CN110511149B - Method for directly preparing dimethylamine from synthesis gas - Google Patents

Method for directly preparing dimethylamine from synthesis gas Download PDF

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CN110511149B
CN110511149B CN201910536137.1A CN201910536137A CN110511149B CN 110511149 B CN110511149 B CN 110511149B CN 201910536137 A CN201910536137 A CN 201910536137A CN 110511149 B CN110511149 B CN 110511149B
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methanol
molecular sieve
reaction
dimethylamine
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CN110511149A (en
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邢闯
李明权
张桂华
童明亮
王佳元
吕鹏
杨瑞芹
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Zhejiang Lover Health Science and Technology Development Co Ltd
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Abstract

The invention relates to a method for directly preparing dimethylamine from synthesis gas, which is characterized by comprising the following steps: the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 The invention realizes the reaction of directly preparing dimethylamine by synthesis gas one-step method by coupling a methanol catalyst and a methylamine catalyst, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1: 3:1:1-3, and the mass ratio of the methanol catalyst to the methylamine catalyst is 1: 0.5-5. The serial catalyst composed of CuZnAl and the core-shell structure composite molecular sieve has the advantages of simple synthesis, low catalyst cost, low equipment investment and the like, and the selectivity of dimethylamine in the product is obviously improved.

Description

Method for directly preparing dimethylamine from synthesis gas
Technical Field
The invention belongs to the field of chemical synthesis, relates to a series catalytic synthesis reaction technology, in particular to a multifunctional composite catalyst, and particularly relates to a method for directly preparing dimethylamine from synthesis gas.
Background
Methylamine is an important organic chemical raw material, is widely applied to industries such as medicines, pesticides, solvents, template agents and the like, and has wide application. Currently, methanol is mostly adopted in industry to synthesize methylamine by a gas phase catalysis method of ammonia, but because of thermodynamic equilibrium control, the equilibrium composition of monomethylamine/dimethylamine/trimethylamine is 23/27/50 (mass ratio), wherein the market demand of dimethylamine is the largest, and accounts for more than 80%, and the dimethylamine is an important raw material for generating a dimethylformamide solvent.
China is rich in coal resources, and the preparation of methanol from synthesis gas with coal as a source is an important energy development approach. Early US patent US2821537 reported that methylamine (CO + H) can be directly prepared from mixed syngas and ammonia gas 2 +NH 3 → CH 3 NH 2 +CH 3 -NH-CH 3 +(CH 3 ) 3 N), the route adopts a one-stage method to directly synthesize the methylamine, and the economic benefit and the environmental protection significance are very important. The route comprises the following two steps: (1) synthesis of methanol, CO + H from synthesis gas 2 →CH 3 OH, a catalyst CuZnAl for industrially synthesizing methanol is well developed; (2) synthesis of methylamine, CH by gas phase ammoniation of methanol 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O, this step is a dehydration reaction and is currently predominantly a molecular sieve catalyst.
Baiker et Al uses Cu/Al 2 O 3 The catalyst is at 0.6MPa, 200 ℃ and 300 ℃ and CO/H 2 /NH 3 Under the reaction condition of 1/1/3, methylamine may be synthesized directly, where Cu is catalyst for hydrogenating synthetic gas to prepare methanol and acidic Al 2 O 3 As a catalyst for catalyzing the amination of methanol (Journal of the Chemical Society, Chemical Communications,1995,1,73-74), but because of Al 2 O 3 Due to the disordered property of the pore channel, the product has no shape-selective catalysis, so that the proportion of trimethylamine in the product is obviously higher, and the selectivity of dimethylamine is lower. In 1978, Mobil corporation developed ZSM series molecular sieves by utilizing the shape-selective catalytic action of pore channels of the molecular sieves, and greatly improved the selectivity of dimethylamine.
The work of high-selectivity dimethylamine synthesis by modified MOR molecular sieve catalyst by Nissan chemical company in 1984 has been industrialized, wherein the selectivity of dimethylamine is as high as 60%. However, MOR is a 12-membered ring and 8-membered ring channel structure, the dynamic diameter of trimethylamine is 0.39nm, and the trimethylamine can freely diffuse in the 12-membered ring molecular sieve channel, so that the pore diameter of the molecular sieve is reduced, the entrance and the exit of the trimethylamine in the molecular sieve channel can be inhibited, and the shape selective catalysis is realized. When the pore diameter of the molecular sieve is less than or equal to the molecular diameter of trimethylamine, the trimethylamine is not easily generated. The literature (Chinese Journal of Catalysis,2017,38, 574-582; Chemical Reviews,2018, 118,5265-5329) reports that the small-pore 8-membered ring molecular sieve effectively inhibits the generation of trimethylamine, wherein the RHO molecular sieve has the highest dimethylamine selectivity and the lowest trimethylamine selectivity.
In summary, both reactions have been industrialized, whether the reaction is a reaction for preparing methanol from synthesis gas or a reaction for preparing methylamine through methanol ammoniation. However, as mentioned above, if the synthesis gas and ammonia gas are used as raw materials, and methanol synthesis and methanol ammoniation reaction are coupled to directly produce dimethylamine, the energy consumption can be effectively reduced, the reaction process can be simplified, and the method is an industrially and economically advantageous process. Therefore, although there are various catalysts for this reaction, there is still a need to find a highly efficient catalyst which simultaneously satisfies:
(1) the two reaction process conditions of methanol synthesis and methanol ammoniation are matched, such as temperature, pressure and other conditions;
(2) compounding the catalyst, such as physical mixing, two-stage process or core-shell structure catalyst;
(3) the shape-selective catalytic effect of the molecular sieve controls the pore channel structure of the molecular sieve, and the selectivity of dimethylamine is realized to the maximum extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for directly preparing dimethylamine from synthesis gas. In addition, the invention provides a method for directly preparing the catalyst of dimethylamine by synthesis gas, the composite molecular sieve synthesized by the solid-phase synthesis method of the catalyst is a molecular sieve catalyst with a core-shell structure, the catalytic efficiency is high, the preparation of the catalyst is simple and easy to operate, the energy consumption is low, and the catalyst cost is further reduced.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a process for directly preparing dimethylamine from synthetic gas includes two serial reactions of reaction for preparing methanol from synthetic gas and ammoniation reaction of methanol, in which the reaction catalyst is composed of methanol catalyst and methylamine catalyst, and is carried out in a continuous fixed-bed reactor at 200-400 deg.C and 0.1-5MPa in volume ratio of raw material gas (H) 2 /CO/NH 3 The mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, wherein the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O。
Moreover, the methanol catalyst is CuZnAl catalyst, and the weight percentage of the CuO catalyst is 30-60%, the ZnO catalyst is 30-60%, and the Al catalyst is 2 O 3 5-10%, and the catalyst is prepared by coprecipitation method.
And the catalyst is formed into tablets and sieved to have the granularity of 20-80 meshes.
Moreover, the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of CuO 30-60%, ZnO 30-60% and Al 2 O 3 Preparing a mixed salt solution by using a metal molar ratio of 5-10%, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloric acid salt solution, a nitric acid salt solution and an acetic acid salt solution;
(2) reacting the mixed salt solution with a precipitant, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitant is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
(3) and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
Moreover, the methylamine catalyst is a composite molecular sieve material with a core-shell structure, wherein the core is one or two of ZSM-5 and ZSM-35, and the shell is SAPO-34 and AlPO 4 -25 in a form comprising at least one of a physically mixed, co-crystallized structure.
The methylamine catalyst is a molecular sieve catalyst and is prepared by a solid-phase synthesis method, the structure of the methylamine catalyst is a core-shell structure of the molecular sieve coated with the molecular sieve, wherein the shell is a molecular sieve with an 8-membered ring topological structure, and SAPO-34 and AlPO can be selected 4 -25, the core is a molecular sieve with 10-membered ring topology, and one or two of ZSM-5 and ZSM-35 can be selected.
Moreover, the preparation method of the methylamine catalyst comprises the following steps:
(1) adding a solid silicon source, an aluminum source, a phosphorus source and a template agent into an agate mortar, grinding for 5-60min, putting into a hydrothermal kettle, crystallizing at 100-250 ℃ for 16-240h, washing and drying a product to obtain a molecular sieve core;
(2) in the step (1), the molecular sieve core is taken as a crystal nucleus, a secondary crystallization method is adopted to grow a molecular sieve shell on the crystal nucleus, the molecular sieve core, a silicon source and a template agent are mixed in an agate mortar, the mixture is ground for 5-60min at room temperature, hydrothermal crystallization is carried out for 24-72h at the temperature of 100-250 ℃, and the product is washed, dried and roasted for 5-10h at the temperature of 300-600 ℃ to obtain the methylamine catalyst.
And the drying temperature in the step (2) is 80-120 ℃, and the drying time is 6-24 h.
Moreover, the selected silicon source is white carbon black and SiO 2 One or more of gel, silicic acid and sodium silicate, wherein the selected aluminum source is one or more of pseudo-boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin, the selected phosphorus source is one or two of phosphoric acid and ammonium dihydrogen phosphate, and the molar ratio of the silicon source, the aluminum source, the phosphorus source and the template is 1-50:0.1-1:0-1: 0.1-1.
Moreover, the mole ratio of the silicon source to the template agent is 1-50:0.1-1, and the mass ratio of the molecular sieve shell to the silicon source is 10-100: 1.
The invention has the advantages and positive effects that:
1. the invention couples the reaction of preparing methanol by CO hydrogenation and the reaction of preparing methylamine by methanol ammoniation, fills a methanol catalyst and a methylamine catalyst in a fixed bed reactor, realizes the matching of the two reaction process conditions of methanol synthesis and methanol ammoniation and the reaction of directly preparing dimethylamine by synthesis gas.
2. The invention adopts a solid-phase synthesis method to prepare the composite molecular sieve catalyst with the core-shell structure, and realizes the high-selectivity synthesis of dimethylamine by methanol ammoniation by controlling the pore channel structure of the molecular sieve and utilizing the shape-selective catalytic effect of the molecular sieve.
3. The invention realizes the reaction of directly preparing dimethylamine by one step of synthesis gas by coupling a methanol catalyst and a methylamine catalyst. The serial catalyst composed of CuZnAl and the core-shell structure composite molecular sieve has the advantages of simple synthesis, low catalyst cost, low equipment investment and the like, and the selectivity of dimethylamine in the product is obviously improved.
Drawings
FIG. 1 is a process diagram of one-step preparation of dimethylamine from synthesis gas;
FIG. 2 is an XRD spectrum of a CuZnAl methanol catalyst;
FIG. 3 is an XRD spectrum of a ZSM-5 molecular sieve;
FIG. 4 is an XRD spectrum of a ZSM-35 molecular sieve;
FIG. 5 is an XRD spectrum of an AlPO4-25 molecular sieve;
FIG. 6 is an XRD spectrum of a SAPO-34 molecular sieve;
FIG. 7 is an XRD spectrum of an HZSM-35@ SAPO-34 molecular sieve;
FIG. 8 is an XRD spectrum of HZSM-5@ SAPO-34 molecular sieve;
FIG. 9 is an XRD spectrum of the HZSM-5@ AlPO4-25 molecular sieve.
Detailed Description
The present invention will be described in more detail below with reference to the following embodiments, which are provided by way of illustration only and are not intended to limit the scope of the present invention.
A method for directly preparing dimethylamine from synthesis gas, as shown in figure1, the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 1-3:1:1-3, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, and the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O。
Moreover, the methanol catalyst is a CuZnAl catalyst which comprises 30 to 60 weight percent of CuO, 30 to 60 weight percent of ZnO and Al 2 O 3 5-10%, and the catalyst is prepared by coprecipitation method.
And the catalyst is formed into tablets and sieved to have the granularity of 20-80 meshes.
Moreover, the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of 30-60 percent of CuO, 30-60 percent of ZnO and Al 2 O 3 Preparing a mixed salt solution by using 5-10% of metal in a molar ratio, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloride solution, a nitrate solution and an acetate solution;
(2) reacting the mixed salt solution with a precipitant, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitant is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
(3) and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
Moreover, the methylamine catalyst is a composite molecular sieve material with a core-shell structure, wherein the core is one or two of ZSM-5 and ZSM-35, and the shell is SAPO-34 and AlPO 4 One of-25And one or two of the composite molecular sieve materials exist in a form including at least one of physical mixing and a cocrystallization structure.
Moreover, the methylamine catalyst is a molecular sieve catalyst and is prepared by adopting a solid-phase synthesis method, the structure of the methylamine catalyst is a core-shell structure of the molecular sieve coated with the molecular sieve, wherein the shell is a molecular sieve with an 8-membered ring topological structure, and SAPO-34 and AlPO can be selected 4 25, the core is a molecular sieve with 10-membered ring topological structure, and one or two of ZSM-5 and ZSM-35 can be selected.
Moreover, the preparation method of the methylamine catalyst comprises the following steps:
(1) adding a solid silicon source, an aluminum source, a phosphorus source and a template agent into an agate mortar, grinding for 5-60min, putting into a hydrothermal kettle, crystallizing at 100-250 ℃ for 16-240h, washing and drying a product to obtain a molecular sieve core;
(2) in the step (1), the molecular sieve core is taken as a crystal nucleus, a secondary crystallization method is adopted to grow a molecular sieve shell on the crystal nucleus, the molecular sieve core, a silicon source and a template agent are mixed in an agate mortar, the mixture is ground for 5-60min at room temperature, hydrothermal crystallization is carried out for 24-72h at the temperature of 100-250 ℃, and the product is washed, dried and roasted for 5-10h at the temperature of 300-600 ℃ to obtain the methylamine catalyst.
And the drying temperature in the step (2) is 80-120 ℃, and the drying time is 6-24 h.
Moreover, the selected silicon source is white carbon black and SiO 2 The aluminum source is one or more of pseudo-boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin, the phosphorus source is one or two of phosphoric acid and ammonium dihydrogen phosphate, and the molar ratio of the silicon source, the aluminum source, the phosphorus source and the template agent is 1-50:0.1-1:0-1: 0.1-1.
And the molar ratio of the silicon source to the template agent is 1-50:0.1-1, and the mass ratio of the molecular sieve shell to the silicon source is 10-100: 1.
The molecular sieve crystal form prepared in the embodiment of the invention is determined by a Nippon pharmacological Ultima type IV X-ray diffractometer (XRD), and the experimental conditions are as follows: CuKa radiation, tube voltage 40kV and tube current 40 mA.
Example 1
Synthesizing a methanol catalyst CuZnAl: 10.87g of copper nitrate trihydrate, 13.38g of zinc nitrate hexahydrate and 3.75g of aluminum nitrate nonahydrate were weighed and added to a beaker containing 200mL of the solution, and the temperature was maintained at 60 ℃ to obtain a solution A. 9.54g of sodium carbonate solution was dissolved in 100mL of deionized water, and the solution was defined as solution B. Slowly dripping the solution B into the solution A while vigorously stirring, maintaining the temperature at 60 ℃, and controlling the pH value in the system to be about 8.6 by the dripping speed of the sodium carbonate solution. And after the precipitation is finished, aging at room temperature overnight, filtering, repeatedly washing the precipitate for 5 times by using deionized water at 60 ℃ until the filtrate is neutral, finally drying at 120 ℃ for 6h, and roasting in a muffle furnace at 350 ℃ for 5h to obtain the CuZnAl methanol catalyst, wherein the CuZnAl molar ratio is 45:45:10, and the XRD spectrogram of a CuZnAl sample is shown in figure 2.
Example 2
HZSM-5 catalyst synthesis: weighing 4.87g of white carbon black, 0.48g of boehmite, 0.28g of sodium hydroxide and 0.25g of tetrapropyl ammonium bromide, adding the white carbon black, the boehmite, the sodium hydroxide and the tetrapropyl ammonium bromide into an agate mortar, grinding for 5-10min, then adding the ground boehmite, the tetrapropyl ammonium bromide into a hydrothermal kettle, crystallizing for 16h at 200 ℃, after crystallization is finished, rapidly cooling the mixture to room temperature in an ice water bath, repeatedly washing the mixture to be neutral by deionized water, and drying the mixture overnight at 120 ℃ to obtain the NaZSM-5 molecular sieve. Adding NaZSM-5 powder into 1M ammonium nitrate aqueous solution with the solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtering, and finally roasting in the air at 500 ℃ for 5h to obtain the HZSM-5 molecular sieve, wherein an XRD spectrogram of a ZSM-5 sample is shown in figure 3.
Example 3
Synthesizing an HZSM-35 molecular sieve: weighing 4.4g of white carbon black, 2.08g of aluminum nitrate, 1.6g of sodium hydroxide and 2.8g of ethylenediamine, adding the white carbon black, the aluminum nitrate, the sodium hydroxide and the ethylenediamine into an agate mortar, grinding for 5-10min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, after crystallization is finished, rapidly cooling to room temperature in an ice water bath, repeatedly washing to be neutral by deionized water, and drying at 120 ℃ overnight to obtain the NaZSM-35 molecular sieve. Adding NaZSM-35 powder into 1M ammonium nitrate aqueous solution with the solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtering, and finally roasting in air at 500 ℃ for 5h to obtain the HZSM-35 molecular sieve, wherein an XRD spectrogram of a ZSM-35 sample is shown in native 4.
Example 4
AlPO 4 -25 molecular sieve synthesis: weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of dimethylamine (40 wt%), adding the white carbon black into an agate mortar, grinding for 15-25min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching the mixture to room temperature in an ice water bath after crystallization is finished, repeatedly washing the mixture to be neutral by deionized water, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain AlPO 4 -25 molecular sieves, AlPO 4 The XRD spectrum of the-25 sample is shown in FIG. 5.
Example 5
SAPO-34 molecular sieve synthesis: weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the white carbon black, the boehmite, the ammonium dihydrogen phosphate and the morpholine into an agate mortar, grinding for 5-10min, then adding the obtained product into a hydrothermal kettle, crystallizing for 24h at 200 ℃, after crystallization is finished, carrying out ice water bath quenching to room temperature, repeatedly washing the product with deionized water to neutrality, drying the product overnight at 120 ℃, and finally roasting the product for 5h in air at 500 ℃ to obtain the SAPO-34 molecular sieve, wherein an XRD spectrogram of an SAPO-34 sample is shown in figure 6.
Example 6
Synthesis of HZSM-35@ SAPO-34 composite molecular sieve: weighing 1.0g of the HZSM-35 molecular sieve prepared in example 3, filling the weighed molecular sieve into agate, weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the weighed molecular sieve into an agate mortar filled with the HZSM-35 molecular sieve, grinding for 5-10min, adding the weighed molecular sieve into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching to room temperature in an ice water bath after crystallization is finished, repeatedly washing the molecular sieve to be neutral by deionized water, drying overnight at 120 ℃, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-35@ SAPO-34 methylamine catalyst, wherein an XRD spectrogram of the HZSM-35@ SAPO-34 molecular sieve is shown in figure 7.
Example 7
Synthesizing an HZSM-5@ SAPO-34 composite molecular sieve: weighing 1.0g of the HZSM-5 molecular sieve prepared in example 2, filling the weighed molecular sieve into agate, weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the mixture into an agate mortar filled with the HZSM-5 molecular sieve, grinding for 5-10min, adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, rapidly cooling to room temperature in an ice water bath after crystallization is finished, repeatedly washing with deionized water to be neutral, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-5@ SAPO-34 methylamine catalyst, wherein an XRD spectrogram of the HZSM-5@ SAPO-34 molecular sieve is shown in figure 8.
Example 8
HZSM-5@AlPO 4 -25 composite molecular sieve synthesis: weighing 2.0g of the HZSM-5 molecular sieve prepared in example 2, putting the molecular sieve into agate, weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of dimethylamine (40 wt%), adding the mixture into an agate mortar, grinding for 15-25min, adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching to room temperature in an ice water bath after crystallization is finished, repeatedly washing with deionized water to be neutral, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain HZSM-5@ AlPO 4 -25 molecular sieves, HZSM-5@ AlPO 4 The XRD spectrum of the-25 molecular sieve is shown in figure 9.
Example 9
0.5g of CuZnAl methanol catalyst is filled, the particle size of the catalyst is 20-40 meshes, the catalyst is filled into a micro-reaction single tube, and the upper end and the lower end of the catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. The reaction results are shown in table 1, the CO conversion is 8.1%, and the methanol selectivity reaches 99%, indicating that the CuZnAl methanol catalyst has very high selectivity.
Example 10
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ SAPO-34 methylamine catalyst and methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reaction single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. The reaction results are shown in table 1, with a CO conversion of 9.5% and a dimethylamine selectivity of 38%. The molecular sieve catalyst has stronger dehydration capability, and compared with the example 1, the dimethylamine selection type is obviously improved, and a small amount of dimethyl ether byproducts are generated.
Example 11
0.5g of CuZnAl methanol catalyst was charged0.5g of HZSM-35@ SAPO-34 methylamine catalyst, methanol and methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reverse single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio is 2/1/1, and the mixed gas flow rate is 20 mL/min. As shown in Table 1, the CO conversion rate was slightly lowered in comparative example 10. Because the HZSM-35 hole is smaller than that of ZSM-5, the selectivity of monomethylamine is obviously improved, and the selectivity of trimethylamine is inhibited.
Example 12
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ AlPO were charged 4 The-25 methylamine catalyst, the methanol and the methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reaction single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 The mol ratio of/CO/NH 3 is 2/1/1, and the flow rate of the mixed gas is 20 mL/min. The reaction results are shown in Table 1, where the CO conversion was 10.2%, and in comparative example 10, dimethylamine was significantly increased, indicating AlPO 4 -25 has strong shape-selective catalytic performance.
Example 13
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ AlPO were charged 4 -25 parts of methylamine catalyst, methanol and methanol catalyst are all granulated into 20-40 meshes, mixed and then put into a micro-reverse single tube, and the upper end and the lower end of the catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. As shown in Table 1, in comparative example 12, the CO conversion rate was further increased to 13.6%, the dimethylamine selectivity was 53%, and the trimethylamine selectivity was significantly decreased.
TABLE 1 catalytic reaction Activity and product Selectivity
Figure RE-GDA0002221960280000071
Figure RE-GDA0002221960280000081
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.

Claims (6)

1. A method for directly preparing dimethylamine from synthesis gas is characterized in that: the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 1-3:1:1-3, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, and the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O, the methanol catalyst is CuZnAl catalyst which comprises 30 to 60 weight percent of CuO, 30 to 60 weight percent of ZnO and Al 2 O 3 5-10%, the catalyst is prepared by coprecipitation method, the methylamine catalyst is a composite molecular sieve material with core-shell structure, wherein the core is ZSM-5, and the shell is AlPO 4 -25。
2. The process of claim 1 for the direct production of dimethylamine from synthesis gas, wherein: the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of 30-60 percent of CuO, 30-60 percent of ZnO and Al 2 O 3 Preparing a mixed salt solution by using 5-10% of metal in a molar ratio, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloride solution, a nitrate solution and an acetate solution;
(2) reacting the mixed salt solution with a precipitating agent, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitation is carried outThe precipitating agent is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
3. The method of claim 1, wherein the method comprises the steps of: the methylamine catalyst is prepared by a solid-phase synthesis method.
4. The process for producing dimethylamine directly from synthesis gas according to claim 1 or 3, wherein: the preparation method of the methylamine catalyst comprises the following steps: weighing 2.0g of HZSM-5 molecular sieve, putting the weighed molecular sieve into agate, weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of 40 wt% dimethylamine, adding the mixture into an agate mortar, grinding for 15-25min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching the mixture to room temperature in an ice water bath after crystallization is finished, repeatedly washing the mixture to be neutral with deionized water, drying the mixture overnight at 120 ℃, and finally roasting the mixture for 5h in air at 500 ℃ to obtain HZSM-5@ AlPO 4 -25 molecular sieves.
5. The process of claim 4 for the direct production of dimethylamine from synthesis gas, wherein: the synthesis method of the HZSM-5 catalyst comprises the following steps: weighing 4.87g of white carbon black, 0.48g of boehmite, 0.28g of sodium hydroxide and 0.25g of tetrapropylammonium bromide, adding the white carbon black, the boehmite, the sodium hydroxide and the tetrapropylammonium bromide into an agate mortar, grinding for 5-10min, then adding the boehmite, the hydrothermally heated kettle, crystallizing for 16h at 200 ℃, after crystallization, rapidly cooling to room temperature in an ice water bath, repeatedly washing to be neutral by deionized water, drying overnight at 120 ℃ to obtain a NaZSM-5 molecular sieve, adding NaZSM-5 powder into a 1M ammonium nitrate aqueous solution with a solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtration, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-5 molecular sieve.
6. The process of claim 1 for the direct production of dimethylamine from synthesis gas, wherein: the catalyst is formed into tablets and sieved until the granularity is 20-80 meshes.
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