CN102924286B - Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine - Google Patents
Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine Download PDFInfo
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- CN102924286B CN102924286B CN201210438301.3A CN201210438301A CN102924286B CN 102924286 B CN102924286 B CN 102924286B CN 201210438301 A CN201210438301 A CN 201210438301A CN 102924286 B CN102924286 B CN 102924286B
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- hydrogenation reaction
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- 238000002360 preparation method Methods 0.000 title description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 10
- 150000002466 imines Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 230000009466 transformation Effects 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229930013930 alkaloid Natural products 0.000 claims description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- KODVEKZCSDEPTL-UHFFFAOYSA-N butane-1,2,4-triamine Chemical compound NCCC(N)CN KODVEKZCSDEPTL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 β-aminoethyl Chemical group 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working effect Effects 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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a two-step hydrogenation method for preparing N1-(2-aminoethyl)-1,2-ethylenediamine. Under the effect of a first hydrogenation catalyst, over 80% and lower than 99% of iminodiacetonitrile is converted into an intermediate imine; and under the effect of a second hydrogenation catalyst and an addition agent, N1-(2-aminoethyl)-1,2-ethylenediamine reaction solution is obtained, and the conversion rate of iminodiacetonitrile is 100%. According to the method, large-scale continuous production of N1-(2-aminoethyl)-1,2-ethylenediamine can be achieved, selectivity of N1-(2-aminoethyl)-1,2-ethylenediamine is improved, the content of by-products is reduced, and generation of high polymer is reduced.
Description
Technical field
The present invention relates to a kind of N
1the preparation method of-(2-aminoethyl)-1，2-diaminoethane.
Background technology
N
1-(2-aminoethyl)-1，2-diaminoethane, molecular formula C
4h
13n
3, vehicle economy TA, is commonly called as diethylenetriamine, diethylenetriamine, Diethylenetriamine, Diethylenetriaminee (DETA), two (β-aminoethyl) amine, two-(2-aminoethyl) amine etc., English name: N
1-(2-aminoethyl) ethane-1,2-diamine, diethylenetriamine, is a kind of saturated fatty polyamines, yellowish or water white transparency thick liquid, has water absorbability, easily absorbs airborne moisture and carbonic acid gas.Mainly be used as air purifying preparation, lubricating oil additive, tensio-active agent, fabric finishing agent, paper strengthening agent, metal chelator, heavy metal hydrometallurgy and cyanideless electro-plating diffusant, ion exchange resin and polyamide resin etc.
In addition, DETA, as high reactivity epoxy curing agent, is mainly used in laminated product; Casted article; Tackiness agent and coating etc.; Also can be used as the intermediate of organic synthesis.
At present, ethyleneamines production line mainly contains two, i.e. dichloroethane law and girbotol process.After dichloroethane law process using ammonia reacts with ethylene dichloride, with sodium hydroxide neutralization, product amine steams together with water.The thick product steaming obtains the polyamines polyene such as quadrol and DETA through separation and purification.This method feature is that product composition distributes extensively, can adjust the product mix by the change of processing parameter, but energy consumption is large, and has a large amount of effluent brines, serious to equipment corrosion.Girbotol process adopts thanomin to face hydrogen amination, and two molecules of ethanol amine condensation dehydrations generate DETA.The defects such as this method exists service temperature higher, the easy coking inactivation of catalyst surface; And in product composition, contain more quadrol, piperazines and polyamines class by product are more, and follow-up separating technology is more complicated.
By iminodiacetonitrile, molecular formula NC-CH
2-NH-CH
2-CN, is called for short IDAN, and direct hydrogenation is prepared DETA, has transformation efficiency high, and selectivity is good, and the three wastes are few, and operational condition gentleness, to advantages such as equipment corrosion are few.
US2002058841 has introduced a kind of method that adopts solid particulate thunder Buddhist nun cobalt catalyst to be prepared by IDAN shortening to DETA in fixed-bed reactor, and under 10Mpa, DETA yield is 89%, the piperazine of by-product 7%.US4721811 has described a kind of method that adopts fixed bed raney catalyst to prepare DETA equally, working pressure 2800psi, and DETA yield is 85%.
But, above-mentioned two pieces of patent Introductions be all the miniature hydrogenator technique of one-part form.Loaded catalyst is few, only 100g loadings or 100ml left and right, and test period is also shorter.For large-scale production, still have many not clear and definite places, as the heat release problem of reactor bed, catalyzer work-ing life, the aspects such as the control device of by product (as piperazine) all do not describe.Meanwhile, because the special physical property of the raw material IDAN using adopts conventional hydrogenation mode can cause its polymerization, thereby stop up reactor, cause beds pressure drop to increase, and then affect reaction yield, even cause bed to subside.These all do not embody or are explained in above-mentioned patent.
Summary of the invention
The object of the present invention is to provide a kind of iminodiacetonitrile (IDAN) Hydrogenation for N
1-(2-aminoethyl)-1, the method of 2-quadrol (DETA), the method has solved the rotten aggregation problem causing because IDAN is unstable in technique amplification process, has guaranteed that Hydrogenation, for the industrialized continous-stable production of DETA, has improved the yield of DETA simultaneously.
The present invention adopts following technical scheme:
The invention provides the method for a kind of two step Hydrogenations for DETA, comprise the following steps: IDAN solution and hydrogen are added the first hydrogenator by (1), under the effect of the first hydrogenation catalyst, IDAN is carried out to the first hydrogenation reaction, obtain the first hydrogenation reaction solution, more than 80% and lower than 99% IDAN, be converted into intermediate imines;
(2) the first hydrogenation reaction solution obtaining in step (1) is added to the second hydrogenator, carry out the second hydrogenation reaction under the effect of the second hydrogenation catalyst and auxiliary agent, obtain DETA reaction solution, IDAN transformation efficiency reaches 100%.
IDAN solution of the present invention, the concentration of IDAN is 0.1～60wt%, preferably 10～30wt%.
The solvent of IDAN solution of the present invention be under normal pressure boiling point higher than the one or two or more containing amine, hydrocarbon, alcohol, ether or the acid amides of 1～5 carbon of 50 ℃, preferably under normal pressure boiling point higher than 50 ℃ containing the alcohol of 1～5 carbon or the one or two or more of ether, more preferably glycol dimethyl ether and methyl tertiary butyl ether, ethylene glycol, diethylene glycol, dioxan, tetrahydrofuran (THF), dioxolane etc.
The mol ratio of hydrogen and IDAN is 10～100: 1 in step of the present invention (1), preferably 20～50: 1.
The second hydrogenation reaction temperature of the present invention is at least higher 10 ℃ than the first hydrogenation reaction temperature; The first hydrogenation reaction temperature is 60～160 ℃, preferably 80～130 ℃; The second hydrogenation reaction temperature is 70～170 ℃, preferably 90～140 ℃.
The first hydrogenation reaction of the present invention and the second hydrogenation reaction pressure are 1～25Mpa, preferably 2～10Mpa.
In step of the present invention (1), the first hydrogenation catalyst is load or Reni catalyst, preferably loading type cobalt series catalyst, load-type nickel series catalysts, thunder Buddhist nun type cobalt series catalyst or thunder Buddhist nun type nickel catalyst, more preferably with silica gel, silicon-dioxide or diatomite are carrier, load is with the catalyzer of active constituent, the cobalt that wherein main active constituent is 20～30wt%, the nickel of 0.5～10wt%, the titanium of 0.01～0.5wt%, rhodium with 0.0003～0.03wt%, manganese with optional 0.01～0.3wt%, chromium, tungsten, vanadium, caesium, strontium, lanthanum, molybdenum, cerium, one or more in phosphorus and boron, with the weighing scale of carrier, for example MC507 (winning wound Degussa), A04 (fast triumphant chemical industry), A-7063 (Johnson Matthey), G67 (German south), G62 (German south),
1004 (winning wound Degussa), R111436 (Aladdin reagent) etc.
In step of the present invention (1), the weight ratio of the consumption of the first hydrogenation catalyst and imido grpup diacetonitrile consumption per hour is 0.05～120: 1, preferably 0.5～30: 1.
In step of the present invention (2), the second hydrogenation catalyst is load or Reni catalyst, preferably loading type cobalt series catalyst, load-type nickel series catalysts, thunder Buddhist nun type cobalt series catalyst or thunder Buddhist nun type nickel catalyst, more preferably thunder Buddhist nun type cobalt series catalyst or thunder Buddhist nun type nickel catalyst, for example ACTICAT
tM1900 (CatAlloy Ltd.), ACTICAT
tM3400 (CatAlloy Ltd.), ERTH2300 (the general Chemical Co., Ltd. in Dalian), ERTH2400 (the general Chemical Co., Ltd. in Dalian), Co55/Cr1.3 (the general Chemical Co., Ltd. in Dalian) etc.
In step of the present invention (2), the weight ratio of the consumption of the second hydrogenation catalyst and imido grpup diacetonitrile consumption per hour is 1～50: 1, preferably 6～20: 1.
In step of the present invention (2), auxiliary agent is liquefied ammonia or alkaline solution, wherein alkaline solution is selected from the one or two or more in alkali-metal hydroxide solution, alkali-metal alcoholate solution, the hydroxide solution of alkaline-earth metal or the alcoholate solution of alkaline-earth metal, or be selected from the one or two or more in quaternary ammonium alkali solution or alkaloid solution, the one or two or more of preferred alkali metal hydroxide solution; Wherein the solvent of alkaline solution is selected from the one or two or more in alcohol, amine, water, is preferably the one or two or more of methyl alcohol, ethanol, water.
In step of the present invention (2), alkaline concentration is 0.001～50wt%, preferably 0.01～10wt%, more preferably 2～5wt%.
After the feeding manner of auxiliary agent can be a) the first hydrogenation reaction solution and auxiliary agent mixing in step of the present invention (2), add the second hydrogenator to contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst; Or b) the first hydrogenation reaction solution and auxiliary agent add respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst.
When in step of the present invention (2), auxiliary agent is liquefied ammonia, the mol ratio of liquefied ammonia consumption and IDAN consumption is 1: 0.005～40, preferably 1: 0.05～10; Or described auxiliary agent is alkaline solution, in alkaline solution, the mol ratio of the consumption of alkali cpd and IDAN consumption is 1: 60～800, preferably 1: 120～500.
The feeding manner of the present invention b) feeding manner of auxiliary agent is sub-thread charging or multiply charging, and in the time of the charging of auxiliary agent multiply, per share inlet amount ratio is any, and preferred per share inlet amount equates.
In step of the present invention (1), the reactor of the first hydrogenation reaction is continuous stirred tank or fixed bed, preferably fixed bed; In step of the present invention (2), the reactor of the second hydrogenation reaction is fixed bed.
In the time that cyano compound is carried out to hydrogenation, in order to improve activity or the selectivity of catalyzer, promote hydrogenation effect thereby tend to add alkaline matter.But very easily polymerization is rotten under alkaline condition for IDAN.Add by conventional methods alkali, can cause a large amount of polymerisates to produce.
In the present invention, adopt two step hydrogenation techniques, first in the first hydrogenation reaction, do not make used additives, and the first hydrogenation reaction temperature is lower than the second hydrogenation reaction temperature, IDAN is after the first hydrogenation reaction, can make the cyano group major part in IDAN be converted into intermediate imines, because intermediate imines has not had the stronger cyano group of electrophilic, stable in properties, under alkaline condition, can as IDAN, there is not again polymerization, therefore, now in the second hydrogenation reaction, add alkaline assistant, can improve on the one hand the activity and selectivity of hydrogenation catalyst, on the other hand, avoid again IDAN polymerization, finally make DETA yield improve, reduced the generation of by product piperazine derivative and polymkeric substance simultaneously.
Positively effect of the present invention is:
(1) improve transformation efficiency and the effective rate of utilization of IDAN, reduced the generation of by-product piperazine and derivative thereof;
(2) add after auxiliary agent, improved catalytic activity, promoted hydrogenation speed, thereby reduced the volume of reactor, cost-saving;
(3) avoided the polymerization of IDAN, reduced reactor plugs risk, thereby made large-scale continuous production become possibility.
(4) reaction solution composition is stable, and steady, the follow-up separating difficulty of technique is low, and between product batches, difference is little.
Embodiment
Describe the present invention below by embodiment example.Scope of the present invention is not limited to this embodiment.
Analytical conditions for gas chromatography in the present invention is as follows: chromatographic column: Agilent HP-5MS or HP-5 (30m × 0.32mm × 0.25um); Temperature of vaporization chamber: 280 ℃; Flame ionization ditector temperature: 300 ℃; Column temperature: first stage program temperature rise, 100 ℃ of initial temperatures, keep rising to 260 ℃ with the speed of 15 ℃/min after 0.5 minute, keep 8 minutes; Splitting ratio: 30: 1; Column flow rate: 1.5ml/min; Carrier gas: high pure nitrogen; Hydrogen flowing quantity: 40ml/min; Air flow quantity: 400ml/min; Area normalization method is calculated the content of each component, is accurate to 0.01%.
Embodiment 1:
The preparation of the first hydrogenation catalyst
Take respectively 101g cobalt chloride hexahydrate, 9.8g Nickel dichloride hexahydrate, 1.1g titanous chloride, 20mg tri-rhodium trichloride hydrates, 0.40g potassium molybdate wiring solution-forming, adopt pickling process, be impregnated on 100g diatomite, under infrared lamp, be dried after 24h, press strip moulding, roasting 5h is for subsequent use at 580 ℃.Based on the weight of carrier, cobalt contents is 25%, and nickel content is 2.4%, and titanium content is 0.3%, and rhodium content is 0.008%, and molybdenum content is 0.16%.
Catalyzer reduces 3 hours before use at 475 ℃ under the gas mixture normal pressure of hydrogen and nitrogen (volume ratio 1: 10), makes the first hydrogenation catalyst, amplifies according to quality proportioning equal proportion as need amplify to produce.
Embodiment 2:
The first hydrogenator is fixed bed, uses homemade the first hydrogenation catalyst in embodiment 1, and consumption is 45kg.The second hydrogenator is fixed bed, uses ERTH2300 (the general Chemical Co., Ltd. in Dalian) to do the second hydrogenation catalyst, and consumption is 22.5kg.The ethylene glycol dimethyl ether solution of the IDAN of 15wt% enters the first hydrogenator with the input speed of 15kg/h,
Under 110 ℃, 8Mpa hydrogen partial pressure, carry out the first hydrogenation reaction, in the time that 86% IDAN in the first hydrogenation reaction solution is converted into intermediate imines, the aqueous sodium hydroxide solution of the first hydrogenation reaction solution, four gangs of 2wt% adds respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst, the amount of the aqueous sodium hydroxide solution of per share 2wt% is 59g/h, and the second hydrogenation reaction is carried out under 125～133 ℃, 8Mpa hydrogen partial pressure.
IDAN transformation efficiency 100% in DETA reaction solution, DETA yield 90.4%, piperazine yield 6.7%.
In the first hydrogenator, collect 10g polymkeric substance, the second hydrogenator non-polymer.
Embodiment 3
The first hydrogenator is continuous stirred tank, use R111436 (Aladdin reagent) to do the first hydrogenation catalyst, consumption is 45kg, the second hydrogenator is fixed bed, use Co55/Cr1.3 (the general Chemical Co., Ltd. in Dalian) to do the second hydrogenation catalyst, consumption is 22.5kg.The tetrahydrofuran solution of the IDAN of 5wt% enters the first hydrogenator with the input speed of 30kg/h, under 110 ℃, 4Mpa hydrogen partial pressure, carry out the first hydrogenation reaction, in the time that 98.9% IDAN in the first hydrogenation reaction solution is converted into intermediate imines, the aqueous sodium hydroxide solution of the first hydrogenation reaction solution, two gangs of 5wt% adds respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst, the amount of the aqueous sodium hydroxide solution of per share 5wt% is 21g/h, and the second hydrogenation reaction is carried out under 150 ℃, 4Mpa hydrogen partial pressure.
IDAN transformation efficiency 100% in DETA reaction solution, DETA yield 94.0%, piperazine yield 2.7%.
In the first hydrogenator, collect 5g polymkeric substance, the second hydrogenator non-polymer.
Embodiment 4
The first hydrogenator is fixed bed, uses homemade the first hydrogenation catalyst in embodiment 1, and consumption is 25.5kg.The second hydrogenator is fixed bed, uses ACTICAT
tM3400 (CatAlloy Ltd.) do the second hydrogenation catalyst, and consumption is 22.5kg.The dioxane solution of the IDAN of 20wt% thinks that the input speed of 15kg/h enters the first hydrogenator, at 124 ℃, under 12Mpa hydrogen partial pressure, carry out the first hydrogenation reaction, in the time that 90% IDAN in the first hydrogenation reaction solution is converted into intermediate imines, the first hydrogenation reaction solution, the potassium hydroxide aqueous solution of four gangs of 3wt% adds respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst, the amount of the potassium hydroxide aqueous solution of per share 3wt% is respectively 51.75g/h, 41.75g/h, 31.75g/h, 21.75g/h, the second hydrogenation reaction is at 140 ℃, under 12Mpa, carry out.
IDAN transformation efficiency 100% in DETA reaction solution, DETA yield 95.7%, piperazine yield 1.8%.
In the first hydrogenator, collect 7.9g polymkeric substance, the second hydrogenator non-polymer.
Embodiment 5
The first hydrogenator is fixed bed, uses
1004 (winning wound Degussa) are done the first hydrogenation catalyst, and consumption is 54kg.The second hydrogenator is fixed bed, uses ERTH2400 (the general Chemical Co., Ltd. in Dalian) to do the second hydrogenation catalyst, and consumption is 45kg.The tetrahydrofuran solution of the IDAN of 30wt% enters the first hydrogenator with the input speed of 10kg/h, under 90 ℃, 10Mpa hydrogen partial pressure, carry out the first hydrogenation reaction, in the time that 90.1% IDAN in the first hydrogenation reaction solution is converted into intermediate imines, the first hydrogenation reaction solution, three strands of liquefied ammonia add respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst, the amount of per share liquefied ammonia is 27.8g/h, and the second hydrogenation reaction is carried out under 120 ℃, 8Mpa hydrogen partial pressure.
IDAN transformation efficiency 100% in DETA reaction solution, DETA yield 93.5%, piperazine yield 3.7%.
In the first hydrogenator, collect 15g polymkeric substance, the second hydrogenator non-polymer.
Comparative example
Only use the first hydrogenator fixed bed in embodiment 2, do not use the second hydrogenator, use ERTH2300 (the general Chemical Co., Ltd. in Dalian) to do hydrogenation catalyst in the first hydrogenator, consumption is 45kg.
Input speed is, after the ethylene glycol dimethyl ether solution of 15wt%IDAN of 15kg/h and 2wt% aqueous sodium hydroxide solution that input speed is 236g/h mix, to enter the first hydrogenator, under 110 ℃, 8Mpa hydrogen partial pressure, carries out hydrogenation reaction.
Sampling analysis after 2h, in DETA reaction solution, IDAN transformation efficiency is increased to 99.6%, DETA yield 78.8%, piperazine yield 11.4%.But after 20h, before and after the first hydrogenator, pressure drop is increased to 1Mpa, now analyzes DETA reaction solution, DETA yield is 46.1%, piperazine yield 19.6%.
In the first hydrogenator, collect 2.8kg polymkeric substance.
Claims (13)
1. a step Hydrogenation is for N
1-(2-aminoethyl)-1, the method of 2-quadrol, comprise the following steps: iminodiacetonitrile solution and hydrogen are added the first hydrogenator by (1), under the effect of the first hydrogenation catalyst, iminodiacetonitrile is carried out to the first hydrogenation reaction, obtain the first hydrogenation reaction solution, more than 80% and lower than 99% iminodiacetonitrile, be converted into intermediate imines, described the first hydrogenation catalyst is supported cobalt series catalysts, load-type nickel series catalysts, thunder Buddhist nun type cobalt series catalyst or thunder Buddhist nun type nickel catalyst, the weight ratio of the consumption of the first hydrogenation catalyst and iminodiacetonitrile consumption per hour is 0.05～120:1, the first hydrogenation reaction does not make used additives,
(2) the first hydrogenation reaction solution step (1) being obtained adds the second hydrogenator, carries out the second hydrogenation reaction under the effect of the second hydrogenation catalyst and auxiliary agent, obtains N
1-(2-aminoethyl)-1，2-diaminoethane reaction solution, iminodiacetonitrile transformation efficiency reaches the consumption of 100%, the second hydrogenation catalyst and the weight ratio of iminodiacetonitrile consumption per hour is 1～50:1;
Described the second hydrogenation reaction temperature is at least higher 10 ℃ than the first hydrogenation reaction temperature, and the first hydrogenation reaction temperature is 60～160 ℃, and the second hydrogenation reaction temperature is 70～170 ℃; The first hydrogenation reaction and the second hydrogenation reaction pressure are 1～25Mpa.
2. method according to claim 1, is characterized in that, described the second hydrogenation reaction temperature is at least higher 10 ℃ than the first hydrogenation reaction temperature of reaction, and the first hydrogenation reaction temperature is 80～130 ℃, and the second hydrogenation reaction temperature is 90～140 ℃.
3. method according to claim 1, it is characterized in that, the first hydrogenation catalyst is take silica gel, silicon-dioxide or diatomite as carrier, load is with the catalyzer of active constituent, the cobalt that wherein main active constituent is 20～30wt%, the nickel of 0.5～10wt%, the titanium of 0.01～0.5wt%, the rhodium of 0.0003～0.03wt%, and one or more in the manganese of 0.01 optional～0.3wt%, chromium, tungsten, vanadium, caesium, strontium, lanthanum, molybdenum, cerium, phosphorus and boron, with the weighing scale of carrier; The weight ratio of the consumption of the first hydrogenation catalyst and iminodiacetonitrile consumption per hour is 0.5～30:1.
4. method according to claim 1, is characterized in that, the second hydrogenation catalyst is supported cobalt series catalysts, load-type nickel series catalysts, thunder Buddhist nun type cobalt series catalyst or thunder Buddhist nun type nickel catalyst.
5. method according to claim 4, is characterized in that, the weight ratio of the consumption of the second hydrogenation catalyst and iminodiacetonitrile consumption per hour is 6～20:1.
6. according to the method described in any one in claim 1-5, it is characterized in that, in described step (2), auxiliary agent is liquefied ammonia or alkaline solution; Wherein alkaline solution is selected from the one or two or more in alkali-metal hydroxide solution, alkali-metal alcoholate solution, the hydroxide solution of alkaline-earth metal or the alcoholate solution of alkaline-earth metal, or is selected from the one or two or more in quaternary ammonium alkali solution or alkaloid solution; The concentration of alkaline solution is 0.001～50wt%.
7. method according to claim 6, is characterized in that, the concentration of alkaline solution is 0.01～10wt%.
8. method according to claim 7, is characterized in that, the concentration of alkaline solution is 2～5wt%.
9. method according to claim 6, is characterized in that, when described auxiliary agent is liquefied ammonia, the mol ratio of liquefied ammonia consumption and iminodiacetonitrile consumption is 1:0.005～40; Or described auxiliary agent is alkaline solution, in alkaline solution, the mol ratio of the consumption of alkali cpd and iminodiacetonitrile consumption is 1:60～800.
10. method according to claim 9, is characterized in that, when described auxiliary agent is liquefied ammonia, the mol ratio of liquefied ammonia consumption and iminodiacetonitrile consumption is 1:0.05～10; Or described auxiliary agent is alkaline solution, in alkaline solution, the mol ratio of the consumption of alkali cpd and iminodiacetonitrile consumption is 1:120～500.
11. according to the method described in claim 1 or 9, it is characterized in that, after the feeding manner of auxiliary agent can be a) the first hydrogenation reaction solution and auxiliary agent mixing in described step (2), add the second hydrogenator to contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst; Or b) the first hydrogenation reaction solution and auxiliary agent add respectively the second hydrogenator, contact and carry out the second hydrogenation reaction with the second hydrogenation catalyst.
12. methods according to claim 11, is characterized in that, the feeding manner b) feeding manner of auxiliary agent is sub-thread charging or multiply charging.
13. according to the method described in claim 1 or 12, it is characterized in that, in described step (1), the reactor of the first hydrogenation reaction is continuous stirred tank or fixed bed; In described step (2), the reactor of the second hydrogenation reaction is fixed bed.
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| PCT/CN2013/071043 WO2014067242A1 (en) | 2012-10-31 | 2013-01-28 | Method of preparing n1-(2-aminoethyl)-1,2-ethylenediamine |
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| CN107188809A (en) * | 2016-03-14 | 2017-09-22 | 史小鸣 | A kind of preparation of diethylenetriamine |
| CN111644196B (en) * | 2020-06-17 | 2021-02-09 | 山东达民化工股份有限公司 | High-selectivity preparation method of methylpentamethylenediamine by adopting composite catalytic system |
| CN112321438B (en) * | 2020-11-25 | 2024-04-16 | 重庆华峰化工有限公司 | Synthesis method of hexamethylenediamine |
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| US4721811A (en) * | 1985-08-26 | 1988-01-26 | W. R. Grace & Co. | Synthesis of aliphatic polyamines |
| NZ232379A (en) * | 1989-02-07 | 1991-05-28 | Grace W R & Co | Batchwise preparation of non-cyclic aliphatic polyamines by catalytic hydrogenation of a non-cyclic aliphatic polynitrile |
| DE19540191C1 (en) * | 1995-10-30 | 1996-11-21 | Degussa | Prepn. of isophorone:di:amine from isophorone nitrile |
| DE10056840A1 (en) * | 2000-11-16 | 2002-05-23 | Basf Ag | Continuous hydrogenation of nitrites to primary amines over activated Raney catalyst, involves hydrogenating nitrites in absence of ammonia and basic alkali or alkaline earth metal compounds |
| DE10056839A1 (en) * | 2000-11-16 | 2002-05-23 | Basf Ag | Process for the hydrogenation of nitriles on Raney catalysts |
| US6649799B2 (en) * | 2000-12-23 | 2003-11-18 | Degussa Ag | Method for producing primary and secondary amines by hydrogenation of nitriles and imines |
| DE102006006625A1 (en) * | 2006-02-14 | 2007-08-16 | Degussa Gmbh | Process for the preparation of amines by conditioning the catalyst with ammonia |
| EP1873137B1 (en) * | 2006-06-29 | 2011-08-31 | Mitsubishi Gas Chemical Company, Inc. | Production of Xylenediamines |
| RU2478092C2 (en) * | 2007-03-01 | 2013-03-27 | Басф Се | Method of producing mixtures of ethylene amines |
| EP2132163A1 (en) * | 2007-03-01 | 2009-12-16 | Basf Se | Method for producing ethyleneamines from untreated aan |
| JP5565799B2 (en) * | 2010-04-22 | 2014-08-06 | 独立行政法人産業技術総合研究所 | Method for producing hydrides of organic nitrile compounds in supercritical carbon dioxide |
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