CN102924286A - A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine - Google Patents
A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine Download PDFInfo
- Publication number
- CN102924286A CN102924286A CN2012104383013A CN201210438301A CN102924286A CN 102924286 A CN102924286 A CN 102924286A CN 2012104383013 A CN2012104383013 A CN 2012104383013A CN 201210438301 A CN201210438301 A CN 201210438301A CN 102924286 A CN102924286 A CN 102924286A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogenation reaction
- hydrogenation
- solution
- preferred
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 103
- 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 42
- 238000000034 method Methods 0.000 claims abstract description 27
- 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 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 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 13
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 230000009466 transformation Effects 0.000 claims description 9
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 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
- 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
- 238000005303 weighing Methods 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
- 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
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- 239000000126 substance Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 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
- 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
- 239000000654 additive Substances 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
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 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
- 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
- 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
- 230000002950 deficient 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
- 150000002431 hydrogen 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
- 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
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical class O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 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
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 is mainly used in laminated product as the high reactivity epoxy curing agent; Casted article; Tackiness agent and coating etc.; Also can be used as the intermediate of organic synthesis.
At present, the ethyleneamines production line mainly contains two, i.e. dichloroethane law and girbotol process.With the sodium hydroxide neutralization, product amine steams with water after dichloroethane law process using ammonia and the ethylene dichloride reaction.The thick product that steams obtains the polyamines polyenes such as quadrol and DETA through separation and purification.These method characteristics are that group of products becomes to distribute extensively, can adjust the product mix by the change of processing parameter, but energy consumption is large, and a large amount of effluent brines are arranged, and are serious to equipment corrosion.Girbotol process adopts thanomin to face the hydrogen amination, and two molecules of ethanol amine condensations dehydration generates DETA.This method exists service temperature higher, the defectives such as the easy coking inactivation of catalyst surface; And product contains more quadrol in forming, and piperazines and polyamines class by product are more, and follow-up separating technology is complicated.
By iminodiacetonitrile, molecular formula NC-CH
2-NH-CH
2-CN is called for short IDAN, and direct hydrogenation prepares DETA, has a transformation efficiency high, and selectivity is good, and the three wastes are few, and operational condition is gentle, to advantages such as equipment corrosion are few.
US2002058841 has introduced a kind of method that adopts solid particulate thunder Buddhist nun cobalt catalyst the IDAN shortening to be prepared DETA in fixed-bed reactor, under 10Mpa, the 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, and working pressure 2800psi, DETA yield are 85%.
But, above-mentioned two pieces of patent Introductions all be the miniature hydrogenator technique of one-part form.Loaded catalyst is few, and only about 100g loadings or 100ml, test period is also shorter.For large-scale production, still have many not clear and definite places, such as the heat release problem of reactor bed, catalyzer work-ing life, the aspects such as control device of by product (such as piperazine) all do not describe.Simultaneously, because the special physical property of the raw material IDAN that uses adopts conventional hydrogenation mode can cause its polymerization, thereby stops up reactor, cause the beds pressure drop to increase, and then affect reaction yield, even cause bed to subside.These all do not embody in above-mentioned patent or are explained.
Summary of the invention
The object of the present invention is to provide the standby N of a kind of iminodiacetonitrile (IDAN) Hydrogenation
1-(2-aminoethyl)-1, the method of 2-quadrol (DETA), the method has solved the rotten aggregation problem that causes because IDAN is unstable in the technique amplification process, has guaranteed the standby industrialized continous-stable production of DETA of Hydrogenation, has improved simultaneously the yield of DETA.
The present invention adopts following technical scheme:
The invention provides the method for the standby DETA of a kind of two step Hydrogenations, may further comprise the steps: (1) adds the first hydrogenator with IDAN solution and hydrogen, under the effect of the first hydrogenation catalyst, IDAN is carried out the first hydrogenation reaction, obtain the first hydrogenation reaction solution, more than 80% and be lower than 99% IDAN and be converted into the intermediate imines;
(2) the first hydrogenation reaction solution that obtains in the step (1) is added the second hydrogenator, carry out the second hydrogenation reaction under the effect of the second hydrogenation catalyst and auxiliary agent, obtain the DETA reaction solution, the IDAN transformation efficiency reaches 100%.
IDAN solution of the present invention, the concentration of IDAN are 0.1～60wt%, preferred 10～30wt%.
The solvent of IDAN solution of the present invention is the one or two or more that boiling point is higher than 50 ℃ the amine that contains 1～5 carbon, hydrocarbon, alcohol, ether or acid amides under the normal pressure, boiling point is higher than 50 ℃ the alcohol that contains 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. under the preferred normal pressure.
The mol ratio of hydrogen and IDAN is 10～100: 1 in the step of the present invention (1), preferred 20～50: 1.
The second hydrogenation reaction temperature of the present invention is higher at least 10 ℃ than the first hydrogenation reaction temperature; The first hydrogenation reaction temperature is 60～160 ℃, preferred 80～130 ℃; The second hydrogenation reaction temperature is 70～170 ℃, preferred 90～140 ℃.
The first hydrogenation reaction of the present invention and the second hydrogenation reaction pressure are 1～25Mpa, preferred 2～10Mpa.
The first hydrogenation catalyst is load or Reni catalyst in the step of the present invention (1), preferred loading type cobalt series catalyst, the 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, wherein main active constituent is the cobalt of 20～30wt%, 0.5 the nickel of～10wt%, 0.01 the titanium of～0.5wt%, rhodium with 0.0003～0.03wt%, manganese with the 0.01～0.3wt% that chooses wantonly, chromium, tungsten, vanadium, caesium, strontium, lanthanum, molybdenum, cerium, in phosphorus and the boron one or more, weighing scale with carrier, MC507 (win wound Degussa) for example, A04 (fast triumphant chemical industry), A-7063 (Johnson Matthey), G67 (German south), G62 (German south)
1004 (winning the wound Degussa), R111436 (Aladdin reagent) etc.
The consumption of the first hydrogenation catalyst is 0.05～120: 1 with the weight ratio of imido grpup diacetonitrile consumption per hour in the step of the present invention (1), preferred 0.5～30: 1.
The second hydrogenation catalyst is load or Reni catalyst in the step of the present invention (2), preferred 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 industry in Dalian company limited), ERTH2400 (the general chemical industry in Dalian company limited), Co55/Cr1.3 (the general chemical industry in Dalian company limited) etc.
The consumption of the second hydrogenation catalyst is 1～50: 1 with the weight ratio of imido grpup diacetonitrile consumption per hour in the step of the present invention (2), preferred 6～20: 1.
Auxiliary agent is liquefied ammonia or alkaline solution in the step of the present invention (2), wherein alkaline solution is selected from the one or two or more in the alcoholate solution of the hydroxide solution of alkali-metal hydroxide solution, alkali-metal alcoholate solution, alkaline-earth metal or alkaline-earth metal, or be selected from one or two or more in quaternary ammonium alkali solution or the 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, the water, is preferably the one or two or more of methyl alcohol, ethanol, water.
Alkaline concentration is 0.001～50wt% in the step of the present invention (2), preferred 0.01～10wt%, more preferably 2～5wt%.
The feeding manner of auxiliary agent can be for after a) the first hydrogenation reaction solution and auxiliary agent mix in the step of the present invention (2), add the second hydrogenator and contact with the second hydrogenation catalyst and carry out the second hydrogenation reaction; Or b) the first hydrogenation reaction solution and auxiliary agent add respectively the second hydrogenator, contact with the second hydrogenation catalyst and carry out the second hydrogenation reaction.
When auxiliary agent was liquefied ammonia in the step of the present invention (2), the mol ratio of liquefied ammonia consumption and IDAN consumption was 1: 0.005～40, preferred 1: 0.05～10; Or described auxiliary agent is alkaline solution, and the mol ratio of the consumption of alkali cpd and IDAN consumption is 1: 60～800 in the alkaline solution, preferred 1: 120～500.
Feeding manner b of the present invention) feeding manner of auxiliary agent is sub-thread charging or multiply charging, and when the charging of auxiliary agent multiply, per share inlet amount ratio is any, and preferred per share inlet amount equates.
The reactor of the first hydrogenation reaction is continuous stirred tank or fixed bed in the step of the present invention (1), preferred fixed bed; The reactor of the second hydrogenation reaction is fixed bed in the step of the present invention (2).
When cyano compound is carried out hydrogenation, for activity or the selectivity of improving catalyzer, promote the 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, at first do not make used additives in the first hydrogenation reaction, and the first hydrogenation reaction temperature is lower than the second hydrogenation reaction temperature, IDAN through the first hydrogenation reaction after, can make the cyano group major part among the IDAN be converted into the intermediate imines, because the intermediate imines has not had the stronger cyano group of electrophilic, stable in properties, under alkaline condition polymerization can not occur as IDAN again, therefore, add alkaline assistant this moment in the second hydrogenation reaction, can improve on the one hand the activity and selectivity of hydrogenation catalyst, on the other hand, avoid again the IDAN polymerization, the DETA yield is improved, reduced simultaneously the generation of by product piperazine derivative and polymkeric substance.
Positively effect of the present invention is:
(1) improves transformation efficiency and the effective rate of utilization of IDAN, reduced the generation of by-product piperazine and derivative thereof;
(2) behind the interpolation auxiliary agent, improve catalytic activity, promoted hydrogenation speed, thereby reduced the volume of reactor, saved cost;
(3) avoided the polymerization of IDAN, reduced the reactor plugs risk, thereby made large-scale continuous production become possibility.
(4) the reaction solution composition is stable, and steady, the follow-up separating difficulty of technique is low, and difference is little between product batches.
Embodiment
Describe the present invention below by the embodiment example.Scope of the present invention is not limited to this embodiment.
Analytical conditions for gas chromatography among the present invention is as follows: chromatographic column: and 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 that the speed with 15 ℃/min rises to 260 ℃ 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 by weighing respectively 101g cobalt chloride hexahydrate, 9.8g Nickel dichloride hexahydrate, 1.1g titanous chloride, 20mg three rhodium trichloride hydrates, 0.40g potassium molybdate wiring solution-forming, adopt pickling process, be impregnated on the 100g diatomite, under infrared lamp behind the dry 24h, the press strip moulding, 580 ℃ of lower roasting 5h are for subsequent use.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 reducing 3 hours under 475 ℃, makes the first hydrogenation catalyst before use under the gas mixture normal pressure of hydrogen and nitrogen (volume ratio 1: 10), amplify to produce such as need and amplify according to quality proportioning equal proportion.
Embodiment 2:
The first hydrogenator is fixed bed, uses homemade the first hydrogenation catalyst among the embodiment 1, and consumption is 45kg.The second hydrogenator is fixed bed, uses ERTH2300 (the general chemical industry in Dalian company limited) 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, when 86% IDAN in the first hydrogenation reaction solution is converted into the intermediate imines, the aqueous sodium hydroxide solution of the first hydrogenation reaction solution, four gangs of 2wt% adds respectively the second hydrogenator, contact with the second hydrogenation catalyst and to carry out the second hydrogenation reaction, 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 the DETA reaction solution, DETA yield 90.4%, piperazine yield 6.7%.
Collect the 10g polymkeric substance in the first hydrogenator, 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, and the second hydrogenator is fixed bed, use Co55/Cr1.3 (the general chemical industry in Dalian company limited) 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, when 98.9% IDAN in the first hydrogenation reaction solution is converted into the intermediate imines, the aqueous sodium hydroxide solution of the first hydrogenation reaction solution, two gangs of 5wt% adds respectively the second hydrogenator, contact with the second hydrogenation catalyst and to carry out the second hydrogenation reaction, 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 the DETA reaction solution, DETA yield 94.0%, piperazine yield 2.7%.
Collect the 5g polymkeric substance in the first hydrogenator, the second hydrogenator non-polymer.
Embodiment 4
The first hydrogenator is fixed bed, uses homemade the first hydrogenation catalyst among the 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 ℃, carry out the first hydrogenation reaction under the 12Mpa hydrogen partial pressure, when 90% IDAN in the first hydrogenation reaction solution is converted into the intermediate imines, the first hydrogenation reaction solution, the potassium hydroxide aqueous solution of four gangs of 3wt% adds respectively the second hydrogenator, contact with the second hydrogenation catalyst and to carry out the second hydrogenation reaction, 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 ℃, carry out under the 12Mpa.
IDAN transformation efficiency 100% in the DETA reaction solution, DETA yield 95.7%, piperazine yield 1.8%.
Collect the 7.9g polymkeric substance in the first hydrogenator, the second hydrogenator non-polymer.
Embodiment 5
The first hydrogenator is fixed bed, uses
1004 (winning the wound Degussa) are done the first hydrogenation catalyst, and consumption is 54kg.The second hydrogenator is fixed bed, uses ERTH2400 (the general chemical industry in Dalian company limited) 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, when 90.1% IDAN in the first hydrogenation reaction solution is converted into the intermediate imines, the first hydrogenation reaction solution, three strands of liquefied ammonia add respectively the second hydrogenator, contact with the second hydrogenation catalyst and to carry out the second hydrogenation reaction, 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 the DETA reaction solution, DETA yield 93.5%, piperazine yield 3.7%.
Collect the 15g polymkeric substance in the first hydrogenator, the second hydrogenator non-polymer.
The comparative example
Only use the first hydrogenator fixed bed among the embodiment 2, do not use the second hydrogenator, use ERTH2300 (the general chemical industry in Dalian company limited) 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, carries out hydrogenation reaction under 110 ℃, 8Mpa hydrogen partial pressure.
Sampling analysis behind the 2h, the IDAN transformation efficiency is increased to 99.6%, DETA yield 78.8% in the DETA reaction solution, piperazine yield 11.4%.But through behind the 20h, pressure drop is increased to 1Mpa before and after the first hydrogenator, and analyze the DETA reaction solution this moment, and the DETA yield is 46.1%, piperazine yield 19.6%.
Collect the 2.8kg polymkeric substance in the first hydrogenator.
Claims (9)
1. a step Hydrogenation is for N
1-(2-aminoethyl)-1, the method of 2-quadrol, may further comprise the steps: (1) adds the first hydrogenator with iminodiacetonitrile solution and hydrogen, under the effect of the first hydrogenation catalyst, iminodiacetonitrile is carried out the first hydrogenation reaction, obtain the first hydrogenation reaction solution, more than 80% and be lower than 99% imido grpup diacetonitrile and be converted into the intermediate imines;
(2) the first hydrogenation reaction solution that step (1) is 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, imido grpup diacetonitrile transformation efficiency reaches 100%.
2. method according to claim 1 is characterized in that, described the second hydrogenation reaction temperature is higher at least 10 ℃ than the first hydrogenation reaction temperature, the first hydrogenation reaction temperature is 60～160 ℃, preferred 80～130 ℃, the second hydrogenation reaction temperature is 70～170 ℃, preferred 90～140 ℃; The first hydrogenation reaction and the second hydrogenation reaction pressure are 1～25Mpa.
3. method according to claim 1, it is characterized in that, the first hydrogenation catalyst is load or Reni catalyst, preferred loading type cobalt series catalyst, the 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, wherein main active constituent is the cobalt of 20～30wt%, 0.5 the nickel of～10wt%, 0.01 the titanium of～0.5wt%, 0.0003 the rhodium of～0.03wt%, and the manganese of 0.01 optional～0.3wt%, chromium, tungsten, vanadium, caesium, strontium, lanthanum, molybdenum, cerium, in phosphorus and the boron one or more are with the weighing scale of carrier; The consumption of the first hydrogenation catalyst is 0.05～120: 1 with the weight ratio of imido grpup diacetonitrile consumption per hour, preferred 0.5～30: 1.
4. method according to claim 1, it is characterized in that, the second hydrogenation catalyst is load or Reni catalyst, preferred 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; The consumption of the second hydrogenation catalyst is 1～50: 1 with the weight ratio of imido grpup diacetonitrile consumption per hour, preferred 6～20: 1.
5. each described method is characterized in that according to claim 1-4, and auxiliary agent is liquefied ammonia or alkaline solution in the described step (2); Wherein alkaline solution is selected from the one or two or more in the alcoholate solution of the hydroxide solution of alkali-metal hydroxide solution, alkali-metal alcoholate solution, alkaline-earth metal or alkaline-earth metal, or be selected from one or two or more in quaternary ammonium alkali solution or the alkaloid solution, the one or two or more of preferred alkali metal hydroxide solution; The concentration of alkaline solution is 0.001～50wt%, preferred 0.01～10wt%, more preferably 2～5wt%.
6. method according to claim 5 is characterized in that, when described auxiliary agent was liquefied ammonia, the mol ratio of liquefied ammonia consumption and imido grpup diacetonitrile consumption was 1: 0.005～40, preferred 1: 0.05～10; Or described auxiliary agent is alkaline solution, and the mol ratio of the consumption of alkali cpd and imido grpup diacetonitrile consumption is 1: 60～800 in the alkaline solution, preferred 1: 120～500.
7. according to claim 1 or 6 described methods, it is characterized in that, the feeding manner of auxiliary agent can be for after a) the first hydrogenation reaction solution and auxiliary agent mix in the described step (2), add the second hydrogenator and contact with the second hydrogenation catalyst and carry out the second hydrogenation reaction; Or b) the first hydrogenation reaction solution and auxiliary agent add respectively the second hydrogenator, contact with the second hydrogenation catalyst and carry out the second hydrogenation reaction.
8. method according to claim 7 is characterized in that, feeding manner b) feeding manner of auxiliary agent is sub-thread charging or multiply charging.
9. according to claim 1 or 8 described methods, it is characterized in that, the reactor of the first hydrogenation reaction is continuous stirred tank or fixed bed in the described step (1), preferred fixed bed; The reactor of the second hydrogenation reaction is fixed bed in the described step (2).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210438301.3A CN102924286B (en) | 2012-10-31 | 2012-10-31 | Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine |
| PCT/CN2013/071043 WO2014067242A1 (en) | 2012-10-31 | 2013-01-28 | Method of preparing n1-(2-aminoethyl)-1,2-ethylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210438301.3A CN102924286B (en) | 2012-10-31 | 2012-10-31 | Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924286A true CN102924286A (en) | 2013-02-13 |
| CN102924286B CN102924286B (en) | 2014-06-11 |
Family
ID=47639249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210438301.3A Active CN102924286B (en) | 2012-10-31 | 2012-10-31 | Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102924286B (en) |
| WO (1) | WO2014067242A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601644A (en) * | 2013-11-21 | 2014-02-26 | 万华化学集团股份有限公司 | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine |
| CN107188809A (en) * | 2016-03-14 | 2017-09-22 | 史小鸣 | A kind of preparation of diethylenetriamine |
| CN111644196A (en) * | 2020-06-17 | 2020-09-11 | 山东达民化工股份有限公司 | High-selectivity preparation method of methylpentamethylenediamine by adopting composite catalytic system |
| CN112321438A (en) * | 2020-11-25 | 2021-02-05 | 重庆华峰化工有限公司 | Synthesis method of hexamethylene diamine |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721811A (en) * | 1985-08-26 | 1988-01-26 | W. R. Grace & Co. | Synthesis of aliphatic polyamines |
| EP0382508A2 (en) * | 1989-02-07 | 1990-08-16 | Hampshire Chemical Corporation | The preparation of polyamines |
| US20020058841A1 (en) * | 2000-11-16 | 2002-05-16 | Andreas Ansmann | Hydrogenation of nitriles over Raney catalysts |
| US20020058842A1 (en) * | 2000-11-16 | 2002-05-16 | Andreas Ansmann | Hydrogenation of nitriles over raney catalysts |
| CN101622222A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethyleneamines from untreated AAN |
| CN101675026A (en) * | 2007-03-01 | 2010-03-17 | 巴斯夫欧洲公司 | Production method for ethyleneamine mixtures |
| CN102485711A (en) * | 2010-12-03 | 2012-06-06 | 烟台万华聚氨酯股份有限公司 | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19540191C1 (en) * | 1995-10-30 | 1996-11-21 | Degussa | Prepn. of isophorone:di:amine from isophorone nitrile |
| WO2002051791A2 (en) * | 2000-12-23 | 2002-07-04 | Degussa Ag | Method for producing primary and secondary amines by hydrogenating 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 |
| 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 |
-
2012
- 2012-10-31 CN CN201210438301.3A patent/CN102924286B/en active Active
-
2013
- 2013-01-28 WO PCT/CN2013/071043 patent/WO2014067242A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721811A (en) * | 1985-08-26 | 1988-01-26 | W. R. Grace & Co. | Synthesis of aliphatic polyamines |
| EP0382508A2 (en) * | 1989-02-07 | 1990-08-16 | Hampshire Chemical Corporation | The preparation of polyamines |
| US20020058841A1 (en) * | 2000-11-16 | 2002-05-16 | Andreas Ansmann | Hydrogenation of nitriles over Raney catalysts |
| US20020058842A1 (en) * | 2000-11-16 | 2002-05-16 | Andreas Ansmann | Hydrogenation of nitriles over raney catalysts |
| CN101622222A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethyleneamines from untreated AAN |
| CN101675026A (en) * | 2007-03-01 | 2010-03-17 | 巴斯夫欧洲公司 | Production method for ethyleneamine mixtures |
| CN102485711A (en) * | 2010-12-03 | 2012-06-06 | 烟台万华聚氨酯股份有限公司 | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601644A (en) * | 2013-11-21 | 2014-02-26 | 万华化学集团股份有限公司 | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine |
| CN103601644B (en) * | 2013-11-21 | 2015-07-29 | 万华化学集团股份有限公司 | A kind of preparation method of N1-(2-aminoethyl)-1，2-diaminoethane |
| CN107188809A (en) * | 2016-03-14 | 2017-09-22 | 史小鸣 | A kind of preparation of diethylenetriamine |
| CN111644196A (en) * | 2020-06-17 | 2020-09-11 | 山东达民化工股份有限公司 | High-selectivity preparation method of methylpentamethylenediamine by adopting composite catalytic system |
| 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 |
| CN112321438A (en) * | 2020-11-25 | 2021-02-05 | 重庆华峰化工有限公司 | Synthesis method of hexamethylene diamine |
| CN112321438B (en) * | 2020-11-25 | 2024-04-16 | 重庆华峰化工有限公司 | Synthesis method of hexamethylenediamine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924286B (en) | 2014-06-11 |
| WO2014067242A1 (en) | 2014-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3375520B1 (en) | Catalyst for aminating polyether polyol and preparation method thereof and method of preparing a polyetheramine using catalyst | |
| CN102285891B (en) | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound | |
| CN104693038B (en) | A kind of method and its device for preparing propane diamine as raw material using propane diols and liquefied ammonia | |
| CN107469813B (en) | A kind of carried noble metal hydrogenation catalyst and its preparation and application | |
| CN102924286B (en) | Preparation method of N1-(2-aminoethyl)-1,2-ethylenediamine | |
| CN106391001A (en) | Active carbon loaded ruthenium-platinum bimetallic composite catalyst, and preparation method and applications thereof | |
| CN105344357A (en) | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis | |
| CN111495373B (en) | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic | |
| CN105801436A (en) | Synthesizing method for N,N,N'-trimethyl-N'-ethoxyl-ethidene diamine | |
| CN102485711B (en) | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine | |
| CN102091641B (en) | Supported silver-cobalt or silver-nickel reductive ammonolysis catalyst as well as preparation method and applications thereof | |
| CN113976131B (en) | Heterogeneous catalyst and method for preparing 2, 5-furandimethylamine from 5-hydroxymethylfurfural | |
| CN101912779A (en) | Catalyst for catalytic synthesis of N-methylpyrrolidine and application thereof | |
| CN101659618B (en) | Preparation method of pentamethyldiethylenetriamine | |
| CN114436852A (en) | Method for preparing hexamethylene diamine by hydrogenation of adiponitrile | |
| CN107245066B (en) | A kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine | |
| CN102491904A (en) | Application of hydrogenation catalyst to preparation of 1,4-cyclohexanediamine | |
| CN110201671B (en) | Catalyst for synthesizing ethylene amine by monoethanolamine prepared by ammonia complex and reductive amination of liquid ammonia and preparation and use methods thereof | |
| TWI471296B (en) | A heterogeneous catalyst and a method of producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran | |
| CN103764616B (en) | The method preparing EDDN and/or EDMN | |
| CN103626721B (en) | A kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether | |
| CN112295569A (en) | Catalyst for preparing aniline by one-step ammoniation of benzene and preparation method thereof | |
| CN103601644B (en) | A kind of preparation method of N1-(2-aminoethyl)-1，2-diaminoethane | |
| CN115041221B (en) | NaY-containing molecular sieve composition of tertiary amine catalyst for continuously synthesizing polyurethane and preparation method thereof | |
| CN103508905A (en) | New serinol synthesis technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai, South Road, Shandong, No. 7 Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Ningbo Wanhua Polyurethane Co., Ltd. Address before: 264002 Yantai, South Road, Shandong, No. 7 Applicant before: Yantai Wanhua Polyurethane Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: YANTAI WANHUA POLYURETHANE CO., LTD. TO: WANHUA CHEMICAL GROUP CO., LTD. |
|
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai, South Road, Shandong, No. 7 Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Wanhua Chemical (Ningbo) Co., Ltd. Address before: 264002 Yantai, South Road, Shandong, No. 7 Applicant before: Wanhua Chemical Group Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 264006 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Co-patentee after: Wanhua Chemical (Ningbo) Co., Ltd. Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 264002 No. 7 happy South Road, Shandong, Yantai Co-patentee before: Wanhua Chemical (Ningbo) Co., Ltd. Patentee before: Wanhua Chemical Group Co., Ltd. |