CN109134278B - Preparation method of polyalcohol amine - Google Patents
Preparation method of polyalcohol amine Download PDFInfo
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- CN109134278B CN109134278B CN201811317681.9A CN201811317681A CN109134278B CN 109134278 B CN109134278 B CN 109134278B CN 201811317681 A CN201811317681 A CN 201811317681A CN 109134278 B CN109134278 B CN 109134278B
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- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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Abstract
The invention relates to a preparation method of polyalcohol amine, belonging to the technical field of chemical industry, comprising the following steps: after the raw materials are pre-reacted in a tubular spiral propelling reactor, transferring the raw materials into a high-pressure kettle, and heating and pressurizing the raw materials to complete the reaction; meanwhile, a continuous desalting wastewater-free discharge process is designed to synthesize the polyalcohol amine. The invention provides a deep processing method of dichloropropane, which solves the problem that other application approaches of dichloropropane pollute the environment and belongs to a green chemical process; the invention provides a preparation method of polyalcohol amine, which has the advantages of low operation cost, high production efficiency, moderate molecular weight of the product polyalcohol amine, high active functionality and suitability for industrial production.
Description
Technical Field
The invention relates to a preparation method of polyalcohol amine, belonging to the technical field of chemical industry.
Background
A large amount of dichloropropane is a byproduct in the process of producing the epichlorohydrin by a chlorohydrination method. Propylene diamine is obtained by the amination of dichloropropane, but the amination of dichloropropane has high pressure and high risk, the post-treatment process is long, and a large amount of waste water is generated to pollute the environment. Under the action of a catalyst, dichloropropane is subjected to chlorination reaction in air flow at 490 ℃ to generate tetrachloroethylene and carbon tetrachloride, and the dichloropropane is subjected to pyrolysis to prepare 3-chloropropene and 1-chloropropene; the chlorination and decomposition reaction conditions are harsh, and the equipment requirement is high. The process for preparing the propylene glycol by hydrolyzing the dichloropropane has low product yield, produces a large amount of industrial salt as a byproduct and produces a large amount of industrial wastewater. In order to improve the comprehensive benefit of producing propylene oxide by a chlorohydrination method, reduce the raw material consumption of propylene oxide products and reasonably treat and utilize byproduct dichloropropane, the technical subject is urgently to be developed.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of polyalcohol amine, which adopts dichloropropane, hydramine and a catalyst to be uniformly mixed and then continuously feed into a tubular spiral propelling reactor; and after desalting, continuously carrying out final reaction on the reaction system in a high-temperature high-pressure kettle type reactor, carrying out vacuum stripping to obtain a pure product, circulating unreacted raw materials and water to a raw material end for continuous use, and discharging salt from the bottom of the kettle before discharging.
The invention takes dichloropropane and alcohol amine as raw materials to carry out substitution reaction under the action of a catalyst (alkali). 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 environment-friendly process, can continuously discharge byproduct industrial salt, does not discharge waste water, 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: pretreatment of raw materials
Dichloropropane, alcohol amine and a catalyst are mixed according to a proportion to form uniform slurry, and the uniform slurry is added into a tubular spiral propelling reactor.
Step two: process for the preparation of a catalyst
Adding the uniform slurry formed by dichloropropane, alcohol amine and catalyst into a tubular spiral propelling reactor from a feed inlet, substituting one or two chlorines of dichloropropane by amino alcohol at a set temperature to generate a mono-substituted polyalcohol amine or di-substituted polyalcohol amine product, and simultaneously generating a byproduct industrial salt by the substituted chlorines. Because the solubility of sodium chloride in water is less than that of alkali which can be dissolved in water in any proportion, salt can be continuously separated out in the reaction process by controlling the water quantity in the reaction process, namely adjusting the alkali concentration. Under the driving of the tubular spiral propelling reactor, industrial salt separated out in the reaction process is propelled from the tubular reactor to a salt collector (namely, the salt is discharged from the reaction system and enters the collector). The reaction system after desalting is sent into a reaction kettle to be pressurized and heated until the substitution reaction is complete under the action of a spiral propelling reactor. In the reaction kettle, unreacted dichloropropane and water are extracted in a vacuum manner and circulated to a raw material end (namely, the raw materials are used as raw materials again and are mixed with alcohol amine and a catalyst to form uniform slurry) for continuous use. The reaction product was packed after further filtration to remove salts.
By controlling the proportion of the raw materials and the catalyst, the reaction system has no wastewater discharge.
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
The designed process can continuously remove the byproduct industrial salt generated in the process, and has no wastewater discharge.
The catalyst in the uniform slurry is commercial liquid alkali, or self-made liquid alkali, or commercial solid alkali, or self-made solid alkali. Specifically, the catalyst in the uniform slurry in the initial stage of the reaction (i.e. when the uniform slurry is not filled in the tubular screw propulsion reactor) is commercial liquid caustic soda or self-made liquid caustic soda; after the tubular screw reactor is filled with the uniform slurry, the catalyst in the raw material is replaced by commercial solid alkali or self-made solid alkali (because after the tubular screw reactor is filled with the uniform slurry, unreacted dichloropropane is extracted in the reaction kettle in a vacuum manner, and water is circulated to the raw material end for use, and only the solid catalyst needs to be added).
The spiral propelling reactor is a tubular spiral propelling reactor; the reaction temperature of the spiral propelling reactor is set to be 50-100 ℃, the flow speed is 0.10-1.00 m/min, and the rotating speed is 10.00-100.00 rad/min. The end of the spiral propelling reactor is collected with the reaction system after desalting (namely, the end of the spiral propelling reactor is desalted through a salt collector to obtain the reaction system after desalting) and transferred to the kettle type reactor; the reaction temperature in the kettle reactor is 100-200 ℃, the stirring speed is 50.00-200.00 rad/min, and the pressure is 1.00-5.00 MPa.
After the kettle type reactor is completely reacted and has stable pressure and the reaction is finished, steam stripping is carried out at the temperature of 50-80 ℃ and the vacuum degree of 0.10-0.50 MPa, and condensate is recycled to a raw material end for use; discharging salt and discharging after the steam stripping (if the reaction is not completed in the spiral propelling reactor, the reaction can be continuously completed in the kettle type reactor, the salt is discharged in the process, so that the reaction in the reaction kettle is finished, a small amount of possible salt is discharged after the steam stripping, and the discharging refers to the collection of reaction products). Stripping conditions: low temperature, with vacuum; the polymerization proceeds at a high temperature, and the viscosity of the product becomes high.
The preparation steps of the catalyst are as follows: placing the coconut shell activated carbon subjected to roasting, alkali washing, acid washing and drying, sodium hydroxide or potassium hydroxide and lanthanum nitrate or cesium nitrate in a muffle furnace, and roasting at 250-550 ℃ in a nitrogen atmosphere to combine alkali and rare earth elements with groups on the surface of the coconut shell activated carbon through chemical bonds to obtain a self-made solid alkali catalyst for later use.
Compared with the prior art, the invention has the beneficial effects that: a continuous feeding, continuous reaction and automatic desalting system is successfully designed, unreacted raw materials and moisture can be recycled to the raw materials after steam stripping for continuous reaction, the conversion rate of the raw materials is high, no wastewater is discharged, and the reaction process is green and environment-friendly; the functionality of the product can be flexibly adjusted.
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 the figures 1 and 2, the uniform slurry formed by dichloropropane, alcohol amine and catalyst is added into a tubular spiral propelling reactor from a feeding port, dichloropropane is replaced by amine alcohol at a set temperature, and mono-substituted polyalcohol amine and di-substituted polyalcohol amine products are generated, and meanwhile, industrial salt as a byproduct is generated. Adjusting and controlling the concentration of the catalyst, and continuously separating out salt in the reaction process; under the push of the spiral propelling reactor, the separated industrial salt is propelled from the tubular spiral propelling reactor to the salt collector and is discharged out of the reaction system. The reaction system after desalting is filtered and collected and then is sent into a reaction kettle (namely a kettle type reactor) to be pressurized and heated until the substitution reaction is completed. And (3) in the reaction kettle, extracting unreacted dichloropropane and water in vacuum, circulating to the raw material end for continuous use, further filtering the product to remove salt, and packaging.
A preparation method of polyalcohol amine comprises the following steps:
dichloropropane and alcohol amine are mixed according to the molar ratio of 1: 1-4, dichloropropane and an alkali catalyst according to the equivalent ratio of 1: 1-4 to form uniform slurry, and the uniform slurry is added into a tubular spiral propelling reactor from a feed inlet. Setting the reaction temperature of the tubular spiral propelling reactor to be 50-100 ℃; the linear speed of the propulsion is 0.10-1.00 m/min, and the rotating speed is 10.00-100.00 rad/min. At a set temperature, one or two chlorines of dichloropropane are replaced by amino alcohol to generate a mono-substituted polyalcohol amine or di-substituted polyalcohol amine product, and a byproduct industrial salt is generated at the same time.
Under the drive of the spiral propelling reactor, the industrial salt separated out in the reaction process is propelled from the tubular reactor to the salt collector to be discharged out of the reaction system. Filtering and collecting the reaction system subjected to desalting in a kettle type reactor at the temperature of 100-200 ℃; stirring at 50.00-200.00 rad/min under 1.00-5.00 MPa until the substitution reaction is complete, and finishing after the pressure is stable. Stripping at 50-80 ℃ and 0.10-0.50 MPa of vacuum degree; and (4) extracting unreacted dichloropropane and water in vacuum, and recycling the unreacted dichloropropane and water to a raw material end for use. And (5) filtering and desalting the product, and then inspecting and packaging.
By controlling the proportion of the raw materials and the catalyst, the reaction system has no wastewater discharge.
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, so 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 the self-made alkali catalyst.
Example 2
Dichloropropane, diisopropanolamine and sodium hydroxide (48.0 wt%) in a molar ratio of 1:2:2 were metered and mixed to form a homogeneous solution, which was then fed into a tubular screw reactor. The tubular screw propulsion reactor is set with a reaction temperature of 80 ℃ and a linear propulsion speed of 0.50 m/min. The salt generated by the reaction enters the salt collector and is discharged out of the reactor under the action of the screw propeller. Filtering and collecting the reaction system after desalting in a kettle type reactor at the temperature of 140 ℃; the stirring speed is 80.0rad/min, the pressure is 2.0MPa, and the reaction is finished after the pressure is stable. Stripping at 80 deg.C and vacuum degree of 0.40 MPa; the unreacted light components and water are extracted by vacuum extraction and recycled to the raw material end for use, the product is inspected (figure 3) and packaged after being filtered and desalted, and the dichloropropane conversion rate is 98.2 percent.
Example 3
Dichloropropane, diisopropanolamine and sodium hydroxide (48.0 wt%) are metered and mixed according to the molar ratio of 1:2:2 to form a uniform solution, the uniform solution is added into a tubular spiral propelling reactor, after materials are filled in the reactor, the raw material ratio is changed to the molar ratio of 1:2:2 of dichloropropane, diisopropanolamine and sodium hydroxide (100.0 wt%), the reaction temperature of the tubular spiral propelling reactor is set to be 70 ℃, and the linear propelling speed is 0.40 m/min. The salt generated by the reaction enters the salt collector and is discharged out of the reactor under the action of the screw propeller. Filtering and collecting the reaction system after desalting in a kettle type reactor at the temperature of 130 ℃; the stirring speed is 90.0rad/min, the pressure is 2.0MPa, and the reaction is finished after the pressure is stable. Stripping at 70 deg.C and 0.20 MPa; the light components are extracted by vacuum pumping and the water is circulated to the raw material end for use. And (5) filtering and desalting the product, and then inspecting and packaging. And (3) detecting tail gas and products, wherein the dichloropropane conversion rate is 100.0%.
Example 4
Dichloropropane, diisopropanolamine and sodium hydroxide (48.0 wt%) are mixed according to a molar ratio of 1:2:2 to form a uniform solution, the uniform solution is added into a tubular spiral propelling reactor, after the reactor is filled with materials, the raw material ratio is changed to a molar ratio of 2:3:3 of dichloropropane, diisopropanolamine and sodium hydroxide (100.0 wt%), the reaction temperature of the tubular spiral propelling reactor is set to be 80 ℃, and the linear propelling speed is 0.30 m/min. The salt generated by the reaction enters the salt collector and is discharged out of the reactor under the action of the screw propeller. The reaction system after the desalting is further filtered and collected and then enters a kettle type reactor, and the temperature is 140 ℃; the reaction was carried out at a stirring speed of 90.0rad/min and a pressure of 1.5MPa until the pressure was stabilized (when the reaction was completed, the vaporized dichloropropane returned from the gas phase to the liquid phase in the vessel, and only air remained, so that the pressure was stabilized). Stripping at 70 deg.C and 0.10 MPa; the light components are extracted by vacuum pumping and the water is circulated to the raw material end for use. And (5) filtering and desalting the product, and then inspecting and packaging. And (5) detecting tail gas and products, wherein the dichloropropane conversion rate is 89.2%.
Example 5
Dichloropropane, diisopropanolamine and a self-made catalyst are metered and mixed according to the molar ratio of 1:2:2 to form uniform slurry, the uniform slurry is added into a tubular spiral propelling reactor, the reaction temperature of the tubular spiral propelling reactor is set to be 80 ℃, and the linear propelling speed is 0.30 m/min. After reaction, the catalyst enters a collector under the action of a screw propeller and is discharged out of the reactor for recycling. Filtering and collecting the reaction system after the catalyst is removed into a kettle type reactor, and carrying out temperature control at 120 ℃; the stirring speed is 90.0rad/min, the pressure is 1.0MPa, and the reaction is finished after the pressure is stable. Stripping at 60 deg.C and 0.10 MPa; the light components are extracted by vacuum pumping and the water is circulated to the raw material end for use. And (5) filtering the product, and then inspecting and packaging. 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. The preparation method of the polyalcohol amine is characterized by comprising the following steps:
the method comprises the following steps: pretreatment of raw materials
Mixing dichloropropane, alcohol amine and a catalyst in proportion to form uniform slurry; the catalyst is alkali;
step two: process for the preparation of a catalyst
Mixing dichloropropane, alcohol amine and a catalyst in proportion to form uniform slurry, and adding the uniform slurry into a spiral propelling reactor from a feed inlet; in a screw propulsion reactor with set temperature, chlorine on dichloropropane is replaced by alcohol amine to generate polyalcohol amine, and the replaced chlorine forms byproduct salt; under the push of the spiral propelling reactor, salt precipitated in the reaction process is propelled to a salt collector from the spiral propelling reactor, and the salt is discharged from the reaction system;
the reaction system after the desalination is sent into a kettle type reactor to be pressurized and heated until the reaction is complete under the action of a spiral propelling reactor; then carrying out vacuum pumping to extract unreacted dichloropropane and water, and circulating the dichloropropane and water to the raw material end for continuous use;
the alcohol amine is
2. 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 consisting of 1, 2-dichloropropane and 1, 3-dichloropropane.
3. The method for preparing polyalcohol amine according to claim 1, wherein the molar ratio of dichloropropane to the polyalcohol amine is 1: 1-4; the equivalent ratio of dichloropropane to alkali is 1: 1-4.
4. The method of claim 1 or 2, wherein the catalyst in the homogeneous slurry is sodium hydroxide.
5. The method for preparing polyalcohol amine according to claim 1, wherein the screw propulsion reactor is a tubular screw propulsion reactor; the reaction temperature of the spiral propelling reactor is set to be 50-100 ℃, the flow speed is 0.10-1.00 m/min, and the rotating speed is 10.00-100.00 rad/min.
6. The method for preparing polyalcohol amine according to claim 1, wherein the reaction system collected at the end of the screw propulsion reactor after desalting is transferred to a tank reactor; the reaction temperature in the kettle reactor is 100-200 ℃, the stirring speed is 50.00-200.00 rad/min, and the pressure is 1.00-5.00 MPa.
7. The method for preparing the polyalcohol amine according to claim 1, wherein after the reaction in the kettle reactor is finished, the reaction is stripped under the conditions of 50-80 ℃ and 0.10-0.50 MPa of vacuum degree, and the condensate is recycled to a raw material end for use; discharging salt and discharging material after the steam stripping is finished.
8. The preparation method of the polyalcohol amine according to claim 1, wherein the roasted, alkali washed, acid washed and dried coconut shell activated carbon, sodium hydroxide or potassium hydroxide and lanthanum nitrate or cesium nitrate are placed in a muffle furnace and roasted at 250-550 ℃ in nitrogen atmosphere, so that alkali, rare earth elements and groups on the surface of the coconut shell activated carbon are combined through chemical bonds, and the self-made solid alkali catalyst is obtained for later use.
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| US4493909A (en) * | 1981-06-25 | 1985-01-15 | Bayer Aktiengesellschaft | Poly-N,N-hydroxyalkylamides of polybasic carboxylic acids and a process for the production thereof |
| US4937269A (en) * | 1986-08-29 | 1990-06-26 | University Of Akron | Macrophage stimulation by homologs or analogs of quadrol |
| RO102817A2 (en) * | 1988-12-16 | 1991-12-09 | Inst De Medicina Si Farmacie I | Hydroxyalkyl-homopiperazines derivatives of theocin and producing |
| CN1160311C (en) * | 1998-05-28 | 2004-08-04 | 埃姆斯化学公司 | Process for preparing beta-hydroxyalkylamides |
| CN102199467A (en) * | 2011-04-06 | 2011-09-28 | 修建东 | Preparation method of Alpha-donamide aqueous antirust lubricant |
| CN102875405A (en) * | 2012-10-24 | 2013-01-16 | 南京工业大学 | Polyhydric alcohols of basic amino acid or ester thereof and preparation method and application of polyhydric alcohols |
-
2018
- 2018-11-07 CN CN201811317681.9A patent/CN109134278B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493909A (en) * | 1981-06-25 | 1985-01-15 | Bayer Aktiengesellschaft | Poly-N,N-hydroxyalkylamides of polybasic carboxylic acids and a process for the production thereof |
| US4937269A (en) * | 1986-08-29 | 1990-06-26 | University Of Akron | Macrophage stimulation by homologs or analogs of quadrol |
| RO102817A2 (en) * | 1988-12-16 | 1991-12-09 | Inst De Medicina Si Farmacie I | Hydroxyalkyl-homopiperazines derivatives of theocin and producing |
| CN1160311C (en) * | 1998-05-28 | 2004-08-04 | 埃姆斯化学公司 | Process for preparing beta-hydroxyalkylamides |
| CN102199467A (en) * | 2011-04-06 | 2011-09-28 | 修建东 | Preparation method of Alpha-donamide aqueous antirust lubricant |
| CN102875405A (en) * | 2012-10-24 | 2013-01-16 | 南京工业大学 | Polyhydric alcohols of basic amino acid or ester thereof and preparation method and application of polyhydric alcohols |
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