CN109422657B - Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds - Google Patents
Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds Download PDFInfo
- Publication number
- CN109422657B CN109422657B CN201710769459.1A CN201710769459A CN109422657B CN 109422657 B CN109422657 B CN 109422657B CN 201710769459 A CN201710769459 A CN 201710769459A CN 109422657 B CN109422657 B CN 109422657B
- Authority
- CN
- China
- Prior art keywords
- mixed gas
- methylamine
- trimethylamine
- gas
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000003948 formamides Chemical class 0.000 title claims abstract description 14
- 238000000926 separation method Methods 0.000 title abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 8
- 238000005924 transacylation reaction Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims description 44
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- -1 formamide compound Chemical class 0.000 claims description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 17
- 230000006315 carbonylation Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000007056 transamidation reaction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 52
- 238000004587 chromatography analysis Methods 0.000 description 26
- 238000003756 stirring Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 150000003857 carboxamides Chemical class 0.000 description 15
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 14
- 238000005070 sampling Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000004434 industrial solvent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 210000001635 urinary tract Anatomy 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及甲胺混合气体的分离同时联产甲酰胺类化合物的方法，将甲胺混合气，特别是一甲胺与二甲胺比例高甲胺混合气中的一甲胺和二甲胺与CO经羰基化和转酰胺化反应，分离转化后，获取高纯度三甲胺，同时联产甲酰胺和N,N‑二甲基甲酰胺的方法。采用CO气体与甲胺的混合气体作为反应物，在Ru/CeO2催化剂的作用下，一甲胺选择性与CO发生羰基化反应生成甲酰胺，继而甲酰胺与二甲胺发生转酰化反应生成N,N‑二甲基甲酰胺，从而达到纯化三甲胺的目的，同时联产两种甲酰胺类化合物。使用后的催化剂进行焙烧还原后即可以重复使用。本发明的方法操作简单，成本低，可用于规模化分离甲胺混合气体，且高收率联产甲酰类化合物。The invention relates to a method for separating methylamine mixed gas and co-producing formamide compounds at the same time. A method for obtaining high-purity trimethylamine through carbonylation and transamidation of CO, after separation and conversion, and co-production of formamide and N,N-dimethylformamide. Using the mixed gas of CO gas and methylamine as the reactant, under the action of Ru/CeO 2 catalyst, monomethylamine selectively undergoes carbonylation reaction with CO to form formamide, and then formamide and dimethylamine undergo transacylation reaction N,N-dimethylformamide is generated, so as to achieve the purpose of purifying trimethylamine and co-produce two formamide compounds. The used catalyst can be reused after being calcined and reduced. The method of the invention has simple operation and low cost, can be used for large-scale separation of methylamine mixed gas, and co-produces formyl compounds in high yield.
Description
Technical Field
The invention relates to a method for separating methylamine mixed gas, in particular to a method for obtaining high-purity trimethylamine after reaction, separation and conversion of monomethylamine, dimethylamine and CO in methylamine mixed gas, namely a method for separating methylamine mixed gas and CO-producing formamide compounds.
Background
The methylamine mixed gas is a generic name of a Mixture of Monomethylamine (MMA), Dimethylamine (DMA) and Trimethylamine (TMA). The monomethylamine is mainly used for pesticides, medicines, dyes, surfactants, water-gel explosives, fuels, photographic developers, gas purifiers and industrial solvents. Dimethylamine is mainly used in pesticides, medicines, rubber accelerators, fatty tertiary amines, industrial solvents (DMF), Dimethylacetamide (DMA), etc., and organic intermediates. The dosage of trimethylamine as feed additive is smaller at present, but the growing space is large. Methylamine is mainly used as an odor additive for pesticides, choline chloride, natural gas, etc. (the new progress of Yangduqin methylamine technology [ J ]. fine chemical raw materials and intermediates, 2007, (11): 8-10).
Currently, the mixed gas of methylamine is mostly obtained by a methanol ammoniation method. The research on the production process for synthesizing methylamine by a gas phase method by taking methanol and ammonia as raw materials begins in 1958, and after years of development, equilibrium type methylamine catalysts and non-equilibrium type methylamine catalysts and processes are formed. In the research process, the distribution of three components in the methylamine mixed gas can be realized by industrial parameters in the methanol ammoniation process, such as reaction temperature, contact time, proportioning ratio and the like. Therefore, the preparation and separation of three methylamine molecules need to pass through a complicated rectification section. Because of the azeotropic phenomenon among methylamine molecules, the separation process has larger energy consumption. Therefore, a simple and effective method for separating methylamine molecules is developed, and the method has important research value and potential application background.
An important industrial application of dimethylamine, the main component of methylamine mixed gas, is the preparation of N, N-dimethylformamide by carbonylation with CO. The method aims at the characteristics of methylamine mixed gas, selects a reaction way through catalysis, particularly separates trimethylamine gas with weaker reaction activity in the mixed gas with high dimethylamine gas ratio, utilizes carbonylation and transacylation and other reactions to co-produce formamide compounds, and is easy to separate the formamide compounds from unreacted trimethylamine gas because the formamide compounds are gas at normal temperature and normal pressure, and the reaction process is simple, the used catalyst is easy to prepare, has better stability and is suitable for industrial production.
Disclosure of Invention
The invention has the significance of overcoming the complicated separation process of the traditional trimethylamine gas, purifying the trimethylamine from the methylamine mixed gas with high efficiency and co-producing formamide compounds with high yield.
The invention relates to a method for separating methylamine mixed gas, which is realized by the following scheme: a process for preparing high-purity trimethylamine and formamide compounds includes such steps as filling Ru-carried metal oxide catalyst in fixed-bed reactor, introducing mixed methylamine gas and CO gas, carbonylating monomethylamine with CO and transacylating dimethylamine with formamide to obtain trimethylamine.
The gas after reaction is purified trimethylamine gas, the liquid phase is a co-produced formamide compound, a liquid phase product is detected by chromatography, and the solid phase catalyst is recycled through simple roasting and reduction processes.
The Ru-supported metal oxide catalyst is prepared by using MoO as metal oxide3、CuO、Co3O4、Nb2O5、Fe2O3、VO2、CeO2One or more of the above; the Ru metal loading is: 0.5 wt% -10 wt%; the preparation of the Ru-supported metal oxide catalyst adopts an impregnation reduction method or a coprecipitation method. The thickness of a catalyst bed layer filled in the reaction tube is 5 mm-30 mm, and the flow rate of the methylamine mixed gas is as follows: 5 to 33 mL/min-1The flow rate of the CO gas is: 5 to 33 mL/min-1The reaction pressure is 0.5-4 MPa, and the reaction temperature is 150-250 ℃; the thickness of a bed layer filled with a catalyst in the reaction tube is preferably 10 mm-15 mm, and the preferable flow rate of methylamine mixed gas is as follows: 10 to 25 mL/min-1The preferred flow rates of the CO gas are: 10 to 25 mL/min-1The reaction pressure is preferably 1-3 MPa, and the reaction temperature is preferably 150-200 ℃.
The method adopts the mixed gas of CO gas and methylamine as a reactant, under the action of a Ru catalyst, the selective carbonylation reaction of monomethylamine and CO is carried out to generate formamide, and then the transacylation reaction of formamide and dimethylamine is carried out to generate N, N-dimethylformamide, so as to achieve the purpose of purifying trimethylamine and CO-produce two formamide compounds.
The reaction process is as follows: filling a Ru catalyst in a fixed bed reactor, introducing methylamine mixed gas and CO gas, wherein the flow rate of the methylamine mixed gas is as follows: 5 to 33 mL/min-1The flow rate of the CO gas is: 5 to 33 mL/min-1The reaction pressure is 0.5-4 MPa, the reaction temperature is 150-250 ℃, and the CO concentration can be increased to more than 90% from 10-50% in the initial stage of the reaction. Liquid for treating urinary tract infectionThe phase product is mainly formamide compound, and the selectivity of the phase product reaches 99 percent at most. The used catalyst can be reused after being roasted and reduced. The method has the advantages of simple operation, low cost and low energy consumption, can be used for separating methylamine mixed gas on a large scale, and can co-produce formyl compounds with high yield.
Compared with the existing method, the method has the following advantages:
1. the huge energy consumption brought by the traditional methods such as rectification separation and the like is effectively reduced, the equipment is simple, and the method is suitable for large-scale industrial production process;
2. the selectivity of the formamide compound of the co-production product is high and can reach more than 95 percent;
3. the catalyst is simple to prepare, can be operated by the existing chemical unit, has good stability and can be used for long time;
the invention relates to a method for separating and obtaining high-purity trimethylamine after reacting monomethylamine, dimethylamine and CO in methylamine mixed gas through catalytic reaction and separating and converting the monomethylamine and the dimethylamine in the methylamine mixed gas, and simultaneously coproducing formamide compounds, wherein the mechanism for realizing the process is shown in figure 1:
drawings
FIG. 1 is a schematic diagram of a reaction process for obtaining high-purity trimethylamine and co-producing formamide compounds through reaction separation; with Ru/CeO2The above reaction processes are respectively described as follows by taking the catalyst as an example: ru is used as an active site to simultaneously activate monomethylamine, dimethylamine and CO molecules to carry out carbonylation reaction to generate formamide and N, N-dimethylformamide (reactions 1 and 2); carrier CeO2As a reducible oxide, it has a certain acidity or basicity after reduction, and catalyzes the transacylation reaction of formamide and dimethylamine (reaction 3). Compared with monomethylamine and dimethylamine, trimethylamine can not carry out carbonylation reaction and transacylation reaction between N and H because of no existence of N-H, and finally still leaves the reactor as gas, thereby achieving the purpose of separation.
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1
20g of MoO are weighed3The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/MoO3The catalyst of 14-25 meshes is filled into a reaction tube by a forming sieve, a bed layer of 15mm is filled, and the flow rate of the methylamine mixed gas is 10 mL/min under the pressure of 3.0MPa-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and increasing the concentration of trimethylamine to 73%; the overall selectivity of the carboxamides was 90% by chromatography.
Example 2
20g of CuO was weighed out and immersed in 48.6 mmol.L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying at 130 ℃, reducing for 3 hours at 350 ℃ in hydrogen atmosphere to prepare 2 wt% of Ru/CuO, forming and screening 14-25 mesh catalyst to fill a reaction tube, filling a 15mm bed layer, filling the catalyst in the reaction tube, placing the reaction tube in a fixed bed reactor, and under the pressure of 3.0MPa, the flow rate of methylamine mixed gas is 10 mL-min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and increasing the concentration of trimethylamine to 78%; the overall selectivity of the carboxamides was 92% by chromatography.
Example 3
Weighing 20g of Co3O4The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/Co3O4Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. In thatReacting at 200 ℃, sampling every 2h, and increasing the concentration of trimethylamine to 86%; the overall selectivity of the carboxamides was 89% by chromatography.
Example 4
Weighing 20g of Nb2O5The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/Nb2O5Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and increasing the concentration of trimethylamine to 88%; the overall selectivity of the carboxamides was 94% by chromatography.
Example 5
20g of Fe are weighed2O3The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/Fe2O3Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and increasing the concentration of trimethylamine to 70%; the overall selectivity of the carboxamides was 85% by chromatography.
Example 6
Weighing 20g of VO2The solution was immersed in 48.6 mmol. L-1Stirring the solution of the hydrated ruthenium trichloride at room temperature for 20 hours, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% Ru/VO2Filling 14-25 mesh catalyst into a reaction tube by a forming sieve, filling a 15mm bed layer, and filling the catalyst into the reaction tubePlacing the reaction tube in a fixed bed reactor, and under the pressure of 3.0MPa, the flow rate of methylamine mixed gas is 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 79%; the overall selectivity of the carboxamides was 90% by chromatography.
Example 7
20g of CeO were weighed2The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/CeO2Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 90%; the overall selectivity of the carboxamides was 99% by chromatography.
Example 8
Weighing 60g of cerous nitrate hexahydrate, dissolving the cerous nitrate hexahydrate in 60mL of water, adding a certain amount of ruthenium trichloride hydrate, stirring at room temperature until the cerous nitrate hexahydrate and the water are completely and uniformly mixed, dropwise adding ammonia water into the solution, adjusting the pH value to be 10, continuously stirring at room temperature for 4 hours, filtering and separating, drying at 130 ℃, reducing at 350 ℃ for 3 hours in a hydrogen atmosphere to obtain 2 wt% of Ru/CeO2Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 85%; the overall selectivity of the carboxamides was 93% by chromatography.
Example 9
Weighing 60g of cerous nitrate hexahydrate, dissolving the cerous nitrate hexahydrate in 60mL of water, adding a certain amount of ruthenium trichloride hydrate, stirring at room temperature until the cerous nitrate hexahydrate and the water are completely and uniformly mixed, dropwise adding ammonia water into the solution, adjusting the pH value to 11, continuously stirring at room temperature for 4 hours, filtering and separating, drying at 130 ℃, reducing at 350 ℃ for 3 hours in a hydrogen atmosphere to obtain 5 wt% of Ru/CeO2Filling 40-60 mesh catalyst into a reaction tube by a forming sieve, filling a 10mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and controlling the flow rate of methylamine mixed gas to be 5 mL/min under the pressure of 2.0MPa-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 5 mL/min-1. Reacting at 150 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 65%; the overall selectivity of the carboxamides was 95% by chromatography.
Example 10
Weighing 60g of cerous nitrate hexahydrate, dissolving the cerous nitrate hexahydrate in 60mL of water, adding a certain amount of ruthenium trichloride hydrate, stirring at room temperature until the cerous nitrate hexahydrate and the water are completely and uniformly mixed, dropwise adding ammonia water into the solution, adjusting the pH value to 11, continuously stirring at room temperature for 4 hours, filtering and separating, drying at 130 ℃, reducing at 350 ℃ for 3 hours in a hydrogen atmosphere to obtain 5 wt% of Ru/CeO2Filling 40-60 mesh catalyst into a reaction tube by a forming sieve, filling a 10mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and controlling the flow rate of methylamine mixed gas to be 5 mL/min under the pressure of 2.0MPa-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 5 mL/min-1. Reacting at 250 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 85%; the overall selectivity of the carboxamides was 85% by chromatography.
Example 11
Weighing 60g of cerous nitrate hexahydrate, dissolving the cerous nitrate hexahydrate in 60mL of water, adding a certain amount of ruthenium trichloride hydrate, stirring at room temperature until the mixture is completely and uniformly mixed, dropwise adding ammonia water into the solution, adjusting the pH value to 11, continuously stirring at room temperature for 4 hours, filtering, separating, drying at 130 ℃, reducing at 350 ℃ for 3 hours in a hydrogen atmosphere to obtain 5 wt% of the cerium nitrate hexahydrate％Ru/CeO2Filling 40-60 mesh catalyst into a reaction tube by a forming sieve, filling a 20mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 4.0MPa, controlling the flow rate of methylamine mixed gas to be 25 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 25 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 76%; the overall selectivity of the carboxamides was 90% by chromatography.
Example 12
Weighing 60g of cerous nitrate hexahydrate, dissolving the cerous nitrate hexahydrate in 60mL of water, adding a certain amount of ruthenium trichloride hydrate, stirring at room temperature until the cerous nitrate hexahydrate and the water are completely and uniformly mixed, dropwise adding ammonia water into the solution, adjusting the pH value to 11, continuously stirring at room temperature for 4 hours, filtering and separating, drying at 130 ℃, reducing at 350 ℃ for 3 hours in a hydrogen atmosphere to obtain 5 wt% of Ru/CeO2Filling 40-60 mesh catalyst into a reaction tube by a forming sieve, filling a 20mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and controlling the flow rate of methylamine mixed gas to be 15 mL/min under the pressure of 2.0MPa-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:1 (volume ratio), and the flow rate of the raw material CO was 15 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 86%; the overall selectivity of the carboxamides was 92% by chromatography.
Example 13
20g of CeO were weighed2The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/CeO2Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:2:3 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reaction at 200 ℃ with samples taken every 2h, chromatography, of trimethylamineThe concentration increased to 95%; the overall selectivity of the carboxamides was 99% by chromatography.
Example 14
20g of CeO were weighed2The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/CeO2Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:8:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 75%; the overall selectivity of the carboxamides was 99% by chromatography.
Example 15
20g of CeO were weighed2The solution was immersed in 48.6 mmol. L-1Stirring the solution of ruthenium trichloride hydrate for 20 hours at room temperature, drying the solution at 130 ℃, and reducing the solution for 3 hours at 350 ℃ in hydrogen atmosphere to obtain 2 wt% of Ru/CeO2Filling a 14-25 mesh catalyst into a reaction tube by using a forming sieve, filling a 15mm bed layer, filling the catalyst into the reaction tube, placing the reaction tube into a fixed bed reactor, and under the pressure of 3.0MPa, controlling the flow rate of methylamine mixed gas to be 10 mL/min-1Wherein the molar ratio of monomethylamine: dimethylamine: trimethylamine 1:1:1 (volume ratio), and the flow rate of the raw material CO was 10 mL/min-1. Reacting at 200 ℃, sampling every 2h, and carrying out chromatographic analysis to increase the concentration of trimethylamine to 85%; the overall selectivity of the carboxamides was 99% by chromatography.
Claims (5)
1. A method for separating methylamine mixed gas and CO-producing formamide compounds is a method for obtaining trimethylamine and CO-producing formamide compounds after reacting monomethylamine, dimethylamine and CO gas in methylamine mixed gas through catalytic reaction, and separating and converting, and is characterized in that: filling a Ru-loaded metal oxide catalyst into a fixed bed reactor, introducing methylamine mixed gas and CO gas, and performing carbonylation reaction of monomethylamine and CO and transacylation reaction of dimethylamine and formamide serving as a product, thereby achieving the purpose of purifying trimethylamine; the gas after the reaction is purified trimethylamine gas, and the liquid phase is a co-produced formamide compound;
the Ru-supported metal oxide catalyst is prepared by using MoO as metal oxide3、CuO、Co3O4、Nb2O5、Fe2O3、VO2、CeO2One or more than two of them; the Ru metal loading is: 0.5 wt% to 10 wt%.
2. The method of claim 1, wherein:
the preparation of the Ru-supported metal oxide catalyst adopts an impregnation reduction method or a coprecipitation method.
3. The method of claim 1, wherein:
the thickness of a catalyst bed layer filled in the reactor is 5 mm-30 mm, and the flow rate of the methylamine mixed gas is as follows: 5 to 33 mL/min-1The flow rate of the CO gas is: 5 to 33 mL/min-1The reaction pressure is 0.5-4 MPa, and the reaction temperature is 150 DEG CoC ~ 250 oC。
4. A method according to claim 1 or 3, characterized by:
the thickness of a catalyst bed layer filled in the reactor is 10 mm-15 mm, and the flow rate of the methylamine mixed gas is as follows: 10 to 25 mL/min-1The flow rate of the CO gas is: 10 to 25 mL/min-1The reaction pressure is 1-3 MPa, and the reaction temperature is 150oC ~ 200 oC。
5. The method of claim 1, wherein: the methylamine mixed gas comprises monomethylamine, dimethylamine and trimethylamine, and the volume composition of the methylamine mixed gas is x: y: z, wherein x, y and z are integers, and 0< x, y, z <100, and x + y + z = 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710769459.1A CN109422657B (en) | 2017-08-31 | 2017-08-31 | Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710769459.1A CN109422657B (en) | 2017-08-31 | 2017-08-31 | Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109422657A CN109422657A (en) | 2019-03-05 |
| CN109422657B true CN109422657B (en) | 2021-08-17 |
Family
ID=65504628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710769459.1A Active CN109422657B (en) | 2017-08-31 | 2017-08-31 | Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109422657B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898175B (en) * | 2019-11-19 | 2022-08-16 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide |
| CN112898174A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Preparation method of N, N-dimethylformamide |
| CN113842852B (en) * | 2021-10-29 | 2023-05-23 | 聊城鲁西甲胺化工有限公司 | Process and system for annual production of 20 ten thousand tons of methylamine |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411286B1 (en) * | 1969-03-10 | 1979-05-14 | ||
| US4224243A (en) * | 1978-06-23 | 1980-09-23 | Mitsubishi Gas Chemical Company, Inc. | Process for producing dimethyl formamide |
| US5189221A (en) * | 1990-11-19 | 1993-02-23 | Texaco Chemical Company | Amine separation process |
| EP1443037A1 (en) * | 2000-01-24 | 2004-08-04 | E.I. Dupont De Nemours And Company | Process for the preparation of substituted formamides |
| CN104447680A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method of methanamide |
| CN104710321A (en) * | 2013-12-12 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide through dimethylamine carbonylation |
| CN105016937A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing formamide by catalytic oxidation of tertiary amine |
| CN106278930A (en) * | 2015-05-13 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of dimethylaminocarbonyl prepares the method for N,N-dimethylformamide |
-
2017
- 2017-08-31 CN CN201710769459.1A patent/CN109422657B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411286B1 (en) * | 1969-03-10 | 1979-05-14 | ||
| US4224243A (en) * | 1978-06-23 | 1980-09-23 | Mitsubishi Gas Chemical Company, Inc. | Process for producing dimethyl formamide |
| US5189221A (en) * | 1990-11-19 | 1993-02-23 | Texaco Chemical Company | Amine separation process |
| EP1443037A1 (en) * | 2000-01-24 | 2004-08-04 | E.I. Dupont De Nemours And Company | Process for the preparation of substituted formamides |
| CN104447680A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method of methanamide |
| CN104710321A (en) * | 2013-12-12 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide through dimethylamine carbonylation |
| CN105016937A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing formamide by catalytic oxidation of tertiary amine |
| CN106278930A (en) * | 2015-05-13 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of dimethylaminocarbonyl prepares the method for N,N-dimethylformamide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109422657A (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103691432B (en) | A kind of ruthenium/aluminium oxide catalyst, method for making and application thereof | |
| CN109422657B (en) | Method for separation of methylamine mixed gas and simultaneous co-production of formamide compounds | |
| CN109574839B (en) | A kind of method for directly producing methyl acetate and/or acetic acid from synthesis gas | |
| CN112125814B (en) | Method for preparing monoisopropanolamine | |
| KR20140130747A (en) | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium | |
| CN114702434A (en) | Continuous synthesis method of tetramethyl piperidinol | |
| CN108863738A (en) | A method of preparing cyclopentanone | |
| CN101898946B (en) | Method for hydrogenolysis catalysis of glycerin | |
| CN103691450B (en) | A kind of Catalysts and its preparation method of acetic acid hydrogenation ethanol | |
| CN102895974B (en) | Method for synthesizing N-methyl piperidine and supported catalyst used by the method | |
| CN114433100A (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN110479292A (en) | A kind of catalyst and preparation method thereof for aniline hydrogenation synthesis cyclohexylamine | |
| CN108043467B (en) | Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof | |
| CN103894232B (en) | A kind of Catalysts and its preparation method of methyl nitrite formylated synthesis methyl formate and application | |
| CN103691440A (en) | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof | |
| CN101463016B (en) | Method for synthesizing 2,6-dimethyl piperazine | |
| CN105111044A (en) | Method for synthesizing isopentenol from butenol | |
| CN104496939B (en) | A kind of catalytic hydrogenation prepares the method for piperazine or alkyl piperazine | |
| CN112517013A (en) | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentanolactone by using same | |
| CN104130210B (en) | The preparation method of N-methylmorpholine | |
| JP2018034090A (en) | HYDROGENATION CATALYST FOR γ-VALEROLACTONE, AND METHOD FOR PRODUCING 1,4-PENTANEDIOL FROM γ-VALEROLACTONE USING THE CATALYST | |
| CN110252302B (en) | Catalyst for preparing methanol by catalyzing methane to be selectively oxidized at low temperature and preparation method and application thereof | |
| CN103880787B (en) | A kind of coupled reaction prepares the method for gamma-butyrolacton and acetone | |
| CN105251507A (en) | Method for Catalyzing Ethanol to Butadiene Using AgO/CuO-MgO-SiO2 Four-Component Composite Oxide Catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |