CN115960000A - Method for synthesizing methylcyclohexanediamine by hydrogenating diaminotoluene - Google Patents
Method for synthesizing methylcyclohexanediamine by hydrogenating diaminotoluene Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title claims description 11
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 title abstract description 7
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims description 113
- 238000002360 preparation method Methods 0.000 claims description 57
- 239000010948 rhodium Substances 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000003283 rhodium Chemical class 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 5
- KHBBRIBQJGWUOW-UHFFFAOYSA-N 2-methylcyclohexane-1,3-diamine Chemical compound CC1C(N)CCCC1N KHBBRIBQJGWUOW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- 238000009826 distribution Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009615 deamination Effects 0.000 description 3
- 238000006481 deamination reaction Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- QTKDDPSHNLZGRO-UHFFFAOYSA-N 4-methylcyclohexane-1,3-diamine Chemical compound CC1CCC(N)CC1N QTKDDPSHNLZGRO-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 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
- 230000002925 chemical effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing methylcyclohexanediamine (HTDA) by continuously hydrogenating diaminotoluene (TDA). The invention can realize high conversion rate and high selectivity of diaminotoluene hydrogenation to obtain methylcyclohexanediamine (HTDA), and the product contains high contents of 2, 6-diamino-1-methyl-cyclohexane and stereoisomer trans, trans-2, 4-diamino-1-methyl-cyclohexane, and has the advantages of long gel time (operation time), high glass transition temperature and the like when being applied to the epoxy curing field. The method is easy to implement and has industrial application prospect.
Description
Technical Field
The invention relates to a synthesis method of methylcyclohexanediamine, in particular to a method for preparing a methylcyclohexanediamine product with high content of 2, 6-diamino-1-methyl-cyclohexane and trans, trans-2, 4-diamino-1-methyl-cyclohexane by continuous hydrogenation of diaminotoluene, belonging to the field of synthesis of amine compounds.
Background
The methylcyclohexanediamine (hereinafter referred to as HTDA) is an epoxy curing agent with excellent performance, has excellent yellowing resistance, is insensitive to air and humidity, has moderate curing speed, is good in compounding performance with other curing agents, and is widely applied to the field of high-end epoxy curing agents; in addition, the isocyanate synthesized by the method has good stability in illumination and air environment, and can be used for producing special polyurethane materials.
Industrially, the synthesis method of HTDA comprises: dinitrotoluene is produced by nitration of toluene, diaminotoluene (hereinafter abbreviated as TDA) is produced by hydrogenation of dinitrotoluene, and HTDA is produced by further hydrogenation of TDA. Among them, the technology threshold of toluene nitration and dinitrotoluene hydrogenation is relatively low, the process is mature, and many manufacturers at home and abroad realize industrial production. Compared with the prior art, HTDA manufacturers have a few and technical reasons that TDA molecules contain two amino groups and one methyl group, and have a great steric hindrance effect on the hydrogenation of benzene rings, so that the TDA hydrogenation needs to be realized under severe conditions of high-activity catalysts, high temperature, high pressure and the like. In addition, hydrogenation of TDA is easy to generate hydrogenolysis deamination side reaction, a large amount of low-value by-products are generated, and the economy is poor. Therefore, at present, the industrial production of TDA hydrogenation is realized by fresh manufacturers at home and abroad.
TDA obtained by industrial nitration and hydrogenation of toluene is generally a mixture of 2, 4-diaminotoluene (hereinafter referred to as 2, 4-TDA) and 2, 6-diaminotoluene (hereinafter referred to as 2, 6-TDA), and the corresponding TDA hydrogenation product is generally a mixture of 2, 4-diamino-1-methyl-cyclohexane (hereinafter referred to as 2, 4-HTDA) and 2, 6-diamino-1-methyl-cyclohexane (hereinafter referred to as 2, 6-HTDA). Due to the difference of the relative positions of the substituents on the benzene rings in the molecules of the 2,4-TDA and the 2,6-TDA, the hydrogenation activity and the selectivity of the two molecules are obviously different, so that the ratio of the 2,4-HTDA in the product is obtained: ratio of 2,6-HTDA to 2,4-TDA in the feed: the proportion of 2,6-TDA is not uniform, and the content of 2,6-HTDA in the product has a significant influence on its application properties. In addition, from the spatial configuration point of view, the 2,4-TDA hydrogenation product comprises four stereoisomers, namely trans, trans-2,4-HTDA, trans, cis-2,4-HTDA, cis, trans-2,4-HTDA, cis-2,4-HTDA; the 2,6-TDA hydrogenation product contains three stereoisomers, namely trans, trans-2,6-HTDA, cis-2,6-HTDA, and therefore, the TDA hydrogenation product usually contains seven stereoisomers, and the different proportion distribution of these isomers, especially the trans, trans-2,4-HTDA content of the key isomer, has an important influence on the application properties of the product as well.
2,4-HTDA stereoisomer:
2,6-HTDA stereoisomer:
the existing HTDA synthesis process and product application technology are reported as follows:
patent CN 105924359A adopts autoclave batch hydrogenation process with Rh/Al 2 O 3 Taking tetrahydrofuran, isopropanol, dioxane and the like as solvents as catalysts, adding inorganic salt assistants such as sodium sulfate, sodium phosphate and the like into a reaction system, carrying out 2,6-TDA hydrogenation under the conditions of substrate concentration of 33%, reaction temperature of 200 ℃ and pressure of 10MPa for 8 hours to obtain 2,6-HTDA with yield of 90%; 2,4-TDA hydrogenation is carried out under similar conditions, the highest yield of the 2,4-HTDA is up to 97%, but the activity of the catalyst is only 83% of the initial activity when the catalyst is used for the third time; under similar conditions, a mixed feed of 2,4-TDA and 2,6-TDA, using 80.
In patent CN 106994344A, an autoclave batch hydrogenation process is also adopted, and one or more of cerium, manganese, lanthanum, etc. are used as an auxiliary agent to synthesize ruthenium catalysts supported on alumina, activated carbon, titanium dioxide, etc. respectively, and 2,4-TDA:2,6-TDA proportion is 80, adding LiOH auxiliary agent into a reaction system by taking tetrahydrofuran as solvent, and mechanically using 20 batches of catalyst under the conditions of substrate concentration of 25%, reaction temperature of 180 ℃ and pressure of 8MPa, wherein the conversion rate is more than 99% and the selectivity is more than 95%. However, as the number of catalyst application batches increased, the reaction time continued to increase (18 h for the first batch and 24h for the 20 th batch), and almost every batch required a fresh amount of catalyst and LiOH to be replenished.
Patent EP 2905272A 1 adopts Ru/Al 2 O 3 With Ni/SiO 2 Mixed catalyst or Ru/Al 2 O 3 With Rh/Al 2 O 3 Mixed catalyst 2,4-TDA: in the method, THF is used as a solvent, organic nitrated compounds such as nitrobenzene, 2, 4-dinitrotoluene, nitromethane and the like are added into a reaction system under the reaction conditions of a lower substrate concentration (TDA: THF =0.8g, namely the TDA mass percentage concentration is 10%), a reaction temperature of 120-250 ℃ and a pressure of 10MPa, so that the reaction rate is remarkably improved on the premise of not influencing HTDA selectivity and content distribution of various stereoisomers, and the preferred reaction result in the embodiment is as follows: the conversion rate is 99.5%, and the HTDA selectivity is 91.3%. Under the same conditions, naNO is added with inorganic nitrite 2 As an auxiliary agent, although the HTDA selectivity can reach 93.2%, the reaction rate is reduced by more than 80% compared with the case of not adding the auxiliary agent. In the patent example, the concentration of the substrate is also examined, and when the mixture ratio of the reaction materials is 10g of TDA:80mL of THF (TDA concentration 12.3 wt%), 20g of TDA:80mL THF (TDA mass percentage concentration 21.9%), 30g TDA:60mL of THF (TDA concentration of 36.0 wt.%), HTDA selectivity of 86.8%, 86.2% and 81.9%, respectively, and HTDA selectivity decreases with increasing substrate concentration.
U.S. Pat. No. 4,10329237B 2 discloses the preparation of supported Ru/ZrO by impregnation 2 Catalyst, and carrying out 2,4-TDA:2,6-TDA in a proportion of 80,dioxane is used as solvent, the concentration of substrate is 25%, the reaction temperature is 170 ℃, the pressure is 190bar, and the space velocity is 0.1kg Stock solution .L -1 Catalyst and process for preparing same .h -1 (i.e., 0.025 kg) TDA .L -1 Catalyst and process for preparing same .h -1 ) The catalyst is operated for 890 hours under the condition, the conversion rate of raw materials is about 95 percent, and the HTDA selectivity<80 percent, and the activity of the catalyst has a tendency of continuous reduction; HTDA is used as a solvent, the concentration of a substrate is 15 percent, the temperature is 185 ℃, the pressure is 190bar, and the space velocity is 0.5kg Stock solution .L -1 Catalyst and process for preparing same .h -1 (i.e., 0.075 kg) TDA .L -1 Catalyst and process for preparing same .h -1 ) When the reaction condition is operated for 840 hours, the conversion rate of raw materials is 83 percent, the selectivity of HTDA is 87 percent, and the catalyst is difficult to maintain stable activity. By adopting the technology to carry out hydrogenation, the TDA conversion rate and the HTDA selectivity are not high, and the activity of the catalyst is reduced rapidly.
Patent EP0443344 (A2) hydrogenates 2,4-HTDA, 2,6-HTDA and a mixed HTDA in a ratio of 89 to 89 using a mixture of two of medium 2,4-TDA, 2,6-TDA and 80, respectively, as a feedstock, and formulated 2,4-HTDA: the 2,6-HTDA ratio of 65 for the mixed HTDA, and the four products were separately tested for epoxy cure performance and found that the gel time extended with increasing 2,6-HTDA content in the product, and curing with the mixed HTDA (2,4-HTDA: 2,6-HTDA ratio 89.
Patent US 20120226017 A1 uses an unsupported Ru catalyst to perform TDA hydrogenation, HTDA products with different stereoisomeric distributions are obtained by changing process conditions such as reaction temperature, and epoxy curing performance tests show that with the increase of trans, trans-2,4-HTDA content in the product, the operation time (the time required for the gel viscosity to reach 10000 mpa.s) is significantly prolonged, and the vitrification temperature is correspondingly increased.
In conclusion, the HTDA synthesis techniques reported in the prior patents mainly have the following problems: (1) Using supported or unsupported Ru, rh or their mixture with supported Ni and other catalyst as catalyst, adding Na 2 SO 4 、Na 3 PO 4 、LiOH、NaNO 2 Inorganic salt or organic nitrated compound such as nitrobenzene, 2, 4-dinitrotoluene, nitromethane and the like is used as an auxiliary agent, and a batch process is adopted to carry out TDA hydrogenation reaction under the conditions of high temperature and high pressure, so that the problems of harsh reaction conditions, low production efficiency, large catalyst dosage, volatility, continuous extension of reaction liquid filtration time along with the increase of the applied batch of the catalyst and the like exist. In addition, na is added 2 SO 4 、Na 3 PO 4 、LiOH、NaNO 2 Inorganic auxiliary agents, such as a catalyst, although having a certain promotion effect on the hydrogenation activity and selectivity of TDA, are easy to have certain physical or chemical effects with the catalyst, so that the activity, the filtration performance and the like of the catalyst are reduced, and the compounds are inevitably mixed into a crude product liquid to influence the separation and purification of the product; organic nitrating additives such as nitrobenzene, 2, 4-dinitrotoluene, nitromethane and the like which are easy to explode are added, so that the safety risk is high, and the separation difficulty of products is increased; (2) In order to improve indexes such as HTDA selectivity and catalyst life, tetrahydrofuran, isopropanol, dioxane and the like are generally adopted as solvents in the prior art, and TDA hydrogenation reaction is carried out under a lower substrate concentration, so that the problems of large solvent consumption, low equipment production efficiency, high product separation cost and the like exist; (3) Although a fixed bed continuous hydrogenation process is reported, the problems of high reaction temperature, high pressure, low space velocity, large solvent consumption, easy inactivation of a catalyst and the like exist, and the general conversion rate and selectivity are not equal to those of an intermittent process, so that the industrial application is difficult to realize; (4) Compared with 2,4-TDA hydrogenation, the 2,6-TDA is easier to generate deamination side reaction, and HTDA obtained by hydrogenation of a mixed raw material of the 2,4-TDA and the 2,6-TDA is a mixture of a plurality of stereoisomers, so that the prior art is difficult to obtain HTDA products with high 2,6-HTDA content and high trans-2,4-HTDA content while simultaneously realizing high activity and high selectivity hydrogenation.
Disclosure of Invention
In order to overcome the various problems of the existing TDA hydrogenation process, the invention develops a method for synthesizing HTDA by continuous hydrogenation of TDA, which is mainly characterized by comprising the following steps: (1) The loaded Ru-Rh/Al with high activity, high selectivity and long service life is prepared by adopting a special preparation method 2 O 3 -ZrO 2 A catalyst, andthe catalyst has good filtering performance and high strength, and can still maintain stable particle size distribution after long-time operation; (2) By adopting a high-pressure autoclave continuous hydrogenation process (CSTR), the problems of high pressure, difficult temperature control, low product selectivity, easy inactivation of a catalyst and the like in the fixed bed continuous hydrogenation process are solved, and the problems of low production efficiency, high solvent separation energy consumption and the like caused by low substrate concentration and low airspeed are also solved; (3) The TDA liquid in a molten state is continuously added into the reaction kettle through the high-temperature feed pump, the HTDA in the kettle can play a role of a solvent, an organic solvent is not required to be additionally introduced, the separation energy consumption is low, and in addition, the content of trans, trans-2,4-HTDA in the product can be improved by controlling the retention time of the materials in the kettle.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing HTDA by TDA hydrogenation comprises the steps of performing TDA hydrogenation in the presence of a TDA hydrogenation catalyst to synthesize HTDA; the TDA hydrogenation catalyst is Ru-Rh/Al 2 O 3 -ZrO 2 A catalyst, wherein the loading rate of the metal Ru in the catalyst is 0.01-20%, preferably 0.1-5%, such as 0.1%, 0.2%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 2%, 4%, 6%, 8%, 10%, 15%; the loading of metallic Rh, expressed as percentage by mass of Rh/support, is between 0.001% and 10%, preferably between 0.05% and 2%, for example between 0.1%, 0.2%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 2%, 4%, 6%, 8%, 10%;
the catalyst carrier is a bimetal oxide Al 2 O 3 -ZrO 2 The mass ratio of Zr/Al in the carrier is 0.001-10, preferably 0.01-1.
In the invention, the preparation method of the catalyst comprises the following steps:
(1-1) preparation of bimetallic oxide Carrier Al 2 O 3 -ZrO 2 。
Al in the invention 2 O 3 -ZrO 2 The carrier can be directly prepared from the conventional commercial Al 2 O 3 -ZrO 2 The carrier may be prepared as followsThe preparation method comprises the following steps: adding a certain amount of alumina and water into a container with stirring and heating functions, stirring, and heating to a certain temperature (T) 1 ) Maintaining, preparing a certain amount of aqueous solution of zirconium salt, adding dropwise the aqueous solution into the container, and stirring for a certain period of time (t) 1 ) Dropwise adding a certain amount of alkali solution with a certain concentration into the container until the pH value of the system is a certain value, stopping adding the alkali, and continuously stirring for a period of time (t) 2 ) Filtering, drying and roasting filter cake to obtain Al 2 O 3 -ZrO 2 A carrier;
(1-2) preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst: weighing a certain mass of ruthenium soluble salt, an auxiliary leaching agent, water and Al obtained in the step (1-1) 2 O 3 -ZrO 2 Adding the carrier into a container with stirring and heating, stirring uniformly, and heating to a certain temperature (T) 2 ) Continuing stirring for a period of time (t) 3 ) Then respectively dripping aqueous solution of alkali solution and aqueous solution of rhodium soluble salt with certain concentration into the system at the same time, controlling pH value of the system to be a certain value in the dripping process, continuously stirring for a period of time (t) 4 ) Filtering, and drying and roasting filter cakes in sequence; finally, the obtained solid powder is put into a tubular furnace to be reduced and activated by hydrogen at a certain temperature and then cooled to room temperature, thus obtaining Ru-Rh/Al 2 O 3 -ZrO 2 A catalyst.
In the present invention, the particle size distribution D of alumina described in the catalyst preparation method (1-1) 10 0.05 to 50 μm, preferably 1 to 40 μm; d 50 10 to 100 μm, preferably 30 to 70 μm; d 90 60 to 200 μm, preferably 80 to 160 μm; the specific surface area is 10 to 1000m 2 Per g, preferably from 50 to 200m 2 (iv) g; the pore diameter is 0.1 to 500nm, preferably 4 to 100nm; the pore volume is 0.01-3 mL/g, preferably 0.1-1.5 mL/g;
the mass ratio of water/alumina in the catalyst preparation method (1-1) is 2 to 1000, preferably 10 to 100;
the temperature T in the catalyst preparation Process (1-1) 1 Is 20 to 100 ℃, preferably 50 to 80 ℃;
the zirconium salt in the catalyst preparation method (1-1) is selected from one or more of zirconium oxychloride octahydrate, zirconium nitrate, zirconium chloride, zirconium sulfate and zirconium acetate, preferably zirconium oxychloride octahydrate, and is added in an amount of 0.001 to 10, preferably 0.01;
in the catalyst preparation method (1-1), the concentration of the aqueous solution of the zirconium salt is 1 to 60 percent, preferably 10 to 30 percent, calculated by the mass of the zirconium salt/(the mass of the zirconium salt + the mass of the water) × 100 percent;
the stirring time t in the catalyst preparation method (1-1) 1 Is 0.5 to 20 hours, preferably 2 to 5 hours;
in the catalyst preparation method (1-1), the base is selected from NaOH, KOH and LiOH. H 2 O、Na 2 CO 3 、K 2 CO 3 、(NH 4 ) 2 CO 3 、NaHCO 3 、KHCO 3 、NH 4 HCO 3 、NH 3 ·H 2 One or more of O, preferably LiOH. H 2 O、Na 2 CO 3 ；
In the catalyst preparation method (1-1), the concentration of the aqueous alkali solution is 1 to 50 percent, preferably 5 to 20 percent, calculated as alkali mass/(alkali mass + water mass) × 100 percent;
after the alkaline solution is dripped in the catalyst preparation method (1-1), the pH value of the system is 6-12, preferably 7-9;
the stirring time t in the catalyst preparation method (1-1) 2 Is 0.2 to 10 hours, preferably 1 to 5 hours;
in the catalyst preparation method (1-1), the drying temperature is 60-120 ℃;
in the catalyst preparation method (1-1), the roasting temperature is 250-1000 ℃, preferably 400-600 ℃;
the calcination time in the catalyst preparation method (1-1) is 0.5 to 20 hours, preferably 2 to 10 hours;
the amount of water added in the catalyst preparation method (1-2) is defined as mass of water/Al 2 O 3 -ZrO 2 The mass ratio of the carrier is 3-1000, preferably 5-100;
the soluble ruthenium salt in the catalyst preparation method (1-2) is RuCl 3 、K 2 RuCl 6 、(NH 4 ) 2 RuCl 6 、Ru(NO)(NO 3 ) 3 、Ru(OAc) 3 Preferably RuCl 3 (ii) a The rhodium soluble salt is selected from RhCl 3 、Rh(NO 3 ) 3 、(NH 4 ) 3 RhCl 6 Preferably RhCl 3 (ii) a The auxiliary leaching agent is selected from one or more of hydrochloric acid, formic acid, acetic acid, glycollic acid, propionic acid, butyric acid, citric acid, tartaric acid, oxalic acid, salicylic acid and p-toluenesulfonic acid, preferably formic acid and salicylic acid;
in the catalyst preparation method (1-2), the addition amount of the leaching aid is 0.01-10, preferably 0.5-5, based on the mass ratio of the leaching aid to Ru;
the temperature T in the catalyst preparation Process (1-2) 2 Is 20 to 100 ℃, preferably 40 to 70 ℃;
the time t described in the catalyst preparation Process (1-2) 3 Is 0.5 to 20 hours, preferably 2 to 10 hours;
the base in the catalyst preparation method (1-2) is selected from (NH) 4 ) 2 CO 3 、NH 4 HCO 3 、HCOONH 4 、CH 3 COONH 4 、CH 3 CH 2 COONH 4 、NH 3 ·H 2 O、(NH 4 ) 2 HPO 4 Preferably (NH) 4 ) 2 CO 3 ；
In the catalyst preparation method (1-2), the concentration of the alkali solution is 1-50%, preferably 5-20%, calculated by the alkali mass/(alkali mass + water mass) × 100%;
in the catalyst preparation method (1-2), the concentration of the rhodium soluble salt is 0.05-10%, preferably 0.5-5%, calculated by Rh mass/water mass x 100%;
the pH value in the catalyst preparation method (1-2) is 6 to 12, preferably 7 to 9;
the stirring time t in the catalyst preparation method (1-2) 4 Is 0.1 to 20 hours, preferably 2 to 10 hours;
in the catalyst preparation method (1-2), the drying temperature of the filter cake is 40-180 ℃, and preferably 70-130 ℃; the drying time is 0.5 to 30 hours, preferably 2 to 10 hours; the roasting temperature is 250-700 ℃, preferably 350-500 ℃; the roasting time is 1-30 h, preferably 4-16 h;
in the catalyst preparation method (1-2), the reduction activation temperature of the catalyst is 100-500 ℃, preferably 160-300 ℃; the reduction activation time of the catalyst is 1 to 20 hours, and preferably 3 to 10 hours.
The invention also provides a method for preparing the Ru-Rh/Al 2 O 3 -ZrO 2 The method for synthesizing HTDA by catalyzing TDA hydrogenation by using catalyst is characterized by that an autoclave containing catalyst, HTDA and hydrogen gas is heated, the material containing TDA is added into the autoclave at a constant speed, and the reaction material is removed at a constant speed by controlling the constant liquid level in the autoclave.
According to the technological technology for synthesizing HTDA by TDA hydrogenation, a built-in metal sintered rod filter is arranged in an autoclave, so that materials are continuously removed from an outlet of the reaction kettle, and a catalyst is kept in the kettle and continuously participates in hydrogenation reaction;
according to the technological technology for synthesizing HTDA by TDA hydrogenation, the TDA retention time is 0.01-10 h, preferably 0.05-1 h;
the TDA feeding rate is expressed by the TDA feeding mass/catalyst mass ratio in unit time and is 0.1-100 h -1 Preferably 1 to 20 hours -1 (ii) a The technological process of synthesizing HTDA by TDA hydrogenation has reaction temperature of 80-300 deg.c, preferably 100-160 deg.c; the reaction pressure is 3 to 20MPa, preferably 5 to 10MPa.
According to the process technology for synthesizing HTDA by TDA hydrogenation, a TDA raw material consists of two isomers of 2,4-TDA and 2,6-TDA, wherein the ratio of 2,4-TDA:2,6-TDA = 80;
according to the technological technology for synthesizing HTDA by TDA hydrogenation, the TDA conversion rate is more than 99%, the HTDA selectivity is more than 97%, and the ratio of 2,4-HTDA in the product is as follows: 2,6-HTDA ratio of 77:23 to 83:17, preferably 79:21 to 81:19,trans, trans-2,4-HTDA isomer content of more than 40%, preferably 45 to 60%;
the invention has the beneficial effects that:
(1)Al 2 O 3 -ZrO 2 the bimetallic oxide support has a specific surface areaThe catalyst has the advantages of high activity, high selectivity and long service life, has high mechanical strength, is not easy to wear, is applied to a high-pressure kettle continuous hydrogenation process, and is beneficial to long-time stable operation under severe conditions of high temperature, high pressure, high speed stirring and the like;
(2) Ru and Rh are bimetal-alloyed to generate synergistic effect on H 2 Benzene rings in molecules and TDA molecules have strong adsorption and activation effects, but the adsorption and activation on amino groups are weak, so that high hydrogenation activity and selectivity are obtained; in addition, al 2 O 3 -ZrO 2 Weak acidity of the carrier compared to Al 2 O 3 、SiO 2 And common carriers such as active carbon and the like have better inhibition effect on deamination side reaction.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
A gas chromatograph: agilent 7890B, FID detector, DB-5 capillary chromatographic column (30m x 250 μm x 0.25 μm), sample inlet 280 deg.C, detector 300 deg.C; temperature rising procedure: the initial temperature is 50 ℃, the temperature is kept for 2min, the temperature is raised to 80 ℃ at the speed of 5 ℃/min, and then the temperature is raised to 300 ℃ at the speed of 15 ℃/min, and the temperature is kept for 15min. And (3) carrying out quantitative analysis by adopting an external standard method, calculating the conversion rate and yield, and calculating the 2,6-HTDA content and the trans, trans-2,4-HTDA isomer content in the product by adopting a peak area normalization method.
Preparation example 1: preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst and process for preparing same
(1) 20g of Al are weighed 2 O 3 Alumina powder (particle size distribution: D) 10 Is 35 μm, D 50 65 μm, D 97 Is 150 μm; specific surface area: 180m 2 Per g, average pore diameter: 10nm; pore volume: 1.5 mL/g) was added to a 1000mL three-necked flask, and 300g of water was added, stirred, and heated to 60 ℃. Weighing 36g ZrOCl 2 ·8H 2 O, adding 100g of water, and stirring to dissolveAnd (4) dropping the mixture into a three-necked bottle within 30min by using a constant-pressure dropping funnel, and continuing stirring for 2.5h after the dropping is finished. Weighing 15g of Na 2 CO 3 Adding 60g of water for dissolving, slowly dripping the mixture into a three-mouth bottle by using a constant-pressure dropping funnel until the pH value of the system is 7.5, and stopping dripping Na 2 CO 3 Stirring the aqueous solution for 1h, filtering, drying the filter cake in a drying oven at 110 ℃ for 4h, then roasting in a muffle furnace at 500 ℃ for 4h, cooling to room temperature, and recording as Al 2 O 3 -ZrO 2 ；
(2) 2.26g of RuCl were weighed 3 (Ru content 37 wt%), 3.2g of formic acid, 100g of water and 20g of Al produced in step (1) 2 O 3 -ZrO 2 And adding the carrier into a 500mL three-necked bottle, uniformly stirring, heating to 70 ℃, and continuously stirring for 3 hours. Weighing 10g (NH) 4 ) 2 CO 3 Adding 40g of water to dissolve, and weighing 0.256g of RhCl 3 (Rh content is 39 wt%), adding 20g of water for dissolving, respectively dripping the two solutions into a three-mouth bottle by using a constant-pressure dropping funnel, maintaining the pH of the system to be 8-9 in the dripping process, and waiting for RhCl 3 After the solution is added dropwise, the solution is continuously stirred for 3h, filtered, the filter cake is placed in an oven to be dried for 5h at the temperature of 120 ℃, then roasted for 5h at the temperature of 400 ℃ in a muffle furnace, cooled to the room temperature, 10g of sample is weighed and placed in a tubular furnace, the hydrogen flow is controlled to be 500mL/min, the temperature is controlled to be 280 ℃, reduction and activation are carried out for 4h, and then the temperature is cooled to the room temperature, thus obtaining the Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst, noted C1. Having a particle size distribution of D 10 ：32μm，D 50 ：60μm，D 97 ：142μm。
Preparation example 2: preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst and process for preparing same
The same as in production example 1 except that the alumina powder in step (1) had a particle size distribution of: d 10 Is 5 μm, D 50 Is 40 μm, D 97 Is 90 μm; specific surface area: 80m 2 G, average pore diameter: 40nm; pore volume: 0.4mL/g; 36g of ZrOCl 2 ·8H 2 Substitution of O for 1g Zr (NO) 3 ) 4 15g of Na 2 CO 3 Replacement was with 10g LiOH.H 2 O, dissolving in 190g of water at a temperature T 1 Is 80 ℃; in step (2), RuCl 3 (Ru content 37 wt%) 0.5g, the infusion aid was replaced with 0.05g salicylic acid, rhCl 3 (Rh content 39 wt.%) mass 1.026g, temperature T 2 Is 30 ℃; the activation temperature of the catalyst is 160 ℃, and the activation time is 8h. The catalyst is designated as C2. Having a particle size distribution of D 10 ：5.3μm，D 50 ：38.3μm，D 97 ：91.2μm。
Preparation example 3: preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst and process for preparing same
Same as preparation example 1, except that 15g of Na was added in step (1) 2 CO 3 Replacing with 20g of KOH, adding 180g of water for dissolving until the pH value of the system is 9, and stopping dripping KOH aqueous solution; time t 1 Is 8h, time t 2 Is 5h; the roasting temperature is 350 ℃, and the roasting time is 8 hours. Replacing the leaching aid in the step (2) with 0.04g of p-toluenesulfonic acid; 10g (NH) 4 ) 2 CO 3 Replacing 20g of 30wt% ammonia water, and adding 80g of water for dilution and dissolution; temperature T 2 At 90 ℃ for a time t 3 Is 8h, time t 4 For 8h, rhCl was added dropwise 3 In the process of the solution and the ammonia solution, the pH value of the system is maintained to be 8-9; the roasting temperature of the catalyst is 550 ℃, and the roasting time is 10 hours; the activation temperature of the catalyst is 350 ℃, and the activation time is 2h. The catalyst was designated as C3. Having a particle size distribution of D 10 ：34μm，D 50 ：57μm，D 97 ：148μm。
Preparation example 4: preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst and process for producing the same
Same as preparation example 1, except that 2.26g of RuCl was added in step (2) 3 Replacement by 6.45g Ru (NO) 3 ) 3 10g of (NH) 4 ) 2 CO 3 Replacement by 40g NH 4 HCO 3 0.256g of RhCl 3 Replacement by 0.0343g Rh (NO) 3 ) 3 Dropwise addition of NH 4 HCO 3 With Rh (NO) 3 ) 3 And in the solution process, the pH value of the system is maintained to be 7-8. The catalyst is designated as C4. Having a particle size distribution of D 10 ：32μm，D 50 ：59μm，D 97 ：151μm。
Preparation of comparative example 1: preparation of Ru-Rh/Al 2 O 3 Catalyst and process for preparing same
As preparation example 1, except that step (1) was omitted and Al in step (1) of preparation example 1 was directly used in step (2) 2 O 3 The catalyst is designated as D1 as support.
Preparation of comparative example 2: preparation of Ru/Al 2 O 3 -ZrO 2 Catalyst and process for preparing same
Same as in preparation example 1, except that RhCl was not added in step (2) 3 The solution, catalyst D2.
Preparation of comparative example 3: preparation of Rh/Al 2 O 3 -ZrO 2 Catalyst and process for preparing same
Same as preparation example 1, except that RuCl was not added in step (2) 3 The catalyst is denoted as D3.
Preparation of comparative example 4: preparation of Ru-Rh/AC catalyst
As in preparation of comparative example 1, except that Al was added in step (2) 2 O 3 -ZrO 2 The catalyst was noted as D4 by replacement with Activated Carbon (AC). The particle size distribution of each catalyst is as follows:
example 1: hydrogenation of TDA
Adding 400g of HTDA and 10g of catalyst C1 into a 1L autoclave with a built-in filter and a liquid level control system, loading the autoclave, discharging the air in the autoclave by using low-pressure nitrogen and hydrogen for 3 times respectively, recharging hydrogen to 2MPa, heating to 160 ℃, keeping the temperature, increasing the pressure to 8MPa, and adjusting the stirring speed to 1200rpm. Adding a TDA raw material (the mass ratio of 2,4-TDA to 2,6-TDA is 80 -1 ) The rate of (2) is fed into the kettle, the constant discharge rate is kept by controlling the liquid level, when the equipment runs for 2000 hours, materials at the outlet are taken out, and the gas chromatography is used for analysis, so that the TDA conversion rate is 99.8%, the HTDA selectivity is 99.3%, and the content of 2,4-HTDA in the product is as follows: 2,6-HTDA ratio of 80, trans,the trans-2,4-HTDA isomer content was 58.6%. Particle size analysis of the catalyst run for 2000h, D 10 ：29.8μm，D 50 ：58.9μm，D 97 ：139.8μm。
Example 2
The same as in example 1, except that the catalyst C1 was replaced by C2 of equal mass, the reaction temperature was 120 ℃ and the pressure was 6MPa, and the TDA feed rate was 100g/h (i.e., the space velocity was 10 h) -1 )。
Example 3
The same as example 1, except that the catalyst C1 was replaced with an equal mass of C3, the reaction temperature was 240 ℃, the pressure was 12MPa, the TDA feed rate was 600g/h (i.e., the feed space velocity was 60 h) -1 )。
Example 4
The same as in example 1, except that the catalyst was changed to 10g C1 and 20g C4, the reaction temperature was 90 ℃ and the pressure was 4MPa.
Comparative examples 1 to 4
The same as in example 1, except that the catalyst C1 was replaced with equal mass of D1, D2, D3, D4, respectively.
Comparative example 5
The same as in example 1, except that 10g of catalyst C1 was replaced by a mixture of 5g of catalyst D2 and 5g of catalyst D3.
The results of the experiment are as follows:
the catalyst was analyzed for particle size at different run times and the results are given in the following table:
Claims (10)
1. a method for synthesizing HTDA by TDA hydrogenation comprises the steps of performing TDA hydrogenation reaction in the presence of a TDA hydrogenation catalyst to synthesize HTDA; the TDA hydrogenation catalyst is Ru-Rh/Al 2 O 3 -ZrO 2 The catalyst has a metal Ru loading rate, expressed by the mass ratio percentage of Ru/carrier, of 0.01-20%, preferably 0.1-5%; the loading rate of metal Rh, expressed as a percentage of the mass ratio of Rh to the carrier, is 0.001% to 10%, preferably 0.05% to 2%.
2. The process of claim 1, wherein the catalyst support is a bimetallic oxide of Al 2 O 3 -ZrO 2 The mass ratio of Zr/Al in the carrier is 0.001 to 10, preferably 0.01 to 1.
3. The method of claim 1 or 2, wherein the catalyst is prepared by:
(1-1) preparation of bimetallic oxide Carrier Al 2 O 3 -ZrO 2 ；
(1-2) preparation of Ru-Rh/Al 2 O 3 -ZrO 2 Catalyst: weighing a certain mass of ruthenium soluble salt, an auxiliary leaching agent, water and Al prepared in the step (1-1) 2 O 3 -ZrO 2 Adding the carrier into a container with stirring and heating, stirring uniformly, and heating to a certain temperature (T) 2 ) Continuing stirring for a period of time (t) 3 ) Then respectively dripping aqueous solution of alkali solution and aqueous solution of soluble rhodium salt with a certain concentration into the system, controlling pH value of the system to be a certain value in the dripping process, continuously stirring for a period of time (t) 4 ) Filtering, and drying and roasting filter cakes in sequence; finally, the obtained solid powder is put into a tubular furnace to be reduced and activated by hydrogen at a certain temperature and then cooled to room temperature, thus obtaining Ru-Rh/Al 2 O 3 -ZrO 2 A catalyst.
4. The process according to any one of claims 1 to 3, wherein the bimetallic oxide support Al 2 O 3 -ZrO 2 The preparation method comprises the following steps: adding a certain amount of alumina and water into a container with stirring and heating functions, stirring, and heating to a certain temperature (T) 1 ) Maintaining and then preparing a certain amountThe aqueous solution of a zirconium salt of (1), dropwise adding the aqueous solution into the above container, and stirring for a certain period of time (t) 1 ) Dropwise adding a certain amount of alkali solution with a certain concentration into the container until the pH value of the system is a certain value, stopping adding the alkali, and continuously stirring for a period of time (t) 2 ) Filtering, drying and roasting filter cake to obtain Al 2 O 3 -ZrO 2 And (3) a carrier.
5. The method according to claim 3 or 4, wherein the soluble ruthenium salt in step (1-2) is RuCl 3 、K 2 RuCl 6 、(NH 4 ) 2 RuCl 6 、Ru(NO)(NO 3 ) 3 、Ru(OAc) 3 Preferably RuCl 3 (ii) a The rhodium soluble salt is selected from RhCl 3 、Rh(NO 3 ) 3 、(NH 4 ) 3 RhCl 6 Preferably RhCl 3 (ii) a And/or the leaching aid is selected from one or more of hydrochloric acid, formic acid, acetic acid, glycolic acid, propionic acid, butyric acid, citric acid, tartaric acid, oxalic acid, salicylic acid and p-toluenesulfonic acid, preferably formic acid and salicylic acid; and/or the base is selected from (NH) 4 ) 2 CO 3 、NH 4 HCO 3 、HCOONH 4 、CH 3 COONH 4 、CH 3 CH 2 COONH 4 、NH 3 ·H 2 O、(NH 4 ) 2 HPO 4 Preferably (NH) 4 ) 2 CO 3 。
6. The production method according to any one of claims 3 to 5, wherein the water is added in the step (1-2) in an amount of water mass/Al 2 O 3 -ZrO 2 The mass ratio of the carrier is 3-1000, preferably 5-100; and/or the addition amount of the leaching aid is 0.01-10, preferably 0.5-5; and/or the alkali solution concentration is 1-50%, preferably 5-20%, calculated as alkali mass/(alkali mass + water mass) × 100%; and/or the concentration of the rhodium soluble salt is calculated as Rh mass/water mass 100 percent0.05 to 10 percent, preferably 0.5 to 5 percent.
7. The method according to any one of claims 3 to 6, wherein the temperature T in step (1-2) 2 Is 20 to 100 ℃, preferably 40 to 70 ℃; and/or the time t 3 Is 0.5 to 20 hours, preferably 2 to 10 hours; and/or the pH value is 6 to 12, preferably 7 to 9; and/or the stirring time t 4 Is 0.1 to 20 hours, preferably 2 to 10 hours; and/or the reduction activation temperature of the catalyst is 100-500 ℃, preferably 160-300 ℃; the reduction activation time of the catalyst is 1 to 20 hours, and preferably 3 to 10 hours.
8. The method according to any one of claims 1 to 7, characterized in that it comprises in particular the steps of: the autoclave containing catalyst, HTDA and hydrogen was heated and the TDA containing material was added to the autoclave at a constant rate and the reaction mass was removed at a constant rate by controlling the constant level in the autoclave.
9. The process according to claim 8, wherein the TDA residence time is between 0.01 and 10h, preferably between 0.05 and 1h; and/or the TDA feeding rate is 0.1 to 100h expressed by TDA feeding mass/catalyst mass ratio in unit time -1 Preferably 1 to 20 hours -1 。
10. The process according to claim 8 or 9, characterized in that the reaction temperature is 80 to 300 ℃, preferably 100 to 160 ℃; the reaction pressure is 3 to 20MPa, preferably 5 to 10MPa.
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| CN118063329A (en) * | 2024-01-23 | 2024-05-24 | 南京工业大学 | Safe and environment-friendly method for preparing 1-methyl-2, 4-cyclohexanediamine by catalytic hydrogenation of 2, 4-dinitrotoluene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741929A (en) * | 1996-03-18 | 1998-04-21 | Bayer Aktiengesellschaft | Process for preparing a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
| CN102627569A (en) * | 2012-03-01 | 2012-08-08 | 江苏清泉化学有限公司 | Method for synthesizing 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane |
| CN106631826A (en) * | 2016-11-29 | 2017-05-10 | 万华化学集团股份有限公司 | Preparation method of H12MDA (diaminodicyclohexylmethane) |
| CN106994344A (en) * | 2017-03-31 | 2017-08-01 | 江苏清泉化学股份有限公司 | The method and catalyst of toluenediamine selection Hydrogenation methyl cyclohexane diamines |
| CN110433823A (en) * | 2019-07-30 | 2019-11-12 | 万华化学集团股份有限公司 | It is a kind of for synthesizing the catalyst and its preparation method and application of diaminomethyl hexamethylene |
| CN114082428A (en) * | 2021-11-30 | 2022-02-25 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN114380698A (en) * | 2022-01-26 | 2022-04-22 | 成都大研科技产业发展有限公司 | Method for synthesizing methylcyclohexanediamine by continuous selective hydrogenation of diaminotoluene |
-
2022
- 2022-12-09 CN CN202211578135.7A patent/CN115960000B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741929A (en) * | 1996-03-18 | 1998-04-21 | Bayer Aktiengesellschaft | Process for preparing a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
| CN102627569A (en) * | 2012-03-01 | 2012-08-08 | 江苏清泉化学有限公司 | Method for synthesizing 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane |
| CN106631826A (en) * | 2016-11-29 | 2017-05-10 | 万华化学集团股份有限公司 | Preparation method of H12MDA (diaminodicyclohexylmethane) |
| CN106994344A (en) * | 2017-03-31 | 2017-08-01 | 江苏清泉化学股份有限公司 | The method and catalyst of toluenediamine selection Hydrogenation methyl cyclohexane diamines |
| CN110433823A (en) * | 2019-07-30 | 2019-11-12 | 万华化学集团股份有限公司 | It is a kind of for synthesizing the catalyst and its preparation method and application of diaminomethyl hexamethylene |
| CN114082428A (en) * | 2021-11-30 | 2022-02-25 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN114380698A (en) * | 2022-01-26 | 2022-04-22 | 成都大研科技产业发展有限公司 | Method for synthesizing methylcyclohexanediamine by continuous selective hydrogenation of diaminotoluene |
Non-Patent Citations (1)
| Title |
|---|
| 钟友坤 等: "LiOH 修饰的Ru-Rh/γ-Al2O3 催化2, 4-甲苯二胺加氢合成1-甲基-2, 4-环己二胺的研究", 《高等化学工程学报》, vol. 31, no. 6, 31 December 2017 (2017-12-31), pages 1379 - 1388 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063329A (en) * | 2024-01-23 | 2024-05-24 | 南京工业大学 | Safe and environment-friendly method for preparing 1-methyl-2, 4-cyclohexanediamine by catalytic hydrogenation of 2, 4-dinitrotoluene |
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