CN109851496A - It is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester - Google Patents
It is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester Download PDFInfo
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Abstract
It is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester, be related to a kind of chemical industry catalytic rectification process, the technique is reacted under certain condition using methyl propionate and various alcohol as raw material, passes through ester exchange reaction synthesizing propionate；Reaction raw materials alcohol is the dihydric alcohols such as the monohydric alcohols such as ethyl alcohol, propyl alcohol, butanol or ethylene glycol, 1,3-PD；Methyl propionate and the specific reaction equation of monohydric alcohol are as follows:Methyl propionate and the specific reaction equation of dihydric alcohol are as follows:；The present invention is catalyst using basic matterials such as homogeneous solvable highly basic, ionic liquid or heterogeneous solid alkali, realizes continuous production high added value, the technique of high-purity propionic ester.
Description
Technical field
The present invention relates to a kind of chemical industry catalytic rectification process, more particularly to it is a kind of by ester alcohol exchange system for propionic ester
Heterogeneous catalysis rectification process.
Background technique
Ethyl propionate (EP) also known as first oil acetoacetic ester, butyl phthaloyl butyl glycolate, n Propanoic acid ethyl ester, molecular weight
102.13, sterling is colourless transparent oil liquid, there is pineapple fragrance, miscible in most organic solvents such as ethyl alcohol, ether, is slightly soluble in
Water.As important Organic Chemicals, be widely used in field of fine chemical such as: it is fragrant that it is mainly used for edible essence, cigarette
In essence, wine composition；As organic intermediate compound body, for producing antimalarial ethamine miaow pyridine etc.；Also be used as it is natural and
The solvent of synthetic resin.
Propyl propionate molecular formula: C6H12O2, molecular weight: 116.16, the colourless liquid with fruit flavor is mainly used as fragrance
With a kind of fine solvent of coating and printing ink industry.
Meanwhile ethyl propionate and propyl propionate are imitated in terms of optimizing lithium battery cryogenic property as electrolyte solution additive
Fruit is prominent, and the viscosity and eutectic point of electrolyte system can be reduced by adding a small amount of ethyl propionate and propyl propionate, played and be conducive to
The migration of lithium ion slows down the polarized effect of low temperature.
There are mainly three types of the synthetic methods of propionic ester: esterification process and carbonyl process, and detailed process is as follows (with third for three kinds of methods
For acetoacetic ester).
(1) esterification process
The method is under the concentrated sulfuric acid or other catalyst, to react the ethyl propionate and first of generation using propionic acid and ethyl alcohol as raw material
Alcohol.The reaction equation of this method is as follows:
Due to generating a large amount of water in reaction process, and the water generated is unfavorable for the positive of esterification and carries out, therefore needs
The water that reaction is generated in time removes system.A certain amount of water entrainer is usually added when industrial production in the reaction system,
To remove a large amount of water produced in reaction process.
Traditional ethyl propionate synthetic method is using propionic acid and ethyl alcohol as raw material, and in the case where the concentrated sulfuric acid is catalyst, reaction is given birth to
At ethyl propionate and methanol.The concentrated sulfuric acid is used to will cause equipment heavy corrosion as catalyst, and this method by-product is more, product
Shade deviation, post-processing trouble, pollutes environment.
Document report solid-carrying heteropolyacid salt catalysis propionic acid and ethyl alcohol lactate synthesis ethyl propionate, with TiSiW12O40/TiO2
For catalyst, hexamethylene is water entrainer, 78-85 DEG C of reaction temperature.Compare different catalyst amounts, reaction time and alkyd
Influence of the molar ratio to ethyl propionate yield, the results showed that optimal reaction condition are as follows: catalyst amount is reaction-ure mixture
2.0 %, acid-alcohol ratio 1.4:1, reaction time are 50.3 % of yield under 1 h condition.This method is simple, and reaction condition is mild, but receives
Rate is lower.With the propionic acid synthesized ethyl ester of heteropoly tungstic acid/bentonite catalyst, using continuous flow method, gas-solid phase reaction is catalyzed and synthesized
Ethyl propionate, 170 DEG C of reaction temperature, 6 mL/h of flow velocity, 3 % of phosphotungstic acid loading concentrations, catalytic effect is good, but reacts temperature
Degree is high, the improper industrialization of catalyst higher cost.Using toluenesulfonic acid as the propionic acid synthesized ethyl ester of catalyst, 85 DEG C of reaction temperature
~92 DEG C, it compared the influence of different catalyst amounts, reaction time, material proportion and water entrainer, the results showed that best anti-
Answer condition: material proportion 1:1.5,2.0 h of reaction time, 1.0 g of catalyst amount, without using esterification yield under the conditions of water entrainer
91.3 %.This method esterification yield is high but to reach equilibration time long.
(2) carbonylation method
The method is mainly synthesized by ethyl alcohol and reaction of carbon monoxide, and the reactive mode is as follows:
It reacts, has using metal complex (such as H in ethanol carbonylation2PO4, the carbonyl complexes such as Fe, Co, Ni) be catalyst, but
It is that yield is very low, and needs to carry out under high pressure；Using high pressure liquid phase tank reactor；Have and uses metal load type (such as Ni-
CuCl/ clay, NiI2And NiCl2It is supported on Al2O3-TiO2On) catalyst, it reacts under high temperature and pressure, ethyl propionate yield is still
It is very low, Rh is supported on X-type, Y type, ZSM-5 type and M type molecular sieve with ion-exchange, makees catalyst, with CH3I is to help to urge
Agent, toluene are solvent, at 200 DEG C, 2.5 MPa, carry out liquid-solid phase reaction, and the conversion ratio of ethyl alcohol is up to 94 %, propionic acid second
69 % that ester selectively reaches, but always there is fractional load metal to be dissolved in liquid phase in liquid-solid phase reaction, catalyst noble metal
Loss is still a problem；High pressure Liquid-phase reactor can be used, vapor solid fixed bed reactors can also be used, it is important to catalyst
Research.
Document report is using ethyl alcohol as feedstock carbonyl is propionic acid synthesized and ethyl propionate, by the bimetallic of activated carbon supported Ni, Cu
The catalyticing research of the catalyst progress propionic acid synthesized ethyl ester of ethanol phase carbonylation.Compare differential responses temperature, raw materials components mole ratio, no
Influence with hydrogen flowing quantity and different air speeds to the conversion ratio of ethyl alcohol and the yield of ethyl propionate；The result shows that reaction is best
Condition are as follows: 250 DEG C of reaction temperature, 0.1 MPa of pressure, liquid air speed is 1 h-1.72 % of ethyl propionate yield, ethanol conversion
95.3 %, 85.51 % of ethyl propionate selectivity.But the reaction is high in reaction temperature and has side reaction.
The shortcomings that esterification process is that by-product is more, and product color is poor, and post-processing trouble pollutes environment.The shortcomings that carbonylation method
It is reaction temperature height and has side reaction.And lithium electricity grade propionic ester requires purity is high, cannot have other trace impurities, both sides
Method is not able to satisfy the requirement of lithium electricity grade propionic ester.Therefore, the new high-purity propionic ester of reaction route large scale preparation is opened up
It is of great significance.As far as we know, there is no prepare propionic ester using the method for transesterification in existing literature and patent
Report.
Summary of the invention
The purpose of the present invention is to provide a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester, originally
Invention is with methyl propionate and various alcohol (including binary such as the monohydric alcohols such as ethyl alcohol, propyl alcohol, butanol or ethylene glycol, 1,3-PD
Alcohol etc.) it is ester exchange reaction raw material, it is catalysis using basic matterials such as homogeneous solvable highly basic, ionic liquid or heterogeneous solid alkali
Continuous production high added value, the technique of high-purity propionic ester are realized in agent.
The purpose of the present invention is what is be achieved through the following technical solutions:
The advantages and effects of the present invention are:
The invention has the advantages that reaction condition is mildly without side reaction, raw material methyl propionate and Methanol product azeotropic, and azeotropic temperature
Minimum, Methanol product carries out reaction system by methyl propionate, and driving a reaction is carried out to positive direction, and controlling excessive methyl propionate can
So that reaction carries out very thorough, reach in tower reactor substantially without raw alcohol residue.Methyl propionate and other propionic esters simultaneously
Boiling point difference is huge, and azeotropic is not present, easily separated, is easy to get high-purity target product.Entire reaction process is succinct, efficiently,
Pollution-free, no coupling product generates, and method flow is simple, is conducive to extensive, inexpensive production propionic ester.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention is described in detail for illustrated embodiment with reference to the accompanying drawing.
The present invention is by methyl propionate and various alcohol (including the monohydric alcohols such as ethyl alcohol, propyl alcohol, butanol or ethylene glycol, 1,3- third
Dihydric alcohols such as glycol etc.) it is reaction raw materials, route synthesizing propionate is exchanged by ester alcohol.Using methyl propionate and ethyl alcohol as reaction
For raw material, the catalytic rectification process process of description is as follows:
By taking methyl propionate and ethyl alcohol ester alcohol exchange process as an example, raw material methyl propionate and ethyl alcohol are mixed simultaneously with molar ratio 1.5-5:1
After the preheated tank V-1 preheating of metering pump P-1, enter from the first reactive distillation column middle and upper part T-1, raw material methyl propionate and ethyl alcohol
Catalyst member of the mixture in the middle part of the first reactive distillation column occurs ester alcohol exchange reaction and generates ethyl propionate and methanol, uses
Heterogeneous insoluble solid base is catalyst (with 10% K2O-15% Rb2For O/Cs-Y), it is seated in T-1 catalytic rectifying tower
Portion.Due to methyl propionate and methanol azeotropic, 61-62 DEG C of azeotropic temperature, overhead reflux ratio is 2:1, controls 61 DEG C of temperature, T-1
The group of rectifying tower top extraction is divided into methyl propionate and methanol azeotropic component, and wherein methyl propionate content is 55wt%, and methanol content is
45wt%。
Due to Methanol product by methyl propionate from first rectifying column T-1 top carry out reaction system, react to positive direction into
Row, while tower bottom continuous supplementation methyl propionate.Closer to first rectifying column bottom, methyl propionate concentration is higher, and concentration of alcohol is got over
It is low.First rectifying column tower reactor group becomes the first of about 59.5 % methyl propionates, 40 % ethyl propionates and 0.4 % ethyl alcohol and 0.1 %
Alcohol, bottom temperature are 80 DEG C.
The methyl propionate and methanol azeotrope of first rectifying column tower top are after condenser E-1 condensation in extraction equipment F-1
It is additional that certain volume water single or repeatedly extraction is added.Wherein more methanol are dissolved in water layer, and remaining methyl propionate is organic
Layer, ratio of the methyl propionate in organic layer and water layer are 45wt%:55wt%.After word extracts, organic layer component is
93wt% methyl propionate, 2.5wt% methanol and 5wt% water.
Organic layer is passed through T-2 rectifying column, and tower top temperature is 61-62 DEG C, and column bottom temperature is 80 DEG C, reflux ratio 2:1, tower
The methyl propionate and methanol azeotropic component for pushing up extraction enter extraction chemical industry operation unit.When overhead extraction temperature reaches 78 DEG C,
The methyl propionate of extraction is recycled as reaction raw materials.The remaining most water of tower bottom and small part methyl propionate conduct
Extractant is recycled to extraction equipment.
Methyl propionate and methanol quality are than being about 36wt%:64wt% in extraction equipment water layer, into T-3 rectifying column, tower top
Temperature is 61-62 DEG C, and column bottom temperature is 68 DEG C, reflux ratio 2:1, the methyl propionate of overhead extraction and methanol azeotropic component into
Enter to extract chemical industry operation unit.When overhead extraction temperature reaches 62-64 DEG C, the methanol of extraction is as product.Tower bottom is remaining
Most water and small part methanol are recycled to extraction equipment as extractant.
The heavy constituent of first rectifying column kettle enters T-4 rectifying column after removing small part methanol and ethyl alcohol by flash distillation plant,
Overhead extraction temperature is 76-78 DEG C, reflux ratio 2:1, and bottom temperature is 85 DEG C.The above are propionic acid first for overhead extraction object content 98%
Ester is recycled to reaction raw materials.Tower reactor component is mainly ethyl propionate, and into T-5 rectifying column, the top of the distillation column T-5 produces temperature
It is 98-99 DEG C, reflux ratio 2:1 produces high purity product ethyl propionate.
For the present invention by the method for methyl propionate and ethyl alcohol transesterification preparation production ethyl propionate, Fig. 1 is reaction raw materials propionic acid
Methyl esters and ethyl alcohol enter the first reactive distillation column of T-1, and methyl propionate and ethanol synthesis are abundant.The synthesis technology reactive distillation carries out
When, the methyl propionate to higher degree for adding water to extract, methyl propionate returns in reaction tower that the reaction was continued, T-4 rectifying column rectifying
Light component methyl propionate afterwards, which returns in reaction tower, to be continued to use, and the method greatly improves the utilization rate of raw material, reduces cost.
The present invention has following additional technology by the production technology that methyl propionate and ethyl alcohol transesterification prepare ethyl propionate
Feature:
Any one or more the mixing of the heterogeneous insoluble solid base of catalyst used in the technique.
The reaction raw materials alcohol and methyl propionate molar ratio 0.5:1-20:1 play raw material liq charging with metering pump P-1, in advance
Hot tank V-1 temperature is 40 DEG C -60 DEG C.
The present invention is prepared the device of ethyl propionate by methyl propionate and ethyl alcohol transesterification, comprising: the first reactive distillation of T-1
Tower, the first reactive distillation column of T-1 centre have raw material methyl propionate and ethyl alcohol import, first reactive distillation column of T-1
Tower top there is the first discharge port, the tower bottom of first reactive distillation column of T-1 has one and T-4 rectifying tower top phase
The second discharge port even, and the tower bottom of the first reactive distillation column of the T-1 has first charging aperture；T-2 rectifying column, the T-2
Rectifying column tower body has the second charging aperture being connected with first discharge port, and there is third to go out for described the top of the distillation column T-2
Material mouth；T-3 rectifying column, the T-3 rectifying tower body have a third feed inlet being connected with first discharge port, institute
The top of tower for stating T-3 rectifying column, which has, feeds the 4th discharge port that material mouth is connected, T-4 rectifying column, the T-4 essence with first
Evaporating tower tower body has the 4th feed inlet that be connected with the second discharge port, and the tower top of the T-4 rectifying column has and first charging aperture
The tower bottom of the 5th connected discharge port, the T-4 rectifying column has the 6th discharge port, T-5 rectifying column, the T-5 rectifying column
Tower body there is the 5th feed inlet that is connected with the 6th discharge port, the tower top of the T-5 rectifying column with the 7th discharge port,
The 8th discharge port of tower bottom of the T-5 rectifying column.
An example according to the present invention, in the first reactive distillation column T-1, raw material ethyl propionate and ethyl alcohol are in catalyst
Under the action of react, obtain the first mixture；The heavy constituent ethyl propionate and ethyl alcohol of first reactive distillation tower bottom are through condensing
Device E-3 condenser pump is pumped into rectifying column T-4, and the recombination of T-4 tower bottom is divided into ethyl propionate, and the third ethyl propionate enters T-5 rectifying column, T-5
The light component ethyl propionate of tower top enters collecting tank G-2.The light component methanol and methyl propionate of first reactive distillation column enter F-1
Extraction, the upper layer of F-1 is methyl propionate and a small amount of methanol enters T-2 rectifying column, and 61-62 DEG C of tower top temperature when is methyl propionate
And methanol, it is recycled into F-1 extraction and T-2 tower top is that methyl propionate is recycled into T-1 the reaction was continued at 78 DEG C of tower top temperature, T-2 tower
Bottom is water, methanol and a small amount of methyl propionate, is recycled into F-1 and continues to extract, and F-1 lower layer methyl propionate, first alcohol and water enter T-3 essence
It evaporating tower, controls rectification temperature, T-3 tower top is that methyl propionate and methanol azeotrope enter F-1 and continue to extract at 61-62 DEG C of tower top,
T-3 tower top is methanol at 62-64 DEG C of tower top temperature, enters collecting tank G-1 after condenser E-4 condensation.
The tower pressure interior force of first reactive distillation column of T-1 is 0.01-5 MPa, and tower top temperature is 61 DEG C, column bottom temperature
It is 78-99 DEG C；The tower pressure interior force of the T-2 rectifying column is 0.1-0.5 MPa, and 61-62 DEG C of tower top temperature after distillate without changing
It is 78 DEG C, column bottom temperature is 80 DEG C；The tower pressure interior force of the rectifying column T-3 is 0.1-0.5 MPa, tower top temperature 61-62
DEG C column bottom temperature is 68 DEG C；The tower pressure interior force of first reactive distillation column of T-4 is 0.01-5 MPa, tower top temperature 76-78
DEG C, 85 DEG C of column bottom temperature；The tower pressure interior force of first reactive distillation column of T-5 is 0.01-5 MPa, and tower top temperature is 99 DEG C,
120 DEG C of column bottom temperature；
The partition of heretofore described reactor and rectifying column is arranged to make the cross-sectional area of the fore-running section and the side line section
The ratio between cross-sectional area be 1:1-3:1.
The number of plates of fore-running section is 1-30 block, and the side line section number of plates is 1-30 block, and the number of plates of public rectifying section is 1-30
Block, the number of plates of public stripping section are 1-30 block.
The first reactive distillation column of T-1, T-2 atmospheric distillation tower, T-3 atmospheric distillation tower are plate column, packed tower in the present invention
Or board-like-filler mixing column
Embodiment 1
Using methyl propionate and excessive ethyl alcohol as raw material, reaction production ethyl propionate and methanol the mass ratio of the material are 1:1, are steamed
Ethyl alcohol out recycles.
Catalyst is alkaline composite material CaO, and the ratio between fore-running section and the cross-sectional area of side line section are 1:1.
T-1, T-2, T-3, T-4 and T-5 tower operating condition are as follows:
First reactive distillation column T-1: 4000 mm of tower diameter；30000 mm of tower height；It is public rectifying section, fore-running section, side line section, public
The number of plates of stripping section is respectively 10,20,30,15；0.5 MPa of tower pressure interior force；61 DEG C of tower top temperature；The tower of public stripping section
90 DEG C of bottom temperature；80 DEG C of the column bottom temperature of side line section.
Atmospheric distillation tower T-2: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 61-62 DEG C and 78 DEG C of tower top temperature, the tower bottom of public stripping section
80 DEG C of temperature.
Atmospheric distillation tower T-3: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 61-62 DEG C and 62-64 DEG C of tower top temperature, public stripping section
68 DEG C of column bottom temperature.
Atmospheric distillation tower T-4: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；Tower pressure interior force 0.1 MPa, 76-78 DEG C of tower top temperature, the column bottom temperature 85 of public stripping section
℃。
Atmospheric distillation tower T-5: 1000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 99 DEG C of tower top temperature, the column bottom temperature 120 of public stripping section
℃。
In the first reactive distillation column T-1, raw material ethyl propionate and ethyl alcohol react under the effect of the catalyst, obtain
First mixture；The heavy constituent ethyl propionate and ethyl alcohol of first reactive distillation tower bottom are pumped into rectifying column through condenser E-3 condenser pump
The recombination of T-4, T-4 tower bottom is divided into ethyl propionate, and ethyl propionate enters T-5 rectifying column, and the light component ethyl propionate of T-5 tower top enters
Collecting tank G-2.The light component methanol and methyl propionate of first reactive distillation column enter F-1 extraction, and the upper layer of F-1 is methyl propionate
Enter T-2 rectifying column with a small amount of methanol, 61-62 DEG C of tower top temperature when is methyl propionate and methanol, is recycled into F-1 extraction and tower
T-2 tower top is that methyl propionate is recycled into T-1 the reaction was continued when 78 DEG C of temperature of top, and T-2 tower bottom is water, methanol and a small amount of propionic acid first
Ester is recycled into F-1 and continues to extract, and F-1 lower layer methyl propionate, first alcohol and water enter T-3 rectifying column, controls rectification temperature, tower top
T-3 tower top is that methyl propionate and methanol azeotrope enter F-1 and continue to extract at 61-62 DEG C, T-3 tower at 62-64 DEG C of tower top temperature
Top is methanol, enters collecting tank G-1 after condenser E-4 condensation.
Embodiment 2
Using ethyl alcohol and excessive methyl propionate as raw material, the molar ratio of ethyl alcohol and methyl propionate is 1:2 in reaction, through depressurizing
The methyl propionate separated after rectifying, which again flows into, participates in ester exchange reaction in T-2.Catalyst is CaO, and dosage is total mass of raw material
The 3% of sum.Operating condition is as follows:
First reactive distillation column T-1: 4000 mm of tower diameter；30000 mm of tower height；It is public rectifying section, fore-running section, side line section, public
The number of plates of stripping section is respectively 10,20,30,15；0.5 MPa of tower pressure interior force；61 DEG C of tower top temperature；The tower of public stripping section
90 DEG C of bottom temperature；80 DEG C of the column bottom temperature of side line section.
Atmospheric distillation tower T-2: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 61-62 DEG C and 78 DEG C of tower top temperature, the tower bottom of public stripping section
80 DEG C of temperature.
Atmospheric distillation tower T-3: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 61-62 DEG C and 62-64 DEG C of tower top temperature, public stripping section
68 DEG C of column bottom temperature.
Atmospheric distillation tower T-4: 2000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；Tower pressure interior force 0.1 MPa, 76-78 DEG C of tower top temperature, the column bottom temperature 85 of public stripping section
℃。
Atmospheric distillation tower T-5: 1000 mm of tower diameter；10000 mm of tower height；Public rectifying section, fore-running section, public stripping section
The number of plates is respectively 10,20,15；0.1 MPa of tower pressure interior force, 99 DEG C of tower top temperature, the column bottom temperature 120 of public stripping section
℃。
The charging of first reactive distillation column T1 and tower reactor composition result are as shown in the table.
Influence of the different total raw material mass flows of table 1 to T-1 the first reactive distillation column tower reactor composition mass fraction
As can be seen from Table 1, with the increase of total feed, when charging rate increases to 3000 kg/h, tower from 2500 kg/h
Kettle composition mass fraction increases rapidly, and charging rate improves again, and decreasing trend occurs in ethyl propionate mass fraction, this is because with
The increase of charging rate, the liquid flow rate in reactive distillation column constantly increase.When inlet amount increases to a certain extent, material
Too short in reactive distillation dwell time in the tower, reaction carries out insufficient.Consider that charging rate is too small from industrial point of view, equipment is raw
Production capacity power is small, and energy consumption is big, and increased production cost, and comprehensively considering 3000 kg/h is optimal total raw material mass flow.
Embodiment 3
Using ethyl alcohol and excessive methyl propionate as raw material, the molar ratio of ethyl alcohol and methyl propionate is 1:2 in reaction, through depressurizing
The methyl propionate separated after rectifying, which again flows into, participates in ester exchange reaction in T-2.Catalyst is 10 % Li2O-15 % Rb2O/K-
β, dosage are the 3% of total mass of raw material sum.Operating condition is as follows:
First reactive distillation column T-1: 1000 mm of tower diameter；19000 mm of tower height；It is public rectifying section, fore-running section, side line section, public
The number of plates of stripping section is respectively 15,25,35,20；0.5 MPa of tower pressure interior force；60 DEG C of tower top temperature；The tower of public stripping section
80 DEG C of bottom temperature；70 DEG C of the column bottom temperature of side line section.
Rectifying column T-2: 3000 mm of tower diameter；40000 mm of tower height；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；0.1 MPa of tower pressure interior force, 62 DEG C of tower top temperature, the tower bottom temperature of public stripping section
70 DEG C of degree；65 DEG C of the column bottom temperature of side line section.
Rectifying column T-3: 3000 mm of tower diameter；40000 mm of tower height；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；0.1 Mpa of tower pressure interior force；79 DEG C of tower top temperature, the tower bottom temperature of public stripping section
85 DEG C of degree；85 DEG C of the column bottom temperature of side line section.
The charging of first reactive distillation column T1 and tower reactor composition result are as shown in table 2 below.
Influence of the different total raw material mass flows of table 2 to T-1 the first reactive distillation column tower reactor composition mass fraction
As can be seen from Table 2, as total mass of raw material 1500 ~ 3000 kg/h of flow, as total mass of raw material flow increases tower reactor group
Increase at mass fraction, when total mass of raw material flow is more than 3000 kg/h, as total mass of raw material flow increases tower reactor group
Reduce at mass fraction, this is because the liquid flow rate in reactive distillation column constantly increases with the increase of charging rate.When into
When doses is increased to a certain extent, material is too short in reactive distillation dwell time in the tower, and reaction carries out insufficient.From industrial point of view
Consider, charging rate is too small, and equipment capacity is small, and energy consumption is big, and increased production cost, and comprehensively considering 3000 kg/h is
Optimal total raw material mass flow.
Embodiment 4
Under the operating condition of embodiment 1, when total raw material mass flow is 3000 kg/h, change T-1 rectifier column reflux ratio, tower
Top composition mass fraction variation is as shown in table 3.
Influence of the different reflux ratios of table 3 to the composition mass fraction variation of the top of the distillation column T-1
As can be seen from Table 3, as the increase of reflux ratio, the mass fraction of methyl propionate reduce, the mass fraction of methanol increases,
When reflux ratio is 3 or more, it is gradually stable that tower top forms mass fraction, the reason is that after reflux ratio reaches certain value, kettle liquid reflux
Composition have reached balance.But excessive reflux ratio will also result in unit capacity reduction, therefore, by reflux ratio when rectifying
Control is best 3.
Embodiment 5
Under the operating condition of embodiment 1, when total raw material mass flow is 3000 kg/h, fixed T-2 rectifier column reflux ratio is 3,
It is as shown in table 4 that tower reactor forms mass fraction variation.
Influence of 4 different ratios of raw materials of table to feed stock conversion and selectivity of product
According to table 4, with the increase (rising to 20:1 from 1:1) of methyl propionate and ethyl alcohol molar ratio, the conversion of methyl propionate
Rate dramatically increases and (rises to 99.95% from 60.56%), 100 % of selectivity of product ethyl propionate.When ethyl alcohol and methyl propionate
When molar ratio is 20:1, methyl propionate conversion ratio is up to 99.95%.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (3)
1. it is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester, which is characterized in that the technique is with third
Sour methyl esters and various alcohol are raw material, react under certain condition, pass through ester exchange reaction synthesizing propionate；Reaction raw materials alcohol is second
The dihydric alcohols such as the monohydric alcohols such as alcohol, propyl alcohol, butanol or ethylene glycol, 1,3-PD；
One-step synthesis propionic ester, reaction equation are as follows:
Methyl propionate and the specific reaction equation of monohydric alcohol are as follows:
Methyl propionate and the specific reaction equation of dihydric alcohol are as follows:
；
Use methyl propionate and alcohol for raw material, reaction raw materials alcohol and methyl propionate molar ratio 0.5:1~20:1, the complete original of unreacted
Expect that methyl propionate returns to reaction zone and carries out conversion and cycle.
2. it is according to claim 1 it is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester, it is special
Sign is, the catalyst is any one or more the mixing of heterogeneous solid base.
3. it is according to claim 1 it is a kind of by ester alcohol exchange system for the heterogeneous catalysis rectification process of propionic ester, it is special
Sign is that the propionic ester production technology, raw material methyl propionate and alcohol mixture enter from catalytic rectifying tower middle and upper part, and tower is built-in
Solid catalyst is filled out, Methanol product carries out reaction system by methyl propionate, and driving a reaction is carried out to positive direction, control excessive third
Sour methyl esters carries out reaction, and reaching in tower reactor does not have raw alcohol remaining；Tower top methyl propionate and methanol azeotrope by add water into
Rectifying separates again for row extraction-, the higher methyl propionate of purity is obtained, as raw material reuse；Tower reactor methyl propionate and higher boiling
Azeotropic is not present in propionic ester, is directly separated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
| CN114917602A (en) * | 2022-05-20 | 2022-08-19 | 胜华新能源科技(东营)有限公司 | Device and process method for preparing propionate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592016A (en) * | 2014-12-11 | 2015-05-06 | 湖南大学 | Efficient catalysis method for direct esterification and transesterification |
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2019
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592016A (en) * | 2014-12-11 | 2015-05-06 | 湖南大学 | Efficient catalysis method for direct esterification and transesterification |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
| CN114917602A (en) * | 2022-05-20 | 2022-08-19 | 胜华新能源科技(东营)有限公司 | Device and process method for preparing propionate |
| CN114917602B (en) * | 2022-05-20 | 2023-08-25 | 胜华新能源科技(东营)有限公司 | Device and technological method for preparing propionate |
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