CN118026853A - Continuous hydrogenation synthesis of H with low content of anti-reflection body12MDA method - Google Patents
Continuous hydrogenation synthesis of H with low content of anti-reflection body12MDA method Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 4
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 31
- 239000010948 rhodium Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- -1 alicyclic amine compound Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000009615 deamination Effects 0.000 description 3
- 238000006481 deamination reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- CCXMRESICWZDNT-UHFFFAOYSA-N butan-1-ol;oxolane Chemical compound CCCCO.C1CCOC1 CCXMRESICWZDNT-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- NQQRTORKNOVXTD-UHFFFAOYSA-N cyclohexyl(phenyl)methanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1CCCCC1 NQQRTORKNOVXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing H 12 MDA with low content of a reverse reaction body through continuous hydrogenation. According to the method, the difference of hydrogenation activity, selectivity and stereoisomer selectivity of Ru and Rh catalysts on MDA and an intermediate H 6 MDA is utilized, so that an MDA-containing reactant sequentially flows through a reactor A filled with the Ru catalyst and a reactor B filled with the Rh catalyst, and hydrogenation is carried out by controlling process conditions to obtain a H 12 MDA product with low anti-reflection body content. The invention is easy to implement and has industrial application prospect.
Description
Technical Field
The invention relates to the field of alicyclic amine compound synthesis, in particular to a method for synthesizing 4,4 '-diamino dicyclohexylmethane (H 12 MDA) by continuous hydrogenation of 4,4' -diamino diphenylmethane (MDA), and especially relates to a method for obtaining H 12 MDA with low anti-reaction content by continuous hydrogenation and high selectivity.
Background
H 12 MDA is an important alicyclic diamine fine chemical and has wide application in the fields of epoxy curing agents, polyurethane, polyamide and the like.
Industrially, H 12 MDA obtained by hydrogenation of MDA as a raw material has three stereoisomers of trans (hereinafter abbreviated as t, t-H 12 MDA), cis-trans (hereinafter abbreviated as c, t-H 12 MDA) and cis-cis (hereinafter abbreviated as c, c-H 12 MDA), and the content of t, t-H 12 MDA in the product determines the properties and the application of the product: the lower the content of t, t-H 12 MDA, the lower the solidifying point of the product, which is more beneficial to the application in the fields of high-end epoxy curing agents and polyurethane.
H 12 MDA stereoisomer:
Because the boiling points of the three isomers are extremely close, the effective separation of the three isomers is difficult to realize in industry through means such as rectification, derivatization and the like, so that H 12 MDA with low content of the anti-reflection body is obtained, and therefore, the direct obtaining of H 12 MDA with low content of the anti-reflection body through MDA hydrogenation is the most effective means.
The MDA hydrogenation is generally carried out in two steps, wherein the reaction process is shown in the following formula, namely, MDA firstly carries out benzene ring hydrogenation to generate diamino monocyclohexyl monophenyl methane (H 6MDA),H6 MDA and then carries out benzene ring hydrogenation to generate H 12MDA.H6 MDA which is composed of two isomers of cis-form and trans-form (hereinafter abbreviated as c-H 6MDA、t-H6 MDA respectively), in the second step, t-H 6 MDA is hydrogenated to generate t, t-H 12 MDA and c, t-H 12MDA,c-H6 MDA is hydrogenated to generate c, c-H 12 MDA and c, t-H 12 MDA, the following formula can show that the c-H 6 hydrogenation does not generate t, t-H 12 MDA is required to obtain H 12 MDA with low anti-reflection content, the first step reaction is required to improve the selectivity of c-H 6 MDA and inhibit the generation of t-H 6 MDA, and the second step is required to inhibit the t-H 6 hydrogenation to generate t, t-H 12.
The prior art for synthesizing H 12 MDA by MDA hydrogenation is reported as follows:
Patent CN115772086A reports an MDA intermittent hydrogenation process, adopts Rh/Al 2O3 catalyst, adds a certain amount of N, N, N ', N' -tetramethyl-MDA compound into a reaction system, and utilizes the weak alkalinity and steric hindrance effect to regulate and control the reaction process, thus obtaining H 12 MDA product with the anti-reaction body content of 10-14%.
Patent CN116023272A reports a process method for producing low-trans-body content H 12 MDA by adopting double kettles in series, wherein both kettles adopt Rh/Al 2O3 catalyst, n-butanol is used as solvent, lithium acetate and the like are added as auxiliary agents, so that the total yield of H 12 MDA reaches about 90%, and the trans-body content in the product is about 17%.
Patent CN116478048A reports an MDA fixed bed hydrogenation process, which adopts Ru/Al 2O3 catalyst and n-butanol-tetrahydrofuran mixed solvent, and although H 12 MDA product with the content of the anti-reaction body of 12-14% can be obtained, the technology adopts a large amount of mixed solvent and is carried out under the conditions of lower substrate concentration and lower feeding airspeed, and has the problems of low production efficiency, high separation energy consumption and the like.
Patent CN109851508a reports a method for synthesizing low trans-trans isomer low tar content H 12 MDA. According to the method, the characteristic of MDA stepwise hydrogenation is utilized, firstly, a supported rhodium catalyst is adopted, MDA is hydrogenated in a reaction kettle to obtain a reaction liquid mainly containing H 6 MDA, the reaction liquid is separated out and then is added into another reaction kettle, the supported ruthenium catalyst is adopted for further hydrogenation, and finally, a H 12 MDA product with the yield of more than 98% and the anti-reaction content of about 12% is obtained.
In summary, the prior art generally uses a single supported Ru or Rh catalyst, and through batch or continuous processes, although H 12 MDA products with lower levels of anti-reflection can be obtained, the following problems still exist:
1) The Rh catalyst is adopted simply, so that the content of a reaction product in the product is controlled, but the Rh catalyst is easy to catalyze MDA to generate deamination side reaction to generate various high-low boiling point impurities, so that the product yield is low; the Ru catalyst is adopted simply, so that deamination side reaction can be effectively inhibited, the product yield is improved, but the control of low-trans-body content is difficult to realize stably; 2) Although the yield can be improved or the generation of anti-reaction bodies can be inhibited by adding auxiliary agents and other means, the post-treatment difficulty of the product is increased; 3) Although patent CN109851508A uses the characteristic of MDA step hydrogenation, respectively adopts Rh and Ru catalysts to hydrogenate MDA and intermediate H 6 MDA to obtain H 12 MDA product with about 12% of anti-reflection body content, the Rh catalysts are required to be modified by MDA trimer with the mass of 10-500 times of that of the catalyst under the high-temperature and high-pressure hydrogen conditions of 150-250 ℃ and 5-15 MPa, the conditions are more severe, and the treatment of the modifier after use is also a problem; secondly, ru catalysts are adopted for the second hydrogenation, and because the Ru catalysts are easy to catalyze the isomerization reaction of c, c-H 12 MDA and c, t-H 12 MDA to generate t, t-H 12 MDA, the content of t, t-H 12 MDA in the product is difficult to control; finally, because the two-step hydrogenation adopts intermittent operation and needs to be filtered and separated twice, the production efficiency is seriously affected.
Therefore, there is a need to develop a high-efficiency and stable continuous hydrogenation process for MDA, which continuously and stably obtains the H 12 MDA product with low content of the anti-reflection body on the premise of ensuring high yield.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention develops a method for synthesizing H 12 MDA with low content of anti-reflection body by continuous hydrogenation, which is mainly characterized in that: the method is characterized in that a reactor A and a reactor B are connected in series, the reactor A is filled with a supported Ru catalyst, and the characteristics that the catalytic MDA hydrogenation activity is high, the catalytic intermediate H 6 MDA hydrogenation activity is relatively low, the selectivity of the catalytic MDA hydrogenation to t-H 6 MDA isomer is low are utilized, a product mainly containing H 6 MDA is obtained at the outlet of the reactor A, and the t-H 6 MDA content in H 6 MDA is low; the reactor B is filled with a supported Rh catalyst, and finally the H 12 MDA product with low anti-reflection body content is obtained by utilizing the characteristics that the catalytic H 6 MDA hydrogenation activity is high, the catalytic t-H 6 MDA hydrogenation has low selectivity to t, t-H 12 MDA isomer, and the isomerization reaction of c, c-H 12 MDA and c, t-H 12 MDA is difficult to generate t, t-H 12 MDA.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a method for synthesizing H 12 MDA with low content of anti-reflection body through continuous hydrogenation, which comprises the steps of sequentially passing a solution containing solvent and MDA through two reactors A and B connected in series to efficiently and stably prepare a H 12 MDA product with low content of anti-reflection body.
Preferably, the reactors A and B are both fixed bed reactors; the reactor feeding and discharging mode can adopt either upper feeding and lower discharging or lower feeding and upper discharging, and preferably upper feeding and lower discharging.
The reactor A is filled with a supported Ru catalyst, and the Ru catalyst comprises a carrier, an active component Ru and an auxiliary agent I, wherein the active component Ru and the auxiliary agent I are attached to the carrier.
The supported Ru catalyst carrier is selected from one or more of alumina, activated carbon, zirconium dioxide and titanium dioxide.
Preferably, the supported Ru catalyst support is alumina selected from one or more of γ-Al2O3、η-Al2O3、δ-Al2O3、θ-Al2O3、k-Al2O3、α-Al2O3, preferably θ -Al 2O3 and/or α -Al 2O3, according to the crystalline form classification.
The specific surface area of the supported Ru catalyst is 0.1-100 m 2/g, preferably 2-20 m 2/g.
The pore volume of the supported Ru catalyst is 0.001-2 cm 3/g, preferably 0.01-0.2 cm 3/g.
The average pore diameter of the supported Ru catalyst is 1-500 nm, preferably 30-200 nm.
The average crystallite size of Ru of the supported Ru catalyst is 0.05-50 nm, preferably 4-10 nm.
The supported Ru catalyst comprises one or more auxiliary agents selected from Li, na, K, rb, cs, ca, ba, la, B, P, ti, zr, ga, preferably one or more of K, ca and B.
The supported Ru catalyst has Ru loading of 0.01-30wt%, preferably 0.5-15wt%, based on the total mass of the catalyst.
The loading amount of the auxiliary agent is 0.001-20wt%, preferably 0.05-10wt%, based on the total mass of the catalyst.
The reactor B is filled with a supported Rh catalyst, and the Rh catalyst comprises a carrier, an active component Rh and an auxiliary agent II, wherein the active component Rh and the auxiliary agent II are attached to the carrier.
The supported Rh catalyst carrier is one or more selected from alumina, activated carbon, zirconium dioxide and titanium dioxide.
Preferably, the supported Rh catalyst support is alumina selected from one or more of γ-Al2O3,η-Al2O3,δ-Al2O3,θ-Al2O3,k-Al2O3,α-Al2O3, preferably gamma-Al 2O3 and/or delta-Al 2O3, according to the crystal form classification.
The specific surface area of the supported Rh catalyst is 50-500 m 2/g, preferably 80-250 m 2/g.
The pore volume of the supported Rh catalyst is 0.05-5 cm 3/g, preferably 0.1-1.5 cm 3/g.
The average pore diameter of the supported Rh catalyst is 0.1-100 nm, preferably 1-20 nm.
The average crystallite diameter of Rh of the supported Rh catalyst is 0.05-10 nm, preferably 0.5-5 nm.
The supported Rh catalyst and the auxiliary agent II are one or more selected from Li, na, K, rb, cs, ca, ba, la, B, P, ti, zr, ga, fe, co, cu, ni, ag, mo, preferably one or more of Li and La.
The supported Rh catalyst has a Rh loading of 0.001 to 10wt%, preferably 0.05 to 5wt%, based on the total mass of the catalyst.
The supported Rh catalyst has an auxiliary agent loading of 0.001-10wt%, preferably 0.01-5wt%, based on the total mass of the catalyst.
In the present invention, the solvent is selected from the group consisting of tetrahydrofuran and mixtures of organic amines.
The organic amine is selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, ethylenediamine, diethylamine, triethylamine, propylamine, propylenediamine, propyltriamine, butylamine, butylenediamine, pentylamine, hexylamine, hexyldiamine, cyclohexylamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, ethanolamine, isopropanolamine, polyetheramine and other organic amines, preferably one or more of trimethylamine, diethylamine and cyclohexylamine.
The mass ratio of the organic amine to the tetrahydrofuran in the mixed solvent is 1:1-1:1000, preferably 1:10-1:100.
The mass ratio of the tetrahydrofuran and organic amine mixed solvent to MDA is 1000:1-1:20, preferably 50:1-1:10.
In the present invention, the reaction temperature of the reactor A is 40 to 200 ℃, preferably 60 to 120 ℃.
In the present invention, the reaction temperature of the reactor B is 80 to 250 ℃, preferably 120 to 200 ℃.
The reactors A and B use the same reaction pressure of 2-20 MPa, preferably 4-10 MPa.
The space velocity of the material feed is 0.01 to 50g MDA.gRu Catalyst -1.h-1, preferably 0.5 to 5g MDA.gRu Catalyst -1.h-1, calculated as the ratio of the mass of MDA feed per unit time to the mass of the supported Ru catalyst in the reactor A.
The molar ratio of the hydrogen feed amount to the MDA feed amount per unit time is 10:1 to 500:1, preferably 15:1 to 50:1.
The mass ratio of the supported Ru catalyst filled in the reactor A to the supported Rh catalyst filled in the reactor B is 1:100-10:1, preferably 1:10-1:1.
In the invention, after the solvent is subtracted from the material at the outlet of the reactor A, the percentage content of MDA is 0-10wt%, preferably 0-5wt%; the percentage content of H 6 MDA is 80-100 wt%, preferably more than or equal to 90wt%; the percentage of H 12 MDA is 0-10wt%, preferably 0-5wt%; the sum of the percentages of other components (referring to various substances except MDA and H 6MDA、H12 MDA) is 0 to 2 weight percent, preferably 0 to 1 weight percent; the percentage of t-H 6 MDA in the intermediate H 6 MDA is 0-20 wt%, preferably 0-15 wt%.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
Aiming at the characteristics that MDA hydrogenation is performed step by step, the Ru catalyst is utilized to catalyze MDA hydrogenation activity to be high, the hydrogenation activity to H 6 MDA is low, the catalytic MDA hydrogenation can effectively inhibit the generation of t-H 6 MDA, the catalytic deamination side reaction is difficult to catalyze and the like, and the MDA is converted into a hydrogenation intermediate H 6 MDA with low t-H 6 MDA content in a reactor A mostly or completely by combining the synergistic effect of catalyst active components, auxiliary agents and carriers and the modulation of hydrogenation process conditions; the method utilizes the characteristics that the Rh catalyst has high hydrogenation activity on H 6 MDA, the hydrogenation of t-H 6 MDA can be catalyzed to effectively inhibit the generation of t, t-H 12 MDA and is not easy to catalyze c, c-H 12 MDA and c, t-H 12 MDA generate t, t-H 12 MDA by isomerization reaction, and finally, the H 12 MDA product with low anti-reflection body content is obtained at the outlet of the B reactor. The invention can realize that the yield of H 12 MDA prepared by MDA hydrogenation reaches more than 98 percent, and the content of the anti-reflection body is less than 10 percent based on the total mass of H 12 MDA.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Gas chromatograph: agilent 7890B, FID detector, DB-5 capillary chromatographic column (30 m x250 μm m x. Mu.0.25 μm), sample inlet 280 ℃, detector 300 ℃; heating program: the initial temperature is 50 ℃, kept for 2min, heated to 80 ℃ at 5 ℃/min, heated to 300 ℃ at 15 ℃/min and kept for 15min.
And (5) quantitatively analyzing by adopting an external standard method, and calculating the conversion rate of raw materials and the yield of products.
The percentage of each isomer in H 6 MDA and H 12 MDA was calculated by peak area normalization. For example, in H 6 MDA, t-H 6 MDA content = t-H 6 MDA peak area/(t-H 6 MDA peak area + c-H 6 MDA peak area) ×100%; in H 12 MDA, t-H 12 MDA content=t, t-H 12 MDA peak area/(t, t-H 2 MDA peak area+c, t-H 12 MDA peak area+c, c-H 12 MDA peak area) is 100%.
The main raw material source information in the examples and comparative examples of the invention is as follows, and other raw materials and reagents are purchased through common commercial routes unless specified otherwise:
MDA is offered by Wanhua chemical group Co., ltd;
Information about Ru catalyst is as follows:
information about Rh catalyst is as follows:
Example 1
30G of 5% Ru-0.5% K/alpha-Al 2O3 catalyst is filled in a fixed bed (namely a reactor A) with the inner diameter of 24mm and the length of 60cm, and inert porcelain balls are filled at the upper end and the lower end of the fixed bed; a fixed bed (i.e., reactor B) with an inner diameter of 24mm and a length of 60cm was connected in series to the outlet of the reactor A, wherein 30g of 2% Rh-0.1% La/gamma-Al 2O3 catalyst was packed, and inert porcelain balls were packed at the upper and lower ends of the fixed bed. The reaction device is replaced by nitrogen and hydrogen respectively, air is exhausted, then hydrogen is introduced to 6MPa, the hydrogen flow is set to 500NL/h, the hydrogen is continuously introduced, then the A, B reactors are heated to 250 ℃ at the heating rate of 120 ℃/h and kept for 4h, and catalyst activation is carried out. After activation, keeping other conditions unchanged, cooling the A, B reactor to 80 ℃ and 140 ℃ respectively, keeping the constant temperature, setting the hydrogen flow to 50.9L/H (the molar ratio of H 2/MDA is 15), introducing MDA solution (a mixed solvent of diethylamine and tetrahydrofuran, the mass ratio of diethylamine and tetrahydrofuran is 1:20, the mass ratio of the mixed solvent and MDA is 1:1, and the space velocity of MDA feeding is 1g MDA.gRu Catalyst -1.h-1) into the reactor at the rate of 60g/H by using a high-pressure constant-flow pump, continuously carrying out hydrogenation reaction under the conditions, sampling at the outlet of the reactor A, B after 200H respectively, and carrying out quantitative analysis by using gas chromatography. Wherein, the composition of the reactor A outlet material after deducting the solvent is: 0.9wt% of MDA, 95.6wt% of H 6 MDA, 3.1wt% of H 12 MDA, 0.4wt% of byproducts (all substances except MDA and H 6MDA、H12 MDA), and 13.0wt% of t-H 6 MDA in H 6 MDA; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 0.5wt%, H 12 MDA content is 98.8wt%,0.7wt% of byproducts (refer to all substances except MDA and H 6MDA、H12 MDA), and t in H 12 MDA and t-H 12 MDA percentage content is 6.7%.
Example 2
30G of 10 percent Ru-5 percent Ca/theta-Al 2O3 catalyst is filled in a fixed bed (namely a reactor A) with the inner diameter of 24mm and the length of 60mm, and inert porcelain balls are filled at the upper end and the lower end of the fixed bed; a fixed bed (i.e. reactor B) with an inner diameter of 36mm and a length of 120mm is connected in series with the outlet of the reactor A, 150g of 0.05% Rh-0.002% Li/θ -Al 2O3 catalyst is filled in the fixed bed, and inert porcelain balls are filled at the upper end and the lower end of the fixed bed. The reaction device is replaced by nitrogen and hydrogen respectively, air is exhausted, hydrogen is introduced to 4MPa, the hydrogen flow is set to 1000NL/h, the hydrogen is continuously introduced, then the A, B reactors are heated to 250 ℃ at the heating rate of 120 ℃/h and kept for 4h, and catalyst activation is carried out. After activation, keeping other conditions unchanged, cooling the A, B reactor to 110 ℃ and 200 ℃ respectively, keeping the constant temperature, setting the hydrogen flow to 848L/H (the molar ratio of H 2/MDA is 50), introducing MDA solution into the reactor at the rate of 225g/H by using a high-pressure constant-flow pump (a mixed solvent of cyclohexylamine and tetrahydrofuran is adopted, the mass ratio of cyclohexylamine and tetrahydrofuran is 1:100, the mass ratio of the mixed solvent and MDA is 1:2, the MDA feeding airspeed is 5g MDA.gRu Catalyst -1.h-1), continuously carrying out hydrogenation reaction under the conditions, sampling at the outlet of the reactor A, B after 200H respectively, and carrying out quantitative analysis by adopting gas chromatography. Wherein, the composition of the reactor A outlet material after deducting the solvent is: MDA content 0.0wt%, H 6 MDA content 98.4wt%, H 12 MDA content 1.4wt%,0.2wt% by-products (all substances except MDA and H 6MDA、H12 MDA), and the percentage of t-H 6 MDA in H 6 MDA is 10wt%; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 0.0wt%, H 12 MDA content is 99.5wt%, and 0.5wt% of byproducts (the sum of all substances except MDA and H 6MDA、H12 MDA) are formed, wherein the percentage content of t-H 12 MDA in H 12 MDA is 7.2%.
Example 3
30G of 0.5 percent Ru-0.01 percent B/gamma-Al 2O3 catalyst is filled in a fixed bed (namely a reactor A) with the inner diameter of 24mm and the length of 60mm, and inert porcelain balls are filled at the upper end and the lower end of the fixed bed; a fixed bed (i.e. reactor B) with an inner diameter of 24mm and a length of 30mm is connected in series with the outlet of the reactor A, 5g of 8% Rh-5% Ba/gamma-Al 2O3 catalyst is filled in the fixed bed, and inert porcelain balls are filled at the upper end and the lower end of the fixed bed. The reaction device is replaced by nitrogen and hydrogen respectively, air is exhausted, then hydrogen is introduced to 12MPa, the hydrogen flow is set to be 200NL/h, the hydrogen is continuously introduced, then the A, B reactors are heated to 250 ℃ at the heating rate of 120 ℃/h and kept for 4h, and the catalyst is activated. After activation, keeping other conditions unchanged, cooling the A, B reactor to 60 ℃ and 100 ℃ respectively, keeping the constant temperature, setting the hydrogen flow to 34L/H (the molar ratio of H 2/MDA is 100), introducing MDA solution into the reactor at a rate of 33g/H by using a high-pressure constant-flow pump (a mixed solvent of trimethylamine and tetrahydrofuran is adopted, the mass ratio of trimethylamine to tetrahydrofuran is 1:1, the mass ratio of the mixed solvent to MDA is 10:1, the MDA feeding airspeed is 0.1g MDA.gRu Catalyst -1.h-1), continuously carrying out hydrogenation reaction under the conditions stably, sampling at the outlet of the reactor A, B after 200H respectively, and carrying out quantitative analysis by adopting gas chromatography. Wherein, the composition of the reactor A outlet material after deducting the solvent is: 8.7wt% of MDA, 90.7wt% of H 6 MDA, 0.2wt% of H 12 MDA, 0.4wt% of byproducts (all substances except MDA and H 6MDA、H12 MDA), and 14.0wt% of t-H 6 MDA in H 6 MDA; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 0.8wt%, H 12 MDA content is 98.6wt%,0.6wt% of byproducts (refer to all substances except MDA and H 6MDA、H12 MDA), and t in H 12 MDA and t-H 12 MDA percentage content is 8.6%.
Comparative example 1
Unlike example 1, both reactors A and B were charged with 30g of 5% Ru to 0.5% K/alpha-Al 2O3 catalyst. The composition obtained after the solvent was subtracted from the material at the outlet of the reactor A was the same as in example 1; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 35.4wt%, H 12 MDA content is 64.1wt%,0.5wt% of byproducts (refer to all substances except MDA and H 6MDA、H12 MDA), and t in H 12 MDA and t-H 12 MDA percentage content is 28.4%.
Comparative example 2
Unlike example 1, both reactors A and B were charged with 30g of 2% Rh-0.1% La/gamma-Al 2O3 catalyst. The composition of the obtained reactor A outlet material after solvent deduction is: 0.0wt% of MDA, 6.4wt% of H 6 MDA, 89.1wt% of H 12 MDA, 4.5wt% of byproducts (all substances except MDA and H 6MDA、H12 MDA), and 25.0wt% of t-H 6 MDA in H 6 MDA; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 0.0wt%, H 12 MDA content is 94.9wt%,5.1wt% of byproducts (refer to all substances except MDA and H 6MDA、H12 MDA), and t in H 12 MDA and t-H 12 MDA percentage content is 16.2%.
Comparative example 3
Unlike example 1, reactor A was charged with 30g of 2% Rh-0.1% La/gamma-Al 2O3 and reactor B was charged with 30g of 5% Ru-0.5% K/alpha-Al 2O3 catalyst. The composition of the obtained reactor A outlet material after solvent deduction is: 0.0wt% of MDA, 6.4wt% of H 6 MDA, 89.1wt% of H 12 MDA, and 4.5wt% of by-products (the sum of all substances except MDA and H 6MDA、H12 MDA), wherein the percentage of t-H 6 MDA in H 6 MDA is 25.0wt%; the composition of the material at the outlet of the reactor B after the solvent is subtracted is as follows: MDA content is 0.0wt%, H 6 MDA content is 0.0wt%, H 12 MDA content is 95.4wt%,4.6wt% of byproducts (refer to all substances except MDA and H 6MDA、H12 MDA), and t in H 12 MDA and t-H 12 MDA percentage content are 34.5%.
Claims (10)
1. A method for synthesizing H 12 MDA with low content of anti-reflection body by continuous hydrogenation comprises the steps of sequentially passing a solution containing solvent and MDA through two reactors A and B connected in series; the reactor A is filled with a supported Ru catalyst, and the Ru catalyst comprises a carrier, an active component Ru and an auxiliary agent I, wherein the active component Ru and the auxiliary agent I are attached to the carrier; the reactor B is filled with a supported Rh catalyst, and the Rh catalyst comprises a carrier, an active component Rh and an auxiliary agent II, wherein the active component Rh and the auxiliary agent II are attached to the carrier.
2. The method of claim 1, wherein the supported Ru catalyst support is selected from one or more of alumina, activated carbon, zirconia, titania; preferably, the supported Ru catalyst support is alumina selected from one or more of γ-Al2O3、η-Al2O3、δ-Al2O3、θ-Al2O3、k-Al2O3、α-Al2O3, preferably θ -Al 2O3 and/or α -Al 2O3, according to the crystalline form classification.
3. The method according to claim 1, characterized in that the supported Ru catalyst has a specific surface area of 0.1-100 m 2/g, preferably 2-20 m 2/g; the pore volume of the supported Ru catalyst is 0.001-2 cm 3/g, preferably 0.01-0.2 cm 3/g; the average pore diameter of the supported Ru catalyst is 1-500 nm, preferably 30-200 nm; the average crystallite size of Ru of the supported Ru catalyst is 0.05-50 nm, preferably 4-10 nm.
4. The method according to claim 1, wherein the supported Ru catalyst, promoter one is selected from one or more of Li, na, K, rb, cs, ca, ba, la, B, P, ti, zr, ga, preferably one or more of K, ca, B.
5. The process according to claim 1, characterized in that the supported Ru catalyst has a Ru loading of 0.01 to 30wt%, preferably 0.5 to 15wt%, based on the total mass of the catalyst; the supported Ru catalyst has an auxiliary agent loading of 0.001-20wt%, preferably 0.05-10 wt%, based on the total mass of the catalyst
wt％。
6. The method according to claim 1, wherein the supported Rh catalyst support is selected from one or more of alumina, activated carbon, zirconia, titania; preferably, the supported Rh catalyst support is alumina selected from one or more of γ-Al2O3、η-Al2O3、δ-Al2O3、θ-Al2O3、k-Al2O3、α-Al2O3, preferably gamma-Al 2O3 and/or delta-Al 2O3, according to the crystal form classification.
7. The process according to claim 1, characterized in that the supported Rh catalyst has a specific surface area of 50-500 m 2/g, preferably 80-250 m 2/g; the pore volume of the supported Rh catalyst is 0.05-5 cm 3/g, preferably 0.1-1.5 cm 3/g; the average pore diameter of the supported Rh catalyst is 0.1-100 nm, preferably 1-20 nm; the average crystallite diameter of Rh of the supported Rh catalyst is 0.05-10 nm, preferably 0.5-5 nm.
8. The method according to claim 1, wherein the supported Rh catalyst, promoter two, is selected from one or more of Li, na, K, rb, cs, ca, ba, la, B, P, ti, zr, ga, fe, co, cu, ni, ag, mo, preferably one or more of Li, la.
9. The process according to claim 1, characterized in that the supported Rh catalyst has an Rh loading of 0.001 to 10wt%, preferably 0.05 to 5wt%, based on the total mass of the catalyst; the supported Rh catalyst has an auxiliary agent loading of 0.001-10wt%, preferably 0.01-5wt%, based on the total mass of the catalyst.
10. The process according to claim 1, characterized in that the reactor a reaction temperature is 40-200 ℃, preferably 60-120 ℃; the reaction temperature of the reactor B is 80-250 ℃, preferably 120-200 ℃; the mass ratio of the supported Ru catalyst filled in the reactor A to the supported Rh catalyst filled in the reactor B is 1:100-10:1, preferably 1:10-1:1.
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