CN117924095A - Process for producing dibenzylamine - Google Patents
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- CN117924095A CN117924095A CN202311781052.2A CN202311781052A CN117924095A CN 117924095 A CN117924095 A CN 117924095A CN 202311781052 A CN202311781052 A CN 202311781052A CN 117924095 A CN117924095 A CN 117924095A
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- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000008569 process Effects 0.000 title claims description 24
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- ITXSHZFXAHDNMK-UHFFFAOYSA-N iron ruthenium Chemical compound [Fe].[Ru] ITXSHZFXAHDNMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000009471 action Effects 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- AFDMODCXODAXLC-UHFFFAOYSA-N phenylmethanimine Chemical compound N=CC1=CC=CC=C1 AFDMODCXODAXLC-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010000372 Accident at work Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention provides a method for preparing dibenzyl amine, which comprises the steps of adding benzonitrile and a reaction solvent into a high-pressure reaction kettle, mixing, carrying out hydrogenation reaction under the action of a cerium oxide supported ruthenium-iron bimetallic catalyst to obtain a reaction crude product, cooling, filtering the catalyst, and rectifying and purifying to obtain a dibenzyl amine finished product. The method has mild reaction conditions and high atom utilization rate, and meets the requirements of clean and green production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing dibenzylamine.
Background
Dibenzylamine is an important organic synthesis intermediate, can be used for synthesizing curing agents for curing penicillin, rubber and plastics, is mainly used for producing high-efficiency nontoxic vulcanization accelerators of tetrabenzyl thiuram disulfide (TBZTD) and zinc dibenzyldithiocarbamate (ZBEC), and can also be used for measuring cobalt, iron, cyanate and the like.
The prior production method of dibenzyl amine mainly comprises a benzyl chloride method and a benzaldehyde method, wherein the former is a traditional old process, elemental iodine is generally used as a catalyst, and dibenzyl amine is produced through the reaction of benzyl chloride and benzylamine under normal pressure, and the process is mature, but the yield of dibenzyl amine is not high (a large amount of tribenzylamine byproducts are produced) and the quality is poor (chlorine is contained), so that the requirements of modern medicine and agriculture on the quality of dibenzyl amine can not be met; the latter is a preparation method of high-purity dibenzylamine, which takes benzaldehyde and ammonia as raw materials, and the raw materials are mixed with a reaction solvent to carry out reduction oxidation reaction under hydrogenation high pressure and a catalyst to prepare dibenzylamine. Liquid ammonia or ammonia gas is inflammable, explosive and volatile, and a special pressure-resistant liquefied gas tank truck is needed during transportation, so that in recent years, the industrial accident rate caused by using the liquid ammonia is always high; meanwhile, accurate metering is troublesome when using liquid ammonia or ammonia, and the reaction is finished, so that excessive liquid ammonia or ammonia is difficult to recycle and reuse, and the difficulty in industrial production operation and waste water and waste gas treatment is increased.
In addition, dibenzylamine is also available as a byproduct of the hydrogenation of benzonitrile to produce benzylamine, and generally the process has very high selectivity to benzylamine and very low selectivity to dibenzylamine, and thus is not the mainstream dibenzylamine production process.
In view of the foregoing, there is a need for an improved process for the manufacture of dibenzylamine which solves the above-mentioned problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing dibenzyl amine by utilizing benzonitrile to prepare dibenzyl amine through high-selectivity hydrogenation, and the method has mild reaction conditions and high atom utilization rate, and meets the requirements of clean and green production.
In order to achieve the above object, the present invention provides a method for producing dibenzylamine, comprising the steps of:
step1, adding benzonitrile and a reaction solvent into a high-pressure reaction kettle, mixing, adding a catalyst for hydrogenation reaction, and obtaining a reaction crude product;
And 2, cooling, filtering and purifying the reaction crude product obtained in the step1 to obtain a dibenzyl amine finished product.
As a further improvement of the invention, in the step 1, the reaction solvent is a mixture of toluene and benzylamine, and the mass ratio of toluene to benzylamine is 1: (0.1-0.5).
Further, the mass ratio of the benzonitrile to the reaction solvent is (0.1-0.5): 1.
Further, the mass ratio of the benzonitrile to the catalyst is 1 (0.01-0.1).
Further, the temperature of the hydrogenation reaction is 50-120 ℃, the reaction pressure is 0.6-3 Mpa, and the reaction time is 0.3-2 h.
Further, the crude reaction product comprises benzylamine and dibenzylamine.
In step 2, the method further comprises collecting the products recovered in the rectification and purification process, wherein the recovered products are toluene and benzylamine.
As a further improvement of the present invention, the catalyst is a cerium oxide supported ruthenium-iron bimetallic catalyst.
Further, the load of ruthenium in the catalyst is 1-10wt% of the carrier, and the load of iron is 1-15wt% of the carrier.
Further, the catalyst is prepared by adopting a sequential impregnation method, and the specific steps are as follows:
Step 1, calcining cerium oxide at 500 ℃ for 1h;
step 2, preparing ruthenium nitrate into an aqueous solution, impregnating the calcined cerium oxide, dehydrating on a rotary evaporator after the impregnation is carried out for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain Ru/CeO 2;
Preparing ferric nitrate into an aqueous solution, impregnating Ru/CeO 2, dehydrating on a rotary evaporator after impregnating for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain RuFe/CeO 2;
Step 4, calcining RuFe/CeO 2 at 450 ℃ for 4 hours;
and 5, reducing the calcined RuFe/CeO 2 with hydrogen at 200 ℃ for 4 hours, and cooling to obtain the cerium oxide supported ruthenium-iron bimetallic catalyst.
The beneficial effects of the invention are as follows:
1. the invention provides a method for preparing dibenzyl amine, which utilizes benzonitrile to prepare dibenzyl amine by high-selectivity hydrogenation under the action of a cerium oxide-supported ruthenium-iron bimetallic catalyst.
2. Compared with the alcohol solvent conventionally used in hydrogenation reaction, the method has the advantages that the vaporization heat of the reaction solvent is relatively low, the energy consumption for recovering the solvent is lower, and the method is beneficial to industrial production.
3. The byproduct ammonia of the invention has low solubility in toluene and benzylamine, and the concentration of ammonia in a liquid phase system is small in the reaction process, thereby being beneficial to the selective promotion of dibenzyl amine.
4. In terms of reaction mechanism, benzonitrile reacts with hydrogen to firstly generate a benzyl imine intermediate, then hydrogenation is continued to generate benzyl amine, meanwhile, the benzyl amine also can generate condensation reaction with benzyl imine to generate N-benzyl imine, and the N-benzyl imine is hydrogenated to generate dibenzylamine. In the process, the rate of generating the benzylamine by hydrogenating the benzylimine is slower, and aiming at the situation, the benzylamine is added into the reaction solvent, wherein part of the benzylamine can react with the benzylimine rapidly, so that the rate of generating the dibenzyl amine is increased, and the reaction time is shortened. And this part of the consumed benzylamine can be supplemented by hydrogenation of the benzylimine.
5. Compared with the method which completely uses benzylamine as the solvent, the method uses the mixture of toluene and benzylamine as the solvent, can reduce the viscosity of the system, and avoids the adsorption accumulation of reaction products on the surface of the catalyst, thereby reducing the activity of the catalyst. In addition, the benzylamine itself can be deaminated to generate toluene in a small amount in the reaction process, and the mixture of toluene and benzylamine is used as a solvent, so that no new substance is introduced, and the reaction and subsequent rectification are facilitated.
6. The invention can obtain crude products of reactions with different proportions of the benzylamine and the dibenzylamine by adjusting the proportions of the methylbenzene and the benzylamine, so that the production proportions of the benzylamine and the dibenzylamine can be adjusted according to market demands.
7. The catalyst adopted by the invention is a cerium oxide supported ruthenium-iron bimetallic catalyst, has high and stable catalytic activity, weak adsorption capacity to ammonia, favorability for the generation of dibenzylamine and high selectivity to dibenzylamine, can react at lower temperature and pressure, and accords with the effects of energy conservation and consumption reduction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific embodiments.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a method for preparing dibenzyl amine, which comprises the following steps:
And step1, adding benzonitrile and a reaction solvent into a high-pressure reaction kettle, mixing, adding a catalyst, and carrying out hydrogenation reaction to obtain a reaction crude product.
Specifically, the mass ratio of the benzonitrile to the reaction solvent is preferably (0.1 to 0.5): 1.
More preferably, the mass ratio of the benzonitrile to the reaction solvent is (0.2 to 0.4): 1.
The reaction solvent is prepared from the following components in percentage by mass: (0.1-0.5) toluene and benzylamine, and the prepared reaction crude product comprises benzylamine and dibenzylamine.
The mass ratio of the benzonitrile to the catalyst is preferably 1 (0.01-0.1).
More preferably, the mass ratio of the benzonitrile to the catalyst is 1 (0.03-0.05).
The hydrogenation reaction temperature is preferably 50-120 ℃, the reaction pressure is preferably 0.6-3 Mpa, and the reaction time is preferably 0.3-2 h.
More preferably, the hydrogenation reaction temperature is 70-90 ℃, the reaction pressure is 1-2 MPa, and the reaction time is 0.5-1.5 h.
The catalyst is a cerium oxide supported ruthenium-iron bimetallic catalyst.
The loading of ruthenium in the catalyst is preferably 1-10wt% of the carrier, and the loading of iron is preferably 1-15wt% of the carrier.
More preferably, the ruthenium loading in the catalyst is 1 to 5wt% of the support and the iron loading is 2.5 to 10wt% of the support.
And 2, cooling, filtering and purifying the reaction crude product obtained in the step1 to obtain a dibenzyl amine finished product.
Specifically, in step 2, the method further comprises collecting the products recovered in the rectification and purification process, wherein the recovered products are toluene and benzylamine.
In the above steps, the catalyst is prepared by adopting a sequential impregnation method, and the specific steps are as follows:
Step 1, calcining cerium oxide at 500 ℃ for 1h;
step 2, preparing ruthenium nitrate into an aqueous solution, impregnating the calcined cerium oxide, dehydrating on a rotary evaporator after the impregnation is carried out for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain Ru/CeO 2;
Preparing ferric nitrate into an aqueous solution, impregnating Ru/CeO 2, dehydrating on a rotary evaporator after impregnating for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain RuFe/CeO 2;
Step 4, calcining RuFe/CeO 2 at 450 ℃ for 4 hours;
and 5, reducing the calcined RuFe/CeO 2 with hydrogen at 200 ℃ for 4 hours, and cooling to obtain the cerium oxide supported ruthenium-iron bimetallic catalyst.
The method for producing dibenzylamine according to the present invention will be described with reference to specific examples.
Example 1
Example 1 provides a process for the manufacture of dibenzylamine comprising the steps of:
Step 1. In a 1000mL autoclave, 150g of benzonitrile, 375g of reaction solvent (wherein 80wt% of toluene and 20wt% of benzylamine) and 7.5g of cerium oxide-supported ruthenium-iron bimetallic catalyst (wherein the load of ruthenium is 5wt% and the load of iron is 5 wt%) are added for hydrogenation reaction, the reaction temperature is 70 ℃, the reaction pressure is 2.0Mpa, and the reaction time is 1h, so that a crude reaction product comprising benzylamine and dibenzylamine is prepared.
And 2, cooling, filtering and purifying the reaction crude product obtained in the step 1 to obtain a dibenzyl amine finished product, wherein toluene and benzyl amine recovered in the rectification process can be recycled.
The reaction product was detected by gas chromatography, the conversion of benzonitrile was 100% and the selectivity to dibenzyl amine was 97.3%.
Example 2
Example 2 provides a process for the production of dibenzylamine which differs from example 1 only in that the temperature of the hydrogenation reaction is 90 ℃, and other experimental parameters and conditions are the same as in example 1 and are not described here again.
The reaction product was detected by gas chromatography with a conversion of benzonitrile of 100% and a dibenzylamine selectivity of 97.6%.
Example 3
Example 3 provides a process for the production of dibenzylamine which differs from example 1 only in that the pressure of the reaction is 3.0MPa, and other experimental parameters and conditions are the same as in example 1 and are not described here again.
The reaction product was detected by gas chromatography with a conversion of benzonitrile of 100% and a dibenzylamine selectivity of 97.7%.
Example 4
Example 3 provides a process for the manufacture of dibenzylamine which differs from example 1 only in that the catalyst is used in an amount of 5g, and other experimental parameters and conditions are the same as in example 1 and are not described in detail herein.
The reaction product was detected by gas chromatography with a conversion of benzonitrile of 99.3% and a dibenzylamine selectivity of 96.9%.
Comparative examples 1 to 2
Comparative examples 1 to 2 each provide a process for producing dibenzylamine, which differs from example 1 only in that toluene is used as the reaction solvent in comparative example 1, benzylamine is used as the reaction solvent in comparative example 2, and other experimental parameters and conditions are the same as those in example 1, and are not described herein.
The reaction product was detected by gas chromatography, the conversion of benzonitrile in comparative example 1 was 99.2% and the selectivity for dibenzylamine was 89.4%; the conversion of benzonitrile was 98.5% and the selectivity to dibenzylamine was 80.3% in comparative example 2.
Comparative example 3
Comparative example 3 provides a method for producing dibenzylamine, which is different from example 1 only in that the amount of ruthenium supported on the catalyst is 15wt% of the support, the amount of iron supported on the catalyst is 5wt% of the support, and other experimental parameters and conditions are the same as in example 1, and will not be described again.
The reaction product was detected by gas chromatography with a conversion of 98.0% of benzonitrile and a dibenzylamine selectivity of 87.7%.
Comparative example 4
Comparative example 4 provides a method for producing dibenzylamine, which is different from example 1 only in that a platinum catalyst supported on carbon is used as the catalyst, and other experimental parameters and conditions are the same as those of example 1, and will not be described again.
The reaction product was detected by gas chromatography with a conversion of benzonitrile of 97.8% and a dibenzylamine selectivity of 5%.
According to the embodiment and the comparative example, the cerium oxide supported ruthenium-iron bimetallic catalyst provided by the invention has high and stable catalytic activity, weak adsorption capacity to ammonia, favorability for the generation of dibenzylamine, and selectivity to dibenzylamine is more than 96% when the conversion rate of the benzonitrile is 100%, and the catalyst can react at lower temperature and pressure, so that the catalyst accords with the effects of energy conservation and consumption reduction; the invention uses the mixture of toluene and benzylamine as the solvent, can reduce the viscosity of the system, and avoid the adsorption accumulation of reaction products on the surface of the catalyst, thereby reducing the activity of the catalyst.
In summary, the method for preparing dibenzyl amine provided by the invention utilizes benzonitrile to selectively hydrogenate and prepare dibenzyl amine under the action of the cerium oxide-supported ruthenium-iron bimetallic catalyst, and has the advantages of mild reaction conditions and high atom utilization rate, and meets the requirements of clean and green production.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A process for producing dibenzylamine, comprising the steps of:
step1, adding benzonitrile and a reaction solvent into a high-pressure reaction kettle, mixing, adding a catalyst for hydrogenation reaction, and obtaining a reaction crude product;
And 2, cooling, filtering and purifying the reaction crude product obtained in the step1 to obtain a dibenzyl amine finished product.
2. The process for producing dibenzylamine according to claim 1, wherein in step 1, the reaction solvent is a mixture of toluene and benzylamine, and the mass ratio of toluene to benzylamine is 1: (0.1-0.5).
3. The process for producing dibenzylamine according to claim 1, characterized in that in step 1, the mass ratio of the benzonitrile to the reaction solvent is (0.1 to 0.5): 1.
4. The process for producing dibenzylamine according to claim 1, characterized in that in step 1, the mass ratio of benzonitrile to the catalyst is 1 (0.01 to 0.1).
5. The process for producing dibenzyl amine according to claim 1, wherein in step 1, the hydrogenation reaction is carried out at a temperature of 50 to 120℃and a pressure of 0.6 to 3MPa for a period of 0.3 to 2 hours.
6. The process for producing dibenzylamine according to claim 1, characterized in that in step 1, the crude reaction product comprises benzylamine and dibenzylamine.
7. The process for producing dibenzylamine according to claim 1, characterized by further comprising collecting the product recovered in the rectification and purification process in step 2; the recovered products were toluene and benzylamine.
8. The process for producing dibenzylamine according to claim 1, wherein the catalyst is a cerium oxide-supported ruthenium-iron bimetallic catalyst.
9. The process for producing dibenzyl amine according to claim 8, wherein the amount of ruthenium supported on the catalyst is from 1 to 10% by weight of the carrier and the amount of iron supported on the catalyst is from 1 to 15% by weight of the carrier.
10. The method for preparing dibenzylamine according to claim 8, characterized in that the catalyst is prepared by a sequential impregnation method comprising the following steps:
Step 1, calcining cerium oxide at 500 ℃ for 1h;
step 2, preparing ruthenium nitrate into an aqueous solution, impregnating the calcined cerium oxide, dehydrating on a rotary evaporator after the impregnation is carried out for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain Ru/CeO 2;
Preparing ferric nitrate into an aqueous solution, impregnating Ru/CeO 2, dehydrating on a rotary evaporator after impregnating for 12 hours, and vacuum drying the obtained solid at 110 ℃ for 12 hours to obtain RuFe/CeO 2;
Step 4, calcining RuFe/CeO 2 at 450 ℃ for 4 hours;
and 5, reducing the calcined RuFe/CeO 2 with hydrogen at 200 ℃ for 4 hours, and cooling to obtain the cerium oxide supported ruthenium-iron bimetallic catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311781052.2A CN117924095A (en) | 2023-12-22 | 2023-12-22 | Process for producing dibenzylamine |
Applications Claiming Priority (1)
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