CN116273011A - Supported catalyst for N, N-dimethyl-1, 3-propylene diamine and preparation and application thereof - Google Patents
Supported catalyst for N, N-dimethyl-1, 3-propylene diamine and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a supported catalyst for N, N-dimethyl-1, 3-propylene diamine and preparation and application thereof, and relates to a catalyst, the catalyst is specifically prepared from metal salt and a carrier, meanwhile, the invention also provides a method for preparing N, N-dimethyl-1, 3-propylene diamine by using the catalyst, a mixture of acrylonitrile and dimethylamine is prepared according to a certain molar ratio and is subjected to low-temperature vaporization, the vaporized mixture is subjected to low-temperature amination reaction under the action of the catalyst, then a reaction product is subjected to high-temperature vaporization, the obtained product is subjected to high-temperature hydrogenation reaction under the action of the catalyst, and after the obtained product is cooled, a liquid phase is collected as a target product; the catalyst and the method for preparing the N, N-dimethyl-1,3-propanediamine are simple in operation, low in manufacturing cost and high in yield.
Description
Technical Field
The invention relates to a catalyst, in particular to a supported catalyst for synthesizing N, N-dimethyl-1,3-propanediamine, and preparation and application thereof.
Background
N, N-Dimethyl-1,3-propanediamine (DMAPA) of formula C 5 H 14 N 2 DMAPA is an important chemical intermediate, mainly used for the production of betaine. Betaine is an excellent cosurfactant and is widely used in personal care products such as shampoo, bath foam and the like, and the dosage of the betaine is rapidly increased in recent years, so that the global demand of DMAPA is also rapidly increased. In addition, the DMAPA can be widely used for synthesizing dye intermediates, lubricating oil additives, electroplating, rubber coupling agents and the like.
The industrial production process mainly adopts dimethylamine and acrylonitrile as raw materials, firstly, N-Dimethylaminopropionitrile (DMAPN) is synthesized by methylamine, then DMAPN is hydrogenated and reduced under the action of a catalyst to synthesize DMAPA, and the prior intermittent batch production process and trickle bed continuous production process are adopted. The similar method mainly comprises the following steps: buc S R and the like react with acrylonitrile by adopting concentrated ammonia water to prepare N- (2-cyanoethyl) -3-aminopropionitrile with the yield of 57-70 percent; the literature (J.am.chem.Soc., 1945, 67:1994-1996) reports a process for the preparation of N- (3-aminopropyl) -1,3-propanediamine by Raney nickel-catalyzed reduction of N- (2-cyanoethyl) -3-aminopropionitrile at 5-25MPa,90-125℃without specific yields being seen. The basf patent (CN 101111468) developed a method for preparing N- (3-aminopropyl) -1,3-propanediamine by introducing dipropylamine and hydrogen into a reaction tower under the action of palladium catalyst loaded by zirconium dioxide and continuously reacting by reactive distillation, and the method greatly inhibits side reaction and can improve the conversion rate of propanediamine to more than 80% by designing the reaction tower, but the biggest disadvantage of the method is that the palladium catalyst is expensive, the production cost is high, and large-scale production is difficult.
(CN 101397266) a reaction-rectification coupling device for preparing 3-aminopropionitrile was disclosed in 2009. In the device, the molar ratio of liquid ammonia to acrylonitrile is 1-10:1, the pressure is 0.3-2.0Mpa, the reaction is carried out for 0.5-2.0h at the temperature of 70-180 ℃, and the selectivity of 3-aminopropionitrile is 62-80%.
(CN 1560177A) proposes a process for preparing N-alkyl-1, 3-propanediamine, wherein the alkyl group can be dodecane, hexadecane or octadecane, and the preparation process mainly comprises the steps of firstly reacting fatty amine with acrylonitrile under the action of a catalyst at 30-60 ℃ to prepare N-alkyl-3-aminopropionitrile; and then the N-alkyl-3-aminopropionitrile is reacted with hydrogen in a solvent and an autoclave at 80-90 ℃ to prepare the corresponding N-alkyl-1, 3-propanediamine. (Shaanxi chemical industry, 1979, 4:55-58) using a novel nickel-based catalyst, the selective hydrogenation of N-alkyl-3-aminopropionitriles to give long aliphatic N-hydrocarbyl-1, 3-propanediamines (wherein alkyl represents long carbon chain aliphatic saturated or unsaturated hydrocarbyl groups) was found to achieve the same objective as the use of sodium metal-N-butanol instead of catalytic hydrogenation.
In the synthetic methods for synthesizing DMAPA and the like reported in the above documents, there is either a problem that the catalyst is expensive or a problem that the yield of the objective compound is not high; furthermore, both amination and hydrogenation step-wise processes are used.
Disclosure of Invention
The invention mainly solves the technical problem of providing a supported catalyst for N, N-dimethyl-1, 3-propylene diamine and preparation and application thereof, and can effectively solve the technical problem.
The invention provides a supported catalyst for synthesizing N, N-dimethyl-1,3-propanediamine, which is specifically prepared from metal salt and a carrier, wherein the metal salt consists of copper salt, ferric salt and zinc salt, the sum of the weight of copper, ferric salt and zinc accounts for 20-40% of the total weight of the supported catalyst, the weight of copper, ferric salt and zinc is respectively more than or equal to 1% of the total weight of the supported catalyst, and the total weight of zinc is less than or equal to 5% of the total weight of the supported catalyst.
Further, the sum of the weight of copper, iron and zinc accounts for 25-30% of the total weight of the supported catalyst.
Further, copper was 12% of the total weight of the supported catalyst, iron was 10% of the total weight of the supported catalyst, and zinc was 3% of the total weight of the supported catalyst.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
step a, immersing the carrier in a phosphoric acid solution with the mass concentration of 10% -20% at the temperature of 30-60 ℃ for 1-3 h; filtering the soaked carrier, drying for 1-3h at 80-120 ℃, and roasting for 2-6 h at 300-500 ℃;
b, measuring the pore volume of the carrier obtained in the step a, wherein the measuring method comprises the steps of soaking the carrier obtained in the step a with water for at least 12 hours, and measuring the volume of water reduction so as to obtain the pore volume of the carrier after roasting;
c, preparing a metal salt aqueous solution prepared by mixing copper salt, ferric salt and zinc salt and desalted water according to the pore volume obtained in the step b, and completely immersing the carrier obtained in the step b in the metal salt aqueous solution for a period of time not less than 12 hours; drying the impregnated carrier for 0.5-3 h at 60-80 ℃, then placing the carrier into a muffle furnace for drying for 2-4 h at 100-140 ℃, and then heating to 400-450 ℃ for roasting for 1-6 h to obtain a supported catalyst;
and the obtained supported catalyst satisfies the following conditions: the total weight of copper, iron and zinc accounts for 20-40% of the total weight of the supported catalyst, the total weight of copper, iron and zinc is more than or equal to 1% of the total weight of the supported catalyst, and the total weight of zinc is less than or equal to 5% of the total weight of the supported catalyst.
Further, the carrier is gamma-Al 2 O 3 Or ZSM-5 type molecular sieve.
Further, the copper salt is copper nitrate;
the ferric salt is ferric nitrate;
the zinc salt is zinc nitrate.
The invention also provides a method for synthesizing N, N-dimethyl-1,3-propanediamine by using the supported catalyst, which comprises the following steps:
step 1, activation of Supported catalyst
Taking two supported catalysts, respectively introducing hydrogen into the two supported catalysts and activating the two supported catalysts for 6 to 9 hours at 160 to 250 ℃ until no water flows out, then introducing hydrogen for cold blowing and cooling, and controlling the activating pressure at 0.1 to 0.3MPa to obtain two activated carriers;
step 2, obtaining a mixture of acrylonitrile and dimethylamine according to a molar ratio of 1:1-3, and vaporizing the mixture at 100-120 ℃ to obtain a primary vaporized mixture;
step 3, the primary vaporization mixture is subjected to amination reaction under the action of an activating carrier, the reaction temperature is 100-120 ℃, the reaction pressure is 0.3-0.5 MPa, and the volume airspeed of acrylonitrile is 0.1-0.25 h -1 Obtaining a primary catalytic mixture;
step 4, vaporizing the primary catalytic mixture at a high temperature of 150-180 ℃ to obtain a secondary vaporized mixture;
step 5, the secondary vaporization mixture is subjected to hydrogenation reaction under the action of another part of activating carrier, the reaction temperature is 150-180 ℃, and the reaction pressure is 0.3-0.5 MPa; the volume airspeed is 0.1 to 0.25h -1 Obtaining a secondary catalyst;
and 6, cooling the secondary catalytic material to 40 ℃, and collecting a liquid phase, wherein the liquid phase is specifically N, N-dimethyl-1, 3-propanediamine.
Further, the pressure control in steps 1 to 6 is achieved by hydrogen regulation.
Further, the volume space velocity of acrylonitrile = raw material acrylonitrile volume flow (L/h)/supported catalyst loading volume (L).
Compared with the prior art, the invention has the following advantages:
(1) The same catalyst can be adopted for amination and hydrogenation, so that the operation is simplified.
(2) The catalyst has low cost, high activity and good selectivity.
(3) The preparation method of the supported catalyst has the characteristics of wide raw material sources, simplicity in operation and the like.
Drawings
FIG. 1 is a schematic diagram of a fixed bed continuous production apparatus based on staged temperature control of supported metal catalyst required for the process of the present invention.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1, fig. 1 shows a fixed bed continuous production device based on temperature field control, which comprises a raw material tank 1 of acrylonitrile, a pressure tank 2 of dimethylamine, a hydrogen steel bottle 3, an acrylonitrile metering pump 4, a fixed bed reaction 5 (a low temperature vaporization chamber 6, a low temperature reaction section 7, a high temperature vaporization chamber 8, a high temperature reaction section 9 respectively from top to bottom), a condenser 10, a crude product collecting tank 11 and the like.
The acrylonitrile raw material tank 1 is communicated with the low-temperature vaporization chamber 6 through a pipeline provided with a ball valve 12, an acrylonitrile metering pump 4 and a ball valve 13; the dimethylamine pressure tank 2 is in communication with the cryogenic vaporization chamber 6 via the lines of ball valve 14, flow meter 21 and check valve 15. The hydrogen steel cylinder 3 is communicated with the low-temperature vaporization chamber 6 through pipelines which are provided with a pressure reducing valve 16, a ball valve 17 and a flowmeter 20. The low-temperature vaporization chamber 6, the low-temperature reaction section 7, the high-temperature vaporization chamber 8 and the high-temperature reaction section 9 are sequentially communicated from the top of the fixed bed to form a fixed bed reactor whole based on temperature control, and the bottom of the fixed bed reactor is provided with a discharge ball valve 22 which is communicated with the condenser 10 through a pipeline. The low temperature vaporization chamber 6 is provided with a pressure gauge and a thermometer, the low temperature reaction section is provided with a thermometer, the high temperature vaporization chamber is provided with a thermometer, and the high temperature reaction section is provided with a thermometer. The liquid phase outlet of the condenser 10 is communicated with a crude product collecting tank 11 through a pipeline provided with a ball valve 23; the gas phase outlet of the condenser 10 is communicated with the gas phase outlet of the crude product collecting tank 11, and the gas phase is discharged after being collected and treated. The supported catalyst is filled in the low-temperature reaction section and the high-temperature reaction section. The N2 bypass is connected before the hydrogen flow meter 20 by a line with a shut-off valve 18 and a check valve 19.
The fixed bed reactor 5 of this example is a stainless steel pipe with an inner diameter of 32mm, an outer diameter of 38mm and a height of 2100mm, wherein the low temperature vaporization chamber 6 has a height of 150mm, the low temperature reaction section 7 has a height of 900mm, the high temperature vaporization chamber 8 has a height of 150mm, and the high temperature reaction section 9 has a height of 900mm. The low-temperature section reaction section 7 removes the inert filler height, the effective height of the internal filler containing the supported catalyst is 600mm, and the filling amount is 480ml; the high temperature reaction section 9 removes the inert filler height, the effective height of the internal filler containing supported catalyst is 600mm and the loading is 480ml.
Example 2, method for synthesizing N, N-dimethyl-1,3-propanediamine and catalyst thereof, the following steps were sequentially carried out:
1) Preparation of the catalyst:
(1) 1000g of gamma-Al 2 O 3 (particle diameter is 2-3 mm, mass volume of the hole is 0.6-0.7 cm) 3 /g) adding 15% by mass of H 3 PO 4 Soaking in the solution at 50deg.C for 1 hr (gamma-Al) 2 O 3 It needs to be completely immersed in the solution). Filtering after soaking, and adding gamma-Al 2 O 3 Drying at 80deg.C for 1 hr, and roasting at 450deg.C for 3 hr.
(2) The obtained gamma-Al after roasting 2 O 3 Soaking part of the mixture with water for 12h to determine the volume of water to be reduced, namely the gamma-Al after roasting 2 O 3 Is 0.8ml/g.
(3) Preparing 352.5g of copper nitrate, 448g of ferric nitrate and 87.2g of zinc nitrate into a metal liquid solution by using 1000ml of desalted water, and taking 750g of roasted gamma-Al obtained in the step (1) 2 O 3 Soaking in the above solution for 12 hr under stirring, drying at 70deg.C for 1.5 hr,and then placing the mixture into a muffle furnace to dry for 3 hours at 120 ℃, and then heating to 400-450 ℃ to bake for 4 hours to obtain the supported catalyst.
In the supported catalyst, copper accounts for 12% of the total weight of the supported catalyst, iron accounts for 10% of the total weight of the supported catalyst, and zinc accounts for 3% of the total weight of the supported catalyst.
The following steps 2) and 3) were carried out using the production apparatus described in example 1:
2) Catalyst activation:
the prepared supported catalyst was charged into the low temperature reaction zone 7 and the high temperature reaction zone 9 of the fixed bed 5, respectively, with a charge of 480ml. Introducing proper amount of N 2 To displace the air in the fixed bed 5 and the pipeline, N 2 The flow rate is regulated by a flow meter 20 and a shut-off valve 18, vented from the condenser 10 blow-down line. After the nitrogen gas purging operation is completed, the shutoff valve 18 is closed.
Heating the fixed bed 5 to 250 ℃ by heating jackets respectively attached to the low-temperature vaporization chamber 6, the low-temperature reaction section 7, the high-temperature vaporization chamber 8 and the high-temperature reaction section 9, and then introducing H 2 Activating the supported catalyst, H 2 The flow rate is regulated by a flow meter 20 and a pressure reducing valve 16, the ball valve 17 is fully opened, and the air is discharged from the condenser 10 by a blow-down pipe. And after no water flows out, continuously introducing hydrogen for 30min to cool. The pressure of the whole fixed bed reactor 5 can be regulated and stabilized between 0.3 and 0.5MPa by a pressure reducing valve 16.
3) Feeding and discharging:
after activation is complete, pressure relief valve 16 regulates H 2 The pressure of the fixed bed 5 is ensured to be stabilized at 0.3MPa, the heating power of the jacket is regulated to keep the temperatures of the low-temperature vaporization chamber 6 and the low-temperature reaction section 7 at 100 ℃ and the temperatures of the high-temperature vaporization chamber 8 and the high-temperature reaction section 9 at 150 ℃.
The ball valve 12, the acrylonitrile metering pump 4 and the ball valve 13 and the shut-off valve 14 are opened. The raw materials of acrylonitrile and dimethylamine are fed into a low-temperature vaporization chamber 6 for mixed vaporization according to the mol ratio of 1:1.5 (for example, acrylonitrile is fed at 75ml/h by adjusting an acrylonitrile metering pump 4, and dimethylamine is fed at 120ml/h by adjusting a stop valve 14). Raw materials enter a low-temperature reaction section 7 after being mixed, vaporized and preheated in a low-temperature vaporization chamber 6, and the raw materials and hydrogen are uniformAmination reaction is carried out through a catalyst bed layer, the reaction temperature is 100 ℃, and the volume space velocity of acrylonitrile is 0.15h -1 . After passing through the low-temperature reaction section 7, the mixed gas enters the high-temperature vaporization chamber 8 again, enters the high-temperature reaction section 9 after being preheated, and uniformly passes through the catalyst bed layer to carry out hydrogenation reaction, wherein the reaction temperature is 150 ℃, and the volume space velocity of the acrylonitrile is 0.15h -1 . After the reaction, the reaction product is cooled to 40 ℃ by a condenser 10, the material is separated into gas phase and liquid phase, the liquid phase enters a crude product collecting tank 11, and the gas phase is emptied after being treated.
The liquid in the crude product collecting tank 11 was subjected to gas chromatography, and the conversion of acrylonitrile was 99.1%, and the yield of N, N-dimethyl-1,3-propanediamine was 97.2%.
The reaction equation for the synthesis of N, N-dimethyl-1,3-propanediamine is as follows:
examples 3 to 9:
the following reaction conditions were changed in example 2: examples 3 to 9 were obtained by the catalyst carrier, the metal content, the molar ratio of acrylonitrile to dimethylamine, the low temperature reaction temperature T1, the high temperature reaction temperature T2, and the like, and the specific data are shown in Table 1. Table 1 examples 1 to 9 data
Comparative examples 1 to 3:
the catalyst used in example 2 was varied (i.e., the Cu, fe, zn contents were varied based on the total weight, respectively) and the reaction conditions were the same as in example 2, and the final yields were shown in Table 2.
Table 2 comparative examples 1 to 3 data
Comparative examples 4 to 5:
the temperatures of the low temperature reaction zone and the high temperature reaction zone in example 2 were changed, and the final yields obtained in example 2 were as shown in Table 3.
Table 3 comparative examples 4 to 5 data
From the above, the method provided by the invention can effectively improve the conversion rate of acrylonitrile and the yield of N, N-dimethyl-1,3-propanediamine, and is simple and low in cost, and the preparation cost is greatly reduced; the catalyst has low manufacturing cost, high activity and high selectivity.
Finally, it should also be noted that the above list is only a few specific embodiments of the invention, and obviously the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as not being inventive.
Claims (4)
1. A method for synthesizing N, N-dimethyl-1,3-propanediamine by using a supported catalyst, which is characterized by comprising the following steps:
step 1, activation of Supported catalyst
Taking two parts of supported catalysts, respectively introducing hydrogen into the two parts of supported catalysts and activating the two parts of supported catalysts for 6 to 9 hours at the temperature of 160 to 250 ℃ until no water flows out, then introducing hydrogen for cold blowing and cooling, controlling the activating pressure at 0.1 to 0.3MPa, and obtaining two parts of activated carriers, wherein the supported catalysts are specifically prepared from metal salts and carriers, and the carriers are prepared from the following components in percentage by weightThe body is gamma-Al 2 O 3 Or ZSM-5 type molecular sieve, wherein the metal salt consists of copper salt, ferric salt and zinc salt, the sum of the weight of copper, iron and zinc accounts for 25-30% of the total weight of the supported catalyst, the weight of copper, iron and zinc is respectively more than or equal to 1% of the total weight of the supported catalyst, and the total weight of zinc is less than or equal to 5% of the total weight of the supported catalyst;
step 2, obtaining a mixture of acrylonitrile and dimethylamine according to a molar ratio of 1:1-3, and vaporizing the mixture at 100-120 ℃ to obtain a primary vaporized mixture;
step 3, the primary vaporization mixture is subjected to amination reaction under the action of an activating carrier, the reaction temperature is 100-120 ℃, the reaction pressure is 0.3-0.5 MPa, and the volume airspeed of acrylonitrile is 0.1-0.25 h -1 Obtaining a primary catalytic mixture, wherein the volume space velocity of acrylonitrile = raw material acrylonitrile volume flow/supported catalyst loading volume;
step 4, vaporizing the primary catalytic mixture at a high temperature of 150-180 ℃ to obtain a secondary vaporized mixture;
step 5, the secondary vaporization mixture is subjected to hydrogenation reaction under the action of another part of activating carrier, the reaction temperature is 150-180 ℃, and the reaction pressure is 0.3-0.5 MPa; the volume airspeed is 0.1 to 0.25h -1 Obtaining a secondary catalyst;
step 6, cooling the secondary catalytic material to 40 ℃, and collecting a liquid phase, wherein the liquid phase is specifically N, N-dimethyl-1, 3-propanediamine;
the preparation method of the supported catalyst comprises the following steps:
step a, immersing the carrier in a phosphoric acid solution with the mass concentration of 10% -20% at the temperature of 30-60 ℃ for 1-3 h; filtering the soaked carrier, drying for 1-3h at 80-120 ℃, and roasting for 2-6 h at 300-500 ℃;
step b, measuring the pore volume of the carrier obtained in the step a;
c, preparing a metal salt aqueous solution prepared by mixing copper salt, ferric salt and zinc salt and desalted water according to the pore volume obtained in the step b, and completely immersing the carrier obtained in the step b in the metal salt aqueous solution for a period of time not less than 12 hours; drying the impregnated carrier for 0.5-3 h at 60-80 ℃, then placing the carrier into a muffle furnace for drying for 2-4 h at 100-140 ℃, and then heating to 400-450 ℃ for roasting for 1-6 h to obtain the supported catalyst.
2. The method for synthesizing N, N-dimethyl-1,3-propanediamine by using a supported catalyst according to claim 1, wherein the method comprises the following steps: the copper accounts for 12% of the total weight of the supported catalyst, the iron accounts for 10% of the total weight of the supported catalyst, and the zinc accounts for 3% of the total weight of the supported catalyst.
3. The method for synthesizing N, N-dimethyl-1,3-propanediamine by using a supported catalyst according to claim 1, wherein the method comprises the following steps: the copper salt is copper nitrate, the ferric salt is ferric nitrate, and the zinc salt is zinc nitrate.
4. The method for synthesizing N, N-dimethyl-1,3-propanediamine by using a supported catalyst according to claim 1, wherein the method comprises the following steps: the pressure control in steps 1 to 6 is achieved by hydrogen regulation.
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| CN113200870A (en) * | 2021-05-07 | 2021-08-03 | 大连理工大学 | Process for continuously preparing N, N-dimethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor |
| CN113896654B (en) * | 2021-06-24 | 2023-09-19 | 万华化学集团股份有限公司 | Method for producing DMAPA and co-producing bis-DMAPA and tri-DMAPA |
| CN113501761B (en) * | 2021-07-16 | 2023-08-11 | 万华化学集团股份有限公司 | Method for continuously producing N, N-diethyl-1, 3-propanediamine by one-step method |
| CN113649060B (en) * | 2021-07-30 | 2023-09-29 | 金浦新材料股份有限公司 | Catalyst for synthesizing 1, 3-propylene diamine, preparation method and application thereof |
| CN115960012A (en) * | 2023-02-06 | 2023-04-14 | 大庆华理生物技术股份有限公司 | Dehydration method in amidation reaction stage of surfactant |
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| CN101274896A (en) * | 2008-05-13 | 2008-10-01 | 浙江大学 | Synthetic method for N, N- diethyl n-butylamine and production device therefor |
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