CN116606212A - Method for economically and continuously preparing tertiary amine - Google Patents
Method for economically and continuously preparing tertiary amine Download PDFInfo
- Publication number
- CN116606212A CN116606212A CN202310584363.3A CN202310584363A CN116606212A CN 116606212 A CN116606212 A CN 116606212A CN 202310584363 A CN202310584363 A CN 202310584363A CN 116606212 A CN116606212 A CN 116606212A
- Authority
- CN
- China
- Prior art keywords
- reaction
- secondary amine
- reactor
- acid
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000012074 organic phase Substances 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000000605 extraction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 9
- -1 aromatic secondary amine Chemical class 0.000 claims description 50
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 48
- 239000008346 aqueous phase Substances 0.000 claims description 46
- 150000001299 aldehydes Chemical class 0.000 claims description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 37
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 24
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 24
- 235000019253 formic acid Nutrition 0.000 claims description 24
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 22
- 238000005086 pumping Methods 0.000 claims description 14
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 13
- 229960003868 paraldehyde Drugs 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000005956 Metaldehyde Substances 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical group [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 229940118019 malondialdehyde Drugs 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 31
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 69
- 239000000243 solution Substances 0.000 description 60
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 56
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 53
- 230000001276 controlling effect Effects 0.000 description 36
- 229940043279 diisopropylamine Drugs 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 18
- 230000001105 regulatory effect Effects 0.000 description 15
- 238000005191 phase separation Methods 0.000 description 13
- 230000032798 delamination Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical group CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 5
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 5
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BBDGYADAMYMJNO-UHFFFAOYSA-N n-butyl-n-ethylbutan-1-amine Chemical compound CCCCN(CC)CCCC BBDGYADAMYMJNO-UHFFFAOYSA-N 0.000 description 3
- XWCCTMBMQUCLSI-UHFFFAOYSA-N n-ethyl-n-propylpropan-1-amine Chemical compound CCCN(CC)CCC XWCCTMBMQUCLSI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- ZGLZWNUJPHIQOP-UHFFFAOYSA-N formic acid;n-propan-2-ylpropan-2-amine Chemical compound [O-]C=O.CC(C)[NH2+]C(C)C ZGLZWNUJPHIQOP-UHFFFAOYSA-N 0.000 description 2
- REINQNFUQDCADG-UHFFFAOYSA-N formic acid;n-propylpropan-1-amine Chemical compound OC=O.CCCNCCC REINQNFUQDCADG-UHFFFAOYSA-N 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- UNYPBYIPJDULHO-UHFFFAOYSA-N dibutylazanium;formate Chemical group [O-]C=O.CCCC[NH2+]CCCC UNYPBYIPJDULHO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DLMICMXXVVMDNV-UHFFFAOYSA-N n,n-di(propan-2-yl)propan-1-amine Chemical compound CCCN(C(C)C)C(C)C DLMICMXXVVMDNV-UHFFFAOYSA-N 0.000 description 1
- VWQMDHRZIPQGJQ-UHFFFAOYSA-N n-ethylethanamine;formic acid Chemical group [O-]C=O.CC[NH2+]CC VWQMDHRZIPQGJQ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for economically and continuously preparing tertiary amine. Which comprises the following steps: 1) Reacting the secondary amine with an excess of acid to obtain a mixture comprising the protic ionic liquid and unreacted acid; 2) Reacting the mixture with aldehyde in a reactor, and taking unreacted acid as a reducing agent to generate tertiary amine, so as to obtain a reaction system containing tertiary amine; 3) Adding secondary amine into the reaction system again for extraction separation to obtain an organic phase and a water phase, wherein the organic phase contains tertiary amine, and recycling the water phase into the reactor for continuous reaction; the secondary amine in step 1) is the same as the secondary amine in step 3). According to the application, secondary amine which is the same as the reaction raw material is added into a reaction system containing the tertiary amine product, the reaction system is extracted, then the organic phase obtained by extraction is rectified, so that the tertiary amine product with high purity is obtained, and meanwhile, the water phase obtained by extraction is recycled, so that the utilization rate of the raw material can be further improved.
Description
Technical Field
The present application relates to a process for the economical continuous preparation of tertiary amines.
Background
Tertiary amine is widely used in industrial production and life, and can be used as fuel additive, pesticide production, medical synthesis, epoxy resin hardener, intermediate of polyurethane catalyst, raw material for preparing quaternary ammonium salt/alkali, plasticizer, dye, desulfurizing agent, etc.
It is known that conventional synthesis of tertiary amine products often uses a high-pressure fixed bed reaction apparatus and uses heterogeneous noble metal catalysts such as Pd, pt, etc. supported on a carrier, and the reaction is also required to be carried out under hydrogen. For example, CN101460445a discloses the preparation of diisopropylethylamine by amination of diisopropylamine and acetaldehyde using a suspension catalyst Pd/C as the catalyst, the reaction requires high pressure, hydrogen conditions, and the noble metal catalyst is expensive.
It is also known that tertiary amines can be produced by reacting secondary amines with aldehydes of 2 or more carbon atoms in the presence of a reducing agent under normal pressure conditions without using a metal catalyst and without using hydrogen. For example, chinese laid-open patent CN101360726a discloses a method for preparing tertiary amine by dropping secondary amine into a mixed solution of aldehyde and acid, which is characterized in that aldehyde and formic acid are mixed first, heated to reflux temperature, and then secondary amine is added for reaction. The method has a requirement on the dropping sequence of the raw materials, and when aldehyde or acid is dropped into the other two raw materials, the reaction yield is obviously reduced. After the reaction is finished, a large amount of alkali (such as NaOH aqueous solution) is added into the reaction system to neutralize the reaction system, so that a large amount of wastewater containing organic matters is generated by the reaction.
It is also known that chinese laid-open patent CN102875385a discloses a method for producing tertiary amine by hydrolysis of metaldehyde using an acidic catalyst and then reacting with diisopropylamine and a reducing agent metal hydride such as sodium borohydride. The patent does not disclose the purity of the tertiary amine product, and at the same time, the reducing agent used, such as sodium borohydride and the like, is highly toxic, easy to explosion, sensitive to water and unfavorable for the operation of the reaction.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the technical problem to be solved by the application is to provide the method for economically and continuously preparing the tertiary amine, the method can continuously produce, the reaction raw materials can be completely utilized, no waste materials are discharged in the production process, the method does not need high-pressure hydrogen and metal catalyst conditions, and the reaction process is safer.
In order to solve the technical problems, the application adopts the following technical scheme:
a process for continuously preparing a tertiary amine, the process comprising the steps of: 1) Reacting the secondary amine with an excess of acid to obtain a mixture comprising the protic ionic liquid and unreacted acid; 2) Reacting the mixture with aldehyde in a reactor, wherein the unreacted acid is used as a reducing agent to generate tertiary amine, so as to obtain a reaction system containing tertiary amine; 3) Adding secondary amine into the reaction system again for extraction separation to obtain an organic phase and a water phase, wherein the organic phase contains tertiary amine, and the water phase is recycled to the reactor for continuous reaction; the secondary amine in step 1) is the same as the secondary amine in step 3).
In some embodiments, the method further comprises the step of adding an aldehyde and an acid to the aqueous phase prior to the recycling, the adding being to an extent such that the molar ratio of secondary amine, aldehyde, and acid in the reactor is unchanged.
In some embodiments, the method further comprises the step of rectifying the organic phase to yield a tertiary amine.
In some embodiments, the secondary amine is added again in step 3) in an amount such that the pH of the aqueous phase is 10-13.
In some embodiments, the reactor is selected from the group consisting of one or more of a microchannel reactor, a continuous tank reactor, and a tubular reactor, preferably a microchannel reactor or a tubular reactor, and more preferably a reactor in which a microchannel reactor and a tubular reactor are used in combination.
In some embodiments, the pressure of the reaction in step 2) is from 0 to 5.0MPa, preferably from 0 to 4.0MPa, particularly preferably from 0 to 3.0MPa. That is, the reaction of the present application can be carried out at normal pressure.
In some embodiments, the temperature of the reaction in step 2) is 60-250 ℃, preferably 120-220 ℃.
In some embodiments, the time of the reaction in step 2) is from 5 to 300 minutes, preferably from 30 to 120 minutes.
In some embodiments, the acid is selected from formic acid or oxalic acid. The acid is firstly reacted with secondary amine in the step 1) to generate proton type ionic liquid, the proton type ionic liquid is then reacted with aldehyde to generate target product tertiary amine, and excessive acid such as formic acid or oxalic acid in the step 1) can be used as a reducing agent for the tertiary amine generation reaction in the step 2), so that no additional reducing agent is needed in the reaction process. And formic acid or oxalic acid is adopted as a reducing agent, so that the method is safer compared with reducing agents such as sodium borohydride and the like in the prior art.
In some embodiments, the molar ratio of acid to secondary amine is from 1.0 to 4.0, preferably from 1.1 to 3.0, particularly preferably from 1.2 to 2.5. The molar ratio is the acid excess.
In some embodiments, the molar ratio of the aldehyde to the secondary amine is from 0.1 to 5.0, preferably from 0.2 to 3.0, particularly preferably from 0.3 to 2.0.
In some embodiments, the secondary amine has a carbon number of 30 or less, preferably 25 or less, and more preferably 20 or less.
In some embodiments, the secondary amine is a secondary aliphatic amine, a secondary aromatic amine, or a secondary cyclic amine.
In some embodiments, the aldehyde is a monoaldehyde, a dialdehyde, or a multimer of an aldehyde.
In some embodiments, the secondary amine has the structural formulaWherein R is 1 、R 2 Independently selected from C 1 -C 8 Alkyl, C 4 -C 8 Cycloalkyl, aryl or C 7 -C 9 Alkylaryl, or R 1 、R 2 Together with NH form C 3 -C 7 Is a ring of (a).
Further, the R 1 、R 2 Independently selected fromMethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, phenyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2,3, 4-trimethylphenyl, 2,3, 5-trimethylphenyl, 2,3, 6-trimethylphenyl, 2,4, 6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 2-n-propylphenyl, 3-n-propylphenyl, 4-n-propylphenyl.
Further, the R 1 、R 2 Together with NH, pyrrole, piperidine, morpholine, piperazine, N-methylpiperazine, cyclohexylimine or silacyclobutane are formed.
In some embodiments, the aldehyde is selected from the group consisting of a structural formula ofIs of the formulaThe monoaldehyde multimer or the structural formula of (B) is +.>Wherein R is 3 Selected from H, C 1 -C 6 Alkyl, hydroxy substituted C 1 -C 6 Alkyl, R 4 Selected from single bonds or C 1 -C 4 An alkylene group.
Further, the R 3 Selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl.
Further, the R 4 Selected from single bond, methylene, ethylene, propylene, butyleneA base.
Further, the aldehyde is selected from acetaldehyde, paraldehyde, metaldehyde, propionaldehyde, glycolaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde or glyoxal.
The structural formula of the proton type ionic liquid isWherein R is 1 、R 2 Independently selected from C 1 -C 8 Alkyl, C 4 -C 8 Cycloalkyl, aryl or C 7 -C 9 Alkylaryl, or R 1 、R 2 Together with N form C 3 -C 7 N is selected from 1,2 or 3, [ X ]] n- Selected from formate or oxalate.
The aldehyde is selected from the structural formulaMonoaldehydes of the formula +.>In the case of a monoaldehyde multimer, the reaction formula of the proton-type ionic liquid and the aldehyde is as follows:
the aldehyde is selected from the structural formulaThe reaction formula of the proton-type ionic liquid and the aldehyde is as follows:
the proton type ionic liquid reacts with the aldehyde to generate corresponding Schiff base, and the Schiff base is reduced by a reducing agent to prepare the tertiary amine.
In some embodiments, the step 1) is performed at room temperature and pressure.
In some embodiments, the secondary amine is selected from dimethylamine, diisopropylamine, piperidine; the aldehyde is selected from acetaldehyde, paraldehyde, propionaldehyde, glycolaldehyde or succinaldehyde; the tertiary amine is selected from dimethylethylamine, dimethylpropylamine, N, N, N ', N' -tetramethylbutanediamine, dimethylbutylamine, diisopropylethylamine, diisopropylpropylamine, N-ethylpiperidine.
In a particularly preferred embodiment, acetaldehyde and dimethylamine are reacted to produce dimethylethylamine.
In a particularly preferred embodiment, propionaldehyde and dimethylamine are reacted to form dimethylpropylamine.
In a particularly preferred embodiment, succinyl aldehyde and dimethylamine are reacted to produce N, N, N ', N' -tetramethylbutanediamine.
In a particularly preferred embodiment, acetaldehyde and diisopropylamine react to form diisopropylethylamine.
In some embodiments, the method comprises the steps of: 1) Reacting the secondary amine with an excess of acid to obtain a mixture comprising the protic ionic liquid and unreacted acid; 2) Pumping the mixture and the aldehyde into the reactor through a plunger pump respectively to react, wherein the unreacted acid is used as a reducing agent to generate tertiary amine, so as to obtain a reaction system containing the tertiary amine, the reaction pressure is 0-5.0MPa, the temperature is 60-200 ℃, and the time is 5-300 minutes; 3) Adding secondary amine with the same type as that in the step 1) into the reaction system again for extraction separation to obtain an organic phase and a water phase; 4) Rectifying the organic phase to obtain tertiary amine, adding aldehyde and acid into the aqueous phase, and recycling the aqueous phase into the reactor to perform continuous reaction, wherein the adding of aldehyde and acid is performed to the extent that the mole ratio of secondary amine, aldehyde and acid in the reactor is unchanged.
Compared with the prior art, the application has the following advantages:
the application creatively synthesizes corresponding tertiary amine in a reaction system taking secondary amine as a raw material and aldehyde in a reducing agent (acid), adds secondary amine which is the same as the reaction raw material into the reaction system containing the tertiary amine as a product, extracts the reaction system, rectifies an organic phase obtained by extraction to obtain a high-purity tertiary amine product, recycles an aqueous phase obtained by extraction, and returns the aqueous phase to a reactor to recycle unreacted complete secondary amine and aldehyde, thus improving the utilization rate of the raw material, and realizing 100% of raw material utilization rate after recycling continuous production. In order to better control the molar ratio of the materials in the reactor, the corresponding aldehyde and acid raw materials are added into the water phase before the water phase is returned to the reactor.
In addition, in a system for generating tertiary amine by taking secondary amine as a raw material, the secondary amine is reacted with acid to generate proton type ionic liquid, and then the proton type ionic liquid and aldehyde are reacted to generate tertiary amine on the premise that excessive acid further serves as a reducing agent, the proton type ionic liquid can play a role of self-catalysis, so that the reaction system can ensure high purity and high yield of tertiary amine products, meanwhile, the reaction condition is mild, high-pressure and hydrogen reaction atmosphere is not needed, and meanwhile, mild and safe acid can be used as the reducing agent in the reaction.
Drawings
FIG. 1 is a diethyl-formate-type ionic liquid;
FIG. 2 is a di-n-propylamine-formate based ionic liquid;
FIG. 3 is a diisopropylamine-formate based ionic liquid;
fig. 4 is a di-n-butylamine-carboxylic acid protic ionic liquid.
Detailed Description
The inventor submits patent application with application number 202210034548.2 in 1 month 2023, the application firstly adopts secondary amine and acid to react at normal temperature and normal pressure to generate proton type ionic liquid, then the proton type ionic liquid and aldehyde react in the presence of a reducing agent to generate target product tertiary amine, compared with the prior art, a noble metal catalyst is adopted, or a large amount of alkali is required to be added into a reaction system, or metal hydride such as sodium borohydride is required to be used as the reducing agent, the proton type ionic liquid in the application can be used as the catalyst, the reaction is homogeneous self-catalytic reaction, high-pressure hydrogen and metal catalyst conditions are not required, and a milder, safer and greener reducing agent can be used.
The reaction product mixture containing tertiary amine is directly subjected to rectification and purification in the application, so that a small amount of unreacted raw materials are not fully utilized and wasted. The present inventors have further developed on the basis of this, and have found that, after the completion of the reaction, the tertiary amine dissolved in the aqueous phase can be extracted into the organic phase by adding a secondary amine of the same kind as the primary secondary amine to the reaction product mixture. On the one hand, secondary amine has smaller steric hindrance and is easier to form corresponding salt with acid radical ions in solution than corresponding tertiary amine; on the other hand, tertiary amines have a lower solubility in water than secondary amines and can be separated from the aqueous phase by simple phase separation. The amount of secondary amine added is preferably such that the pH in the aqueous phase is from 10 to 13, which ensures that the tertiary amine is present in molecular form in the organic phase and that unreacted small amounts of acid and aldehyde starting materials are also in the aqueous phase, so that the reaction product can be isolated by extraction, the tertiary amine and small amounts of unreacted aldehyde and acid starting materials are separated, after which the tertiary amine can be subjected to further rectification purification to increase the purity, and the secondary amine in the aqueous phase, as well as unreacted aldehyde and acid, can be recycled and returned to the reactor for use, and in order to ensure a constant ratio of raw materials in the reactor, the corresponding amounts of aldehyde and acid are fed to the reverse phase before the aqueous phase is returned to the reactor. By adopting the scheme, the continuous production of tertiary amine can be realized, and the utilization rate of raw materials can be 100%.
The application is further described below with reference to examples. The present application is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present application may be combined with each other as long as they do not collide with each other.
Example 1
Synthesizing the dimethylethylamine by reacting dimethylamine and acetaldehyde:
the method comprises the steps of preparing dimethylamine and formic acid into a solution A according to a molar ratio of 1:1.5, pumping the solution A and acetaldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of acetaldehyde to dimethylamine of 1:1 by a plunger pump, controlling the reaction pressure to be 1MPa, controlling the reaction temperature to be 140 ℃, and controlling the residence time of materials to be 120 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with dimethylamine, added in such an amount that the pH in the aqueous phase after delamination was 10. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain the dimethylethylamine with the purity of 99.5 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding formic acid, and is returned to the solution A as a raw material, and is continuously pumped into a reactor together with acetaldehyde for reaction.
After the reaction was completed, the final yield of dimethylethylamine was 98.6%.
Example 2
Synthesis of dimethylethylamine from dimethylamine and paraldehyde:
the method comprises the steps of preparing a solution A from dimethylamine and oxalic acid according to a molar ratio of 1:1.6, pumping the solution A and paraldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of paraldehyde to dimethylamine of 0.35:1 by a plunger pump, controlling the reaction pressure to 2MPa, controlling the reaction temperature to 160 ℃, and controlling the residence time of materials to 90 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with dimethylamine, added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain the dimethylethylamine with the purity of 99.6 percent, the obtained lower aqueous phase is prepared into the same composition as the solution A by adding oxalic acid, and the solution A is returned to serve as a raw material, and the solution A and acetaldehyde are continuously pumped into a reactor for reaction.
After the reaction, the final yield of dimethylethylamine was 99.2%.
Example 3
Dimethylamine and propionaldehyde synthesis of dimethylpropylamine:
the method comprises the steps of preparing dimethylamine and formic acid into a solution A according to a molar ratio of 1:1.4, pumping the solution A and propanal into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 1.1:1 of propanal and dimethylamine by a plunger pump, controlling the reaction pressure to be 1.8MPa, controlling the reaction temperature to be 180 ℃, and controlling the residence time of materials to be 80 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with dimethylamine, added in such an amount that the pH in the aqueous phase after delamination was 10.5. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain the dimethylpropylamine with the purity of 99.7 percent. The lower aqueous phase obtained was prepared to the same composition as solution a by adding formic acid and returned to solution a as the starting material, and was continuously pumped into the reactor together with propionaldehyde for the reaction.
After the reaction, the final yield of dimethylethylamine was 99.1%.
Example 4
Dimethylamine and butyraldehyde react to synthesize dimethylbutylamine:
the method comprises the steps of preparing a solution A from dimethylamine and oxalic acid according to a molar ratio of 1:1.7, pumping the solution A and butyraldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of butyraldehyde to dimethylamine of 1.2:1 by a plunger pump, controlling the reaction pressure to 2.5MPa, controlling the reaction temperature to 180 ℃, and controlling the residence time of materials to 90 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with dimethylamine, added in such an amount that the pH in the aqueous phase after delamination was 10. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain dimethylbutylamine with the purity of 99.8 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding oxalic acid, and the solution A is returned to serve as a raw material, and the lower aqueous phase and butyraldehyde are continuously pumped into a reactor for reaction.
After the reaction, the final yield of dimethylbutylamine was 99.4%.
Example 5
Synthesizing N, N, N ', N' -tetramethyl butanediamine by reacting dimethylamine with butanedialdehyde:
the method comprises the steps of preparing dimethylamine and formic acid into a solution A according to a molar ratio of 1:1.6, pumping the solution A and succinyl aldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of succinyl aldehyde to dimethylamine of 0.5:1 through a plunger pump, controlling the reaction pressure to 2.5MPa, controlling the reaction temperature to 180 ℃, and controlling the residence time of materials to 120 minutes through regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with dimethylamine, added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain N, N, N ', N' -tetramethyl butanediamine with the purity of 99.5 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding oxalic acid, and returns the solution A as a raw material, and the lower aqueous phase and succinaldehyde are continuously pumped into a reactor for reaction.
After the reaction, the final yield of N, N, N ', N' -dimethylbutylamine was 99.3%.
Example 6
Triethylamine is synthesized by the reaction of diethylamine and acetaldehyde:
the method comprises the steps of preparing a solution A from diethylamine and formic acid according to a molar ratio of 1:1.5, pumping the solution A and acetaldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 1.1:1 of acetaldehyde and diethylamine through a plunger pump, controlling the reaction pressure to be 2.1MPa, controlling the reaction temperature to be 200 ℃, and controlling the residence time of materials to be 60 minutes through regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with diethylamine, which was added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain triethylamine with the purity of 99.5 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding formic acid, and is returned to the solution A as a raw material, and is continuously pumped into a reactor together with acetaldehyde for reaction.
After the reaction was completed, the final yield of triethylamine was 99.7%.
The nuclear magnetism of the component A of the solution is shown in figure 1, and the diethylamine-formic acid proton type ionic liquid is formed.
Example 7
Di-n-propylamine and acetaldehyde react to synthesize di-n-propylethylamine:
the di-n-propylamine and formic acid are prepared into a solution A according to the molar ratio of 1:1.5, the solution A and acetaldehyde are pumped into a microchannel reactor-tubular reactor combined reactor according to the molar ratio of 1.1:1 by a plunger pump, the reaction pressure is controlled at 2.2MPa, the reaction temperature is controlled at 220 ℃, and the residence time of materials is controlled at 100 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with di-n-propylamine, which was added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain di-n-propylethylamine with the purity of 99.6 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding formic acid, and is returned to the solution A as a raw material, and is continuously pumped into a reactor together with acetaldehyde for reaction.
After the reaction, the final yield of di-n-propylethylamine was 99.3%.
The nuclear magnetism of the component A of the solution is shown in figure 2, and di-n-propylamine-formic acid proton ionic liquid is formed.
Example 8
Diisopropylamine and paraldehyde react to synthesize diisopropylethylamine:
the method comprises the steps of preparing diisopropylamine and formic acid into a solution A according to a molar ratio of 1:1.8, pumping the solution A and paraldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 0.3:1 of paraldehyde and diisopropylamine through a plunger pump, controlling the reaction pressure to 3MPa, controlling the reaction temperature to 220 ℃, and controlling the residence time of materials to 60 minutes through regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with diisopropylamine, which was added in such an amount that the pH in the aqueous phase after delamination was 10. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain diisopropylethylamine with the purity of 99.6 percent. The lower aqueous phase obtained is prepared to have the same composition as the solution A by adding formic acid, and is returned to the solution A as a raw material, and is continuously pumped into a reactor together with the paraldehyde for reaction.
After the reaction was completed, the final yield of diisopropylethylamine was 99.4%.
The nuclear magnetism of the component A of the solution is shown in figure 3, and the diisopropylamine-formic acid proton type ionic liquid is formed.
Example 9
Diisopropylamine and propionaldehyde react to synthesize diisopropylamine:
the diisopropylamine and formic acid are prepared into solution A according to the molar ratio of 1:2.0, the solution A and the propionaldehyde are pumped into a microchannel reactor-tubular reactor combined reactor according to the molar ratio of 1.1:1 of the propionaldehyde and the diisopropylamine through a plunger pump, the reaction pressure is controlled at 2MPa, the reaction temperature is controlled at 200 ℃, and the residence time of the materials is controlled at 60 minutes through regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with diisopropylamine, which was added in such an amount that the pH in the aqueous phase after delamination was 10. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain diisopropylamine with the purity of 99.7 percent. The lower aqueous phase obtained was prepared to the same composition as solution a by adding formic acid and returned to solution a as the starting material, and was continuously pumped into the reactor together with propionaldehyde for the reaction.
After the reaction was completed, the final yield of dimethylpropylamine was 99.3%.
Example 10
Diisopropylamine and n-butyraldehyde react to synthesize diisopropylamine:
the method comprises the steps of preparing diisopropylamine and formic acid into a solution A according to a molar ratio of 1:1.8, pumping the solution A and butyraldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of n-butyraldehyde to diisopropylamine of 1:1 by a plunger pump, controlling the reaction pressure to 2.5MPa, controlling the reaction temperature to 200 ℃, and controlling the residence time of materials to 90 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with diisopropylamine, which was added in such an amount that the pH in the aqueous phase after delamination was 10. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain diisopropylamine with the purity of 99.7 percent. The lower aqueous phase obtained was prepared to have the same composition as that of the solution A by adding formic acid, and was returned to the solution A as a raw material, and was continuously pumped into the reactor together with butyraldehyde for reaction.
After the reaction, the final yield of dimethylbutylamine was 99.2%.
Example 11
Synthesizing N-ethylpiperidine by reacting piperidine with acetaldehyde:
the method comprises the steps of preparing a solution A from piperidine and oxalic acid according to a molar ratio of 1:1.8, pumping the solution A and acetaldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 1.1:1 of acetaldehyde and piperidine through a plunger pump, controlling the reaction pressure to 2.5MPa, controlling the reaction temperature to 220 ℃, and controlling the residence time of materials to 120 minutes through regulating the flow rate of the pump.
The reaction mass at the outlet of the reactor was mixed with piperidine and the piperidine was added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The upper organic phase obtained was distilled to obtain N-ethylpiperidine having a purity of 99.5%. The lower aqueous phase is prepared into the same composition as the solution A by adding oxalic acid, and returns the solution A as a raw material, and the lower aqueous phase and acetaldehyde are continuously pumped into a reactor for reaction.
After the completion of the reaction, the final yield of N-ethylpiperidine was 99.1%.
Example 12
Di-n-butylamine and acetaldehyde react to synthesize di-n-butylethylamine:
the di-n-butylamine and formic acid are prepared into a solution A according to the molar ratio of 1:1.6, the solution A and acetaldehyde are pumped into a microchannel reactor-tubular reactor combined reactor according to the molar ratio of 1.05:1 by a plunger pump, the reaction pressure is controlled at 2.3MPa, the reaction temperature is controlled at 220 ℃, and the residence time of materials is controlled at 90 minutes by regulating the flow rate of the pump.
The reaction mass at the reactor outlet was mixed with di-n-butylamine, added in such an amount that the pH in the aqueous phase after delamination was 11. The mixture was subjected to phase separation. The obtained upper organic phase is rectified to obtain di-n-butylethylamine with the purity of 99.5 percent. The lower aqueous phase is prepared into the same composition as the solution A by adding formic acid, and is returned to the solution A as a raw material, and is continuously pumped into a reactor together with acetaldehyde for reaction.
After the reaction, the final yield of di-n-butylethylamine was 99.5%.
The nuclear magnetism of the component A of the solution is shown in figure 4, and the di-n-butylamine-formic acid proton type ionic liquid is formed.
Comparative example 1
Dimethylamine and acetaldehyde reaction:
the method comprises the steps of preparing dimethylamine and formic acid into a solution A according to a molar ratio of 1:1.5, pumping the solution A and acetaldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of acetaldehyde to dimethylamine of 1:1 by a plunger pump, controlling the reaction pressure to be 1MPa, controlling the reaction temperature to be 140 ℃, and controlling the residence time of materials to be 120 minutes by regulating the flow rate of the pump.
The reaction materials at the outlet of the reactor directly enter a rectifying tower for separation, and the dimethylethylamine with the purity of 99.5 percent is obtained, and the final yield of the dimethylethylamine is 95.1 percent.
As can be seen from comparison of comparative example 1 with example 1, the present application further improves the yield of the tertiary amine, which is a target product, by adding secondary amine after the reaction is completed, performing extraction separation and recycling the aqueous phase, and fully utilizes the reaction raw materials, thereby improving the utilization rate of the reaction raw materials.
Comparative example 2
Diisopropylamine and paraldehyde react to synthesize diisopropylethylamine:
the method comprises the steps of preparing diisopropylamine and formic acid into a solution A according to a molar ratio of 1:1.8, pumping the solution A and paraldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 0.3:1 of paraldehyde and diisopropylamine through a plunger pump, controlling the reaction pressure to 3MPa, controlling the reaction temperature to 220 ℃, and controlling the residence time of materials to 60 minutes through regulating the flow rate of the pump.
The reaction material at the outlet of the reactor directly enters a rectifying tower for separation, so that diisopropylethylamine with the purity of 99.2% is obtained, and the final yield of diisopropylethylamine is 96.2%.
As can be seen from comparison of comparative example 2 with example 8, the present application can further increase the yield of the target tertiary amine by adding secondary amine for extraction separation and recycling the aqueous phase after the reaction is completed, fully utilize the reaction raw materials, and increase the utilization rate of the reaction raw materials.
Comparative example 3
Synthesizing N-ethylpiperidine by reacting piperidine with acetaldehyde:
the method comprises the steps of preparing a solution A from piperidine and oxalic acid according to a molar ratio of 1:1.8, pumping the solution A and acetaldehyde into a microchannel reactor-tubular reactor combined reactor according to a molar ratio of 1.1:1 of acetaldehyde and piperidine through a plunger pump, controlling the reaction pressure to 2.5MPa, controlling the reaction temperature to 220 ℃, and controlling the residence time of materials to 120 minutes through regulating the flow rate of the pump.
The reaction material at the outlet of the reactor directly enters a rectifying tower for separation, so that the N-ethylpiperidine with the purity of 99.5% is obtained, and the final yield of the N-ethylpiperidine is 97.1%.
As can be seen from comparison of comparative example 2 with example 11, the present application further improves the yield of the tertiary amine, which is a target product, by adding the secondary amine after the reaction is completed, performing extraction separation and recycling the aqueous phase, and fully utilizes the reaction raw materials, thereby improving the utilization rate of the reaction raw materials.
The above embodiments are provided to illustrate the technical concept and features of the present application and are intended to enable those skilled in the art to understand the content of the present application and implement the same, and are not intended to limit the scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application should be construed to be included in the scope of the present application.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (12)
1. A process for continuously preparing a tertiary amine, characterized by: the method comprises the following steps: 1) Reacting the secondary amine with an excess of acid to obtain a mixture comprising the protic ionic liquid and unreacted acid; 2) Reacting the mixture with aldehyde in a reactor, wherein the unreacted acid is used as a reducing agent to generate tertiary amine, so as to obtain a reaction system containing tertiary amine; 3) Adding secondary amine into the reaction system again for extraction separation to obtain an organic phase and a water phase, wherein the organic phase contains tertiary amine, and the water phase is recycled to the reactor for continuous reaction; the secondary amine in step 1) is the same as the secondary amine in step 3).
2. The method for continuously producing tertiary amines according to claim 1, wherein: the process further comprises, prior to the recycling, a step of feeding aldehyde and acid into the aqueous phase to such an extent that the molar ratio of secondary amine, aldehyde and acid in the reactor is unchanged; and/or the method further comprises the step of rectifying the organic phase to obtain tertiary amine.
3. The method for continuously producing tertiary amines according to claim 1, wherein: the secondary amine is added again in step 3) in an amount such that the pH of the aqueous phase is between 10 and 13.
4. The method for continuously producing tertiary amines according to claim 1, wherein: the reactor is selected from one or more of a microchannel reactor, a continuous tank reactor, and a tubular reactor.
5. The method for continuously producing tertiary amines according to claim 1, wherein: the pressure of the reaction in step 2) is 0-5.0MPa; and/or the temperature of the reaction in step 2) is 60-250 ℃; and/or the reaction in step 2) takes 5 to 300 minutes.
6. The method for continuously producing tertiary amines according to claim 1, wherein: the acid is selected from formic acid or oxalic acid.
7. The method for continuously producing tertiary amines according to claim 1, wherein: the molar ratio of the acid to the secondary amine is 1.0-4.0; and/or the molar ratio of the aldehyde to the secondary amine is 0.1 to 5.0.
8. The method for continuously producing tertiary amines according to claim 1, wherein: the secondary amine has a carbon number of 30 or less; and/or the secondary amine is a fatty secondary amine, an aromatic secondary amine, or a cyclic secondary amine; and/or the aldehyde is a monoaldehyde, a dialdehyde, or a multimer of an aldehyde.
9. The method for continuously producing tertiary amines according to claim 1, wherein: the structural formula of the secondary amine isWherein R is 1 、R 2 Independently selected from C 1 -C 8 Alkyl, C 4 -C 8 Cycloalkyl, aryl or C 7 -C 9 Alkylaryl, or R 1 、R 2 Together with NH form C 3 -C 7 Is a ring of (2); and/or the aldehyde is selected from the group consisting of a structural formula +>Is of the formulaThe monoaldehyde multimer or the structural formula of (B) is +.>Wherein R is 3 Selected from H, C 1 -C 6 Alkyl, hydroxy substituted C 1 -C 6 Alkyl, R 4 Selected from single bonds or C 1 -C 4 An alkylene group.
10. The method for continuously producing tertiary amines according to claim 1, wherein: the R is 1 、R 2 Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, phenyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2,3, 4-trimethylphenyl, 2,3, 5-trimethylphenyl, 2,3, 6-trimethylphenyl, 2,4, 6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-n-propylphenyl, 3-n-propylphenyl, 4-propylphenyl, or R 1 、R 2 Together with NH, pyrrole, piperidine, morpholine, piperazine, N-methylpiperazine, cyclohexylimine or silacyclobutane; and/or, the R 3 Selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl; and/or, the R 4 Selected from single bond, methylene, ethylene, propylene, butylene.
11. The method for continuously producing tertiary amines according to claim 1, wherein: the aldehyde is selected from acetaldehyde, paraldehyde, metaldehyde, propionaldehyde, glycolaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde or glyoxal.
12. The method for continuously producing tertiary amines according to claim 1, wherein: the method comprises the following steps: 1) Reacting the secondary amine with an excess of acid to obtain a mixture comprising the protic ionic liquid and unreacted acid; 2) Pumping the mixture and the aldehyde into the reactor through a plunger pump respectively to react, wherein the unreacted acid is used as a reducing agent to generate tertiary amine, so as to obtain a reaction system containing the tertiary amine, the reaction pressure is 0-5.0MPa, the temperature is 60-250 ℃, and the time is 5-300 minutes; 3) Adding secondary amine with the same type as that in the step 1) into the reaction system again for extraction separation to obtain an organic phase and a water phase; 4) Rectifying the organic phase to obtain tertiary amine, adding aldehyde and acid into the aqueous phase, and recycling the aqueous phase into the reactor to perform continuous reaction, wherein the adding of aldehyde and acid is performed to the extent that the mole ratio of secondary amine, aldehyde and acid in the reactor is unchanged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310584363.3A CN116606212A (en) | 2023-05-23 | 2023-05-23 | Method for economically and continuously preparing tertiary amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310584363.3A CN116606212A (en) | 2023-05-23 | 2023-05-23 | Method for economically and continuously preparing tertiary amine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116606212A true CN116606212A (en) | 2023-08-18 |
Family
ID=87683159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310584363.3A Pending CN116606212A (en) | 2023-05-23 | 2023-05-23 | Method for economically and continuously preparing tertiary amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116606212A (en) |
-
2023
- 2023-05-23 CN CN202310584363.3A patent/CN116606212A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107674195B (en) | Catalyst for synthesizing polyethylene oxide polymer and synthesis method thereof | |
| CN101318944A (en) | Purification process for epoxypropane | |
| CN114276254B (en) | Synthesis method of 3-methoxypropylamine | |
| CN112237749B (en) | Device and method for synthesizing trioxymethylene through salt effect reaction rectification | |
| CN110317138B (en) | Preparation method of tetramethylethylenediamine | |
| CN102382294A (en) | Preparation method for series products of polyether amine | |
| CN116606212A (en) | Method for economically and continuously preparing tertiary amine | |
| CN109364991A (en) | A kind of glyoxaline ion liquid catalyst | |
| CN116284159B (en) | Aqueous phase double-function catalyst and method for preparing dihydric alcohol in outer loop reaction process | |
| CN108752217B (en) | Synthesis method of dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| CN115785028B (en) | Preparation method of cardanol glycidyl ether with high epoxy value | |
| CN104829559A (en) | Method of preparing Nu-valerolactone from methyl levulinate | |
| CN112457157A (en) | Treatment method for preparing dimethyl carbonate by-products of methyl formate and methylal through carbonylation method | |
| CN103254101A (en) | Method and equipment for preparation of methyl carbamate | |
| CN113072449B (en) | Synthesis method of 4,4, 4-trifluoroacetylacetic acid ethyl ester | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| WO2023134439A1 (en) | Method for preparing tertiary amine by using secondary amine as raw material | |
| CN108484853B (en) | Production of butylated amino resin from low-methylol melamine | |
| CN102391070A (en) | Method for producing trimethylolpropane by utilizing formaldehyde | |
| CN109384654B (en) | Method for producing ethylene glycol mono-tert-butyl ether | |
| CN105820056B (en) | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines | |
| CN112279783B (en) | Method for preparing 3-hydroxypropionitrile under supercritical condition | |
| CN115806495B (en) | Method for co-producing propylene glycol methyl ether and isopropanolamine | |
| CN111018664B (en) | Synthesis method of 2-alkyl-1, 3-propanediol compound | |
| CN112479892B (en) | Methylation method of polymethine propane diamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |