CN110498746B - Method for improving quality of fatty tertiary amine - Google Patents
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Abstract
The invention relates to a method for improving the quality of fatty tertiary amine, which comprises the following steps: 1) Putting fatty alcohol and a catalyst into an amination kettle, respectively replacing the fatty alcohol and the catalyst with nitrogen and hydrogen, heating, and supplementing hydrogen to activate the catalyst; 2) Heating and introducing monomethylamine, and adding excessive monomethylamine for continuous reaction when the temperature is increased to 215-225 ℃; 3) Recovering amine after the monomethylamine is introduced, and determining the content of primary amine and secondary amine when the pressure is not reduced any more; 4) And (3) according to the content of primary and secondary amine, supplementing fatty alcohol to continue amination reaction, sampling and analyzing to be qualified, cooling, settling and rectifying to obtain the product. The invention provides a simple and easily-implemented method for controlling an aldol condensation compound in a dialkyl tertiary amine, which is mainly suitable for controlling the aldol condensation compound in the dialkyl tertiary amine, and the aldol condensation compound in the monoalkyl tertiary amine can be removed by a rectification method, and the invention can be used as one of the methods for controlling the aldol condensation compound in the monoalkyl.
Description
Technical Field
The invention relates to the field of production of fatty tertiary amine, in particular to a method for improving the quality of fatty tertiary amine.
Background
The aliphatic tertiary amine is a higher aliphatic amine, is one of the most important organic amine compounds in the aliphatic amine, and can be divided into single long-chain alkyl dimethyl tertiary amine, double long-chain alkyl methyl tertiary amine and tri-long-chain alkyl tertiary amine according to different structures, wherein the structural formula of the double long-chain alkyl tertiary amine (called as the double-chain alkyl tertiary amine for short) is as follows, and R in the formula is C8-22 alkyl:
tertiary fatty amines are important intermediates in the domestic and industrial fields. The quaternary ammonium salt derived from the quaternary ammonium salt, the amphoteric surfactant and the like are widely applied to textile softeners, antistatic agents, bactericides, cleaning agents and the like.
The preparation method of the fatty tertiary amine comprises the following steps: fatty alcohol amination (including fatty alcohol methylamine and dimethylamine), chloroalkane amination, bangter's method (formic acid, formaldehyde methylation method), reductive methylation method (primary amine formaldehyde hydrogenation method), etc., wherein fatty alcohol amination is one of the major methods for preparing dialkyl tertiary amines at present (huanghongzhou, fatty amine production method and demand, fine petrochemical, 1993, 4 th year, 59-64).
The reaction principle of the fatty alcohol amination method (hereinafter referred to as alcohol one-step method) is that in the presence of a high-activity and selective amination catalyst, mixed gas of methylamine or dimethylamine and hydrogen is introduced into liquid-phase fatty alcohol heated to the reaction temperature, the fatty alcohol reacts with dimethylamine, and a part of water is removed to generate alkyl dimethyl tertiary amine.
Further described for the one-step process of alcohols is the document "fatty amine production method and demand" (Huanghongzhou, fatty amine production method and demand, fine petrochemical, 1993, 4 th, 59-64), which is written in the right column part of page 61 of 3.1: the method is developed in countries such as Meide Ri, and the light industry institute for Changzhi treatment of Shanxi province and City in China is also developed, and the reaction formula is as follows:
dodecyl, dihexadecyl and dioctadecyl methyl amine can be prepared respectively by using dodecyl, hexadecyl and octadecyl alcohol as raw materials, the dosage of the catalyst is 0.15-0.2kg/t of the product, and the reaction time is 3-5 hours.
The main by-products of the fatty alcohol amination method are 1) the polyalkyl tertiary amine is generated by disproportionation of raw material monomethyl or dimethylamine amine and then reaction with alcohol, and 2) the aldol condensation is generated by self-condensation of raw material fatty alcohol.
For the monoalkyl tertiary amine, the main impurities are dialkyl tertiary amine, trialkyl tertiary amine and aldol condensate, and the three by-products and the monoalkyl tertiary amine have larger boiling points difference and can be removed by a rectification method.
For the dialkyl tertiary amine, the main impurities are monoalkyl tertiary amine, trialkyl tertiary amine and aldol condensation compound, the boiling points of the monoalkyl tertiary amine and the trialkyl tertiary amine are greatly different from that of the dialkyl tertiary amine and can be removed by a rectification method, the aldol condensation compound and the corresponding dialkyl tertiary amine are two carbon chain products, the boiling points are very close, the products are difficult to separate by the rectification method, and although the method is improved, the content of the aldol condensation compound is still about 2 percent. And the aldol condensate itself is difficult to dissolve in water and affects the appearance of the product after quaternization of the tertiary amine.
In order to reduce aldol condensation compounds, the amination catalyst with excellent performance is considered as a precondition for ensuring smooth reaction in the literature "process control for producing tertiary amine by alcohol one-step method" (spanwise gold, liu hai ting, bright, process control for producing tertiary amine by alcohol one-step method, daily chemical industry, 2 months in 2009, volume 39, phase 1, 71-74) and the patent literature cn201210558521.X (publication number CN102976950A, the name of the invention is an improved process for preparing tertiary amine), but the process control is a necessary condition for fully exerting the performance of the catalyst. The amination reaction time and the high-boiling-point substance content in the final product crude tertiary amine are key indexes for measuring the production process, and the purposes of shortening the reaction time and reducing the generation of the high-boiling-point substance can be achieved by finely controlling process parameters.
The inventors have developed an alcohol one-step process in which an excess of monomethylamine is fed directly into a closed reactor to substantially eliminate free alcohol in the latter stage of the reaction, thereby reducing the amount of aldol condensate.
Disclosure of Invention
The invention aims to provide a method for improving the quality of a tertiary fatty amine by reducing aldol condensation compounds in the tertiary amine.
The invention provides a method for improving the quality of fatty tertiary amine, which comprises the following steps:
1) Placing the dried fatty alcohol and the catalyst into an amination kettle, respectively replacing with nitrogen and hydrogen, heating to 160-190 ℃, supplementing hydrogen, maintaining the pressure at 0.1-0.2Mpa, and reducing with hydrogen for 30-60 minutes to activate the catalyst;
2) Heating and introducing monomethylamine, wherein the dosage of monomethylamine is 50% of the molar weight of the fatty alcohol, the introduction speed is 270-510 kg/h, when the temperature is increased to 215-225 ℃, the monomethylamine which is 1-5% of the molar weight of the fatty alcohol is supplemented for continuous reaction, and the whole process is maintained at 0.1-0.4Mpa by introducing ammonia gas;
3) Recovering amine after the monomethylamine is introduced, preserving the heat for 2-3 hours, and determining the content of primary amine and secondary amine when the pressure is not reduced any more;
4) According to the content of primary and secondary amine, supplementing fatty alcohol to continue amination reaction, keeping the temperature at 215-225 ℃ after completing alcohol supplementation to continue reaction for 2-3 hours, cooling and settling after sampling and analyzing are qualified, and rectifying to obtain the product.
In the above reaction:
in step 1):
the fatty alcohol is a C8 to C14 fatty alcohol;
controlling the water content of the fatty alcohol to be less than 0.1%;
the catalyst consists of 15-25% of copper oxide, 15-25% of nickel oxide, 0-10% of transition metal oxide, 0-10% of alkaline earth metal oxide and 30-70% of carrier, wherein the transition metal oxide is zinc oxide, chromium oxide and lanthanum fireworks, the alkaline earth metal oxide is magnesium oxide, calcium oxide or barium oxide, and the catalyst is specifically shown in CN101530800A (application No. 200910074170.3, the name of the invention is a catalyst for preparing tri-long-chain alkyl tertiary amine and application), and the dosage of the catalyst is 0.1-2%, preferably 0.5-1.5%.
The pressure of the hydrogen supplement gas is maintained at 0.1-0.15Mpa.
In the step 2):
the amount of the replenished monomethylamine is 2 to 5 percent of the molar weight of the fatty alcohol.
The whole process is carried out by introducing ammonia gas to maintain the reaction pressure at 0.2-0.4MPa, preferably 0.3-0.4MPa.
In the step 4):
the amount of the added fatty alcohol and the detected secondary amine are in a mass ratio of 1:1, for example, the secondary amine content is 4.2%, and the amount of fatty alcohol used is 4.2% by weight of the fatty alcohol in step 1, i.e., 10000 × 4.2% =420.
Preferably, the method provided by the invention comprises the following steps:
1) Placing the dried fatty alcohol with the content less than 0.1% and the catalyst into an amination kettle, respectively replacing with nitrogen and hydrogen, heating to 160-190 ℃, supplementing hydrogen, maintaining the pressure at 0.1-0.15Mpa, and reducing with hydrogen for 30-60 minutes to activate the catalyst;
2) Heating and introducing monomethylamine, wherein the dosage of monomethylamine is 50% of the molar weight of the fatty alcohol, the introducing speed is 270-510 kg/h, when the temperature is increased to 215-225 ℃, 2-5% of monomethylamine of the molar weight of the fatty alcohol is supplemented for continuing reaction, and the reaction pressure is maintained at 0.2-0.4Mpa by introducing ammonia gas in the whole process;
3) Recovering amine after the monomethylamine is introduced, preserving the heat for 2-3 hours, and determining the content of primary amine and secondary amine when the pressure is not reduced any more;
4) According to the content of primary and secondary amine, supplementing fatty alcohol to continue amination reaction, keeping the temperature at 215-225 ℃ after completing alcohol supplementation to continue reaction for 2-3 hours, cooling and settling after sampling and analyzing are qualified, and rectifying to obtain the product.
The invention provides a method for improving the quality of fatty tertiary amine, which has the following advantages:
1. the method provided by the invention comprises two reaction processes:
main reaction:
in the formula: R-OH is a fatty alcohol wherein R is C8-14;
side reaction: (the final product is an aldol condensate)
The reaction principle is as follows: the method comprises the steps of introducing monomethylamine in an excess amount compared with a theoretical amount at a proper temperature, wherein the alcohol has more chances to contact and react with the monomethylamine due to the excess amount of the monomethylamine, and the purpose is that the alcohol in a system is almost completely converted into secondary amine shown in a formula 1) and a main product shown in a formula 2) due to the excess amount of the monomethylamine, so that the condensation probability of the alcohol and the alcohol is greatly reduced at a later stage, and the generation of an aldol condensate shown in a formula 3) is reduced.
2. In order to reduce the content of the aldol condensate, the inventors made the following improvements:
1) Before adding the catalyst, the raw material alcohol is dried to ensure that the moisture content is less than 0.1 percent, because the catalyst is metal oxide baked at the high temperature of 500-600 ℃, the catalyst can become hydroxide and lose activity if meeting water, the lower the moisture content is, the better the parameter of the invention is less than 0.1 percent, because the production is difficult to control;
2) Theoretically, the fatty alcohol and the catalyst are replaced by introducing nitrogen and hydrogen, and then the catalyst is activated by introducing hydrogen for reduction at 160-190 ℃. (reduction by hydrogen is a conventional practice)
3) The conventional procedure in the tertiary amination stage is to introduce the theoretical amount or excess monomethylamine into a non-closed reactor, and since monomethylamine is not recovered from the reactor one port in one port and one port out, the amount of monomethylamine is still insufficient at the end, resulting in the product still having a part of residual alcohol and further forming aldol condensate. The inventors controlled the progress of the reaction by the following scheme:
firstly, the adding speed of monomethylamine is controlled, the disproportionation of monomethylamine is related to concentration and temperature, the higher the concentration and the higher the temperature, the higher the disproportionation reaction speed, therefore, the inventor injects 50% mol amount of amine of fatty alcohol at the speed of 270-510 kg/h at 190 ℃ to avoid generating more disproportionate.
Second, a slight excess of monomethylamine is added in order to convert all of the alcohol to secondary and tertiary amines, reducing the chance of condensate formation. The timing of adding the small excess monomethylamine is that when the reaction temperature reaches 215-225 ℃, when the temperature rises to the temperature range, the main reaction speed is accelerated, and the generation speed of the aldol condensation product is also accelerated, and the monomethylamine is added to inhibit the generation of the aldol condensation product at the time. The excess monomethylamine is supplemented at a temperature of 215-225 ℃, mainly because the reaction rate is relatively slow at a lower temperature, so that the concentration of monomethylamine in the system is easy to accumulate, the higher the concentration of monomethylamine in the system is, the more easily disproportionated, and meanwhile, before the excess monomethylamine is supplemented, an aldol condensate is not raised due to the relatively low reaction temperature.
4) After the reaction is finished, according to the detected content of the secondary amine, adding fatty alcohol (the secondary amine to the tertiary amine belongs to a conventional reaction), and adding alcohol to complete the tertiary amination reaction, wherein the mass of the added alcohol is 1: about 1.
4. The invention provides a simple and easily-implemented method for controlling an aldol condensation compound in a dialkyl tertiary amine, which is mainly suitable for controlling the aldol condensation compound in the dialkyl tertiary amine, and the aldol condensation compound in the monoalkyl tertiary amine can be removed by a rectification method, and the invention can be used as one of the methods for controlling the aldol condensation compound in the monoalkyl.
5. The invention mainly improves the quality of the tertiary amine product by reducing the content of aldol condensation compounds in the product in the amination stage. The method can effectively reduce the content of the aldol condensation compound in the fatty tertiary amine from about 2 percent to below 1 percent, thereby improving the product quality of the fatty tertiary amine to meet the requirements of some high-end customers, and the method is simple and easy to implement industrially.
Drawings
FIG. 1: a process flow diagram.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
1. 10000kg (63.18 kmol) of decanol with the moisture of 0.09 percent after being dried and 100kg of catalyst (copper catalyst, the preparation method thereof refers to CN107540557A, the application number is CN201710843685.X, the invention name is 1 percent of the quality of decanol) are transferred into an amination kettle, the reaction kettle is replaced by nitrogen for 3 times and hydrogen for 3 times, then the temperature is raised, and the reaction kettle is reduced by hydrogen for 1 hour at the temperature of 160-190 ℃, and the hydrogen pressure is maintained at 0.1MPa in the process.
2. After the reduction is finished and the temperature is raised to 190 ℃, introducing monomethylamine into the reaction kettle for amination reaction, heating while introducing monomethylamine, controlling the reaction temperature to be not higher than 220 ℃, and introducing 980kg of monomethylamine (31.55 kmol, the molar ratio of fatty alcohol to monomethylamine is 1; when the temperature rises to 220 ℃, 40kg of monomethylamine (1.29 kmol, the molar ratio of fatty alcohol to monomethylamine is 1.02) is introduced, the pressure of the reaction kettle is maintained at 0.3MPa, if the pressure is higher, the ammonia introducing speed is properly reduced, after the monomethylamine is introduced, an ammonia recovery kettle valve is opened, and the ammonia dissolved in the generated water is recovered to an amination kettle for reaction.
3. After the ammonia recovery is finished, preserving the heat for 2-3 hours, sampling and analyzing when the pressure is not reduced basically, and determining the content of secondary amine;
the content of the primary and secondary amines is determined by chemical titration, and the specific operation steps refer to QB-T2853-2007, and the same is carried out in the following examples.
4. The content of secondary amine is 4.2 percent, 420kg of decanol is supplemented to continue tertiary amination and heat preservation at 215-225 ℃ for continuous reaction, and after the reaction is finished, the content of aldol condensate is detected to be 0.7 percent, the content of residual alcohol is 0.12 percent, and the content of dialkyl tertiary amine is 92.0 percent. And (4) rectifying the crude product.
The specific reaction scheme is shown in figure 1.
Example 2
1. 10400kg (72.07 kmol) of dried octadecanol with a moisture content of 0.085% and 108kg of catalyst (1% by mass of octadecanol in example 1 of CN 107540557A) were transferred to an amination kettle, and the reaction mixture was replaced with nitrogen and hydrogen for 3 times, and then the temperature was raised to 160 to 190 ℃ and the reaction mixture was reduced with hydrogen for 1 hour, while maintaining a hydrogen pressure of 0.1MPa.
2. After the reduction is finished and the temperature is raised to 190 ℃, introducing monomethylamine into the reaction kettle for amination reaction, heating while introducing monomethylamine, controlling the reaction temperature to be not higher than 215 ℃, introducing 1020kg of monomethylamine (36.01 kmol, the molar ratio of fatty alcohol to monomethylamine is 1.
3. After ammonia recovery is finished, keeping the temperature for 2-3 hours, and sampling for analysis when the pressure is not reduced basically, wherein the content of secondary amine is detected to be 2.1%;
4. adding 218.4kg of octyl and decyl alcohol, continuing tertiary amination and keeping the temperature at 215-225 ℃ for continuing reaction, and detecting the content of aldol condensate of 0.95 percent, residual alcohol of 0.15 percent and dialkyl tertiary amine of 91.8 percent after the reaction is finished.
Example 3
1. The dried dodecaitol (10200 kg, 52.84 kmol) having a moisture content of 0.07% and 105kg of the catalyst (1% by mass of dodecaitol in example 1 of CN 107540557A) was transferred to an amination kettle, and the catalyst was replaced with nitrogen and hydrogen 3 times, followed by heating to 160 to 190 ℃ and reducing with hydrogen for 1 hour, while maintaining a hydrogen pressure of 0.12Mpa.
2. After the reduction is finished and the temperature is raised to 190 ℃, introducing monomethylamine into the reaction kettle for amination reaction, heating while introducing monomethylamine, controlling the reaction temperature to be not higher than 225 ℃, introducing 820kg monomethylamine (26.40 kmol, the molar ratio of fatty alcohol to monomethylamine is 1: 0.5) in 2-3 hours, and introducing 82kg monomethylamine (2.64 kmol, the molar ratio of fatty alcohol to monomethylamine is 1: 0.05) when the temperature is raised to 225 ℃, wherein the process maintains the pressure of the reaction kettle to be 0.4Mpa.
3. After the ammonia recovery is finished, sampling and analyzing when the temperature is kept for 2-3 hours and the pressure is not reduced basically, wherein the content of secondary amine is 8.2%;
4. 836.40kg of dodecatetraethanol is added, the temperature is kept between 215 ℃ and 225 ℃ for continuing tertiary amination reaction, and after the reaction is finished, the content of aldol condensate is detected to be 0.69 percent, the content of residual alcohol is detected to be 0.1 percent, and the content of dialkyl tertiary amine is detected to be 92.3 percent.
Comparative example 1
10200kg (64.4 kmol) of decanol having a moisture of 0.09% after drying and 100kg of a catalyst (refer to example 1 of CN 107540557A) were transferred to an amination kettle, the reaction kettle was replaced 3 times with nitrogen and 3 times with hydrogen, and then heated, and reduced with hydrogen at 160-190 ℃ for 1 hour, and the hydrogen pressure was maintained at 0.1MPa during this process. After the reduction is finished and the temperature is raised to 190 ℃, introducing monomethylamine into the reaction kettle for amination reaction, heating while introducing monomethylamine, controlling the reaction temperature to be not higher than 220 ℃, introducing 1000kg monomethylamine (32.15 kmol) within 2-3 hours, and finally, ensuring that the total molar ratio of decanol to monomethylamine is 1:0.5, maintaining the pressure of the reaction kettle to be 0.3Mpa in the process, if the pressure is higher, properly slowing down the ammonia introducing speed, opening an ammonia recovery kettle valve after the monomethylamine is introduced, and recovering the ammonia dissolved in the generated water to the amination kettle for reaction.
After the ammonia recovery is finished, sampling and analyzing when the temperature is kept for 2-3 hours and the pressure is not reduced basically, wherein the residual alcohol is 1.2 percent, the aldol condensate content is detected to be 1.8 percent, and the content of the dialkyl tertiary amine is 90.2 percent.
Comparative example 2
Transferring 10200kg (64.4 kmol) of dried decanol with a water content of 0.08% and 100kg of catalyst (refer to example 1 of CN 107540557A) into an amination kettle, replacing the reaction kettle with nitrogen for 3 times and hydrogen for 3 times, heating, and reducing with hydrogen at 160-190 ℃ for 1 hour, wherein the hydrogen pressure is maintained at 0.1MPa in the process.
After the reduction is finished and the temperature is raised to 190 ℃, introducing monomethylamine into the reaction kettle for amination reaction, introducing monomethylamine and raising the temperature, controlling the reaction temperature to be not higher than 220 ℃, introducing 950kg monomethylamine (30.5 kmol) in 2-3 hours, and finally, the total molar ratio of decanol to monomethylamine is 1:0.474, the pressure in the reaction kettle is maintained at 0.2Mpa, if the pressure is higher, the ammonia feeding speed is properly slowed, after the monomethylamine is fed, a valve of the ammonia recovery kettle is opened, and the ammonia dissolved in the generated water is recovered to the amination kettle for reaction.
After the ammonia recovery is finished, sampling and analyzing when the temperature is kept for 2-3 hours and the pressure is not reduced basically, wherein the residual alcohol is 2 percent, the aldol condensate content is detected to be 2.5 percent, and the content of the dialkyl tertiary amine is 87.2 percent.
Experimental example 1: sample detection
1. The detection method comprises the following steps:
the contents of residual alcohol, aldol condensate and dialkyl tertiary amine were analyzed by gas chromatography, and the specific conditions are shown in Table 1.
Table 1: chromatographic conditions
2. Sample preparation: examples 1-3 and comparative examples 1, 2 provided the final product.
3. And (3) detection results: see tables 2-1 and 2-2.
Table 2-1: crude product detection result before distillation
TABLE 2-2 Final product testing after distillation
The results show that: the method provided by the invention has the advantages of less by-products, less acetal polymer content and higher purity of the fatty tertiary amine.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A method for improving the quality of fatty tertiary amine comprises the following steps:
1) Putting the dried fatty alcohol with the moisture content of less than 0.1% and the catalyst into an amination kettle, respectively replacing the fatty alcohol and the catalyst with nitrogen and hydrogen, heating the mixture to 160-190 ℃, supplementing hydrogen and maintaining the pressure at 0.1-0.2Mpa, and reducing the hydrogen for 30-60 minutes to activate the catalyst, wherein the catalyst consists of 15-25% of copper oxide, 15-25% of nickel oxide, 0-10% of transition metal oxide, 0-10% of alkaline earth metal oxide and 30-70% of carrier, the transition metal oxide is zinc oxide, chromium oxide and lanthanum Firework, and the alkaline earth metal oxide is magnesium oxide, calcium oxide or barium oxide;
2) After the reduction is finished, heating to 190 ℃, starting to introduce monomethylamine, wherein the using amount of the monomethylamine is 50% of the molar weight of the fatty alcohol, the introduction speed is 270-510 kg/h, when the temperature is increased to 215-225 ℃, the monomethylamine which is 1-5% of the molar weight of the fatty alcohol is supplemented to continue the reaction, and the whole process maintains the reaction pressure at 0.1-0.4MPa by introducing ammonia gas;
3) Recovering amine after the monomethylamine is introduced, preserving the heat for 2-3 hours, and determining the content of primary amine and secondary amine when the pressure is not reduced any more;
4) According to the content of primary and secondary amine, supplementing fatty alcohol to continue amination reaction, wherein the content ratio of the added fatty alcohol to the detected secondary amine is 1:1, keeping the temperature of 215-225 ℃ after completing alcohol supplement, continuing to react for 2-3 hours, cooling, settling and rectifying after sampling and analyzing to be qualified, and thus obtaining the product.
2. The method according to claim 1, characterized in that in step 1): the fatty alcohol is a C8 to C14 fatty alcohol.
3. The method according to claim 1, characterized in that in step 1): the pressure of the hydrogen replenishing gas is maintained between 0.1 and 0.15MPa.
4. The method according to claim 1, wherein in step 2): the amount of the supplemented monomethylamine is 2-5% of the molar weight of the fatty alcohol.
5. The method according to claim 1, wherein in step 2): the whole process is carried out by introducing ammonia gas to maintain the reaction pressure at 0.2-0.4MPa.
6. Method according to claim 1, characterized in that it comprises the following steps:
1) Placing the dried fatty alcohol with the content of less than 0.1 percent and the catalyst into an amination kettle, respectively replacing the fatty alcohol and the catalyst by nitrogen and hydrogen, then heating the amination kettle to 160-190 ℃, supplementing hydrogen to maintain the pressure of 0.1-0.15Mpa, and reducing the hydrogen for 30-60 minutes to activate the catalyst;
2) Heating and introducing monomethylamine, wherein the dosage of the monomethylamine is 50% of the molar weight of the fatty alcohol, the introduction speed is 270-510 kg/h, when the temperature is increased to 215-225 ℃, 2-5% of monomethylamine of the molar weight of the fatty alcohol is supplemented for continuous reaction, and the whole process is carried out by introducing ammonia to maintain the reaction pressure at 0.2-0.4Mpa;
3) Recovering amine after the monomethylamine is introduced, preserving the heat for 2-3 hours, and determining the content of primary amine and secondary amine when the pressure is not reduced any more;
4) Supplementing fatty alcohol according to the content of primary and secondary amine, continuing amination reaction, preserving heat at 215-225 ℃ for continuing reaction for 2-3 hours after alcohol supplementation, cooling, settling and rectifying after sampling and analyzing to be qualified, thus obtaining the product.
7. The method as claimed in claim 6, wherein the reaction pressure in step 2) is maintained at 0.3-0.4MPa by introducing ammonia gas.
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| US4957893A (en) * | 1987-03-05 | 1990-09-18 | Ethyl Corporation | Catalyst for making amines from alcohols |
| CN101801908A (en) * | 2007-09-20 | 2010-08-11 | 花王株式会社 | Method for producing tertiary amine |
| CN102630223A (en) * | 2009-12-22 | 2012-08-08 | 花王株式会社 | Method for producing tertiary amine |
| CN103270015A (en) * | 2010-12-27 | 2013-08-28 | 花王株式会社 | Tertiary amine preparation process |
| CN107540557A (en) * | 2017-09-15 | 2018-01-05 | 江苏万盛大伟化学有限公司 | A kind of preparation method of tri-n-octyl amine |
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