CN118164868A - Method for preparing formamide compound from mixed methylamine - Google Patents
Method for preparing formamide compound from mixed methylamine Download PDFInfo
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- CN118164868A CN118164868A CN202211584952.3A CN202211584952A CN118164868A CN 118164868 A CN118164868 A CN 118164868A CN 202211584952 A CN202211584952 A CN 202211584952A CN 118164868 A CN118164868 A CN 118164868A
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 26
- -1 formamide compound Chemical class 0.000 title claims description 19
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title abstract description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 52
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 52
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003948 formamides Chemical class 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 230000006315 carbonylation Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000003956 methylamines Chemical class 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 238000004587 chromatography analysis Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005924 transacylation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing formamide compounds from mixed methylamine, which comprises the steps of carrying out carbonylation reaction on mixed methylamine (including monomethylamine, dimethylamine and trimethylamine) and CO to obtain the formamide compounds. The method adopts CO gas and mixed methylamine as reactants, and under the action of a cobalt-based catalyst, the mixed methylamine and CO undergo carbonylation reaction to generate mixed formamide, including N-methylformamide and N, N-dimethylformamide. The reaction process is as follows: filling a cobalt-based catalyst in a fixed bed reactor, and introducing mixed methylamine and CO gas, wherein the flow rate of the mixed methylamine gas is as follows: 10-30 mL min ‑1, the flow rate of CO gas is: 20-100 mL/min ‑1, the reaction pressure is 1.0-5.0 MPa, the reaction temperature is 120-180 ℃, the product is mainly formamide compounds, and the selectivity is up to 99%. The method has the advantages of simple operation, low cost and low energy consumption, not only has high catalyst stability and can continuously run, but also has adjustable duty ratio of two formamide compounds in the product, and can be used for large-scale production of the formamide compounds.
Description
Technical Field
The invention relates to a preparation method of a formamide compound, in particular to a method for preparing the formamide compound from mixed methylamine.
Background
The methylamine mixture gas is a generic name for a Mixture of Monomethylamine (MMA), dimethylamine (DMA) and Trimethylamine (TMA). At present, the mixed gas of methylamine is mostly obtained by a methanol ammonification method, and the production process for synthesizing methylamine by using methanol and ammonia as raw materials by a gas phase method is relatively mature. Because of the azeotropic phenomenon between methylamine molecules, the separation process has larger energy consumption. Therefore, the method for utilizing the methylamine mixed gas simply and effectively without separation is developed, and has important research value and potential application background.
The formamide compound is an important chemical, wherein N, N-dimethylformamide is a good solvent for various high polymers such as polyethylene, polyamide and the like, and can be used for wet spinning of synthetic fibers such as polyacrylonitrile fibers and the like and synthesis of polyurethane; is used for plastic film making; can also be used as paint remover for removing paint; it also dissolves some low solubility pigments, making them dye-bearing. In organic reactions, dimethylformamide is widely used not only as a solvent for the reaction but also as an important intermediate for organic synthesis. Carboxamide compounds are generally obtainable either by the transacylation reaction path between amine and transacylating reagent or by the direct carbonylation path of amine and CO. The catalytic direct carbonylation route of amine and CO is an ideal way for producing formamide compounds because of atom economy of 100% and no by-product generation. Although the catalytic systems currently used for the direct carbonylation of formamide are relatively well studied, there are problems such as: the catalyst has complex preparation process, noble metal is adopted as the catalyst, the price is high, the catalyst activity is poor, the catalyst is easy to deactivate after the reaction, and the like. Therefore, a non-noble metal catalyst with high activity and simple preparation is developed, and the direct carbonylation process of the methylamine mixed gas and CO is catalyzed with high efficiency, so that the high-efficiency synthesis of formamide and the separation of the methylamine mixed gas can be realized.
Disclosure of Invention
The invention has the significance of overcoming the problem that the homogeneous catalyst of the formamide compound prepared by direct carbonylation of methylamine is difficult to separate or the problem that noble metal is expensive to catalyze, developing a non-noble catalytic system with high activity and simple preparation, realizing direct carbonylation of methylamine mixed gas, and the ratio of N-methylformamide to N, N-dimethylformamide in the product is adjustable.
The invention relates to a method for preparing formamide compounds from mixed methylamine, which can be obtained through the following processes: and (3) subjecting mixed methylamine (comprising monomethylamine, dimethylamine and trimethylamine) to carbonylation reaction with CO to obtain formamide compounds comprising N-methylformamide and N, N-dimethylformamide. The method is characterized in that: filling a cobalt-based catalyst in a fixed bed reactor, introducing mixed methylamine, and preparing formamide compounds including N-methylformamide and N, N-dimethylformamide by carbonylation reaction of methylamine and CO, wherein the ratio of the N-methylformamide to the N, N-dimethylformamide is adjustable; the cobalt-based catalyst consists of cobalt active metal, an auxiliary agent and a catalyst carrier; the cobalt-based catalyst comprises the following auxiliary agents: one, two or more of carbon, nitrogen and phosphine; wherein the catalyst carrier is one, two or more than two of pure silicon molecular sieves 、SiO2,Al2O3,TiO2,ZrO2,Cr2O3,CeO2,ZnO; the cobalt-based catalyst, wherein the preferred auxiliary agent is: one or two of carbon and nitrogen; preferred supports for the catalyst are: one, two or more than two of Silica-1 molecular sieve, al 2O3,ZrO2 and ZnO; the cobalt-based catalyst comprises 5-25 wt% of cobalt and the addition agent; 0.1 to 10 weight percent; the preparation of the cobalt-based catalyst adopts an impregnation method, a coprecipitation method and a pyrolysis method; the thickness of the catalyst bed filled in the reactor is 5 mm-30 mm, and the flow rate of the methylamine mixed gas is as follows: 10-30 mL min -1, the flow rate of CO gas is: 20-100 mL/min -1, the reaction pressure is 1.0-5.0 MPa, and the reaction temperature is 120-180 ℃; the methylamine mixture gas comprises monomethylamine, dimethylamine and trimethylamine, and has a volume composition of x: y: z (where x, y, z are integers and satisfy 0< x, y, z <100, and x+y+z=100).
Taking Co-N/ZrO 2 catalyst as an example, the reaction processes are respectively described as follows: co acts as an active site to adsorb and activate CO molecules. The structural auxiliary agent N is introduced to realize the regulation and control of the electronic state of Co species, so that the CO adsorption and activation capacity of the Co species is enhanced. The interfacial acid-base pair formed by the carrier ZrO 2 and Co interface activates N-H bond of monomethylamine and dimethylamine, promotes the carbonylation reaction with activated CO molecules to generate N-methyl formamide and N, N-dimethyl formamide; in contrast to monomethylamine and dimethylamine, trimethylamine, due to the absence of N-H, cannot undergo the carbonylation reaction between N-H and finally leaves the reactor as a gas.
The product of the invention is mainly formamide compound, and the selectivity is up to 99%. The method has the advantages of simple operation, low cost and low energy consumption, not only has high catalyst stability and can continuously run, but also has adjustable duty ratio of two formamide compounds in the product, and can be used for large-scale production of the formamide compounds.
Compared with the existing preparation process of formamide, the invention has the following advantages:
1) The non-noble cobalt-based material is used as the catalyst, so that the cost is low, the preparation is simple, and the catalytic activity is excellent;
2) The control of the duty ratio of the carboxamide compound in the carboxamide compound can be realized.
For further detailed description of the present invention, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Detailed Description
Example 1
Weighing 20g of ZnO, soaking in a solution of cobalt nitrate of 10 mmol.L -1, stirring at room temperature for 20h, evaporating to dryness at 130 ℃, and roasting in a muffle furnace at 550 ℃ for 3h to obtain 10wt% Co/ZnO (based on the mass of the carrier, the same applies below); the above materials were placed in an ammonia nitriding furnace and ammonia gas was treated at 500℃for 10 hours to obtain 10wt% Co-N/ZnO (based on the mass of the carrier, the same applies hereinafter), wherein the N content was determined to be 0.5wt% by elemental analysis results. The forming sieve is used for filling the cobalt-based catalyst into a reaction tube, filling a bed layer of 15mm, and the flow rate of the methylamine mixed gas is 20 mL/min -1 under the pressure of 3.0MPa, wherein the monomethylamine is as follows: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 40ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 80 percent, the total selectivity of formamide compounds is 99 percent, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:2.
Example 2
20G of ZrO 2 is weighed and immersed in a solution of cobalt nitrate of 10 mmol.L -1, stirred for 20h at room temperature, evaporated to dryness at 130 ℃, and baked for 3h in a muffle furnace at 550 ℃ to prepare 10wt% Co/ZrO 2; the materials are placed in a normal pressure quartz tube reactor, ethylene is treated for 10 hours at 700 ℃ to obtain 10wt% of Co-C/ZrO 2, wherein the content of N is determined to be 0.7wt% through element analysis results. The forming sieve is used for filling the cobalt-based catalyst into a reaction tube, filling a bed layer of 15mm, and the flow rate of the methylamine mixed gas is 20 mL/min -1 under the pressure of 3.0MPa, wherein the monomethylamine is as follows: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 40ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 67% by chromatographic analysis, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:1.
Example 3
60G of zinc nitrate hexahydrate is weighed and dissolved in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 1.8g of phenanthroline are added and stirred at room temperature until the mixture is completely and uniformly mixed, ammonia water is dropwise added into the solution, the pH value is regulated to be 11, stirring is continued for 4 hours at room temperature, filtering and separation are carried out, drying is carried out at 130 ℃, roasting is carried out for 3 hours under the nitrogen atmosphere at 550 ℃,10 wt% Co-CN/ZnO is prepared, wherein the element content of C, N is respectively 1.0wt% and 0.11wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 150℃with samples taken every 2 hours, the total yield of formamide was 67% and the total selectivity of the formamide compound was 99% with a molar ratio of N-methylformamide to N, N-dimethylformamide of 1:2 by chromatographic analysis.
Example 4
20G of SiO 2 is weighed and dispersed in 60mL of water, 10.02g of cobalt nitrate hexahydrate and 7.5g of diethylenetriamine are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 15wt% Co-CN/SiO 2, wherein the content of C, N element is respectively 1.0wt% and 0.1wt% as determined by element analysis results. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 150℃with samples taken every 2 hours, the total yield of formamide was 78% and the total selectivity of the formamide compound was 99% with a molar ratio of N-methylformamide to N, N-dimethylformamide of 1:2 by chromatographic analysis.
Example 5
20G of SiO 2 is weighed and dispersed in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 5.8g of urea are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, roasting is carried out at 550 ℃ under nitrogen atmosphere for 3h, 10wt% of Co-CN/SiO 2 is prepared, wherein the content of C, N element is respectively 1.3wt% and 0.2wt% as determined by the result of element analysis. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 74 percent, the total selectivity of formamide compounds is 99 percent, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:2.
Example 6
20G of Al 2O3 is weighed and dispersed in 60mL of water, 10.02g of cobalt nitrate hexahydrate and 6.8g of urea are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, evaporation is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 15wt% Co-CN/Al 2O3, wherein the content of C, N element is respectively 1.3wt% and 0.2wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 75% by chromatographic analysis, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:2.
Example 7
20G of SiO 2 is weighed and dispersed in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 8.5g of triethylene tetramine are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 10wt% Co-CN/SiO 2, wherein the content of C, N element is respectively 1.35wt% and 0.25wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 75% by chromatographic analysis, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:2.
Example 8
20G of SiO 2 is weighed and dispersed in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 7.0g of triethylene tetramine are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 10wt% Co-CN/SiO 2, wherein the content of C, N element is respectively 1.35wt% and 0.25wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. At 140 ℃, sampling every 2h, and analyzing by chromatography, wherein the total yield of formamide is 65%, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:1.8.
Example 9
20G of SiO 2 is weighed and dispersed in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 6.0g of triethylene tetramine are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 10wt% Co-CN/SiO 2, wherein the content of C, N element is respectively 1.35wt% and 0.25wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 170℃with samples taken every 2 hours, the total yield of formamide was 82% and the total selectivity of the formamide compounds was 99% with a molar ratio of N-methylformamide to N, N-dimethylformamide of 1:2.
Example 10
20G of SiO 2 is weighed and dispersed in 60mL of water, 15.1g of cobalt nitrate hexahydrate and 5.4g of diethylenetriamine are added, stirring is continued at room temperature until the mixture is completely and uniformly mixed, stirring is continued at room temperature for 4h, drying is carried out at 130 ℃, roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃,20 wt% of Co-CN/SiO 2 is prepared, wherein the content of C, N element is respectively 1.15wt% and 0.34wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 150℃with samples taken every 2 hours, the total yield of formamide was 83% by chromatographic analysis, the total selectivity of the formamide compounds was 99% and the molar ratio of N-methylformamide to N, N-dimethylformamide was 1:2.
Example 11
20G of SiO 2 is weighed and dispersed in 60mL of water, 15.1g of cobalt nitrate hexahydrate and 5.4g of melamine are added to disperse in the system, stirring is continued until the mixture is completely and uniformly mixed, stirring is continued for 4h at room temperature, drying is carried out at 130 ℃, and roasting is carried out for 3h under a nitrogen atmosphere at 550 ℃ to obtain 20wt% Co-CN/SiO 2, wherein the content of C, N element is respectively 0.34wt% and 0.10wt% as determined by element analysis results. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 150℃with samples taken every 2 hours, the total yield of formamide was 83% by chromatographic analysis, the total selectivity of the formamide compounds was 99% and the molar ratio of N-methylformamide to N, N-dimethylformamide was 1:2.
Example 12
20G of Silica-1 molecular sieve is weighed and dispersed in 60mL of water, 15.1g of cobalt nitrate hexahydrate and 7.4g of melamine are added and dispersed in the system, stirring is continued for 4h at room temperature until the mixture is completely and uniformly mixed, the mixture is evaporated to dryness at 130 ℃, and roasting is carried out for 3h at 650 ℃ under nitrogen atmosphere, thus 20wt% Co-CN/Silica-1 is prepared, wherein the element content of C, N is respectively 0.35wt% and 0.15wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 1.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 76% by chromatographic analysis, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:1.7.
Example 13
60G of zinc nitrate hexahydrate is weighed and dissolved in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 5.8g of diethylenetriamine are added, stirring is carried out at room temperature until the mixture is completely and uniformly mixed, ammonia water is dropwise added into the solution, pH=11 is regulated, stirring is continued at room temperature for 4 hours, filtering and separation are carried out, drying is carried out at 130 ℃, roasting is carried out for 3 hours under the nitrogen atmosphere at 750 ℃,10 wt% Co-CN/ZnO is prepared, wherein the element content of C, N is respectively 0.53wt% and 0.12wt% as determined by the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 20mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 160℃with samples taken every 2 hours, the total yield of formamide was 81% and the total selectivity of the formamide compound was 99% with a molar ratio of N-methylformamide to N, N-dimethylformamide of 1:2 by chromatographic analysis.
Example 14
60G of zinc nitrate hexahydrate is weighed and dissolved in 60mL of water, 7.52g of cobalt nitrate hexahydrate and 2.5g of phenanthroline are added and stirred at room temperature until the mixture is completely and uniformly mixed, 3mol/L of sodium hydroxide solution is dropwise added into the solution, the pH=11 is regulated, stirring is continued for 4 hours at room temperature, filtering and separation are carried out, deionized water is used for washing three times, drying is carried out at 130 ℃, roasting is carried out for 3 hours under the nitrogen atmosphere at 550 ℃,10 wt% Co-CN/ZnO is prepared, wherein the element content of C, N is respectively 0.58wt% and 0.13wt% according to the element analysis result. The catalyst with 40-60 meshes is filled into a reaction tube, a bed layer with 10mm is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of the methylamine mixed gas is 25mL min -1 under the pressure of 2.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 50ml·min -1. The reaction was carried out at 150℃with samples taken every 2 hours, the total yield of formamide was 67% and the total selectivity of the formamide compound was 99% with a molar ratio of N-methylformamide to N, N-dimethylformamide of 1:2 by chromatographic analysis.
Example 15
20G of CeO 2 is weighed and immersed in 48.6 mmol.L -1 of ruthenium trichloride hydrate solution, stirred for 20h at room temperature, dried at 130 ℃, reduced for 3h under the hydrogen atmosphere at 350 ℃ to prepare 2wt% Ru/CeO 2, a 14-25 mesh catalyst is formed and sieved to be filled in a reaction tube, a 15mm bed layer is filled in the reaction tube, the reaction tube is placed in a fixed bed reactor after the catalyst is filled in the reaction tube, and the flow rate of methylamine mixed gas is 10 mL/min -1 under the pressure of 3.0MPa, wherein monomethylamine: dimethylamine: trimethylamine=1:1:1 (volume ratio), the flow rate of raw material CO was 10ml·min -1. Reacting at 200 ℃, sampling every 2h, and performing chromatographic analysis to increase the concentration of trimethylamine to 78%; the total selectivity of the formamide compounds is 99% by chromatographic analysis, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:1.8.
Example 16
Weighing 20g of ZnO, dipping in a solution of cobalt nitrate of 10 mmol.L -1, adding 3g of triphenylphosphine, stirring for 20h at room temperature, evaporating to dryness at 130 ℃, and performing heat treatment at 550 ℃ under nitrogen atmosphere to obtain 10wt% Co-P/ZnO; the catalyst was tested by XPS, with a P content of 0.23atom%. The forming sieve is used for filling the cobalt-based catalyst into a reaction tube, filling a bed layer of 15mm, and the flow rate of the methylamine mixed gas is 20 mL/min -1 under the pressure of 3.0MPa, wherein the monomethylamine is as follows: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 40ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 75% by chromatographic analysis, the total selectivity of formamide compounds is 99%, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 1:1.5.
Comparative example 1
Weighing 20g of ZnO, soaking in a solution of cobalt nitrate of 10 mmol.L -1, stirring at room temperature for 20h, drying at 130 ℃, and reducing at 350 ℃ under hydrogen atmosphere for 3h to prepare 10wt% Co/ZnO; the forming sieve is used for filling the cobalt-based catalyst into a reaction tube, filling a bed layer of 15mm, and the flow rate of the methylamine mixed gas is 20 mL/min -1 under the pressure of 3.0MPa, wherein the monomethylamine is as follows: dimethylamine: trimethylamine=1:2:1 (volume ratio), and the flow rate of raw material CO was 40ml·min -1. The reaction is carried out at 150 ℃ and samples are taken every 2 hours, the total yield of formamide is 50 percent, the total selectivity of formamide compounds is 99 percent, and the molar ratio of N-methylformamide to N, N-dimethylformamide is 2:1.
Claims (7)
1. A process for preparing a carboxamide compound from mixed methylamines, by carbonylation of mixed methylamines (including monomethylamine, dimethylamine and trimethylamine) with CO to obtain a carboxamide compound comprising N-methylformamide and N, N-dimethylformamide, characterized in that: filling a cobalt-based catalyst in a fixed bed reactor, introducing mixed methylamine, and preparing formamide compounds including N-methylformamide and N, N-dimethylformamide through carbonylation reaction of methylamine and CO;
The cobalt-based catalyst consists of cobalt active metal, an auxiliary agent and a catalyst carrier.
2.A method according to claim 1, characterized in that:
the cobalt-based catalyst comprises the following auxiliary agents: one, two or more of carbon, nitrogen and phosphine; wherein the catalyst carrier is one, two or more than two of pure silicon molecular sieves 、SiO2、Al2O3、TiO2、ZrO2、Cr2O3、CeO2,ZnO.
3. A method according to claim 1, characterized in that:
The cobalt-based catalyst, wherein the preferred auxiliary agent is: one or two of carbon and nitrogen; preferred supports for the catalyst are: one, two or more of Silica-1 molecular sieve, al 2O3、ZrO2 and ZnO.
4. A method according to claim 1 or 2 or 3, characterized in that:
The cobalt-based catalyst has a cobalt content of 5 to 25wt% (based on the carrier content), preferably 10 to 20wt% (based on the carrier mass); the content of the auxiliary agent is as follows; 0.1 to 10wt% (based on the mass of the support), preferably 0.5 to 5wt%, most preferably 0.1 to 2wt% (based on the mass of the support).
5. A method according to claim 1, characterized in that:
the cobalt-based catalyst can be prepared by one or more of an impregnation method, a coprecipitation method or a pyrolysis method.
6. A method according to claim 1, characterized in that:
The thickness of the catalyst bed filled in the reactor is 5 mm-30 mm, and the flow rate of the methylamine mixed gas is as follows: 10-30 mL min -1, the flow rate of CO gas is: 20-100 mL min -1, reaction pressure of 1.0-5.0 MPa and reaction temperature of 120-180 ℃.
7. A method according to claim 1 or 2, characterized in that: the methylamine mixture gas comprises monomethylamine, dimethylamine and trimethylamine, the volume composition of which is x: y: z (wherein x, y, z are integers and satisfy 0< x, y, z <100, preferably 25< x, y <100, and x+y+z=100).
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