CN110878005A - Continuous condensation process of trimethylolpropane and ditrimethylolpropane - Google Patents
Continuous condensation process of trimethylolpropane and ditrimethylolpropane Download PDFInfo
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- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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Abstract
The invention discloses a continuous condensation process of trimethylolpropane and ditrimethylolpropane, which comprises the following specific steps: adding a formaldehyde solution with the mass percent of 37% into a continuous reaction heat exchanger before feeding, and starting a circulating pump; the n-butyl aldehyde and the formaldehyde are evenly put into a continuous reaction heat exchanger through an aldehyde mixer and alkali and water through an alkali mixer according to the strict proportion; then continuously feeding the materials into a continuous reactor; then continuously feeding the materials into a continuous neutralization reactor; adding formic acid to the continuous neutralization reactor to neutralize residual alkali in the material; and (3) after the neutralization is finished and the condensation reaction is finished, separating and refining the condensation liquid to obtain qualified trimethylolpropane, ditrimethylolpropane and formate. The invention adopts the continuous condensation process to produce the trimethylolpropane and the ditrimethylolpropane condensation liquid, and has the advantages of less equipment investment, large production capacity, low formaldehyde consumption, high ditrimethylolpropane selective yield and the like.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a continuous condensation process of trimethylolpropane and ditrimethylolpropane.
Background
Trimethylolpropane (TMP) is a few of polyhydric alcohol products containing quaternary carbon atoms, has the advantages of good thermal stability, difficult decomposition and the like, contains 3 active hydroxyl groups, can form a polyester structure, is widely applied to high polymer materials, and is an important fine chemical product. Trimethylolpropane is a commonly used chain extender in the resin industry. It has low melting point and can react with organic acid to produce monoester or multiester, aldehyde and ketone to produce acetal and ketal, and diisocyanate to produce carbamate. The product is mainly used in the technical fields of alkyd resin, polyurethane, unsaturated resin, polyester resin or paint and the like, can also be used for synthesizing aviation lubricating oil, plasticizer, surfactant, wetting agent, explosive, printing ink and the like, and can also be used as a textile auxiliary agent and a heat stabilizer of polyvinyl chloride resin.
The di-trimethylolpropane (di-TMP) contains 2 quaternary carbon atoms and 4 active hydroxyl groups in the molecule and is 4-membered alcohol with excellent thermal stability. The uses of ditrimethylolpropane can be divided into two categories: the first kind is used as raw material for synthesizing fine chemicals such as paint, printing ink, cosmetics or defoaming agent, the ditrimethylolpropane is used for synthesizing hyperbranched polymer, is used as charring agent of flame-retardant paint, synthesizing polyether/polyester polyphenol, synthesizing surfactant for cosmetics, synthesizing polyol acrylate for photocuring paint, synthesizing PVC stabilizer, synthesizing ester lubricant from ditrimethylolpropane and mono fatty acid, synthesizing defoaming agent, etc.; the second kind is used as raw material for synthesizing electronic information chemicals, and ditrimethylolpropane is used for synthesizing colloidal polymer electrolyte, synthesizing organic electroluminescent layer protective film, preparing thermal imaging photosensitive material, using as neutralizer of liquid crystal material, and synthesizing nitrogen-phosphorus intumescent flame retardant. The ditrimethylolpropane has wide application, but has low yield and high added value.
The trimethylolpropane is prepared by condensing n-butyl aldehyde, formaldehyde and alkali serving as raw materials, wherein the trimethylolpropane and formate are obtained by firstly carrying out aldol condensation reaction and then carrying out Cannizzaro reaction in the condensation process. The trimethylolpropane condensation reaction is also accompanied by ditrimethylolpropane and other byproducts, the amount of the ditrimethylolpropane byproduct is small, and the price of the ditrimethylolpropane byproduct is 2-4 times that of trimethylolpropane. As ditrimethylolpropane has wide application, low yield, short supply, high additional value and good economic benefit, production enterprises hope to produce ditrimethylolpropane as a byproduct in a condensation reaction. The trimethylolpropane condensation reaction usually adopts a batch reaction process, the batch reaction process has long material retention time, large equipment investment, low production capacity and high formaldehyde consumption, and the byproduct quantity of ditrimethylolpropane in the batch reaction process is small and is usually less than 5 percent.
Disclosure of Invention
The invention provides a continuous condensation process of trimethylolpropane and ditrimethylolpropane, aiming at overcoming the defects in the prior art and solving the technical problems in the prior art.
The invention is realized by the following technical scheme: a continuous condensation process of trimethylolpropane and ditrimethylolpropane comprises the following steps in sequence:
1) before feeding, adding a formaldehyde solution with the mass percent of 37 percent into the continuous reaction heat exchanger, starting a circulating pump, and indirectly controlling the temperature in the continuous reaction heat exchanger to be between 10 and 70 ℃ by controlling the adding amount of a refrigerant or a heating medium.
2) The n-butyl aldehyde and the formaldehyde are evenly put into a continuous reaction heat exchanger through an aldehyde mixer and alkali and water through an alkali mixer strictly according to the proportion, and the materials stay in the continuous reaction heat exchanger for 10min to 30 min;
3) after the material stays in the continuous reaction heat exchanger for 10min to 30min, the material continuously enters the continuous reactor from the continuous reaction heat exchanger and stays in the continuous reactor for 30min to 180min, and the temperature in the continuous reactor is indirectly controlled to be 10 ℃ to 70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
4) after the material stays in the continuous reactor for 30-180 min, the material continuously enters the continuous neutralization reactor from the continuous reactor and stays in the continuous neutralization reactor for 10-30 min, and the temperature in the continuous neutralization reactor is indirectly controlled to be 30-70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
5) formic acid is continuously and accurately added into a continuous neutralization reactor to neutralize residual alkali in the material, so that the pH value of the material is controlled to be weakly acidic;
6) and (3) finishing neutralization, finishing the condensation reaction, feeding the material into a condensation liquid storage tank, and separating and refining the condensation liquid to obtain qualified trimethylolpropane, ditrimethylolpropane and formate.
In step 2), the feeding molar ratio of n-butyraldehyde, formaldehyde and base to n-butyraldehyde: formaldehyde: base (in hydroxide) = 1: 2.5-3.5: 1.05-1.4, and the adding amount of water is calculated according to the amount of the condensed liquid obtained by feeding 1kmol n-butyl aldehyde, wherein the condensed liquid is 800-1200 kg.
Preferably, the aldehyde mixer is a line mixer or a stirred tank mixer. The alkali mixer adopts a pipeline mixer or a stirring tank mixer. The heat exchange area of the continuous reaction heat exchanger needs to be large enough, the effective volume is small, and the heat exchanger in the form of a tube heat exchanger, a plate heat exchanger or a coil heat exchanger is adopted.
Preferably, the continuous reactor adopts a pipeline reactor or a multi-kettle series stirring reactor or other forms, and the core of the continuous reactor is to have the heat exchange function and the stirring function.
The continuous neutralization reactor has the functions of automatic pH value detection and control, and can automatically control the addition of formic acid according to the set pH value and automatically adjust the pH value of the condensation liquid.
The alkali used in the reaction is an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, a suspension of calcium hydroxide or a suspension of a mixed alkali, and a suspension of calcium hydroxide is preferably used.
The invention has the beneficial effects that: the invention has the advantages that the trimethylolpropane and ditrimethylolpropane condensation liquid are produced by adopting a continuous condensation process, and the invention has the advantages of less equipment investment, large production load, low formaldehyde consumption, high ditrimethylolpropane selective yield and the like. The continuous condensation process of the invention consists of an aldehyde mixer, an alkali mixer, a continuous reaction heat exchanger, a circulating pump, a continuous reactor, a continuous neutralization reactor, a condensation liquid storage tank and other equipment. The invention has the advantages of large continuous reaction production capacity, high labor efficiency, rapid reaction heat removal, stable reaction temperature control, short material average residence time, less formaldehyde disproportionation reaction and low formaldehyde consumption. The invention realizes higher selective yield of the ditrimethylolpropane by flexibly adjusting the reaction proportion, the temperature and the average residence time.
The invention can produce more byproduct ditrimethylolpropane to meet the market demand during the trihydroxy condensation reaction, and the special continuous condensation process disclosed by the invention also has the following advantages: 1. compared with a simple tubular reactor, the method has the advantages of large heat exchange area, rapid reaction heat exchange, accurate control of reaction temperature, no over-temperature, high selective yield of the ditrimethylolpropane and the like; 2. compared with a simple multi-kettle continuous reactor, the method has the advantages of rapid heat removal, less material back mixing, high reaction speed, high selective yield of the ditrimethylolpropane and the like; 3. compared with a batch reactor, the method has the advantages of short average material retention time, less formaldehyde disproportionation reaction, low formaldehyde consumption, constant proportion of reaction raw materials and the like, and has the advantages of no change along with the feeding time, constant reaction temperature, large production load, high equipment utilization rate and high selective yield of the ditrimethylolpropane.
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FIG. 1 is a block process flow diagram of a continuous condensation process of trimethylolpropane and ditrimethylolpropane.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As shown in figure 1, the invention discloses a continuous condensation process of trimethylolpropane and ditrimethylolpropane, which sequentially comprises the following steps:
1) before feeding, adding a formaldehyde solution with the mass percent of 37 percent into the continuous reaction heat exchanger, starting a circulating pump, and indirectly controlling the temperature in the continuous reaction heat exchanger to be between 10 and 70 ℃ by controlling the adding amount of a refrigerant or a heating medium.
2) The n-butyl aldehyde and the formaldehyde are evenly put into a continuous reaction heat exchanger through an aldehyde mixer and alkali and water through an alkali mixer strictly according to the proportion, and the materials stay in the continuous reaction heat exchanger for 10min to 30 min;
3) after the material stays in the continuous reaction heat exchanger for 10min to 30min, the material continuously enters the continuous reactor from the continuous reaction heat exchanger and stays in the continuous reactor for 30min to 180min, and the temperature in the continuous reactor is indirectly controlled to be 10 ℃ to 70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
4) after the material stays in the continuous reactor for 30-180 min, the material continuously enters the continuous neutralization reactor from the continuous reactor and stays in the continuous neutralization reactor for 10-30 min, and the temperature in the continuous neutralization reactor is indirectly controlled to be 30-70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
5) formic acid is continuously and accurately added into a continuous neutralization reactor to neutralize residual alkali in the material, so that the pH value of the material is controlled to be weakly acidic;
6) and (3) finishing neutralization, finishing the condensation reaction, feeding the material into a condensation liquid storage tank, and separating and refining the condensation liquid to obtain qualified trimethylolpropane, ditrimethylolpropane and formate.
In step 2), the feeding molar ratio of n-butyraldehyde, formaldehyde and base to n-butyraldehyde: formaldehyde: base (in hydroxide) = 1: 2.5-3.5: 1.05-1.4, and the adding amount of water is calculated according to the amount of the condensed liquid obtained by feeding 1kmol n-butyl aldehyde, wherein the condensed liquid is 800-1200 kg.
The aldehyde mixer is a pipeline mixer or a stirred tank mixer. The alkali mixer adopts a pipeline mixer or a stirring tank mixer. The heat exchange area of the continuous reaction heat exchanger needs to be large enough, the effective volume is small, and the heat exchanger in the form of a tube heat exchanger, a plate heat exchanger or a coil heat exchanger is adopted. The continuous reactor adopts a pipeline reactor or a multi-kettle series stirring reactor or other forms, and the core of the continuous reactor is to have the heat exchange function and the stirring function. The continuous neutralization reactor has the functions of automatic pH value detection and control, and can automatically control the addition of formic acid according to the set pH value and automatically adjust the pH value of the condensation liquid. The alkali used in the reaction is an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, a suspension of calcium hydroxide or a suspension of a mixed alkali, and a suspension of calcium hydroxide is preferably used.
Example 1: a continuous condensation process of trimethylolpropane and ditrimethylolpropane.
Raw material specification: 99.5 percent of n-butyraldehyde, 37 percent of formaldehyde, 32 percent of sodium hydroxide and distilled water.
Feeding speed: 725 kg/h of n-butyraldehyde, 2386 kg/h of formaldehyde, 1500 kg/h of sodium hydroxide and 6300 kg/h of distilled water.
Controlling the temperature of the continuous reaction heat exchanger at 35 ℃, and allowing the temperature to fluctuate by 1 ℃ up and down; the temperature of the continuous reactor is controlled at 40 ℃, and the temperature is allowed to fluctuate up and down by 1 ℃; controlling the temperature of the continuous neutralization reactor at 40 ℃, and allowing the temperature to fluctuate up and down by 1 ℃; the average residence time of the materials in the continuous reaction heat exchanger is 6min, the average residence time of the materials in the continuous reactor is 60min, and the average residence time of the materials in the continuous neutralization reactor is 10 min. The reaction was terminated by neutralizing the batch with formic acid in a continuous neutralization reactor to PH = 6.8.
The condensation liquid is detected by a gas chromatography area normalization method, and the trihydroxy content is 84 percent and the ditrimethylol content is 11 percent.
Example 2: a continuous condensation process of trimethylolpropane and ditrimethylolpropane.
Raw material specification: 99.5 percent of n-butyraldehyde, 37 percent of formaldehyde, 32 percent of sodium hydroxide and distilled water.
Feeding speed: 725 kg/h of n-butyraldehyde, 2435 kg/h of formaldehyde, 1500 kg/h of sodium hydroxide and 6300 kg/h of distilled water.
Controlling the temperature of the continuous reaction heat exchanger at 35 ℃, and allowing the temperature to fluctuate by 1 ℃ up and down; the temperature of the continuous reactor is controlled at 50 ℃, and the temperature is allowed to fluctuate up and down by 1 ℃; the temperature of the continuous neutralization reactor is controlled at 50 ℃, and the temperature is allowed to fluctuate up and down by 1 ℃; the average residence time of the materials in the continuous reaction heat exchanger is 6min, the average residence time of the materials in the continuous reactor is 45min, and the average residence time of the materials in the continuous neutralization reactor is 10 min. The reaction was terminated by neutralizing the batch with formic acid in a continuous neutralization reactor to PH = 6.8.
The condensation liquid is detected by a gas chromatography area normalization method, and the trihydroxy content is 91 percent, and the ditrimethylol content is 6 percent.
Example 3: a continuous condensation process of trimethylolpropane and ditrimethylolpropane.
Raw material specification: 99.5 percent of n-butyraldehyde, 37 percent of formaldehyde, 32 percent of sodium hydroxide and distilled water.
Feeding speed: 725 kg/h of n-butyraldehyde, 2597 kg/h of formaldehyde, 1500 kg/h of sodium hydroxide and 5940 kg/h of distilled water.
Controlling the temperature of the continuous reaction heat exchanger at 35 ℃, and allowing the temperature to fluctuate by 1 ℃ up and down; the temperature of the continuous reactor is controlled at 55 ℃, and the temperature is allowed to fluctuate up and down by 1 ℃; the temperature of the continuous neutralization reactor is controlled at 50 ℃, and the temperature is allowed to fluctuate up and down by 1 ℃; the average residence time of the materials in the continuous reaction heat exchanger is 6min, the average residence time of the materials in the continuous reactor is 30min, and the average residence time of the materials in the continuous neutralization reactor is 10 min. The reaction was terminated by neutralizing the batch with formic acid in a continuous neutralization reactor to PH = 6.8.
The condensation liquid is detected by a gas chromatography area normalization method, and the content of the trihydroxy group is 93 percent, and the content of the ditrimethylol group is 5 percent.
Finally, it should be noted that the above-mentioned contents only show and describe the basic principle and main features of the present invention and the advantages of the present invention, and are only used for illustrating the technical solutions of the present invention, not for limiting the protection scope of the present invention, and the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A continuous condensation process of trimethylolpropane and ditrimethylolpropane is characterized in that: the continuous condensation process of the trimethylolpropane and the ditrimethylolpropane sequentially comprises the following steps:
1) before feeding, adding a formaldehyde solution with the mass percent of 37 percent into the continuous reaction heat exchanger, starting a circulating pump, and indirectly controlling the temperature in the continuous reaction heat exchanger to be between 10 and 70 ℃ by controlling the adding amount of a refrigerant or a heating medium.
2) The n-butyl aldehyde and the formaldehyde are evenly put into a continuous reaction heat exchanger through an aldehyde mixer and alkali and water through an alkali mixer strictly according to the proportion, and the materials stay in the continuous reaction heat exchanger for 10min to 30 min;
3) after the material stays in the continuous reaction heat exchanger for 10min to 30min, the material continuously enters the continuous reactor from the continuous reaction heat exchanger and stays in the continuous reactor for 30min to 180min, and the temperature in the continuous reactor is indirectly controlled to be 10 ℃ to 70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
4) after the material stays in the continuous reactor for 30-180 min, the material continuously enters the continuous neutralization reactor from the continuous reactor and stays in the continuous neutralization reactor for 10-30 min, and the temperature in the continuous neutralization reactor is indirectly controlled to be 30-70 ℃ by controlling the adding amount of a refrigerant or a heating medium;
5) formic acid is continuously and accurately added into a continuous neutralization reactor to neutralize residual alkali in the material, so that the pH value of the material is controlled to be weakly acidic;
6) and (3) finishing neutralization, finishing the condensation reaction, feeding the material into a condensation liquid storage tank, and separating and refining the condensation liquid to obtain qualified trimethylolpropane, ditrimethylolpropane and formate.
2. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1, characterized in that: in the step 2), the molar ratio of the n-butyraldehyde to formaldehyde to the base is as follows: formaldehyde: base = 1: 2.5-3.5: 1.05-1.4, and the adding amount of water is calculated according to the amount of the condensed liquid obtained by feeding 1kmol n-butyl aldehyde, wherein the condensed liquid is 800-1200 kg.
3. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1 or 2, characterized in that: the aldehyde mixer is a pipeline mixer or a stirred tank mixer.
4. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1 or 2, characterized in that: the alkali mixer adopts a pipeline mixer or a stirring tank mixer.
5. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1 or 2, characterized in that: the continuous reaction heat exchanger adopts a tube-in-tube heat exchanger, a plate heat exchanger or a coil heat exchanger.
6. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1 or 2, characterized in that: the continuous reactor adopts a pipeline reactor or a multi-kettle series stirring reactor.
7. The continuous condensation process of trimethylolpropane and ditrimethylolpropane according to claim 1 or 2, characterized in that: the alkali used in the reaction is potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, calcium hydroxide suspension or mixed alkali suspension.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956132A (en) * | 2021-11-19 | 2022-01-21 | 吉林化工学院 | Preparation method of trimethylpentanediol |
| CN118908807A (en) * | 2024-08-08 | 2024-11-08 | 赤峰瑞阳化工有限公司 | Preparation method capable of improving quality of trimethylolpropane product by calcium method |
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| GB958654A (en) * | 1958-12-15 | 1964-05-21 | Fritz Meissner | Process for the manufacture of polyhydric alcohols |
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| CN113956132A (en) * | 2021-11-19 | 2022-01-21 | 吉林化工学院 | Preparation method of trimethylpentanediol |
| CN113956132B (en) * | 2021-11-19 | 2024-03-19 | 吉林化工学院 | A kind of preparation method of trimethylpentanediol |
| CN118908807A (en) * | 2024-08-08 | 2024-11-08 | 赤峰瑞阳化工有限公司 | Preparation method capable of improving quality of trimethylolpropane product by calcium method |
| CN118908807B (en) * | 2024-08-08 | 2025-10-21 | 赤峰瑞阳化工有限公司 | A preparation method capable of improving the quality of calcium-process trimethylolpropane products |
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