CN105732369A - Method for synthesizing polyol fatty acid ester by adopting falling-film evaporator - Google Patents
Method for synthesizing polyol fatty acid ester by adopting falling-film evaporator Download PDFInfo
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Abstract
The invention discloses a method for synthesizing polyol fatty acid ester by adopting a falling-film evaporator. The method comprises the following steps: mixing polyol and fatty acid in accordance with that the mole ratio of hydroxyl to carboxyl is 1: (1 to 1.6), carrying out heating and stirring so as to mutually dissolve the polyol and the fatty acid and obtain a reaction mixture solution; setting the temperature of the falling-film evaporator to 180 DEG C to 250 DEG C, setting the pressure to 5KPa to 60KPa, and setting the external condenser temperature to -20 DEG C to 30 DEG C; and enabling the reaction mixture solution to flow into the falling-film evaporator so as to form a continuous flowing liquid film, carrying out heating, and then, carrying out an esterification reaction so as to synthesize the polyol fatty acid ester. According to the method disclosed by the invention, the technical effects of high efficiency, environment-friendliness and environmental protection can be achieved.
Description
Technical field
The present invention relates to the synthetic method of ester type compound in a kind of organic chemistry, particularly to a kind of method of synthesizing polyatomic alcohol fatty acid ester.
Background technology
Polyol esters of fatty acids has excellent heat stability, non-oxidizability and good low temperature viscosity and high viscosity index (HVI), it is widely used in the lubrication of various machinery, in particular as aeroengine oil, hydraulic fluid, compressor wet goods, by the carbon chain lengths of fatty acid and structure are adjusted, can obtain and disclosure satisfy that the product used under different working condition.Also there is natural biological degradability due to it, polyol esters of fatty acids is again the lubricant of a kind of green, additionally, polyol esters of fatty acids also can make the plasticizer of insulating properties, temperature tolerance excellence, it is widely used in producing resistant to elevated temperatures cable material and producing the production field of artificial leather, plastic processing.
The esterification of polyhydric alcohol and fatty acid is a reversible endothermic reaction.The construction features of the long-chain of polyhydric alcohol polyhydroxy and fatty acid, the reaction causing polyhydric alcohol and fatty acid is comparatively difficult, it usually needs adds catalyst and promotes the carrying out of reaction.The addition of catalyst reduces the activation energy of reaction so that reaction better can react in identical situation of being heated.Traditional synthesis generally adopts the liquid acid as catalyst such as sulphuric acid, exist etching apparatus, product post processing is loaded down with trivial details, the difficult separation of catalyst, easily cause the shortcomings such as pollution.In recent years, the report of research employing new catalyst catalytic esterification was of common occurrence.As Chinese patent CN200710307720.2 adopts ionic liquid to be catalyst synthesizing polyatomic alcohol fatty acid ester, there is esterification yield height, the advantages such as operation is simple.Chinese patent CN101229999A has reported and has used SO4 2-/ZrO2The method of type solid superacid as catalyst synthesis oleic acid esters, catalyst amount is only 0.05-0.5%, it is possible to the well esterification of catalysis oleic acid and Polyethylene Glycol；Chinese patent CN101139288.A has reported and has used SO4 2-/TiO2-SiO2The reaction of type presence of compound solid superacid catalyst linoleic acid and dehydrated alcohol, esterification yield can to more than 95%.Chinese patent CN102557849A discloses a kind of method continuously performing reaction, relate to esterification and falling film evaporator, but it is mentioned that the carrier that occurs of esterification remain reactor and rectifying column (catalyst be positioned over rectifier bottoms, and rectifying column is connected to above reactor；The water that the esterification starting stage generates is got rid of by the water knockout drum of reactor, esterification continuously performs the water of stage generation and is discharged by rectifying tower top), it adopts the purpose of falling film evaporator to be constantly realize the separation of raw material and product, and make unreacted raw material reenter reactor, to ensure the seriality produced, but not as the carrier that reaction occurs.The form of its reaction is still that traditional autoclave rectification pattern, and esterification still needs catalyst to carry out the good esterification yield of catalysis guarantee.
But no matter be adopt ionic liquid or solid super-strong acid, or other novel effective catalysts, the preparation problem of existence catalyst all more or less.Prepare solid super-strong acid such as the sedimentation method and only wash sucking filtration one step just need more than four times; till not measuring, with indicator inspection, the anion that source metal introduces; the oxide particle generated is very thin, causes that sucking filtration is abnormal slowly, and large-scale production can expend great lot of water resources and the energy；Source metal or be slaine or for metallo-organic compound, its raw material is non-renewable, and price is high year by year.And after all of catalyst is again repeated utilization, still face the emission problem of waste residue.
It addition, esterification is a reversible endothermic reaction, therefore promote the heat exchange efficiency of reaction, accelerate the removal generating water to promote that molecular balance moves to right, be another effective way promoting esterification.And in traditional reactor, the contact area of liquid and heating surface is limited, heat exchange efficiency is relatively low, and the water that is internally generated of reaction system to be crossed the obstruction of molecule layer by layer and could overflow liquid level, and molecular balance moves to right slower.
In sum, adopting all kinds of catalyst, thus face cost and trash discharge problem in prior art, the tank reactor heat-transfer effect generally adopted in prior art is poor, and the water that course of reaction generates not easily is overflowed from system.How to develop the synthetic method of a kind of polyol fatty acid ester so that it is the defect of above-mentioned prior art can be overcome, namely become those skilled in the art's problem demanding prompt solution.
Summary of the invention
It is an object of the invention to provide a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester so that it is reach technique effect efficient, environmental protection.
For achieving the above object, the present invention provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to mol ratio 1:1～1.6 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；
2) setting the temperature of falling film evaporator as 180-250 DEG C, pressure is 5-60KPa, and external condenser temperature is-20-30 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described polyhydric alcohol is trimethylolpropane or tetramethylolmethane.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described polyhydric alcohol and fatty acid are preferably that 1:1.1～1.3 mix by hydroxyl and the mol ratio of carboxyl.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, described fluid film thickness is 0.1-2mm.In step 3) in, using dehvery pump to make reaction mixture continuously flow in falling film evaporator with certain flow rate, formed and there is certain thickness fluid film, the form of the fluid film to flow continuously is heated and is carried out esterification.In this course, the present invention only limits fluid film thickness, and the falling film evaporator of specifically chosen which kind of specification and set which kind of flow velocity, then by those skilled in the art under selected fluid film thickness, can determine according to practical situation (falling film evaporator inner surface parameter etc.).
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, this reaction mixture is made to pass through distributor, and the inwall of falling film evaporator is flowed through under gravity from top to bottom with the form of fluid film, it is heated and esterification occurs.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, the water generated in esterification is pulled out falling film evaporator in a gaseous form under vacuum, is then collected by external condenser.Vacuum condition described herein, namely the pressure condition of its indication is step 2) in set pressure 5-60Kpa.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, esterification reaction product is exported by falling film evaporator through dehvery pump.
Compared with prior art, the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, details are as follows for its know-why and technique effect:
1) say from outside, the method of the present invention is the reactive mode of a kind of continuous flowing, adopt the esterification process of this continuous flowing, reactant can constantly be inputted falling film evaporator and react by dehvery pump, product can also constantly be exported falling film evaporator by dehvery pump, thus realizing continuous continual production.
2) traditionally, falling film evaporator is a kind of equipment separating post processing of chemical industry product, and the present invention does the reactor of synthesizing polyatomic alcohol fatty acid ester with falling film evaporator, make full use of the feature of its film forming, determine by factors such as the removal speed of the water produced that conducts heat, reacts in conjunction with esterification, it is achieved combination；Inside falling film evaporator, reaction mass is heated soon and uniformly, and the water that reaction generates can be overflowed rapidly and be made esterification balance move to right, and has significantly high esterifying efficiency；Specifically, the mixed liquor of polyhydric alcohol and fatty acid continuously flows through evaporator inner wall with the form of fluid film, owing to liquid film is relatively thin, liquid fully quickly can be heated to reaction temperature and esterification occurs, and, the water generated in reaction also is able to overflow from liquid film rapidly, makes esterification balance quickly move to right, conducts heat efficiently and dewater so that esterifying efficiency is greatly promoted.
3) the autoclave rectification pattern of prior art is both needed to use catalyst, and the method for the present invention is without any catalyst, environmental protection.
4) present invention is applicable to the synthesis of polyol fatty acid ester, adopting falling film evaporator to carry out esterification, heat transfer efficiency is high, the speed that dewaters is fast, molecular balance moves to right soon, it may be achieved produce continuously, and the inventive method does not use catalyst, has broad application prospects.
5) it needs to be noted, the position that the esterification of the present invention occurs is falling film evaporator (being specially falling film evaporator inwall), but not reactor general in prior art, even if rectifying column prior art have employed falling film evaporator, also conventional separation only it is as, with product, raw material unreacted in esterification reaction mixture is carried out continuous print separate, isolated raw material is made to reenter reactor and distillation column reactor, to realize the seriality of integrated operation process, the form of its reaction is still that traditional autoclave rectification pattern, its esterification efficiency need nonetheless remain for catalyst and ensures；Compared with prior art, the present invention utilizes the carrier that falling film evaporator occurs as reaction, mainly by its construction features, promote the formation of reaction mass liquid film, it is heated simultaneously and reacts, meanwhile, owing to the reaction form of material is fluid film, the water generated in reaction can quickly be overflowed, promote molecular balance quickly to move to right so that esterification can quickly carry out without rely on any catalyst auxiliary (can successive reaction only because have employed this reaction carriers of falling film evaporator and along with obtain a feature)；By a traditional separation equipment, obtaining fluid film reaction form, the breakthrough (not needing catalyst) of lifting and technology to realize esterification efficiency, this is the major embodiment of the invention.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention；
Fig. 2 is schematic diagram when adopting the falling film evaporator that uses of method of falling film evaporator synthesizing polyatomic alcohol fatty acid ester for esterification of the present invention；
Wherein, accompanying drawing labelling:
1 mixing of materials liquid entrance
2 dehvery pumps
3 evaporator inner wall
The 4 additional hot jackets of vaporizer
5 conduction oil entrances
The steam outlet that 6 reactions generate
7 conduction oil outlets
8 reacting product outlets
9 external condensers
10 vacuum pumping opening
11 condensation-water drains
12 material distributors
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail, and what listed illustrative embodiments was only used as to illustrate, it is not intended as the restriction of the present invention.
Refer to Fig. 1, the flow chart of steps of the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention.For reaching technique effect efficient, environmental protection, the present invention provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to mol ratio 1:1～1.6 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；
2) setting the temperature of falling film evaporator as 180-250 DEG C, pressure is 5-60KPa, and external condenser temperature is-20-30 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester.
Refer to Fig. 2, the schematic diagram when falling film evaporator that its method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester being the present invention uses is for esterification.Falling film evaporator used in the present invention is conventional falling film evaporator, the power that material is provided by dehvery pump 2 is conveyed into falling film evaporator from mixing of materials liquid entrance 1, evaporator inner wall 3 is entered by material distributor 12, the additional hot jacket 4 of vaporizer has conduction oil entrance 5 and conduction oil outlet 7, flowed by conduction oil and realize the heating of evaporator inner wall 3, material reacts with liquid film form at evaporator inner wall 3, product is discharged by reacting product outlet 8, the steam that reaction generates is discharged by steam outlet 6, enter external condenser 9, under the vacuum pumping opening 10 of external condenser 9 is bled, final water vapor condensation is that water is discharged from condensation-water drain 11.It it is more than the course of reaction of the present invention, but it is to be noted, falling film evaporator in accompanying drawing of the present invention is only signal, it is not intended as the restriction of the present invention, those skilled in the art can select suitable falling film evaporator or other similar devices according to practical situation, as long as being capable of the purpose reacted with form of liquid film.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described polyhydric alcohol is trimethylolpropane or tetramethylolmethane.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 1) in, described polyhydric alcohol and fatty acid are preferably that 1:1.1～1.3 mix by hydroxyl and the mol ratio of carboxyl.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, described fluid film thickness is 0.1-2mm.In step 3) in, using dehvery pump to make reaction mixture continuously flow in falling film evaporator with certain flow rate, formed and there is certain thickness fluid film, the form of the fluid film to flow continuously is heated and is carried out esterification.In this course, the present invention only limits fluid film thickness, and the falling film evaporator of specifically chosen which kind of specification and set which kind of flow velocity, then by those skilled in the art under selected fluid film thickness, can determine according to practical situation (falling film evaporator inner surface parameter etc.).
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, this reaction mixture is made to pass through distributor, and the inwall of falling film evaporator is flowed through under gravity from top to bottom with the form of fluid film, it is heated and esterification occurs.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, the water generated in esterification is pulled out falling film evaporator in a gaseous form under vacuum, is then collected by external condenser.Vacuum condition described herein, namely the pressure condition of its indication is step 2) in set pressure 5-60Kpa.
Wherein, in method one better embodiment adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, in step 3) in, esterification reaction product is exported by falling film evaporator through dehvery pump.
Embodiment a
The present embodiment provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to the mol ratio 1:1 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；Described polyhydric alcohol is trimethylolpropane；Described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid；
2) setting the temperature of falling film evaporator as 180 DEG C, pressure is 5KPa, and the temperature of external condenser is-20 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester, and esterification reaction product is exported by falling film evaporator through dehvery pump；Described fluid film thickness is 0.1mm.
Embodiment b
The present embodiment provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to the mol ratio 1.6 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；Described polyhydric alcohol is tetramethylolmethane；Described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid；
2) setting the temperature of falling film evaporator as 250 DEG C, pressure is 60KPa, and the temperature of external condenser is 30 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester, and esterification reaction product is exported by falling film evaporator through dehvery pump；Described fluid film thickness is 2mm.
Embodiment c
The present embodiment provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to the mol ratio 1:1.1 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；Described polyhydric alcohol is trimethylolpropane；Described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid；
2) setting the temperature of falling film evaporator as 200 DEG C, pressure is 20KPa, and the temperature of external condenser is 0 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester, and esterification reaction product is exported by falling film evaporator through dehvery pump；Described fluid film thickness is 1mm.
Embodiment d
The present embodiment provides a kind of method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, comprises the steps:
1) polyhydric alcohol and fatty acid being mixed according to the mol ratio 1:1.3 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；Described polyhydric alcohol is tetramethylolmethane；Described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid (configuration proportion does not limit) of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid；
2) setting the temperature of falling film evaporator as 220 DEG C, pressure 40KPa, the temperature of external condenser is 10 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester, and esterification reaction product is exported by falling film evaporator through dehvery pump；Described fluid film thickness is 1.5mm.
Compared with prior art, the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention, details are as follows for its know-why and technique effect:
1) say from outside, the method of the present invention is the reactive mode of a kind of continuous flowing, adopt the esterification process of this continuous flowing, reactant can constantly be inputted falling film evaporator and react by dehvery pump, product can also constantly be exported falling film evaporator by dehvery pump, thus realizing continuous continual production.
2) traditionally, falling film evaporator is a kind of equipment separating post processing of chemical industry product, and the present invention does the reactor of synthesizing polyatomic alcohol fatty acid ester with falling film evaporator, make full use of the feature of its film forming, determine by factors such as the removal speed of the water produced that conducts heat, reacts in conjunction with esterification, it is achieved combination；Inside falling film evaporator, reaction mass is heated soon and uniformly, and the water that reaction generates can be overflowed rapidly and be made esterification balance move to right, and has significantly high esterifying efficiency；Specifically, the mixed liquor of polyhydric alcohol and fatty acid continuously flows through evaporator inner wall with the form of fluid film, owing to liquid film is relatively thin, liquid fully quickly can be heated to reaction temperature and esterification occurs, and, the water generated in reaction also is able to overflow from liquid film rapidly, makes esterification balance quickly move to right, conducts heat efficiently and dewater so that esterifying efficiency is greatly promoted.
3) the autoclave rectification pattern of prior art is both needed to use catalyst, and the method for the present invention is without any catalyst, environmental protection.
4) present invention is applicable to the synthesis of polyol fatty acid ester, adopting falling film evaporator to carry out esterification, heat transfer efficiency is high, the speed that dewaters is fast, molecular balance moves to right soon, it may be achieved produce continuously, and the inventive method does not use catalyst, has broad application prospects.
5) it needs to be noted, the position that the esterification of the present invention occurs is falling film evaporator (being specially falling film evaporator inwall), but not reactor general in prior art, even if rectifying column prior art have employed falling film evaporator, also conventional separation only it is as, with product, raw material unreacted in esterification reaction mixture is carried out continuous print separate, isolated raw material is made to reenter reactor and distillation column reactor, to realize the seriality of integrated operation process, the form of its reaction is still that traditional autoclave rectification pattern, its esterification efficiency need nonetheless remain for catalyst and ensures；Compared with prior art, the present invention utilizes the carrier that falling film evaporator occurs as reaction, mainly by its construction features, promote the formation of reaction mass liquid film, it is heated simultaneously and reacts, meanwhile, owing to the reaction form of material is fluid film, the water generated in reaction can quickly be overflowed, promote molecular balance quickly to move to right so that esterification can quickly carry out without rely on any catalyst auxiliary (can successive reaction only because have employed this reaction carriers of falling film evaporator and along with obtain a feature)；By a traditional separation equipment, obtaining fluid film reaction form, the breakthrough (not needing catalyst) of lifting and technology to realize esterification efficiency, this is the major embodiment of the invention.
Below by the embodiment under different technology conditions, and the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester of the present invention is described further by the esterification yield experimental data of embodiment, to clearly show that its technique effect.
Embodiment 1
In the present embodiment, it is 1:1 mixing by trimethylolpropane and n-caproic acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 180 DEG C, pressure is 60KPa, and external condenser temperature is 20 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator.After reacting, product is exported by membrane evaporator bottom by gear pump, esterification yield 96%.
Embodiment 2
In the present embodiment, it is 1:1.05 mixing by tetramethylolmethane and positive enanthic acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 185 DEG C, pressure is 56KPa, and external condenser temperature is-5 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator.After reacting, product is exported by membrane evaporator bottom by gear pump, esterification yield 95%.
Embodiment 3
In the present embodiment, it is 1:1.1 mixing by trimethylolpropane and caprylic acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 185 DEG C, pressure is 55KPa, and external condenser temperature is 10 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 96%.
Embodiment 4
In the present embodiment, it is 1:1.2 mixing by tetramethylolmethane and isooctyl acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 195 DEG C, pressure is 40KPa, and external condenser temperature is 5 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 95%.
Embodiment 5
In the present embodiment, it is 1:1.2 mixing by trimethylolpropane and pelargonic acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 190 DEG C, pressure is 46KPa, and external condenser temperature is 0 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 96%.
Embodiment 6
In the present embodiment, it is 1:1.3 mixing by tetramethylolmethane and n-capric acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 190 DEG C, pressure is 36KPa, and external condenser temperature is-5 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 95%.
Embodiment 7
In the present embodiment, it is 1:1.4 mixing by trimethylolpropane and oleic acid according to the mol ratio of hydroxyl and carboxyl, heats and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 220 DEG C, pressure is 8KPa, and external condenser temperature is-20 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 96%.
Embodiment 8
In the present embodiment, being 1:1.5 mixing by tetramethylolmethane and oleic acid, linoleic acid according to the mol ratio of hydroxyl and carboxyl, wherein oleic acid and linoleic mol ratio are 4:1, heat and stir so that it is dissolving each other.Set the temperature of falling film evaporator as, 230 DEG C, pressure is 5KPa, and external condenser temperature is-15 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 97%.
Embodiment 9
In the present embodiment, being 1:1.6 mixing by trimethylolpropane and Palmic acid, oleic acid, linoleic acid according to the mol ratio of hydroxyl and carboxyl, wherein Palmic acid, oleic acid, linoleic mol ratio are 1:16:3, heat and stir so that it is dissolving each other.Setting the temperature of falling film evaporator as 225 DEG C, pressure is 10KPa, and external condenser temperature is-10 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 94%.
Embodiment 10
In the present embodiment, by trimethylolpropane and positive enanthic acid and pelargonic acid be 1:1 mixing according to the mol ratio of hydroxyl and carboxyl, wherein the mol ratio of positive enanthic acid and pelargonic acid is 1:1, heats and stirs so that it is dissolving each other.Setting the temperature of falling film evaporator as 185 DEG C, pressure is 50KPa, and external condenser temperature is-10 DEG C.Reach after setup parameter until equipment, use dehvery pump by mixed liquor with certain flow velocity input falling film evaporator so that it is to react with the fluid film form flowed continuously.After reacting, product is exported by membrane evaporator bottom by gear pump.In the present embodiment, the esterification yield that esterification is final can reach 93%.
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (9)
1. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester, it is characterised in that comprise the steps:
1) polyhydric alcohol and fatty acid being mixed according to mol ratio 1:1～1.6 of hydroxyl and carboxyl, heating stirring make it dissolve each other, and obtain a reaction mixture；
2) setting the temperature of falling film evaporator as 180-250 DEG C, pressure is 5-60KPa, and external condenser temperature is-20-30 DEG C；
3) step 1 is made) this reaction mixture of gained flows in falling film evaporator, and the form of the fluid film to flow continuously carries out esterification, synthesizing polyatomic alcohol fatty acid ester.
2. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 1, it is characterised in that in step 1) in, described polyhydric alcohol is trimethylolpropane or tetramethylolmethane.
3. the method for employing falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 1 or claim 2, it is characterized in that, in step 1) in, described fatty acid be meet simultaneously saturated or containing double bond, straight chain or with side chain, carbon number be the mixed acid of the monoacid of three conditions of 6-18 or the preparation of two or more monoacid.
4. the method for employing falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 1 or claim 2, it is characterised in that in step 1) in, described polyhydric alcohol and fatty acid are that 1:1.1～1.3 mix by hydroxyl and the mol ratio of carboxyl.
5. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 3, it is characterised in that in step 1) in, described polyhydric alcohol and fatty acid are that 1:1.1～1.3 mix by hydroxyl and the mol ratio of carboxyl.
6. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 1, it is characterised in that in step 3) in, described fluid film thickness is 0.1-2mm.
7. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 1, it is characterized in that, in step 3) in, this reaction mixture is made to pass through distributor, and the inwall of falling film evaporator is flowed through under gravity from top to bottom with the form of fluid film, it is heated and esterification occurs.
8. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 7, it is characterized in that, in step 3) in, the water generated in esterification is pulled out falling film evaporator in a gaseous form under vacuum, is then collected by external condenser.
9. the method adopting falling film evaporator synthesizing polyatomic alcohol fatty acid ester according to claim 8, it is characterised in that in step 3) in, esterification crude product is exported by falling film evaporator through dehvery pump.
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| CN115894246A (en) * | 2021-08-20 | 2023-04-04 | 南京理工大学 | Method for continuously, safely and efficiently synthesizing 1,3, 5-triethoxy-2, 4,6 trinitrobenzene |
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| CN1285342A (en) * | 1999-08-19 | 2001-02-28 | Basf公司 | Process for preparation of 2-keto-gulonoester |
| DE102008013023A1 (en) * | 2008-03-07 | 2008-08-07 | Clariant International Ltd. | Preparation of octanoic acid glycerin esters, useful e.g. for producing a cosmetic, pharmaceutical or dermatological formulation, comprises reacting glycerin and octanoic acid without adding a catalyst |
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| CN1285342A (en) * | 1999-08-19 | 2001-02-28 | Basf公司 | Process for preparation of 2-keto-gulonoester |
| DE102008013023A1 (en) * | 2008-03-07 | 2008-08-07 | Clariant International Ltd. | Preparation of octanoic acid glycerin esters, useful e.g. for producing a cosmetic, pharmaceutical or dermatological formulation, comprises reacting glycerin and octanoic acid without adding a catalyst |
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| CN115894246A (en) * | 2021-08-20 | 2023-04-04 | 南京理工大学 | Method for continuously, safely and efficiently synthesizing 1,3, 5-triethoxy-2, 4,6 trinitrobenzene |
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