CN108863821B - Preparation method of polyalcohol amine - Google Patents
Preparation method of polyalcohol amine Download PDFInfo
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- CN108863821B CN108863821B CN201810889199.6A CN201810889199A CN108863821B CN 108863821 B CN108863821 B CN 108863821B CN 201810889199 A CN201810889199 A CN 201810889199A CN 108863821 B CN108863821 B CN 108863821B
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Abstract
The invention relates to a preparation method of polyalcohol amine, belonging to the technical field of organic chemical industry, comprising the following steps: on the designed equipment, continuously flowing dichloropropane and alcohol amine added step by step are reacted on the solid catalyst to synthesize polyol amine. The invention provides a deep processing method of dichloropropane, which solves the problem that other application approaches of dichloropropane pollute the environment, and the used catalyst can be regenerated and reused, and belongs to a green chemical process; the invention provides a preparation method of polyalcohol amine, which has mild conditions, low operation cost, high production efficiency and flexible adjustment of the functionality of the polyalcohol amine and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of polyalcohol amine, belonging to the technical field of organic chemical industry.
Background
A large amount of dichloropropane is byproduct in the process of producing the epichlorohydrin by a chlorohydrination method. Carrying out ammonification reaction on dichloropropane, and obtaining a product propane diamine through the processes of neutralization, concentration, desalination, rectification and the like; high ammoniation reaction pressure and high danger, and a large amount of waste water produced in the post-treatment process pollutes the environment. Under the action of a catalyst, dichloropropane is subjected to chlorination reaction in air flow at 490 ℃ to generate carbon tetrachloride and tetrachloroethylene; the dichloropropane can also be decomposed at high temperature to prepare 3-chloropropene and 1-chloropropene; the chlorination and decomposition reaction conditions are harsh, and the equipment requirement is high. The propylene glycol is prepared by hydrolyzing the dichloropropane, the product yield is low in the process, a large amount of industrial salt is produced as a byproduct, and a large amount of industrial wastewater is produced at the same time. At present, all domestic propylene oxide manufacturers do not find an effective utilization way of the byproduct dichloropropane, and the method is a technical research subject to be developed urgently in order to further improve the comprehensive benefit of producing the propylene oxide by a chlorohydrin method, reduce the raw material consumption of propylene oxide products and reasonably treat and utilize the byproduct dichloropropane.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of polyalcohol amine, which adopts dichloropropane continuous feeding, alcohol amine is added into reaction operation step by step, and after three-stage catalytic action, low-boiling-point components are extracted in vacuum to obtain a pure product.
The invention takes dichloropropane and alcohol amine as raw materials to carry out substitution reaction under the catalysis action. The reaction formula is as follows:
wherein R1 and R2 are CH3-，CH3CH2-，CH3CH2CH2-，
CH3CH2CH2CH2-，
One or more of the above; r1 is the same as or different from R2. The hydroxyl number of the product can be adjusted.
The method for synthesizing the polyalcohol amine has the advantages of mild reaction conditions, low operation cost and high product yield, opens up a new way for comprehensively utilizing the dichloropropane, has an environment-friendly process, can regenerate and recycle the catalyst, and is suitable for industrial production. In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of polyalcohol amine comprises the following steps:
the method comprises the following steps: catalyst preparation
Roasting, alkali washing and acid washing the granular coconut shell activated carbon, then drying, uniformly mixing the granular coconut shell activated carbon, alkali or alkali oxide and rare earth elements, putting the mixture into a crucible, putting the crucible into a muffle furnace in a nitrogen atmosphere, so that the alkali and the rare earth elements are melted and permeated into a space between an activated carbon pore passage and a carbon layer and interact with surface groups of the granular coconut shell activated carbon to form a uniform solid phase, sieving the uniform solid phase and then putting the uniform solid phase into a catalyst filling column for later use;
step two: process route
After the dichloropropane and the alcohol amine are metered, 1 is added#Elevated tank, homogeneous solution of dichloropropane and alcohol amine from 1#Catalytic column bottom entry 1#A catalytic column, after reaction under the action of a catalyst, from 1#Catalytic column top exit 1# Catalytic column entry 2#Elevated tank at 2#Fully mixing the alcohol amine with the metered alcohol amine in the head tank; then from 2#Catalytic column bottom entry 2#Catalytic column, after catalytic action of catalyst, from 2#Catalytic column top exit 2#Catalytic column entry 3#Head tank at 3#Mixing the mixture with added alcohol amine in the head tank; then from 3#Catalytic column bottom entry 3#A catalytic column, after the catalytic reaction under the action of catalyst, from 3#Catalytic column top exit 3#The catalytic column enters a product tank; the product tank is driven by a vacuum system to remove low-boiling point components to obtain a final product.
In the first step, the coconut shell activated carbon is roasted for 3-6 hours at 250-350 ℃ in a nitrogen atmosphere, is soaked for 1-10 hours by using 1-10 mol/L sodium hydroxide or potassium hydroxide aqueous solution after being cooled, is washed for 2-6 times by distilled water after being filtered, is dried for 3-12 hours at 110-150 ℃, is soaked for 1-12 hours by using 1-10 mol/L nitric acid aqueous solution, is washed for 2-6 times by using distilled water after being filtered, and is dried for 3-12 hours at 110-150 ℃.
In the first step, the coconut shell activated carbon after roasting, alkali washing, acid washing and drying, sodium hydroxide or potassium hydroxide and lanthanum nitrate or cesium nitrate are placed in a muffle furnace and roasted at 250-550 ℃ in a nitrogen atmosphere, so that alkali, rare earth elements and groups on the surface of the coconut shell activated carbon are combined through chemical bonds to obtain a solid alkali catalyst, and the solid alkali catalyst is loaded into a catalytic column for later use.
In the second step, the following steps are also provided: after the alcohol amine and the dichloropropane are metered according to the molar ratio of 1: 1-10, 1 is added#Elevated tank at 1#Mixing in the head tank to form a uniform solution, and then mixing from 1#a or 1#b catalytic column bottom entry 1#a or 1#b catalytic column, or simultaneously into 1#a and 1#b a catalytic column, after the catalytic reaction under the action of catalyst, from 1#Catalytic column top exit entry 2#Elevated tank at 2#From 1 in the head tank#The material leaving the top of the catalytic column is thoroughly mixed with the alcohol amine metered in, the alcohol amine being mixed with 1#The mole ratio of dichloropropane originally added into the head tank is 1: 1-10; under the action of gravity, 2#The solution mixed uniformly in the elevated tank is from 2#Catalytic column bottom entry 2#a or 2#b a catalytic column, or 2#a and 2#b catalytic column, after catalytic action of catalyst, from 2#Catalytic column top exit entry 3#A head tank; in 3#From 2 in the head tank#The material leaving the top of the catalytic column is thoroughly mixed with the alcohol amine metered in, the alcohol amine being mixed with 1#The mole ratio of dichloropropane initially added into the head tank is 1: 1-10; under the action of gravity, 3#The solution mixed uniformly in the elevated tank is from 3#Catalytic column bottom entry 3#a or 3#b a catalytic column, or 3#a and 3#b, a catalytic column is arranged on the catalyst,after catalytic reaction of the catalyst, from 3#Catalytic column top exit 3#The catalytic column enters a product tank; when the liquid level of the product tank is two-thirds to three-fourths, the liquid level triggers and starts a vacuum system, and a product is obtained after low-boiling-point components are removed; wherein 1 is#The catalytic column comprises 1 arranged in parallel#a、1#b, a catalytic column; 2#The catalytic column comprises 2 arranged in parallel#a、2#b, a catalytic column; 3#The catalytic column comprises 3 arranged in parallel#a、3#b a catalytic column.
The dichloropropane is 1, 2-dichloropropane or 1, 3-dichloropropane or a mixed solution of 1, 2-dichloropropane and 1, 3-dichloropropane.
The alcohol amine is
Or
Wherein R1 and R2 are CH3-，CH3CH2-，CH3CH2CH2-，
CH3CH2CH2CH2-，
R1 is the same as or different from R2.
The prepared catalyst can be regenerated after being used and recycled after being regenerated.
In step two, 1#The alcohol amine and the dichloropropane are added after being metered according to the molar ratio of 1: 1-10, preferably the molar ratio of 1: 2-6, mixed to form a uniform solution, and then enter the reaction tank from the bottom of the catalytic column to 1 under the action of gravity according to the flow rate of 500-1500 mL/min#a or 1#b a catalytic column, or 1#a and 1#b catalytic column, preferably into 1#a or 1#b, carrying out catalytic reaction in a catalytic column at 45-80 ℃; the reaction system leaves the reaction from the top of the catalytic columnColumn entry 2#A head tank, which is fully mixed with the alcohol amine added by metering, the alcohol amine is mixed with 1#Adding dichloropropane into the elevated tank at a molar ratio of 1: 1-10, preferably at a molar ratio of 1: 2-6; under the action of gravity, the uniformly mixed solution is extracted from the liquid 2#Catalytic column bottom entry 2#a or 2#b a catalytic column, or 2#a and 2#b catalytic column, preferably into 1#a or 1#b a catalytic column, in 2#After the catalytic action is completed at 55-90 ℃ in the catalytic column, the reaction system leaves the reaction column from the top of the catalytic column and enters the reaction column 3#A head tank. In 3#The alcohol amine metered in by the head tank is fully mixed, and the alcohol amine is mixed with 1#Adding dichloropropane into the elevated tank at a molar ratio of 1: 1-10, preferably at a molar ratio of 1: 2-6; the uniformly mixed solution is subjected to the action of gravity from 3#Catalytic column bottom entry 3#a or 3#b a catalytic column, or 3#a and 3#b a catalytic column, preferably into 3#a or 3#b a catalytic column at 3#Carrying out catalytic reaction at 65-100 ℃ in the catalytic column, and enabling a reaction system to leave the reaction column from the top of the catalytic column and enter a product tank; and when the liquid level of the product tank reaches three quarters, the liquid level triggers and starts a vacuum system, a feed valve and a product outlet valve of the product tank are automatically closed, after the low-boiling-point components are separated, the vacuum system is closed, and the outlet valve is opened to obtain the product.
In the second step, the catalyst a column and the catalyst b column are connected in parallel and can be switched randomly; when the a-column catalyst is regenerated, after the valve of the b-column connecting pipeline is opened, the valve of the a-column connecting pipeline is closed, and the a-column catalyst is regenerated to recover the activity of the catalyst; the whole system can realize continuous production; and vice versa.
Compared with the prior art, the invention has the beneficial effects that: the solid super-alkali with the low-temperature catalysis function is successfully prepared, the catalyst has the centers of the Bronsted alkali and the Lewis base, the conversion of the Bronsted alkali and the Lewis base on the surface of the catalyst is realized through the adjustment of trace moisture, and the catalyst has high activity at low temperature under the synergistic effect of different alkali centers. Dichloropropane and alcohol amine react mildly in the center of catalyst alkali to prepare the polyalcohol amine, and the product yield is high; the catalyst can be regenerated and recycled, the reaction system has no pollution to the environment, and the reaction process is green and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of a polyol amine production route according to the present invention;
FIG. 2 is a diagram of a device for preparing polyalcohol amine;
FIG. 3 is a schematic diagram of the foaming properties of a polyol amine.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
According to FIG. 2, the alcohol amine and the dichloropropane are metered in proportion and then added with 1#An elevated tank, which is mixed to form a uniform solution and is driven to flow from 1 under the action of the gravity of the liquid#Catalytic column bottom entry 1#A catalytic column, after the catalytic reaction is carried out under the action of a catalyst, the reaction system is from 1#The top of the catalytic column leaves the reaction column and enters 2#Elevated tank at 2#From 1 in the head tank#The reaction system leaving from the top of the catalytic column is thoroughly mixed with the alcohol amine metered in, and then the reaction system is treated by the reaction from 2#Catalytic column bottom entry 2#Catalytic column, after completion of the reaction at the set temperature, from 2#The top of the catalytic column leaves the reaction column and enters 3#Head tank at 3#From 2 in the head tank#The reaction system leaving at the top of the catalytic column is thoroughly mixed with the alcohol amine metered in from 3#Catalytic column bottom entry 3#A catalytic column, after the set reaction is completed, the material system is from 3#The top of the catalytic column leaves the reaction column and enters a product tank; and (3) triggering and starting a vacuum system by setting the liquid level of the product tank, namely starting the vacuum system when the liquid level of the product tank reaches a certain height, separating out low-boiling-point components by vacuum distillation to obtain a product, and performing performance test by inspection.
A preparation method of polyalcohol amine comprises the following steps:
the method comprises the following steps: catalyst preparation
Roasting coconut shell carbon in a nitrogen atmosphere at 250-350 ℃ for 3-6 h, cooling, soaking for 1-10 h by using 1-10 mol/L sodium hydroxide or potassium hydroxide aqueous solution, filtering, washing for 2-6 times by using distilled water, drying for 3-12 h at 110-150 ℃, soaking for 1-12 h by using 1-10 mol/L nitric acid aqueous solution, washing for 2-6 times by using filtered coconut shell carbon distilled water, and drying for 3-12 h at 110-150 ℃ for later use.
Uniformly mixing the pretreated granular coconut shell carbon, sodium hydroxide or potassium hydroxide and lanthanum nitrate or cesium nitrate, placing the mixture in a muffle furnace, roasting the mixture for 6-12 hours at 250-550 ℃ in a nitrogen atmosphere, so that the sodium hydroxide, the potassium hydroxide, the lanthanum nitrate and the cesium nitrate are melted and penetrate into an active carbon pore channel and a graphite layer, and are chemically bonded with carbon or groups on the surface of the granular coconut shell carbon to obtain a solid super-strong base catalyst, and screening the solid super-strong base catalyst, filling and filling the solid super-strong base catalyst into a catalytic column.
Step two: process route
Mixing alcohol amine and dichloropropane according to the molar ratio of 1: 1-10 to form a uniform solution, adjusting the flow rate of the solution to 500-1500 mL/min, and under the action of gravity, controlling the flow rate to be 1-1500 mL/min#Elevated tank 1#Enter 1#Bottom of catalytic column, again from 1#Catalytic column bottom entry 1#Catalytic column, control 1#Reacting at the column temperature of 45-80 ℃ of the catalytic column; reaction system from 1#Catalytic column top exit 1#Catalytic column entry 2#A head tank; in 2#Head tank from 1#The material of the catalytic column is fully mixed with the alcohol amine (the molar ratio of the alcohol amine to the original dichloropropane is 1: 1-10) which is added in a metering manner, and the mixed solution is mixed from 2 under the action of gravity# Head tank access 2#Bottom of catalytic column, reentry 2#In the catalytic column, the catalytic reaction is completed at the temperature of 55-90 ℃, and the reaction materials are 2 DEG#The top of the catalytic column leaves the reaction column and enters 3#A head tank. In 3#Metering alcohol amine (the molar ratio of the newly added alcohol amine to the original dichloropropane is 1: 1-10) and adding alcohol amine from 2 in an overhead tank#The materials of the catalytic column are uniformly mixed, and the mixed solution is subjected to the action of gravity from 3#Head tank access 3#Bottom of catalytic column, further from 3#Catalytic column bottom entry 3#Within the catalytic column, at 3#The catalytic reaction is carried out in the catalytic column at the temperature of 65-100 ℃, and the reaction product is from 3 DEG C#The top of the catalytic column leaves the reaction column and enters a product tank. Product tank liquorWhen the level reaches three quarters, the liquid level triggers and starts the vacuum system, automatically closes the product tank feed valve and the product outlet valve, closes the vacuum system after the low boiling point component is separated, and opens the outlet valve to obtain the final product. Low boiling components, refers to other components having boiling points lower than the final target product.
In the three-stage catalytic reaction, the reaction system maintains micro-positive pressure. 1#The catalytic column controls the reaction temperature to be 45-80 ℃ to realize the pre-reaction of the product; 2#The reaction temperature of the catalytic column is controlled to be 55-90 ℃, and most of raw material reaction is completed; 3#The reaction temperature of the catalytic column is controlled to be 65-100 ℃, the raw material reaction is completed, and the product namely the polyalcohol amine is generated. The produced product was subjected to foaming property test. The catalytic temperature in the three catalytic columns is gradually increased, i.e. 1#Reaction temperature of catalytic column<2#Reaction temperature of catalytic column<3#Catalytic column reaction temperature.
Example 1
Roasting coconut charcoal in nitrogen atmosphere at 300 ℃ for 6h, cooling, soaking in 7mol/L aqueous solution of sodium hydroxide for 6h, filtering, washing with distilled water for 4 times, drying at 120 ℃ for 6h, soaking in 7mol/L aqueous solution of nitric acid for 8h, washing with distilled water for 3 times, filtering, drying at 120 ℃ for 6h, and roasting at 300 ℃ for 6h for later use.
Preparing the treated granular coconut shell carbon, sodium hydroxide and lanthanum nitrate into a mixed solution according to the mass ratio of 100:5:1, excessively impregnating and adsorbing the coconut shell carbon for 10 hours under a stirring state, drying the coconut shell carbon at 120 ℃ for 8 hours, then placing the coconut shell carbon in a muffle furnace, roasting the coconut shell carbon in a nitrogen atmosphere at 350 ℃ for 8 hours to ensure that the sodium hydroxide and the lanthanum nitrate are melted and penetrated into an active carbon pore channel and a graphite layer and are chemically bonded with carbon or groups on the surface of the granular coconut shell carbon to obtain a solid super-strong base catalyst, and screening the solid super-strong base catalyst, filling and filling the solid super-strong base catalyst into.
Example 2
In 1#The alcohol amine and the dichloropropane are mixed according to the molar ratio of 1:1 to form a uniform solution, and the flow rate is adjusted to 1000mL/min under the action of gravity from 1#Catalytic column bottom entry 1#Catalyzing the column, and controlling the column temperature to be 60 ℃ for reaction; the reaction system leaves from the top of the catalytic column 1#Column entry 2#A head tank; in 2#Head tank from 1#The column material is fully mixed with the alcohol amine which is added in a metering way (the molar ratio of the alcohol amine to the original dichloropropane is 1:2), and the mixed solution is extracted from the column 2 under the action of gravity#Catalytic column bottom entry 2#A catalytic column for completing the catalytic reaction at 70 ℃, and the reaction material leaves the reaction column from the top of the catalytic column and enters the reaction column 3#A head tank. In 3#The alcohol amine (molar ratio of alcohol amine to original dichloropropane is 1:2) metered into the head tank and the alcohol amine from 2#The materials of the column are mixed uniformly, and the solution is from 3 under the action of gravity#Bottom of column entering 3#And the catalytic column is used for carrying out catalytic reaction at the temperature of 80 ℃ in the column, and the reaction product leaves the reaction column from the top of the catalytic column and enters the product tank. And when the liquid level of the product tank reaches three quarters, the liquid level triggers and starts a vacuum system, a feed valve and a product outlet valve of the product tank are automatically closed, after the low-boiling-point components are separated, the vacuum system is closed, and the outlet valve is opened to obtain the product. And (3) detecting tail gas and products, wherein the dichloropropane conversion rate is 100.0%.
Example 3
In 1#In the elevated tank, after alcohol amine and dichloropropane are metered and mixed according to the molar ratio of 1:2 to form a uniform solution, under the action of gravity, the flow rate of 1200mL/min is regulated to be 1#Catalytic column bottom entry 1#Catalyzing the column, and controlling the column temperature to be 60 ℃ for reaction; the reaction system leaves from the top of the catalytic column 1#Column entry 2#A head tank; in 2#Head tank from 1#The column material is fully mixed with the alcohol amine which is added in a metering way (the molar ratio of the alcohol amine to the original dichloropropane is 1:1), and the mixed solution is extracted from the column 2 under the action of gravity#Catalytic column bottom entry 2#A catalytic column for completing the catalytic reaction at 70 ℃, and the reaction material leaves the reaction column from the top of the catalytic column and enters the reaction column 3#A head tank. In 3#The alcohol amine (molar ratio of alcohol amine to original dichloropropane is 1:2) metered into the head tank and the alcohol amine from 2#The materials of the column are mixed uniformly, and the solution is from 3 under the action of gravity#Bottom of column entering 3#And the catalytic column is used for carrying out catalytic reaction at the temperature of 80 ℃ in the column, and the reaction product leaves the reaction column from the top of the catalytic column and enters the product tank. Product produced by birthAnd when the liquid level of the material tank reaches three quarters, the liquid level triggers and starts a vacuum system, a product tank feed valve and a product outlet valve are automatically closed, after the low-boiling-point components are separated, the vacuum system is closed, and the outlet valve is opened to obtain the product. And (3) detecting tail gas and products, wherein the dichloropropane conversion rate is 98.2%.
Example 4
In 1#In the elevated tank, after alcohol amine and dichloropropane are metered and mixed according to the molar ratio of 1:2 to form a uniform solution, under the action of gravity, the flow rate of 1200mL/min is regulated to be 1#Catalytic column bottom entry 1#Catalyzing the column, and controlling the column temperature to be 60 ℃ for reaction; the reaction system leaves from the top of the catalytic column 1#Column entry 2#A head tank; in 2#Head tank from 1#The column material is fully mixed with the alcohol amine which is added in a metering way (the molar ratio of the alcohol amine to the original dichloropropane is 1:2), and the mixed solution is extracted from the column 2 under the action of gravity#Catalytic column bottom entry 2#A catalytic column for completing the catalytic reaction at 70 ℃, and the reaction material leaves the reaction column from the top of the catalytic column and enters the reaction column 3#A head tank. In 3#The alcohol amine (molar ratio of alcohol amine to original dichloropropane is 1:1) metered into the head tank and the alcohol amine from 2#The materials of the column are mixed uniformly, and the solution is from 3 under the action of gravity#Bottom of column entering 3#And the catalytic column is used for carrying out catalytic reaction at the temperature of 80 ℃ in the column, and the reaction product leaves the reaction column from the top of the catalytic column and enters the product tank. And when the liquid level of the product tank reaches three quarters, the liquid level triggers and starts a vacuum system, a feed valve and a product outlet valve of the product tank are automatically closed, after the low-boiling-point components are separated, the vacuum system is closed, and the outlet valve is opened to obtain the product. And (3) detecting tail gas and products, wherein the dichloropropane conversion rate is 97.6%.
Example 5
In 1#In the elevated tank, after alcohol amine and dichloropropane are metered and mixed according to the molar ratio of 1:2 to form a uniform solution, under the action of gravity, the flow rate of 1500mL/min is regulated to be 1#Catalytic column bottom entry 1#Catalyzing the column, and controlling the temperature of the column to be 70 ℃ for reaction; the reaction system leaves from the top of the catalytic column 1#Column entry 2#A head tank; in 2#Head tank from 1#The column material is fully mixed with the alcohol amine which is added in a metering way (the molar ratio of the alcohol amine to the original dichloropropane is 1:1), and the mixed solution is extracted from the column 2 under the action of gravity#Catalytic column bottom entry 2#A catalytic column for completing the catalytic reaction at 80 ℃, and the reaction material leaves the reaction column from the top of the catalytic column and enters the reaction column 3#A head tank. In 3#The alcohol amine (molar ratio of alcohol amine to original dichloropropane is 1:2) metered into the head tank and the alcohol amine from 2#The materials of the column are mixed uniformly, and the solution is from 3 under the action of gravity#Bottom of column entering 3#And the catalytic column is used for carrying out catalytic reaction at the temperature of 80 ℃ in the column, and the reaction product leaves the reaction column from the top of the catalytic column and enters the product tank. And when the liquid level of the product tank reaches three quarters, the liquid level triggers and starts a vacuum system, a feed valve and a product outlet valve of the product tank are automatically closed, after the low-boiling-point components are separated, the vacuum system is closed, and the outlet valve is opened to obtain the product. And (3) detecting tail gas and products, wherein the dichloropropane conversion rate is 100.0%.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. A preparation method of polyalcohol amine comprises the following steps:
the method comprises the following steps: catalyst preparation
Roasting, alkali washing and acid washing the granular coconut shell activated carbon, then drying, uniformly mixing the granular coconut shell activated carbon, sodium hydroxide and rare earth elements, putting the mixture into a crucible, putting the crucible into a muffle furnace in a nitrogen atmosphere to ensure that the sodium hydroxide and the rare earth elements are molten and permeated into a pore passage of the activated carbon and a carbon layer to interact with surface groups of the granular coconut shell activated carbon to form a uniform solid phase, sieving the solid phase and then putting the solid phase into a catalyst filling column for later use;
step two: process route
After the dichloropropane and the alcohol amine are metered, 1 is added#Elevated tank, the homogeneous solution of dichloropropane and alcohol amine is formed from 1 under the action of gravity#Bottom of catalytic columnEnter 1#A catalytic column, after reaction under the action of a catalyst, from 1#Catalytic column top exit 1#Catalytic column entry 2#Elevated tank at 2#Fully mixing the alcohol amine with the metered alcohol amine in the head tank; then from 2#Catalytic column bottom entry 2#Catalytic column, after catalytic action of catalyst, from 2#Catalytic column top exit 2#Catalytic column entry 3#Head tank at 3#Mixing the mixture with added alcohol amine in the head tank; then from 3#Catalytic column bottom entry 3#A catalytic column, after the catalytic reaction under the action of catalyst, from 3#Catalytic column top exit 3#The catalytic column enters a product tank; the product tank is driven by a vacuum system to remove low-boiling point components to obtain a final product.
2. The preparation method of the polyalcohol amine according to claim 1, wherein in the first step, the coconut shell activated carbon is roasted at 250-350 ℃ in nitrogen atmosphere for 3-6 h, is soaked in 1-10 mol/L sodium hydroxide or potassium hydroxide aqueous solution for 1-10 h after being cooled, is washed with distilled water for 2-6 times after being filtered, is dried at 110-150 ℃ for 3-12 h, is soaked in 1-10 mol/L nitric acid aqueous solution for 1-12 h, is washed with distilled water for 2-6 times after being filtered, and is dried at 110-150 ℃ for 3-12 h.
3. The preparation method of the polyalcohol amine according to claim 2, characterized in that in the first step, the coconut shell activated carbon after roasting, alkali washing, acid washing and drying, sodium hydroxide or potassium hydroxide and lanthanum nitrate are placed in a muffle furnace and roasted at 250-550 ℃ in nitrogen atmosphere, so that alkali, rare earth elements and the surface groups of the coconut shell activated carbon are combined through chemical bonds to obtain a solid alkali catalyst, and the solid alkali catalyst is loaded into a catalytic column for later use.
4. The method for preparing polyalcohol amine according to claim 1, wherein in the second step, the following steps are provided: after the alcohol amine and the dichloropropane are metered according to the molar ratio of 1: 1-10, 1 is added#Elevated tank at 1#Mixing in the head tank to form a uniform solution, and then mixing from 1#a or 1#b catalytic column bottom entry 1#a or 1#b catalytic column, or simultaneously into 1#a and 1#b a catalytic column, after the catalytic reaction under the action of catalyst, from 1#Catalytic column top exit entry 2#Elevated tank at 2#From 1 in the head tank#The material leaving the top of the catalytic column is thoroughly mixed with the alcohol amine metered in, the alcohol amine being mixed with 1#The mole ratio of dichloropropane originally added into the head tank is 1: 1-10; under the action of gravity, 2#The solution mixed uniformly in the elevated tank is from 2#Catalytic column bottom entry 2#a or 2#b a catalytic column, or 2#a and 2#b catalytic column, after catalytic action of catalyst, from 2#Catalytic column top exit entry 3#A head tank; in 3#From 2 in the head tank#The material leaving the top of the catalytic column is thoroughly mixed with the alcohol amine metered in, the alcohol amine being mixed with 1#The mole ratio of dichloropropane initially added into the head tank is 1: 1-10; under the action of gravity, 3#The solution mixed uniformly in the elevated tank is from 3#Catalytic column bottom entry 3#a or 3#b a catalytic column, or 3#a and 3#b a catalytic column, after catalytic reaction of the catalyst, from 3#Catalytic column top exit 3#The catalytic column enters a product tank; when the liquid level of the product tank is two-thirds to three-fourths, the liquid level triggers and starts a vacuum system, and a product is obtained after low-boiling-point components are removed; wherein 1 is#The catalytic column comprises 1 arranged in parallel#a、1#b, a catalytic column; 2#The catalytic column comprises 2 arranged in parallel#a、2#b, a catalytic column; 3#The catalytic column comprises 3 arranged in parallel#a、3#b a catalytic column.
5. The method of claim 1, wherein 1 is#The reaction temperature of the catalytic column is 45-80 ℃; 2#The reaction temperature of the catalytic column is 55-90 ℃; 3#The reaction temperature of the catalytic column is 65-100 ℃.
6. The method for preparing polyalcohol amine according to claim 1, wherein: the dichloropropane is 1, 2-dichloropropane or 1, 3-dichloropropane or a mixed solution of 1, 2-dichloropropane and 1, 3-dichloropropane.
7. The method for preparing polyalcohol amine according to claim 1, wherein: the alcohol amine is
Or
Wherein R1 and R2 are CH3-，CH3CH2-，CH3CH2CH2-，
CH3CH2CH2CH2-，
R1 is the same as or different from R2.
8. The method for preparing polyalcohol amine according to any one of claims 1 to 5, wherein: the prepared catalyst can be regenerated after being used and recycled after being regenerated.
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