave is raised to 40 ℃ (the temperature raising process is carried out for 25 minutes), raw materials of 2-hydroxymethyl propionaldehyde (125.86g,1.3mol, content 91%), 37 wt% formaldehyde aqueous solution (316.49g,3.9mol) and lithium chloride (0.28g,6.5mmol) are sequentially added into the autoclave, reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the temperature of 40 ℃ for reacting for 3h, then raising the temperature of the reaction kettle to 80 ℃, and continuing to rapidly stir for reacting for 2h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the small amount of aqueous phase into a certain amount of methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product, namely the 2, 2-dihydroxymethyl propionaldehyde is 99 percent.
Example 4
N, N-dimethyl N-octadecylamine catalyzes the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde.
And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Evacuating nitrogen, opening the autoclave, adding catalysts N, N-dimethyl N-octadecylamine (8.33g,0.028mol) and benzyl chloride (0.53g,0.0042mol) firstly, resealing the autoclave, then inflating and deflating nitrogen for 3 times, each time at 0.3MPa, completely replacing the air in the autoclave, and finally reducing the pressure in the autoclave to normal pressure. The autoclave is started to stir and the jacket is externally accompanied by heat, and the stirring speed is 800r/min for fully mixing and reacting the amine and the benzyl chloride. After the temperature in the autoclave is raised to 50 ℃ (25 minutes in the temperature raising process), 2-hydroxymethyl propionaldehyde (148.61g,1.4mol, content 83%), 50 wt% formaldehyde aqueous solution (126.11g,2.1mol), purified water (60g) and lithium bromide (0.05g,0.6mmol) are sequentially added into the autoclave, the reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the constant temperature at 50 ℃ for reacting for 2h, then raising the temperature of the reaction kettle to 80 ℃, and continuing to rapidly stir for reacting for 1h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the small amount of aqueous phase into a certain amount of methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product 2, 2-dimethylolpropionaldehyde is 98 percent.
Example 5
N, N-dimethyl N-decaamine catalyzes the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde.
And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. The nitrogen is evacuated, the autoclave is opened, the catalysts N, N-dimethyl N-decaamine (20.56g,0.09mol) and benzyl bromide (1.54g,0.009mol) are added firstly, the autoclave is sealed again, then the nitrogen is charged and discharged for 3 times, 0.3MPa is added every time, the air in the autoclave is replaced thoroughly, and finally the autoclave is reduced to the normal pressure. And starting the high-pressure kettle for stirring and carrying out heat tracing outside the jacket, wherein the stirring speed is 800-1000 r/min for fully mixing and reacting the amine and the benzyl bromide. After the temperature in the autoclave is raised to 50 ℃ (the temperature raising process is carried out for 25 minutes), raw materials of 2-hydroxymethyl propionaldehyde (145.23g,1.5mol, content 91%), paraformaldehyde (67.56g,2.25mol, calculated by formaldehyde), water (135g) and zinc chloride (1.23g,9mmol) are sequentially added into the autoclave, reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the constant temperature at 50 ℃ for reaction for 3h, then raising the temperature of the reaction kettle to 80 ℃, and continuously and rapidly stirring for reaction for 2h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the small amount of aqueous phase into a certain amount of methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product, namely the 2, 2-dihydroxymethyl propionaldehyde is 96 percent.
Example 6
N, N-dimethyl N-octadecylamine is used for catalyzing the condensation of 2-hydroxymethyl propionaldehyde and formaldehyde, and the catalyst is applied mechanically.
And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. The nitrogen is evacuated, the autoclave is opened, N-dimethyl N-octadecylamine (44.63g,0.15mol) and benzyl chloride (1.9g,0.015mol) are added firstly, the autoclave is sealed again, then the nitrogen is charged and discharged for 3 times, 0.3MPa is charged each time, the air in the autoclave is replaced thoroughly, and finally the inside of the autoclave is reduced to the normal pressure. The autoclave is started to stir and the jacket is externally accompanied by heat, and the stirring speed is 800r/min for fully mixing and reacting the amine and the benzyl chloride. After the temperature in the autoclave is raised to 50 ℃ (the temperature raising process is carried out for 25 minutes), raw materials of 2-hydroxymethyl propionaldehyde (145.23g,1.5mol), 37 wt% formaldehyde water solution (182.59g,2.25mol) and zinc acetate (1.38g,7.5mol) are sequentially added into the autoclave, reaction liquid is water and oil, the oil phase is a catalyst phase, and the upper layer of the reaction liquid is formed. Keeping the constant temperature at 50 ℃ for reacting for 2h, then raising the temperature of the reaction kettle to 80 ℃, and continuing to rapidly stir for reacting for 1h to promote the complete conversion of the raw materials. After the reaction is finished, sampling and analyzing, sampling by adopting a double valve, taking out a sample, standing and splitting phases, taking an upper organic phase as a catalyst phase and a lower aqueous phase as a product phase, taking a small amount of aqueous phase, adding the small amount of aqueous phase into a certain amount of methanol solvent, analyzing the content of raw materials and products in a reaction solution by GC, and determining the reaction conversion rate and selectivity, wherein the conversion rate of the 2-hydroxymethyl propionaldehyde is more than 99 percent, and the selectivity of the target product, namely the 2, 2-dihydroxymethyl propionaldehyde is 99 percent.
The catalyst is mechanically used: and (3) bringing the reaction kettle to room temperature, taking out the reaction liquid, placing the reaction liquid into a phase separation funnel, standing for phase separation, keeping an organic phase, extracting a water phase for 2 times by using n-hexane, combining the extracted n-hexane phase with the organic phase separated for the first time, and performing rotary evaporation to remove the n-hexane to obtain the recovered catalyst. The resulting catalyst was again charged to the autoclave and the starting material 2-hydroxymethylpropanal (145.23g,1.5mol), 37 wt% aqueous formaldehyde (182.59g,2.25mol) and zinc acetate (1.38g,7.5mol) were added. The autoclave is sealed again, then nitrogen is charged and discharged for 3 times, each time under 0.3MPa, the air in the autoclave is replaced thoroughly, and finally the pressure in the autoclave is reduced to normal pressure. The high-pressure kettle is started to stir and the external heat tracing of the jacket is started, and the stirring speed is 800 r/min. After the temperature in the kettle rises to 50 ℃, keeping constant temperature and reacting for 2 hours; then the temperature of the reaction kettle is raised to 80 ℃, and the rapid stirring reaction is continued for 1 hour. Sampling analysis shows that the conversion rate of the 2-hydroxymethyl propionaldehyde is 99 percent, and the selectivity of the target product, namely the 2, 2-dihydroxymethyl propionaldehyde is 98 percent. The catalyst is recovered and recycled, and the activity and selectivity of the catalyst are kept unchanged after 6 times of reaction.
Example 7
Raney nickel is used for catalyzing 2, 2-dimethylolpropionaldehyde to be hydrogenated to synthesize the trimethylolethane.
The reaction solution obtained in example 1 was allowed to stand for phase separation to leave an aqueous phase, and then residual formaldehyde was removed by rotary evaporation (30 ℃ C., 2kPa), and the resulting aqueous 2, 2-dimethylolpropionaldehyde solution was used directly for hydrogenation. And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Nitrogen was evacuated, the autoclave was opened, and an aqueous solution (content: 149.0g) of 2, 2-dimethylolpropionaldehyde as a raw material, purified water (100g), Raney's nickel as a catalyst (1.5g), and sodium hydroxide (15.0mg) were sequentially added to the autoclave to obtain a black suspension. After all the raw materials are added, the autoclave is sealed again, nitrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the air in the autoclave is replaced thoroughly, hydrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the nitrogen in the autoclave is replaced thoroughly, and finally the hydrogen in the autoclave is increased to 2 MPa. The autoclave was started to stir and the jacket was externally heated, and the stirring speed was 800r/min in order to bring the catalyst and the substrate into sufficient contact. After the temperature in the kettle rises to 80 ℃ (the temperature rise process lasts for 25 minutes), the constant temperature reaction is kept for 2 hours. Sampling and analyzing at regular time in the reaction process, sampling by adopting a double valve, taking out a sample, adding the sample into a certain amount of methanol solvent, and analyzing the content of raw materials and products in reaction liquid by GC (gas chromatography), so as to determine the reaction conversion rate and selectivity, wherein the conversion rate of 2, 2-dimethylolpropionaldehyde is more than 99 percent, and the selectivity of a target product, namely trimethylolethane is 99 percent.
Example 8
Raney nickel is used for catalyzing 2, 2-dimethylolpropionaldehyde to be hydrogenated to synthesize the trimethylolethane.
The reaction solution obtained in example 2 was allowed to stand for phase separation to leave an aqueous phase, and then residual formaldehyde was removed by rotary evaporation (30 ℃ C., 2kPa), and the resulting aqueous 2, 2-dimethylolpropionaldehyde solution was used directly for hydrogenation. And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Nitrogen was evacuated, the autoclave was opened, and an aqueous solution (content: 147.0g) of 2, 2-dimethylolpropionaldehyde as a raw material, purified water (100g), Raney's nickel as a catalyst (4.4g), and sodium hydroxide (1.5mg) were sequentially added to the autoclave to obtain a black suspension. After all the raw materials are added, the autoclave is sealed again, nitrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the air in the autoclave is replaced thoroughly, hydrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the nitrogen in the autoclave is replaced thoroughly, and finally the pressure of the hydrogen in the autoclave is increased to 0.5 MPa. The autoclave was started to stir and the jacket was externally heated, and the stirring speed was 800r/min in order to bring the catalyst and the substrate into sufficient contact. After the temperature in the kettle rises to 50 ℃ (the temperature rise process lasts for 25 minutes), the constant temperature reaction is kept for 2 hours. Sampling and analyzing at regular time in the reaction process, sampling by adopting a double valve, taking out a sample, adding the sample into a certain amount of methanol solvent, and analyzing the content of raw materials and products in reaction liquid by GC (gas chromatography), so as to determine the conversion rate and selectivity of the reaction, wherein the conversion rate of 2, 2-dimethylolpropionaldehyde is 99.1 percent, and the selectivity of the target product, namely trimethylolethane is 99.1 percent.
Example 9
Raney nickel is used for catalyzing 2, 2-dimethylolpropionaldehyde to be hydrogenated to synthesize the trimethylolethane.
The reaction solution obtained in example 3 was allowed to stand for phase separation to leave an aqueous phase, and then residual formaldehyde was removed by rotary evaporation (30 ℃ C., 2kPa), and the resulting aqueous 2, 2-dimethylolpropionaldehyde solution was used directly for hydrogenation. And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Nitrogen was evacuated, the autoclave was opened, and an aqueous solution (content: 150.0g) of 2, 2-dimethylolpropionaldehyde as a raw material, purified water (50g), Raney's nickel as a catalyst (0.75g), and potassium hydroxide (7.5mg) were sequentially added to the autoclave to obtain a black suspension. After all the raw materials are added, the autoclave is sealed again, nitrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the air in the autoclave is replaced thoroughly, hydrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the nitrogen in the autoclave is replaced thoroughly, and finally the hydrogen in the autoclave is increased to 3 MPa. Starting the high-pressure kettle for stirring and carrying out external heat tracing by a jacket, wherein the stirring speed is 600-800 r/min in order to fully contact the catalyst and the substrate. After the temperature in the kettle rises to 100 ℃ (the temperature rise process lasts for 25 minutes), the constant temperature reaction is kept for 2 hours. Sampling and analyzing at regular time in the reaction process, sampling by adopting a double valve, taking out a sample, adding the sample into a certain amount of methanol solvent, and analyzing the content of raw materials and products in reaction liquid by GC (gas chromatography), so as to determine the reaction conversion rate and selectivity, wherein the conversion rate of 2, 2-dimethylolpropionaldehyde is more than 99 percent, and the selectivity of a target product, namely trimethylolethane is 99 percent.
Example 10
Raney cobalt catalyzes 2, 2-dimethylolpropionaldehyde to synthesize trimethylolethane by hydrogenation.
The reaction solution obtained in example 4 was allowed to stand for phase separation to leave an aqueous phase, and then residual formaldehyde was removed by rotary evaporation (30 ℃ C., 2kPa), and the resulting aqueous 2, 2-dimethylolpropionaldehyde solution was used directly for hydrogenation. And (3) cleaning a 2L stainless steel autoclave at room temperature, sealing, filling 0.5MPa nitrogen, maintaining the pressure for at least 30min, and ensuring that the pressure in the autoclave is not reduced, which indicates that the equipment has good sealing property. Nitrogen was evacuated, the autoclave was opened, and an aqueous solution of 2, 2-dimethylolpropionaldehyde as a raw material (content: 162.0g), methanol (100g), Raney cobalt as a catalyst (1.6g) and sodium hydroxide (16.2mg) were successively added to the autoclave to obtain a black suspension. After all the raw materials are added, the autoclave is sealed again, nitrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the air in the autoclave is replaced thoroughly, hydrogen is charged and discharged for 3 times, each time the pressure is 0.3MPa, the nitrogen in the autoclave is replaced thoroughly, and finally the hydrogen in the autoclave is increased to 2 MPa. Starting the high-pressure kettle for stirring and carrying out external heat tracing by a jacket, wherein the stirring speed is 600-800 r/min in order to fully contact the catalyst and the substrate. After the temperature in the kettle rises to 80 ℃ (the temperature rise process lasts for 25 minutes), the constant temperature reaction is kept for 2 hours. Sampling and analyzing at regular time in the reaction process, sampling by adopting a double valve, taking out a sample, adding the sample into a certain amount of methanol solvent, and analyzing the content of raw materials and products in reaction liquid by GC (gas chromatography), so as to determine the reaction conversion rate and selectivity, wherein the conversion rate of 2, 2-dimethylolpropionaldehyde is more than 99 percent, and the selectivity of a target product, namely trimethylolethane is 99 percent.
Comparative example 1
Reference is made to patent CN 105669370.
Formaldehyde and 150.0g of 2-hydroxymethyl propionaldehyde enter a two-stage series condensation reaction according to the molar ratio of 2.2:1, the condensation catalyst is trimethylamine, the using amount of the trimethylamine is 10 percent of the molar amount of the 2-hydroxymethyl propionaldehyde, the condensation reaction temperature is 30 ℃, the reaction pressure is 0.5MPa, and the retention time is 1.5 hours. After the reaction, the reaction product enters a second reaction kettle (closed system), the pH value is adjusted to 7 by formic acid, a Pt/C catalyst which is 2 percent of the formic acid is added into the reaction kettle, the reaction kettle is heated to 70 ℃, the retention time is 0.5 hour, the reaction product enters a condensation rectifying tower for reduced pressure rectification, the temperature at the bottom of the tower is 90 ℃, the temperature at the top of the tower is 75 ℃, unreacted light components (mainly water, unreacted olefine aldehyde, propionaldehyde and amine) circularly retract the reaction kettle to continue the reaction, and the dimethylolpropionaldehyde and 4 percent of exothermic acetal components at the bottom of the tower enter a hydrogenation reactor for hydrogenation reaction; the temperature of the hydrogenation reactor is 120 ℃, the pressure is 4.5MPa, and the space velocity is 0.6; the molar ratio of hydrogen to aldehyde group is 20:1, the reaction liquid after hydrogenation enters a separation tower for separation and refining to obtain the trimethylolethane, and the product yield is 90.1%.
Claims (10)
1. A method for recycling a BDO byproduct by an allyl alcohol method is characterized by comprising the following steps:
s1: carrying out base-catalyzed condensation on the 2-hydroxymethyl propionaldehyde serving as a byproduct of the BDO of the allyl alcohol method and formaldehyde to obtain a 2, 2-dihydroxymethyl propionaldehyde intermediate;
s2: hydrogenating 2, 2-dimethylolpropionaldehyde to obtain trimethylolethane.
2. The method of claim 1, wherein the base catalyst in S1 is a long chain dialkylamine organic base, preferably one or more of N, N-dimethyl-N-decaamine, N-dimethyl-N-dodecylamine, N-dimethyl-N-tetradecylamine, N-diethyl-N-tetradecylamine, N-dimethyl-N-hexadecylamine, N-diethyl-N-hexadecylamine, N-dimethyl-N-octadecylamine;
preferably, the dosage of the alkali catalyst is 2.0-10.0% of the molar weight of the 3-hydroxy-2-methylpropionaldehyde.
3. The process according to claim 1 or 2, wherein the alkylation reagent alkyl halide, preferably one or more of methyl bromide, ethyl bromide, 1-propyl bromide, 1-butyl bromide, methyl iodide, ethyl iodide, 1-propyl iodide, benzyl chloride, benzyl bromide, is added to S1 to react in situ with the long chain dialkylamine based organic base to partially quaternize it;
preferably, the alkyl halide is used in an amount of 10 to 20% by mole of the long chain dialkylamine.
4. The method according to claim 1, wherein a Lewis acid, preferably one or more of lithium chloride, lithium bromide, zinc chloride, zinc bromide and zinc sulfate is added in S1;
preferably, the lewis acid is 1 to 10% of the molar amount of base catalyst.
5. The method according to claim 1, wherein the feeding molar ratio of the condensation of the 3-hydroxy-2-methylpropionaldehyde and the formaldehyde in the S1 is 1: 1.5-1: 3;
and/or the S1 is fed in the form of one or more of formaldehyde gas, paraformaldehyde and aqueous formaldehyde solution, preferably the aqueous formaldehyde solution;
preferably, the concentration of formaldehyde in the aqueous formaldehyde solution is from 37 to 50 wt%.
6. The method according to claim 1, wherein the S1 is carried out in the presence or absence of a solvent, preferably by directly mixing the two materials for reaction without using a solvent;
and/or if a solvent is added to the S1, the solvent is one or more of water, methanol, ethanol, benzene, toluene, xylene, n-hexane, n-heptane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, acetone, ethyl acetate, dichloromethane and dichloroethane.
7. The method according to claim 1, wherein the S1 is a batch reaction or a continuous reaction;
preferably, the reaction time is 2-5 hours when the batch reaction is adopted;
and/or the reaction temperature of S1 is 40-80 ℃, and the reaction pressure is normal pressure.
8. The method according to claim 1, wherein the S2 uses a hydrogenation catalyst;
preferably, the hydrogenation catalyst is one or more of palladium carbon, palladium alumina, palladium silica, ruthenium carbon, raney nickel and raney cobalt, preferably raney nickel and/or raney cobalt;
preferably, the dosage of the hydrogenation catalyst is 0.5-3.0 wt% of the mass of the 2, 2-dimethylolpropionaldehyde;
and/or, S2 uses a cocatalyst;
preferably, the cocatalyst is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide;
preferably, the using amount of the cocatalyst is 1-100 ppm of the mass of the 2, 2-dimethylolpropionaldehyde.
9. The process of claim 1, wherein the S2 reaction is carried out in a batch or continuous mode in an autoclave;
and/or, adding a solvent into the S2 reaction;
preferably, the solvent is one or more of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, n-butanol, tert-butanol, acetone and tetrahydrofuran, preferably water and/or methanol;
and/or, the hydrogen in the reaction kettle is kept stable in the S2 reaction process;
preferably, the hydrogen pressure is 0.5 to 3.0 MPa;
and/or the reaction temperature in the S2 is 50-100 ℃.
10. A trimethylolethane product produced by the method according to any one of claims 1 to 9, wherein the trimethylolethane is produced by condensing 2-hydroxymethylpropanal, which is a by-product of BDO produced by the allyl alcohol method, with formaldehyde and hydrogenating the same.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB866365A (en) * | 1957-04-23 | 1961-04-26 | Celanese Corp | Trimethylolethane |
| CN101891594A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Synthesizing method of 2-borneol alkenyl propanol |
| CN105669371A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Production method of trimethylolethane |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
| CN106278817A (en) * | 2016-08-20 | 2017-01-04 | 湖北泰元新材料科技有限公司 | A kind of method that continuous condensating hydrogenation method prepares trimethylolethane |
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- 2022-01-07 CN CN202210016136.6A patent/CN114349595B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB866365A (en) * | 1957-04-23 | 1961-04-26 | Celanese Corp | Trimethylolethane |
| CN101891594A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Synthesizing method of 2-borneol alkenyl propanol |
| CN105669371A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Production method of trimethylolethane |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
| CN106278817A (en) * | 2016-08-20 | 2017-01-04 | 湖北泰元新材料科技有限公司 | A kind of method that continuous condensating hydrogenation method prepares trimethylolethane |
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