CN109134247A - A kind of preparation method and system of pentaerythritol ester - Google Patents
A kind of preparation method and system of pentaerythritol ester Download PDFInfo
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- CN109134247A CN109134247A CN201710503170.5A CN201710503170A CN109134247A CN 109134247 A CN109134247 A CN 109134247A CN 201710503170 A CN201710503170 A CN 201710503170A CN 109134247 A CN109134247 A CN 109134247A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The present invention provides the preparation method and system of a kind of pentaerythritol ester.The preparation method includes: to make pentaerythrite and fatty acid that esterification occur, the reactive distillation column for realizing esterification includes: tower reactor and rectifying section, the lower part of tower reactor is equipped with air inlet, the top of tower reactor is equipped with exhaust outlet, exhaust outlet is connected to the entrance of rectifying pars infrasegmentalis, and the outlet of rectifying section bottom is connected to the entrance at the top of tower reactor；Preparation method includes: to make pentaerythrite and fatty acid that esterification occur in tower reactor, inert gas is continually fed into tower reactor by air inlet simultaneously, and the admixture of gas made enters progress rectifying separation in rectifying section through exhaust outlet, the outlet of the isolated double distilled lease making rectifying section bottom of rectifying is back in tower reactor.The preparation method reaction condition is mild, can be realized the efficient utilization of raw material of fatty acid, and can be improved the yield of pentaerythritol ester, reduces the difficulty of subsequent products separation.
Description
Technical field
The present invention relates to a kind of preparation method of pentaerythritol ester and systems, belong to organic chemical industry's synthesis technical field.
Background technique
With the development of society and the progress of science and technology, people propose more stringent requirement to lubricant, wherein closing
Base oil at ester as high performance lubricant is widely used in aerospace field, is also applied to special type in recent years
IC engine lubricating oil field is to make up the defects of the certain performances of mineral oil；Although its price is relatively high, because it has preferably
Thermal stability, cryogenic property, biological degradability and hypotoxicity and gradually have been favored by people.
As the important component of lubricating oil in esters base oil, pentaerythritol ester is by pentaerythrite and C5~C9Unitary
Fatty acid, C5~C9Or mixtures thereof binary of fatty acids is generated by esterification.Due to the β-position carbon atom at alcohol end in molecule
There is no active hydrogen atom on position, so that pentaerythritol ester has splendid thermal stability and oxidation stability, it is domestic at present
Outer II type synthesis aeroengine oil uses oil based on such compound mostly.
Traditional polyol ester is that esterification directly occurs using fatty acid and polyalcohol, the then reaction to obtaining
Obtained from product is separated and is purified.The esterification of polyol ester is usually to carry out in conventional reactive distillation column,
The popular response destilling tower includes stripping section and rectifying section, and the conversion zone being arranged between stripping section and rectifying section；Usually
Make with more low-boiling material from reaction pars infrasegmentalis feed inlet enter, the material with higher from conversion zone top into
Material mouth enters, and during conversion zone counter current contacting esterification occurs for gas-liquid two-phase.But due to pentaerythrite and fatty acid
Esterification reaction rate is relatively slow, longer the time required to esterification, the reactive distillation column of traditional structure is not particularly suited for Ji Wusi
The preparation of alcohol ester.
Also, since esterification is a reversible reaction process, limited by reaction balance, reactant polyalcohol and fat
It is sour to convert completely, cause some unreacted fatty acid, polyalcohol with the water for reacting generation to be present in product polynary
In alcohol ester, the difficulty of subsequent products separating-purifying is increased.In order to improve the yield and product property of polyol ester, at present usually
The technological means of use is the process conditions by improving esterification, breaks the thermodynamical equilibrium limitation of esterification, promotes
Esterification is carried out to the positive reaction direction for generating polyol ester.For example increase acid alcohol molar ratio, or add in the reaction system
Enter azeotropic agent (also referred to as water entrainer), to remove the water of esterification generation, promotes the progress of positive reaction, and then improve esterification
Rate.But a large amount of unreacted fatty acid will increase the load of subsequent products separation；The presence of azeotropic agent, needs in subsequent products
The step of increasing solvent removal in separation process, not only increases operating cost and equipment investment, and be unfavorable for obtaining high-purity
The product of degree；In addition, attempting to control the absolute pressure of esterification system 5~15Pa's there are also some researchers at present
Within the scope of high vacuum, prevent the entrance of oxygen in air and influence the color and purity of esterification products, but due to reaction condition compared with
To be harsh, practical large-scale promotion and application are not utilized.
Therefore, it is severe that low yield existing for current pentaerythritol ester synthesis process, product separation difficulty and reaction condition are solved
The problems such as quarter, has important practical significance.
Summary of the invention
The present invention provides the preparation method and system of a kind of pentaerythritol ester, the preparation method can be realized pentaerythrite and
The efficient utilization of raw material of fatty acid improves the yield of pentaerythritol ester, reduces the difficulty of subsequent products separation.And the preparation side
Method reaction condition is mild, is easy to apply.
The present invention provides a kind of preparation method of pentaerythritol ester, comprising: makes pentaerythrite and fatty acid that esterification occur anti-
It answers, fatty acid C5~C9Unary fatty acid and C5~C9At least one of binary of fatty acids；
The reactive distillation column for realizing above-mentioned esterification includes: tower reactor and rectifying section, and the lower part of tower reactor is equipped with air inlet, tower
The top of kettle is equipped with exhaust outlet, and exhaust outlet is connected to the entrance of rectifying pars infrasegmentalis, at the top of the outlet and tower reactor of rectifying section bottom
Entrance connection；
Above-mentioned preparation method includes: to make pentaerythrite and fatty acid that esterification occur in tower reactor, while passing through air inlet
The admixture of gas that mouth is continually fed into inert gas into tower reactor, and makes enters through exhaust outlet carries out rectifying point in rectifying section
From the outlet of the isolated double distilled lease making rectifying section bottom of rectifying returns in tower reactor.
In above-mentioned esterification reaction process, the inert gas being continually fed into is had the effect that
(1) in the esterification reaction process of pentaerythrite and fatty acid, obtained intermediate product easily with the oxygen in air
The side reactions such as oxidation, carbonization occur, to reduce the yield of pentaerythritol ester, intuitively show as the esterification products color of preparation compared with
It is deep.The inert gas being continually fed into can be used as protection gas, and starvation avoids the generation of side reaction in esterification reaction process,
The yield for improving pentaerythritol ester, keeps the appearance luster of esterification products faint yellow.
(2) since esterification is reversible reaction, the inert gas that the water generated in esterification reaction process is constantly flowed
Take reaction system out of, and then it is mobile to the positive reaction direction for generating pentaerythritol ester to push reversible esterification to balance, and plays strong
Change the effect of esterification, so as to improve the yield of pentaerythritol ester.In this way, the inert gas of flowing can replace routine
Azeotropic agent, such as toluene there is no need to use azeotropic agent, and save the equipment investment and operating cost of subsequent solvent removal process.
While esterification carries out, inert gas not only can during being discharged at the top of reactive distillation column tower reactor
Take the water of esterification generation out of, nor can avoid ground can carry the fatty acid for having neither part nor lot in esterification on a small quantity, i.e. gas
Mixture includes the vapor and a small amount of fatty acid vapor of inert gas and its carrying.The admixture of gas in rectifying section into
Row rectifying separation, wherein most unreacted fatty acid are carried over into heavy distillat, and is collected at the bottom of rectifying section,
It is flowed back under gravity and continues to participate in esterification in tower reactor, to realize the effective use of raw material of fatty acid, improved
The yield of product；And water, extremely least a portion of fatty acid vapor will be used as light fraction, be carried by inert gas to the top of rectifying section
Portion.
The present invention is not specially limited specific rectifying separating technology, and the rectifying separation work of this field routine can be used
Specifically process conditions can be rationally arranged according to the boiling-point difference of fatty acid and water in skill.
Above-mentioned light fraction can be directly discharged in atmosphere after processing, can also be sharp to recycling after its further purified treatment
With, for example light fraction can be condensed, and separate the fatty acid in light fraction, water and inert gas.Of the invention preferred
Embodiment in, above-mentioned reactive distillation column can further include: the outlet at the top of condenser, with rectifying section,
And it is condensed for the light fraction isolated to the rectifying from rectifying section；Separator is connected to condenser, and is used for
Separate fatty acid, water and the inert gas in light fraction.
Specifically, light fraction enters in condenser at the top of rectifying section, after condensing, vapor and fatty acid therein steam
Vapour is converted into liquefied mixture, and inert gas is separated in the separator being connected to condenser.The liquefied mixture can be with
It is further separated in the separator, specifically in the middle and lower part of separator, is separated further, is obtained by sedimentation
The reflux that fatty acid can be used as rectifying section, which returns in rectifying section, to be additionally separated.The inert gas can pass through separation
The outlet of device is directly discharged in atmosphere, or can also be recycled after dehydration, for example be back in tower reactor, with drop
Low production cost.
In specific implementation process of the invention, since at the same temperature, the density of fatty acid is usually less than the close of water
Degree, and the solubility of fatty acid in water is smaller under normal temperature conditions, above-mentioned liquefied mixture will occur lower part in the separator
Layering, the fatty acid after layering are gathered in the middle part of separator, are adjusted by liquid level, can flow back into the fatty acid of partially aqueous
The top of rectifying section continues to separate and recover, and then realizes the efficient utilization of fatty acid, reduces fatty acid in esterification reaction process
Consumption.
The present invention is not specially limited used inert gas, for example can be relatively inexpensive nitrogen.Specifically,
The flow of inert gas can be rationally arranged according to the additional amount and reaction rate of pentaerythrite and fatty acid.Of the invention specific real
During applying, it is usually 20~50mL/min by every liter of reaction mixture control inert gas flow, can not only will be esterified in this way
The water that reaction generates is taken out of in time, and unreacted fatty acid is avoided largely to be taken out of.
It is appreciated that the pressure in reactive distillation column should at least be not less than in order to guarantee smoothly flowing out for admixture of gas
Standard atmospheric pressure (101.325kPa).In specific implementation process of the present invention, esterification carries out under the conditions of micro-positive pressure, usually
Be control tower reactor in pressure be higher than 20~70kPa of standard atmospheric pressure, i.e., the pressure in tower reactor be 121.325kPa~
171.325kPa, this moisture for being beneficial to esterification generation are taken out of reaction system in time.
The present invention prepares the fatty acid of pentaerythritol ester selection, can be one or more C5~C9Unary fatty acid, can also
To be one or more C5~C9Binary of fatty acids is also possible to C5~C9Unary fatty acid and C5~C9The mixing of binary of fatty acids
Object.
Heretofore described C5~C9Unary fatty acid refers to that the aliphatic hydrocarbon chain for containing carboxyl in one end, general formula are
CnH2n+1COOH, wherein n is 4~8, such as isooctyl acid, isononanoic acid；The C5~C9Binary of fatty acids is aliphatic hydrocarbon chain
The organic compound of the upper carboxyl containing there are two, carbon atom number is 5~9, such as glutaric acid, adipic acid.
It is appreciated that esterification can be effectively facilitated towards generation season due to using preparation method provided by the invention
The positive reaction direction of Doutrate carries out, thus without the acid alcohol molar ratio of large scale, pentaerythritol ester can be realized
High yield.In specific implementation process of the present invention, controls the sum of quantity of carboxyl in fatty acid and be not less than hydroxyl in pentaerythrite
The sum of quantity.For example hydroxyl quantity is substantially suitable in the quantity of carboxyl and pentaerythritol ester in controllable fatty acid, leads to
The ratio of number of hydroxyl is (1.0~1.05) in the quantity of carboxyl and pentaerythrite in normal fatty acid: 1.0.
For example when fatty acid selects isooctyl acid (2 ethyl hexanoic acid), the molar ratio for controlling isooctyl acid and pentaerythrite is (4.0
~4.2): 1.0.The a small amount of of fatty acid can excessively push reversible esterification to balance to the positive reaction direction for generating pentaerythritol ester
It is mobile, so the ratio of number of hydroxyl is preferably (1.010~1.025) in the quantity of carboxyl and pentaerythrite in fatty acid:
1.0, for example, isooctyl acid and pentaerythrite molar ratio preferably (4.05~4.10): 1.0, can further improve pentaerythritol ester
Yield.
Common acidic catalyst in esterification reaction process may be selected in catalyst used in the present invention.Have in the present invention
In body implementation process, generally select the organic sulfonic acid solid catalyst weak to reaction unit corrosivity, for example, toluenesulfonic acid, to first
Benzene sulfonic acid etc., it is possible to use solid super-strong acid relatively conventional at present.
Specifically, the dosage of catalyst is related to the activity of reaction raw materials (i.e. fatty acid and pentaerythrite) and catalyst,
The dosage of usually control catalyst is the 0.5~2% of pentaerythrite and fatty acid quality sum.
The present invention is not specially limited the actual temp of esterification, can be according to the property of specific reaction mixture
It reasonably adjusts, it is generally the case that the temperature for controlling esterification is 130~180 DEG C.
In the present invention, the terminal of esterification is determined by the acid value testing result of reaction mixture, when reaction mixture
When acid value is down to specified value, i.e., it is believed that esterification is completed, esterification then is terminated by modes such as coolings.General feelings
Under condition, after 3h esterification, the acid value of reaction mixture can reach specified value, and the proper extension reaction time is beneficial to
Promote the further conversion of fatty acid and pentaerythrite, improves hydroxyl conversion ratio, so in the actual production process, it usually can root
The factor controllings such as proportion according to fatty acid and pentaerythrite reaction time of esterification was at 3 hours or more, such as 3~24 hours.
After the completion of above-mentioned esterification, practical obtained esterification products are polyol ester crude product, and it is normal that this field can be used
The method of rule carries out refinement treatment to esterification products, for example the polyol ester crude product after the completion of esterification is filtered,
The solid catalyst filtered out is washed again, it is dry after recycle and use, filtrate is washed with excessive sodium hydrate aqueous solution, is obtained
Organic phase is washed with water to neutrality, and the oily liquids for obtaining pale yellow transparent is pentaerythritol ester product.
The present invention also provides a kind of for implementing the system of above-mentioned preparation method, comprising:
Reactive distillation column, reactive distillation column include: tower reactor and rectifying section, and the lower part of tower reactor is equipped with air inlet, the top of tower reactor
Portion is equipped with exhaust outlet, and exhaust outlet is connected to the entrance of rectifying pars infrasegmentalis, and the outlet of rectifying section bottom and the entrance at the top of tower reactor connect
It is logical.
Above-mentioned is the unconventional reactive distillation column for preparing pentaerythritol ester Aided design, and popular response destilling tower is omitted
Stripping section, and conversion zone is moved in tower reactor, fatty acid and pentaerythrite is enable to come into full contact in tower reactor and ester occurs
Change reaction；The setting of tower reactor lower part air inlet and top vent can make inert gas continue through and constantly take away in time
The water that esterification generates promotes esterification to carry out to the positive reaction direction for generating pentaerythritol ester；The design of rectifying section, energy
It is enough to realize that the effective of unreacted fatty acid recycles and make full use of while esterification carries out, further improve Ji Wusi
The yield of alcohol ester.
It is appreciated that the esterification carried out in above-mentioned tower reactor need to carry out under lasting stirring condition.The present invention for
The agitating mode of tower reactor is not specially limited, and can be stirred, can also be separately provided using the agitating device that tower reactor carries
Blender.
The present invention is not specially limited the heating method of tower reactor, can be the included heating device of tower reactor, can also be with
Heater is separately provided, for example can be the hotline heater that tower reactor exterior bottom is set, and controls the reaction in tower reactor
Mixture temperature maintains in the range of esterification temperature.
In specific implementation process of the present invention, which can also further be arranged the product reservoir being connected to tower reactor, with
The collection of products that esterification is obtained is into product reservoir.
Further, the feed inlet entered for fatty acid, pentaerythrite and catalyst is additionally provided on tower reactor top.Further
, the fatty acid storage tank being connected to the feed inlet, pentaerythrite storage tank and catalyst storage tank can also be set, are stored with respectively
Fatty acid, pentaerythrite and catalyst.Before esterification starts, fatty acid storage tank, pentaerythrite storage tank and catalyst are stored up
Reaction raw materials in tank are added in tower reactor.
It is appreciated that the fatty acid as reaction raw materials may be in a liquid state under normal temperature conditions, so can store up in fatty acid
Feed pump is further set between tank and tower reactor, to improve the powder feeding efficiency of raw material.
Further, reactive distillation column further include:
Condenser is connected to rectifying section top exit, and is condensed for the light fraction isolated to rectifying；
Separator is connected to condenser, and for separating fatty acid, water and inert gas in the light fraction.
The present invention is not specially limited the selection of separator, in specific implementation process of the present invention, can choose oil
Separator.
The present invention provides a kind of preparation methods of pentaerythritol ester, by carrying out season under the inert gas shielding of flowing
The esterification of penta 4 pure and mild fatty acid, only esterification does not provide good reaction environment, and can promote to be esterified
It reacts and is carried out to the positive reaction direction for generating pentaerythritol ester, thus improve the yield of pentaerythritol ester.Simultaneously as in ester
Change the fatty acid that synchronous recycling is not reacted completely while reaction carries out, and continue to participate in esterification, therefore rouge can be improved
The utilization rate of fat acid starting material further ensures the yield of pentaerythritol ester, and the high conversion rate of hydroxyl is in 92%.
Simultaneously as without introducing the organic solvents such as azeotropic agent in esterification reaction process, without using large scale
The high yield of pentaerythritol ester can be realized in molar ratio of alcohol to acid, not only contributes to the later period to the separation and recovery of product, but also can
Reduce cost of material and process costs.Above-mentioned preparation method, mild condition is applied widely, conducive to actual production with answer
With.
The present invention also provides a kind of systems for being more suitable for pentaerythritol ester preparation method, with popular response destilling tower phase
Than the reactive distillation column in the system is without stripping section, and conversion zone is moved in tower reactor, makes reaction raw materials fatty acid and season penta
Tetrol is directly entered in tower reactor and occurs wherein esterification, can guarantee going on smoothly for esterification, and the system
Structure is simple, industrial applications easy to accomplish.
Detailed description of the invention
Fig. 1 is the system structure signal for implementing pentaerythritol ester preparation method that a specific embodiment of the invention provides
Figure；
Fig. 2 is that the system structure for implementing pentaerythritol ester preparation method that another specific embodiment of the present invention provides is shown
It is intended to.
Description of symbols:
1- tower reactor；2- blender；3- heater；4- rectifying section；
5- condenser；6- separator；7- product reservoir；8- fat acid storage tank；
9- pentaerythrite storage tank；10- catalyst storage tank；11- feed pump.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In following embodiment, " HG/T2709-1995 polyester is more according to professional standard for the hydroxyl value of reaction front and back reaction mixture
The measurement of first alcohol middle hydroxyl value " it is measured,
Hydroxyl conversion ratio=(the first hydroxyl value of hydroxyl value/reaction after 1- reaction) × 100%.
Embodiment 1
The present embodiment provides a kind of preparation method of pentaerythritol ester and systems.
Fig. 1 is the system structure signal for implementing pentaerythritol ester preparation method that a specific embodiment of the invention provides
Figure.As shown in Figure 1, the system includes reactive distillation column, blender 2, heater 3, product reservoir 7, fatty acid storage tank 8, season penta
Tetrol storage tank 9, catalyst storage tank 10, feed pump 11.
Wherein, above-mentioned reactive distillation column specifically includes: tower reactor 1 and rectifying section 4, and the lower part of tower reactor 1 is equipped with air inlet, tower reactor
1 top is equipped with exhaust outlet, and exhaust outlet is connected to the entrance of 4 lower part of rectifying section, 1 top of 4 outlet at bottom of rectifying section and tower reactor
Entrance connection.
Heater 3 is specially hotline heater, is arranged in 1 exterior bottom of tower reactor.The setting of blender 2 is in 1 outside of tower reactor
Top.Product reservoir 7, fatty acid storage tank 8, pentaerythrite storage tank 9 and catalyst storage tank 10 are connected to tower reactor 1 respectively, and rouge
Feed pump 11 is equipped between fat acid storage tank 8 and tower reactor 1.
The specific preparation method of pentaerythritol ester provided in this embodiment includes: first will be different pungent in fatty acid storage tank 8
Acid is pumped into tower reactor 1 by feed pump 11, and the pentaerythrite in pentaerythrite storage tank 9 is added in tower reactor 1, wherein different
The molar ratio of octanoic acid and pentaerythrite is 4.1:1；Nitrogen is then passed to, enters nitrogen by the air inlet of 1 lower part of tower reactor
In tower reactor 1 and displace air present in tower reactor 1, it is ensured that entire esterification reaction process carries out under nitrogen protection；Then open
Blender 2 is opened, is uniformly mixed isooctyl acid and pentaerythrite in tower reactor 1, while heater 3 heats tower reactor 1
It is warming up to 160 DEG C and maintains temperature constant；Finally p-toluenesulfonic acid catalyst is added in tower reactor 1, and controls toluenesulfonic acid
Quality is about the 2.0% of isooctyl acid and pentaerythrite quality sum, starts esterification.
During esterification carries out, the reaction pressure in tower reactor 1 maintains 161.325kPa or so, mixed by every liter of reaction
Object (including fatty acid, pentaerythrite, catalyst, intermediate product, water and pentaerythritol ester) meter is closed, nitrogen flow control exists
40mL/min or so.Nitrogen constantly enters from the air inlet of 1 lower part of tower reactor, enters liquid by the gas distributor in tower reactor 1
In reaction mixture, the water and a small amount of isooctyl acid steam " stripping " that esterification is generated arrive 1 top of tower reactor, including nitrogen
The mixed gas of gas and water steam and isooctyl acid steam enters progress rectifying separation in rectifying section 4 through the exhaust outlet at 1 top of tower reactor.
Rectifying separation in the present embodiment makes isooctyl acid and water in mixed gas exist using conventional rectifying separating technology
It is separated in rectifying section 4.Under the effect of gravity, isooctyl acid most in mixed gas is back to tower reactor 1 from 4 bottom of rectifying section
In continue to participate in esterification, and water, least a portion of isooctyl acid will be carried by nitrogen to being discharged at the top of rectifying section 4.
After reacting 4h, heater 3 is closed, when the temperature of 1 reaction mixture of tower reactor is down to 90 DEG C, closes blender 2
And stop being passed through nitrogen, the reaction product in tower reactor 1 is delivered to product reservoir 7, and to the reaction product in product reservoir 7 into
Row test, hydroxyl conversion ratio are 92.00%.
Embodiment 2
The present embodiment provides a kind of preparation method of pentaerythritol ester and systems.Wherein, in the system structure and embodiment 1
System it is completely the same, for details, reference can be made to Fig. 1.
The specific preparation method of pentaerythritol ester provided in this embodiment includes: first will be different pungent in fatty acid storage tank 8
Acid and the mixture of isononanoic acid are pumped into tower reactor 1 by feed pump 11, and the pentaerythrite in pentaerythrite storage tank 9 is added
Into tower reactor 1, wherein the molar ratio of pentaerythrite, isooctyl acid and isononanoic acid is 1.0:2.02:2.03；Nitrogen is then passed to, is made
Nitrogen is entered in tower reactor 1 by the air inlet of 1 lower part of tower reactor and displaces air present in tower reactor 1, it is ensured that entire esterification
Reaction process carries out under nitrogen protection；Later on blender 2 keeps isooctyl acid, isononanoic acid and pentaerythrite in tower reactor 1 mixed
It closes uniformly, while heater 3 carries out being heated to 170 DEG C and maintains temperature constant to tower reactor 1；Finally by toluenesulfonic acid
Catalyst is added in tower reactor 1, and the quality for controlling toluenesulfonic acid is about pentaerythrite, isooctyl acid and pentaerythrite quality sum
2.0%, start esterification.
During esterification carries out, the reaction pressure in tower reactor 1 maintains 151.325kPa or so, mixed by every liter of reaction
Object meter is closed, nitrogen flow is controlled in 40mL/min or so.Nitrogen constantly enters from the air inlet of 1 lower part of tower reactor, by gas point
Cloth device enters in liquid reaction mixture, the water and a small amount of isooctyl acid steam and isononanoic acid steam that esterification is generated
" stripping " to 1 top of tower reactor, the admixture of gas including nitrogen, vapor, isooctyl acid steam and isononanoic acid steam is pushed up through tower reactor 1
The exhaust outlet in portion enters progress rectifying separation in rectifying column 4.
Rectifying separation in the present embodiment makes isooctyl acid in admixture of gas and different using conventional rectifying separating technology
N-nonanoic acid separates in rectifying section 4 with water, and under the effect of gravity, most isooctyl acids and isononanoic acid are from essence in admixture of gas
It evaporates 4 bottom of section and is back in tower reactor 1 and continue to participate in esterification, and water, least a portion of isooctyl acid, least a portion of isononanoic acid will be by
Nitrogen is carried to being discharged at the top of rectifying section 4.
After reacting 15h, heater 3 is closed, when the temperature of 1 reaction mixture of tower reactor is down to 90 DEG C, closes blender 2
And stop being passed through nitrogen.Reaction product is transported in product reservoir 7, and the reaction product in product reservoir 7 is tested,
Hydroxyl conversion ratio is 94.00%.
Embodiment 3
The present embodiment provides a kind of preparation method of pentaerythritol ester and systems.Wherein, in the system structure and embodiment 1
System it is completely the same, for details, reference can be made to Fig. 1.
The specific preparation method of pentaerythritol ester provided in this embodiment includes: first by penta 2 in fatty acid storage tank 8
The mixture of acid and adipic acid is added in tower reactor 1, and the pentaerythrite in pentaerythrite storage tank 9 is added in tower reactor 1,
The molar ratio of middle pentaerythrite, glutaric acid and adipic acid is 1.0:1.02:1.01；Nitrogen is then passed to, nitrogen is made to pass through tower reactor 1
The air inlet of lower part enters in tower reactor 1 and displaces air present in tower reactor 1, it is ensured that entire esterification reaction process is in nitrogen
Protection is lower to be carried out；Later on blender 2 is uniformly mixed glutaric acid, adipic acid and pentaerythrite in tower reactor 1, opens simultaneously
Heater 3 carries out being heated to 160 DEG C and maintains temperature constant to tower reactor 1；P-toluenesulfonic acid catalyst is finally added to tower
In kettle 1, and the quality for controlling toluenesulfonic acid is about the 2.0% of pentaerythrite, glutaric acid and adipic acid quality sum, starts to be esterified
Reaction.
During esterification carries out, the reaction pressure in tower reactor 1 maintains 141.325kPa or so, mixed by every liter of reaction
Object meter is closed, nitrogen flow is controlled in 40mL/min or so.Nitrogen constantly enters from the air inlet of 1 lower part of tower reactor, by gas point
Cloth device enters in liquid reaction mixture, the water and a small amount of glutaric acid steam and adipic acid steam that esterification is generated
" stripping " to 1 top of tower reactor, the exhaust outlet through 1 top of tower reactor enters progress rectifying separation in rectifying column 4.
Rectifying separation in the present embodiment makes glutaric acid and adipic acid and water in rectifying using conventional rectifying separating technology
It is separated in section 4, most glutaric acids and adipic acid are back in tower reactor 1 from 4 bottom of rectifying section continue under the effect of gravity
Participate in esterification, and water, least a portion of glutaric acid and least a portion of adipic acid will be carried by nitrogen to arranging at the top of rectifying section 4
Out.
After reacting 10h, heater 3 is closed, when the temperature of 1 reaction mixture of tower reactor is down to 90 DEG C, closes blender 2
And stop being passed through nitrogen.Reaction product in tower reactor 1 is transported in product reservoir 7, and to the reaction product in product reservoir 7
It is tested, hydroxyl conversion ratio is 93.50%.
Embodiment 4
The present embodiment provides a kind of preparation method of pentaerythritol ester and systems.
Fig. 2 is the system structure signal for implementing pentaerythritol ester preparation method that a specific embodiment of the invention provides
Figure.As shown in Fig. 2, the system is to increase nitrogen dynamical system (not shown), condenser 5 on the basis of embodiment 1 and divide
From device 6.
Wherein nitrogen dynamical system is connected to the air inlet of 1 lower part of tower reactor；Condenser 5 is connected to 4 top exit of rectifying section；
Separator 6 is specially gas-liquid separator, and entrance is connected to condenser 5, and outlet is connected to the entrance on 4 top of rectifying section.
The specific preparation method of pentaerythritol ester provided in this embodiment includes: first will be different pungent in fatty acid storage tank 8
Acid is pumped into tower reactor 1 by feed pump 11, and the pentaerythrite in pentaerythrite storage tank 9 is added in tower reactor 1, wherein different
The molar ratio of octanoic acid and pentaerythrite is 4.05:1.0；Be then turned on nitrogen dynamical system, make nitrogen by tower reactor 1 lower part into
Port enters in tower reactor 1 and displaces air present in tower reactor 1, it is ensured that entire esterification reaction process under nitrogen protection into
Row；Later on blender 2 is uniformly mixed isooctyl acid and pentaerythrite in tower reactor 1, while heater 3 is to tower reactor 1
It carries out being heated to 160 DEG C and maintains temperature constant；Finally the Catalyzed by p-Toluenesulfonic Acid agent in catalyst storage tank 10 is added
Into tower reactor 1, and the quality for controlling p-methyl benzenesulfonic acid is about the 2.0% of pentaerythrite and isooctyl acid quality sum, starts to be esterified
Reaction.
During esterification carries out, the reaction pressure in tower reactor 1 maintains 161.325kPa or so, mixed by every liter of reaction
Object meter is closed, nitrogen flow is controlled in 40mL/min or so.Nitrogen constantly enters from the air inlet of 1 lower part of tower reactor, by gas point
Cloth device enters in liquid reaction mixture, and the water and a small amount of isooctyl acid steam " stripping " that esterification is generated arrive tower reactor 1
Top, the exhaust outlet through 1 top of tower reactor enter progress rectifying separation in rectifying section 4.
Rectifying separation in the present embodiment divides isooctyl acid and water in rectifying section 4 using conventional rectifying separating technology
From, most isooctyl acids is back in tower reactor 1 from 4 bottom of rectifying section continues to participate in esterification under the effect of gravity, and
Water, least a portion of isooctyl acid will be carried by nitrogen to 4 top of rectifying section, and the temperature at 4 top of rectifying section is controlled at 110 DEG C or so,
Then it will be entered in condenser 5 by the water and least a portion of isooctyl acid of nitrogen and its carrying, and control 5 outlet temperature of condenser 50
DEG C or so, realize gas-liquid separation.Nitrogen be directly vented or it is purified after return nitrogen dynamical system be recycled, and by water with it is different
The liquefied mixture of octanoic acid composition, which will enter in separator 6, to be separated.Since the density of isooctyl acid under normal temperature condition is lower than water
Density, and the solubility of isooctyl acid in water is very small, so the liquefied mixture will be layered, is made by liquid level adjusting
The isooctyl acid on top, which flows back into rectifying section 4, carries out further rectifying separation.
After reacting 13h, heater 3 is closed, continue to be passed through nitrogen and is kept stirring device normal work, to be reacted in tower reactor 1
When the temperature of mixture is down to 80 DEG C or less, closes blender 2 and close nitrogen dynamical system.Reaction product to product is transported to store up
Tank 7, and the reaction product in product reservoir 7 is tested, hydroxyl conversion ratio is 95.6%.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (9)
1. a kind of preparation method of pentaerythritol ester characterized by comprising make pentaerythrite and fatty acid that esterification occur anti-
It answers, wherein the fatty acid is C5~C9Unary fatty acid and C5~C9At least one of binary of fatty acids；
The reactive distillation column for realizing the esterification includes: tower reactor and rectifying section, and the lower part of the tower reactor is equipped with air inlet, institute
The top for stating tower reactor is equipped with exhaust outlet, and the exhaust outlet is connected to the entrance of the rectifying pars infrasegmentalis, the rectifying section bottom
Outlet is connected to the entrance at the top of the tower reactor；
The preparation method includes: to make pentaerythrite and fatty acid that esterification occur in the tower reactor, while passing through described
Air inlet is continually fed into inert gas into the tower reactor, and the admixture of gas made enters the essence through the exhaust outlet
Progress rectifying separation in section is evaporated, the outlet of rectifying section bottom described in the isolated double distilled lease making of rectifying returns to the tower reactor
In.
2. preparation method according to claim 1, which is characterized in that the preparation method further includes isolated to rectifying
Light fraction condensed, and separate fatty acid, water and inert gas in the light fraction.
3. preparation method according to claim 2, which is characterized in that the reactive distillation column further include:
Condenser is connected to rectifying section top exit, and for condensing to the light fraction；
Separator is connected to condenser, and for separating fatty acid, water and inert gas in the light fraction.
4. preparation method according to claim 1, which is characterized in that the pressure of the esterification is higher than standard atmospheric pressure
20~70kPa.
5. preparation method according to claim 1, which is characterized in that the temperature of the esterification is 130~180 DEG C,
Reaction time of esterification be 3~for 24 hours.
6. preparation method according to claim 1, which is characterized in that the sum of the quantity of carboxyl is not less than in the fatty acid
The sum of the quantity of hydroxyl in the pentaerythrite.
7. preparation method according to claim 1 or 6, which is characterized in that catalyst used in the esterification is
Organic sulfonic acid solid catalyst, the additional amount of the catalyst are the 0.5~2% of pentaerythrite and fatty acid quality sum.
8. a kind of for implementing the system of any one of the claims 1-7 preparation method characterized by comprising
Reactive distillation column, the reactive distillation column include: tower reactor and rectifying section, and the lower part of the tower reactor is equipped with air inlet, described
The top of tower reactor is equipped with exhaust outlet, and the exhaust outlet is connected to the entrance of the rectifying pars infrasegmentalis, and the rectifying section bottom goes out
Mouth is connected to the entrance at the top of the tower reactor.
9. system according to claim 8, which is characterized in that the reactive distillation column further include:
Condenser is connected to rectifying section top exit, and is condensed for the light fraction isolated to rectifying；
Separator is connected to condenser, and for separating fatty acid, water and inert gas in the light fraction.
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| CN112552976A (en) * | 2020-12-30 | 2021-03-26 | 南京威尔药业集团股份有限公司 | Complex ester type refrigerator oil and synthetic method thereof |
| CN114426484A (en) * | 2022-01-21 | 2022-05-03 | 中国石油化工股份有限公司 | Synthetic method of pentaerythritol ester |
| CN114621803A (en) * | 2020-12-10 | 2022-06-14 | 中国石油天然气股份有限公司 | Self-emulsifying ester and preparation method thereof |
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