CN110218151A - A kind of device and method that tower reactor Flash Type heat pump reactive distillation prepares propyl propionate - Google Patents
A kind of device and method that tower reactor Flash Type heat pump reactive distillation prepares propyl propionate Download PDFInfo
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- CN110218151A CN110218151A CN201910479188.5A CN201910479188A CN110218151A CN 110218151 A CN110218151 A CN 110218151A CN 201910479188 A CN201910479188 A CN 201910479188A CN 110218151 A CN110218151 A CN 110218151A
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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
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention is disclosed a kind of tower reactor Flash Type heat pump reactive distillation and prepares the device of propyl propionate and the preparation method of the propyl propionate carried out based on the device, and wherein device includes reactive distillation column and recovery tower.In whole preparation process, throttle valve is added by the logistics for needing to boil again to two tower tower reactors, after the temperature and pressure for reducing tower reactor logistics, the heat that the logistics of tower reactor obtains overhead vapours in heat exchanger is heated, and temperature and pressure is improved using compressor, as tower bottom of rectifying tower heat source.Instead of the heat exchanger of big calorimetric public work heat supply is needed, further, since the latent heat of overhead vapours is utilized, the condensing heat-exchange load of overhead condenser is reduced, which only needs the extraneous hot public work of offer that the logistics of raw material propionic acid is added, save energy.
Description
Technical field
The invention belongs to technical field of rectification, are related to the production method of propyl propionate, specifically, being related to a kind of tower
The device and method that kettle Flash Type heat pump reactive distillation prepares propyl propionate.
Background technique
Propyl propionate is a kind of fine chemicals that purposes is very extensive, is mainly used in ink, coating, detergent and food
The industries such as product industry condiment, it is a kind of excellent solvent, can dissolve each other with ethyl alcohol and ether, be slightly soluble in water；As a kind of nothing
Malicious, harmless compound is instead of some arene compound solvents that can cause air pollution, such as benzene.
The production technology of Synthesis of Propyl Propionate is mainly the following at present, and a kind of such as method is exactly that propionic acid and propyl alcohol are former
Material, direct esterification generates propyl propionate, in document " fine petroleum industry progress ", 2001 under the action of strongly acidic catalyst
Year, volume 7, the present industrial application of middle proposition it is most catalyst is done with the concentrated sulfuric acid or boron trifluoride, by n Propanoic acid and just
The esterification process of propyl alcohol prepares propyl propionate.Since catalyst is easy to get, price is low, technical maturity, but its major defect is device
Environment perishable, easy to pollute, the separation of product complicated difficult, have the water of equimolar quality to generate, post-processing process is longer, whole after reaction
Energy consumption is high for a process, and product purification is difficult.Document " fine chemistry industry ", nineteen ninety-five, volume 12, another method of middle proposition is to use
Propionic aldehyde utilizes propyl alcohol Al catalysts, and zinc chloride is co-catalyst, and by the direct Synthesis of Propyl Propionate of one step of propionic aldehyde, which is saved
The consumption of raw material, it is only necessary to which the reaction time is greatly saved just up to 98% in 50min, the yield of propyl alcohol Al catalysts.Propionic acid third
The yield of ester is up to 92%, and selectivity is up to 93%, but there is also shortcomings for the technique, and process route is complicated, but does not have
Overcome corrosion and problem of environmental pollution of the inorganic acid to equipment, and energy consumption is very high in process of production, is difficult large-scale production and answers
With.The third method is document " using chemical industry ", and in August, 2004, volume 33, the 4th phase, document is mentioned super using the solid of preparation
Strong acid SO4 2-/Fe2O3Catalyst is made instead of the concentrated sulfuric acid, by n Propanoic acid and normal propyl alcohol lactate synthesis propyl propionate, although catalyst
Cheap and corrosivity is low, and ester yield is up to 97.2%.But whole process process flow is complicated, entirely reacts preparation time
Too long, energy consumption is very big, can not large-scale promotion.Last one kind is using propionic acid and propyl alcohol as raw material, using titanium sulfate as catalysis
Agent Synthesis of Propyl Propionate, although propyl propionate yield can achieve 96.5%, process route is excessively complicated, side reaction compared with
It is more, relatively it is difficult to control.Therefore domestic and international researcher has energetically carried out the preparation research of propyl propionate, it is desirable to can simplify work
Skill process improves the yield of propyl propionate and reduces process energy consumption.
Reactive distillation is a kind of emerging chemical process reinforcement technique to grow up the eighties in last century, which will react
With PROCESS COUPLING the most key in the two field of chemical engineering of separation in same equipment, become innovation traditional unit operations
A representative art, it is considered to be the pioneer of process intensification.There is open source literature report reference reactive distillation to be synthetically prepared
The method of propyl propionate, such as document " VERSITA ", 2008, volume 62, the 1st is interim, and Kotora mentions a kind of pilot-scale system
The reactive distillation processes of standby propyl propionate, but the purity of propyl propionate is only 0.698, and the energy consumption of whole process is excessive.Text
It offers " petroleum journal (PETROLEUM PROCESSING) ", in December, 2015, volume 31, the 6th phase proposed that the single tower reaction rectifying of equimolar charging was closed
At propyl propionate, purity is up to 99.88%, but due to using equimolar when expects, industrially can not normal operating, document
" Chemical Engineering and Processing ", 2014, the 85th is interim, and Xu proposes a kind of double tower reaction essence
Process is evaporated, the yield of propyl propionate can be made to reach 99.5% or more, but overhead condenser and tower reactor heat exchanger can all use
A large amount of cold and hot public work, causes energy consumption excessively high, economy is greatly affected.
Summary of the invention
Product yield existing for technology of the present invention for above-mentioned document is not high, process flow too complex, and energy consumption is excessively high
The deficiencies of, one kind is proposed using propionic acid and propyl alcohol as raw material, and solid acid is catalyst, and the tower reactor of esterification Synthesis of Propyl Propionate is dodged
The characteristics of steaming formula heat pump reaction and rectification device and technique, process set heat pump distillation and reactive distillation, have that low energy consumption, produces
The advantage of product purity is high.It is insufficient to solve heat utilization in prior art, energy waste problem caused by heat exchange mismatches.And
And the rate of recovery of product is improved to 99% or more.
Technical scheme is as follows:
A kind of tower reactor Flash Type heat pump reactive distillation prepares the device of propyl propionate, comprising:
Propionic acid feed pipe, the propionic acid feed pipe are equipped with propionic acid preheater；
Propyl alcohol feed pipe, the propyl alcohol feed pipe are equipped with propyl alcohol preheating heat exchanger；
Reactive distillation column is divided into tower top separated region inside the reactive distillation column, filled with solid from top to bottom
The conversion zone of acid catalyst and tower reactor recovery zone；The first steam pipe of outside connection at the top of the tower top separated region, first
Steam pipe sets gradually reactive distillation column tower reactor heat exchanger, the first condenser and separator along fluid flow direction, and described point
From device bottom to two discharge nozzles are externally provided with, wherein one connect with reactive distillation column overhead separated region, another for adopting
Byproduct water out；The conversion zone top of the reactive distillation column is equipped with the propionic acid feed inlet connecting with propionic acid feed pipe, lower part
Equipped with the propyl alcohol feed inlet being connect with propyl alcohol feed pipe；The bottom of reactive distillation column tower reactor recovery zone is equipped with two dischargings
Pipe a, wherein pipeline by being equipped with first throttle valve connects the reactive distillation column tower reactor heat exchanger, the reactive distillation
Tower tower reactor heat exchanger is connect by being equipped with the pipeline of the first compressor with reactive distillation column tower reactor recovery zone；
Recovery tower, the recovery tower middle part are equipped with feed inlet, the feed inlet and reactive distillation column tower reactor recovery area
Another discharge nozzle connection of domain bottom setting, the recycling tower section are that recycling column overhead separated region and propyl propionate return
Receive region；The top of the recycling column overhead separated region is to the second steam pipe is externally connected with, and the second steam pipe is along fluid stream
Dynamic direction sets gradually recovery tower tower reactor heat exchanger, the second condenser, the second condensation two discharge nozzles of connection, and wherein one
Root discharge nozzle is connect with propyl alcohol feed pipe, and another discharge nozzle is connect with the recycling column overhead separated region；The propionic acid third
The bottom of ester recovery zone is equipped with two discharge nozzles, and wherein a pipeline by being equipped with second throttle connects the recycling
Tower tower reactor heat exchanger, the recovery tower tower reactor heat exchanger connect the propyl propionate recycling by being equipped with the pipeline of the second compressor
Region, another connect with the propyl alcohol preheating heat exchanger, and the propyl propionate in this another is via propyl alcohol preheating heat exchanger
It is produced after heat exchange.
Further, the recovery tower is packed tower or plate column；And/or the reactive distillation column is packed tower or plate
Formula tower.
Further, the reactive distillation column is plate column, and the number of theoretical plate of tower top separated region is 5~15 pieces, instead
Answering Region Theory plate number is 25~35 pieces, and the theoretical cam curve of tower reactor recovery zone is 5~15 pieces, and propionic acid feed inlet is located at reaction
The 1st block of region column plate, propyl alcohol feed inlet are located at last block column plate of conversion zone；
The recovery tower is plate column, and the recovery tower number of plates is 32~40 pieces, and the feed inlet in the middle part of recovery tower is located at the 20th
At~24 blocks of column plates.
A kind of method that tower reactor Flash Type heat pump reactive distillation prepares propyl propionate, the method use tower as described above
The device that kettle Flash Type heat pump reactive distillation prepares propyl propionate is implemented, and specifically comprises the following steps:
The propionic acid after bubble point will be preheating to and be preheating to the excessive propyl alcohol after bubble point respectively via propionic acid feed pipe and third
Alcohol feed pipe is sent into the conversion zone of reactive distillation column and is contacted with solid acid catalyst, and Reaction Separation is carried out, and generates thick produce
Object and the first vapour mixture, water, part propyl propionate and unreacted third of first vapour mixture by reaction generation
Alcohol is formed；
First vapour mixture is flowed out via the first steam pipe at the top of tower top separated region, and passes through reactive distillation
Enter the first condenser after the heat exchange of tower tower reactor heat exchanger, separator is entered after condensing and isolates organic phase and water phase, wherein having
Machine mutually flows back to reactive distillation column overhead separated region；
The crude product is the mixture of target product propyl propionate and unreacted propyl alcohol, and the crude product is smart from reaction
The extraction of tower tower reactor recovery zone is evaporated, and is divided into two strands, wherein one is delivered to recovery tower, enters after another stock-traders' know-how throttle valve decompression
Reactive distillation column tower reactor heat exchanger, and exchange heat to form the second vapour mixture with first vapour mixture, then via pressure
Reactive distillation column tower reactor recovery area is returned to after the pressurization of contracting machine, for providing boiling hot amount again to reactive distillation column；
Crude product into recovery tower isolates unreacted propyl alcohol steam and propyl propionate object through rectifying, wherein third
Alcohol steam, which enters to enter after the second condenser condenses after recovery tower tower reactor heat exchanger exchanges heat, is divided into two strands, and wherein one flows into propyl alcohol
Feed pipe, another plume Huis receive column overhead separated region；The propyl propionate object is flowed out from propyl propionate recovery zone
After be divided into two strands, wherein one flow into propyl alcohol preheating heat exchanger to the propyl propionate product is obtained after propyl alcohol raw material preheating, separately
One after throttle valve is depressured enter flow into recovery tower tower reactor heat exchanger, in recovery tower tower reactor heat exchanger with propyl alcohol steam heat-exchanging
Recovery tower tower reactor recovery area is returned to after pressurizeing by compressor, for providing boiling hot amount again to recovery tower.
Further, the reactive distillation column operating pressure is 100~150kPa, reactive distillation column overhead separated region
Temperature is 100~120 DEG C, and the temperature of tower reactor recovery zone is 115~138 DEG C；The operating pressure of the recovery tower be 100~
120kPa, recycling column overhead Disengagement zone operation temperature are 90~120 DEG C, and recovery tower tower reactor recovery area temperature is 120~130 DEG C；
The power of first compressor is 213-226kW, and the outlet pressure of first throttle valve is 17-19kpa；Second compressor
Power be 82-86kW, the outlet pressure of second throttle is 30-32kpa.
In whole process, throttle valve is added by the logistics for needing to boil again to two tower tower reactors, reduces the temperature of tower reactor logistics
After pressure, the heat that the logistics of tower reactor obtains overhead vapours in heat exchanger is heated, and improves temperature using compressor
And pressure, as tower bottom of rectifying tower heat source.Instead of the heat exchanger for needing big calorimetric public work heat supply, further, since utilizing
The latent heat of overhead vapours, reduces the condensing heat-exchange load of overhead condenser, which only needs extraneous a small amount of heat supply public
With engineering, energy is saved.
Compared with the existing technology, effect of the invention is that: prepare propyl propionate in tower reactor Flash Type heat pump reactive distillation
Realize that the production of the propyl propionate of high-purity is reduced by the energy coupling of liquid phase stream stock in tower by throttle valve in device
It after temperature and pressure, exchanges heat in tower reactor heat exchanger with overhead vapours, pressurizeing to heat up using compressor returns to tower bottom of rectifying tower
As heat source.Heat possessed by overhead vapours can be used as the heat source of heat exchanger, and the effect of original reboiler is replaced, was both saved
The heat source of reboiler has been saved, and has reduced the condensing heat-exchange load of overhead condenser.External heat source is not needed to reboiler
Energy is provided, energy consumption is significantly reduced.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is that tower reactor Flash Type heat pump reactive distillation of the invention prepares propyl propionate apparatus structure and process flow.
In figure: 1- reactive distillation column, 2- recovery tower, 3- reactive distillation column tower reactor heat exchanger, 4- recovery tower tower reactor heat exchanger,
5- propyl alcohol preheating heat exchanger, 6- propionic acid preheater, the first condenser of 7-, the second condenser of 8-, the first compressor of 9-, 10- second
Compressor, 11- first throttle valve, 12- second throttle, 13- separator, 14- propyl alcohol feed pipe, 15- propionic acid feed pipe, 16-
Reactive distillation column overhead separated region, 17- reactive distillation column conversion zone 18- reactive distillation column tower reactor recovery zone, 19- recycling
Column overhead separated region, 20- propyl propionate recovery zone.
Specific embodiment
Be described in further detail with reference to the accompanying drawing with case study on implementation to the content of present invention: arrow represents fluid stream in figure
Dynamic direction.
Tower reactor Flash Type heat pump reactive distillation prepares propyl propionate device as shown in Figure 1:, including with reactive distillation column 1,
First condenser 7, reactive distillation column tower reactor heat exchanger 3, raw material propionic acid preheater 6, first throttle valve 11, the first compressor 9, point
From device 13, reactive distillation tower section is reactive distillation column overhead separated region 16, reactive distillation column conversion zone 17 and reaction
Tower bottom of rectifying tower recovery zone 18, recovery tower 2, recovery tower tower reactor heat exchanger 4, raw material propyl alcohol preheating heat exchanger 5, the second condenser
8, second throttle 12, the second compressor 10.Recycling tower section is recycling column overhead separated region 19 and propyl propionate recycling
Region 31.
The first steam pipe of connection, the first steam pipe connect reactive distillation outward at reactive distillation column overhead separated region 16 top
Tower tower reactor heat exchanger 3 reconnects the first condenser 7 and reconnects separator 13；13 bottom of separator connects two by tee tube and goes out
Expects pipe, wherein a connection reactive distillation column overhead separated region 16, another extraction byproduct water；The reaction of conversion zone 17
Rectifying column is externally connected to raw material propionic acid feed pipe 15 and raw material propyl alcohol feed pipe 14, reactive distillation column tower reactor recovery zone 18
Bottom is equipped with discharge port, and discharge port connects 2 discharge nozzles by tee tube, wherein a connection first throttle valve 11 reconnects instead
It answers tower bottom of rectifying tower heat exchanger 3 to reconnect the first compressor 9 and reconnects reactive distillation column tower reactor recovery zone 18, another connection
Recovery tower 2；19 top of recycling column overhead separated region connects recovery tower tower reactor to the second steam pipe, the second steam pipe is externally connected with
Heat exchanger 4 reconnects the second condenser 8, and the second condenser 8 connects two discharge nozzles by tee tube, wherein one and raw material third
Alcohol feed pipe connection, so that the propyl alcohol being condensed out mixes with raw material propyl alcohol and be delivered to reactive distillation column 1, another connection recycling
Column overhead separated region 19；The bottom of propyl propionate recovery zone 20 connects 2 discharge nozzles by tee tube, wherein one goes out
Expects pipe connects second throttle 12 and reconnects reconnection the second compressor 10 reconnection propyl propionate time of recovery tower tower reactor heat exchanger 4
Region 31 is received, another discharge nozzle connection raw material propyl alcohol preheating heat exchanger 5 produces propyl propionate.
The technique that tower reactor Flash Type heat pump reactive distillation of the present invention prepares propyl propionate device are as follows: raw material propionic acid
Enter reactive distillation column conversion zone 17 after raw material propionic acid preheater 6 is heated to bubble point, raw material propyl alcohol passes through raw material propyl alcohol
Preheating heat exchanger 5 is heated to entering reactive distillation column conversion zone after mixing with the product from recycling column overhead again after bubble point
17, high boiling reactant propionic acid is fed from 17 top of Reaction Separation region, and low-boiling raw material propyl alcohol is returned with from recovery tower
Unreacted propyl alcohol mixing, from 17 lower part of conversion zone feed, two raw materials solid acid catalyst effect under in conversion zone
17 occur esterifications, generate crude product, i.e. target product propyl propionate and by-product water, wherein target product propyl propionate and
The unreacted reacted tower bottom of rectifying tower recovery zone 18 of propyl alcohol further after separation, produces and is divided into from reactive distillation tower bottom
Two strands, one enters recovery tower 2 and continues rectifying separation, after another stock first passes through the reduction temperature and pressure of first throttle valve 11, then
It exchanges heat in reactive distillation column tower reactor heat exchanger 3 with the first vapour mixture produced from reactive distillation column overhead separated region 16
The second vapour mixture is formed, the second vapour mixture is compressed using the first compressor 9, is returned instead after improving temperature and pressure
Tower bottom of rectifying tower recovery area is answered to provide again boiling hot amount for reactive distillation column.It is obtained at the top of reactive distillation column overhead separated region 16
The vapour mixture (i.e. aforementioned first vapour mixture) of propyl propionate, water and propyl alcohol is that reactive distillation column tower reactor heat exchanger 3 mentions
It after heating load, is condensed into the first condenser 7, enters back into separator 13 and divide for organic phase and water phase, organic phase fluid stock returns anti-
Answer the top of the distillation column separated region 16, water phase extraction.In recovery tower, propyl propionate object is from propyl propionate recovery zone 20
Produce and be divided into two strands, after a stock-traders' know-how second throttle 12 reduces pressure, in recovery tower tower reactor heat exchanger 4 with tower top Disengagement zone
After the propyl alcohol steam heat-exchanging of domain extraction, propyl propionate recovery zone 20 is flowed back into after the compression of the second compressor 10.Another stock
For the propyl propionate of high-purity, produced after raw material propyl alcohol preheating heat exchanger 5 provides heat as target product to raw material propyl alcohol.
After tower top propyl alcohol steam is by providing heat to recovery tower tower reactor heat exchanger 4, is condensed in the second condenser 8 and is divided into two strands,
One returns to recycling column overhead Disengagement zone, and another stock enters reactive distillation column conversion zone together with the raw material propyl alcohol after preheating.
Embodiment 1
Using attached process flow shown in FIG. 1, used reactive distillation column 1 shares 45 blocks of column plates, and propionic acid feed inlet is
7th block of column plate, propyl alcohol feed inlet are the 31st block of column plate；The operating pressure of reactive distillation column 1 is 101.3kPa, reactive distillation column
16 head temperature of top region is 104 DEG C, and 18 bottom temp of reactive distillation column tower reactor recovery zone is 117 DEG C, the first compressor 9
Power be 213kW, the outlet pressure of first throttle valve 11 is 19kPa.
Raw material propionic acid after raw material propionic acid preheater 6 is heated to bubble point, is divided with 50kmol/h from reactive distillation column reaction
From 17 top of region feed, low-boiling propyl alcohol 50kmol/h after raw material propyl alcohol preheating heat exchanger 5 is heated to bubble point and from
Propyl alcohol and propyl propionate mixture the 10kmol/h mixing that the second condenser of recovery tower 8 returns, from reactive distillation column Reaction Separation
In reactive distillation column conversion zone 17 esterification occurs for the charging of 19 lower part of region, two raw materials under solid acid catalyst effect,
Target product propyl propionate and by-product water are generated, wherein target product propyl propionate and excessive unreacted propyl alcohol are returned through tower reactor
After receiving the further separation in region 18, is produced from 18 bottom of tower reactor recovery zone, be then divided into two strands, one is delivered to recovery tower 2
Feed inlet, another stock-traders' know-how cross first throttle valve 11 reduce temperature and pressure, then with come from reactive distillation column overhead separated region
The steam of extraction exchanges heat in reactive distillation column tower reactor heat exchanger 3, later after the pressurization of the first compressor, returns to reactive distillation
Tower tower reactor recovery zone 18 is used as heat source.The steam produced from reactive distillation column overhead separated region 16 is in reactive distillation column tower reactor
After providing heat in heat exchanger 3, condenses in the first condenser 7, be then separated into separator 13 containing unreacted
The water phase of the organic phase and mass fraction 99.7% of propyl alcohol and target product propyl propionate, water phase produce as by-product, have
Machine mutually returns to reactive distillation column overhead separated region.
Recovery tower 2 shares 35 blocks of column plates, and feed inlet is the 20th block of column plate, and the operating pressure of recovery tower 2 is 101.3kPa,
Recycling 19 head temperature of column overhead separated region is 97 DEG C, 125 DEG C of 20 bottom temp of propyl propionate recovery zone, the second compressor
10 power is 82kW, and the outlet pressure of second throttle 12 is 32kPa.
It in recovery tower 2, is separated by rectifying, the propyl propionate of mass fraction 99.95% is from propyl propionate recovery zone
31 extraction, and it is divided into two strands, after one is provides heat in raw material propyl alcohol preheating heat exchanger 5, produced as target product.It is another
Stock-traders' know-how, which crosses second throttle 12, reduces temperature and pressure, in recovery tower tower reactor heat exchanger 4 and from recycling column overhead Disengagement zone
After the steam in domain 19 is exchanged heat, propyl propionate tower reactor recovery zone 20 is returned to using the second compressor compresses and is used as heat source.
After the steam that recycling column overhead separated region 19 produces provides heat in recovery tower tower reactor heat exchanger 4, then in the second condensation
8 condensations are divided into two strands in device, one enters 1 conversion zone 17 of reactive distillation column with raw material propyl alcohol, and another stock is back to recovery tower
Tower top separated region 19.The temperature and pressure that steam is improved by compressor, recycle internal heat, thus
Reactive distillation column and recovery tower tower reactor do not need additional thermal technology's recruitment journey.
Embodiment 2
Using attached process flow shown in FIG. 1, used reactive distillation column 1 shares 48 blocks of column plates, and propionic acid feed inlet is
8th block of column plate, propyl alcohol feed inlet are the 32nd block of column plate；The operating pressure of reactive distillation column 1 is 101.3kPa, reactive distillation column
16 head temperature of tower top separated region is 104 DEG C, and 18 bottom temp of reactive distillation column tower reactor recovery zone is 117 DEG C, the first pressure
The power of contracting machine 9 is 226kW, and the outlet pressure of first throttle valve 11 is 17kPa.
Raw material propionic acid with 100kmol/h by raw material propionic acid preheater 6 heating after, from reactive distillation column Reaction Separation region
The charging of 17 tops, low-boiling propyl alcohol 100kmol/h are cold after the heating of raw material propyl alcohol preheating heat exchanger 5 and from recovery tower second
Condenser 8 return propyl alcohol and propyl propionate mixture 20kmol/h mixing, from 18 lower part of reactive distillation column Reaction Separation region into
Material, two raw materials occur esterification in reactive distillation column conversion zone 17 under solid acid catalyst effect, generate target product
Propyl propionate and by-product water, wherein target product propyl propionate and excessive unreacted propyl alcohol are through tower reactor recovery zone 18 into one
After step separation, is produced from 18 bottom of tower reactor recovery zone, be then divided into two strands, one is delivered to the feed inlet of recovery tower 2, another
Stock-traders' know-how, which crosses first throttle valve 11, reduces temperature and pressure, then with the steam that produces from reactive distillation column overhead separated region anti-
It answers and exchanges heat in tower bottom of rectifying tower heat exchanger 3, return to reactive distillation column tower reactor recovery zone after the pressurization of the first compressor later
18 are used as heat source.The steam produced from reactive distillation column overhead separated region 16 provides in reactive distillation column tower reactor heat exchanger 3
After heat, in the first condenser 7 then condensation is separated into containing unreacted propionic acid in separator 13, propyl alcohol and
The organic phase of target product propyl propionate and the water phase of mass fraction 99.8%, water phase are produced as by-product, and organic phase returns
Reactive distillation column overhead separated region.
Recovery tower 2 is tower diameter 700mm, tower height 24m, shares 35 blocks of column plates, and feed inlet is the 20th block of column plate, recovery tower 2
Operating pressure is 101.3kPa, and recycling 19 head temperature of column overhead separated region is 97 DEG C, 20 bottom of propyl propionate recovery zone
125 DEG C of temperature, the power of the second compressor 10 is 86kW, and the outlet pressure of second throttle 12 is 30kPa.
It in recovery tower, is separated by rectifying, the propyl propionate of mass fraction 99.95% is from propyl propionate recovery zone 20
Extraction, and it is divided into two strands, after one provides heat in raw material propyl alcohol preheating heat exchanger 5, produced as target product.Another stock
Temperature and pressure is reduced by second throttle 12, in recovery tower tower reactor heat exchanger 4 and from recycling column overhead separated region
After 19 steam is exchanged heat, is compressed using the second compressor 10 and return to propyl propionate tower reactor recovery zone 20 as heat source.
After the steam that recycling column overhead separated region 30 produces provides heat in recovery tower tower reactor heat exchanger 4, then in the second condensation
8 condensations are divided into two strands in device, one enters 1 Reaction Separation region 17 of reactive distillation column with raw material propyl alcohol, and another stock is back to back
Receive column overhead separated region 19.The temperature and pressure that steam is improved by compressor, recycle internal heat,
To which reactive distillation column and recovery tower do not need additional thermal technology's recruitment journey.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Design is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. the device that a kind of tower reactor Flash Type heat pump reactive distillation prepares propyl propionate, it is characterised in that: include:
Propionic acid feed pipe (15), the propionic acid feed pipe (15) are equipped with propionic acid preheater (6)；
Propyl alcohol feed pipe (14), the propyl alcohol feed pipe (14) are equipped with propyl alcohol preheating heat exchanger (5)；
Reactive distillation column (1), the reactive distillation column (1) is internal to be divided into tower top separated region (16), filling from top to bottom
There are conversion zone (17) and tower reactor recovery zone (18) of solid acid catalyst；Connect outward at the top of the tower top separated region (16)
Connect the first steam pipe, the first steam pipe sets gradually reactive distillation column tower reactor heat exchanger (3), first cold along fluid flow direction
Condenser (7) and separator (13), the bottom of the separator (13) is to two discharge nozzles are externally provided with, wherein one and reactive distillation
Column overhead separated region (16) connection, another for producing byproduct water；The conversion zone (17) of the reactive distillation column
Top is equipped with the propionic acid feed inlet that connect with propionic acid feed pipe (15), lower part equipped with the propyl alcohol being connect with propyl alcohol feed pipe (14) into
Material mouth；The bottom of reactive distillation column tower reactor recovery zone (18) be equipped with two discharge nozzles, wherein one by be equipped with first
The pipeline of throttle valve (11) connects the reactive distillation column tower reactor heat exchanger (3), and the reactive distillation column tower reactor heat exchanger (3) is logical
The pipeline equipped with the first compressor (9) is crossed to connect with reactive distillation column tower reactor recovery zone (18)；
Recovery tower (2), the middle part of the recovery tower (2) are equipped with feed inlet, and the feed inlet and the reactive distillation column tower reactor are returned
Another discharge nozzle connection of the bottom setting of region (8) is received, the inside of the recovery tower (2) is divided into recycling from top to bottom
Column overhead separated region (19) and propyl propionate recovery zone (20)；The top of recycling column overhead separated region (19) is outside
It is connected with the second steam pipe, the second steam pipe sets gradually recovery tower tower reactor heat exchanger (4), second cold along fluid flow direction
Condenser (8), second condenser (8) connects two discharge nozzles, and wherein a discharge nozzle is connect with propyl alcohol feed pipe (14),
Another discharge nozzle is connect with the recycling column overhead separated region (19)；The bottom of the propyl propionate recovery zone (20) is set
There are two discharge nozzles, and wherein a pipeline by being equipped with second throttle (12) connects the recovery tower tower reactor heat exchanger
(4), the recovery tower tower reactor heat exchanger (4) connects the propyl propionate recovery area by being equipped with the pipeline of the second compressor (10)
Domain (20), another connect with the propyl alcohol preheating heat exchanger (5), and the propyl propionate in this another is changed via propyl alcohol preheating
It is produced after hot device (5) heat exchange.
2. the device that tower reactor Flash Type heat pump reactive distillation according to claim 1 prepares propyl propionate, it is characterised in that:
The recovery tower (2) is packed tower or plate column；
And/or the reactive distillation column (1) is packed tower or plate column.
3. the device that tower reactor Flash Type heat pump reactive distillation according to claim 1 prepares propyl propionate, it is characterised in that:
The reactive distillation column (1) is plate column, and the number of theoretical plate of tower top separated region (16) is 5~15 pieces, conversion zone (17)
Number of theoretical plate be 25~35 pieces, the theoretical cam curve of tower reactor recovery zone (18) is 5~15 pieces, and propionic acid feed inlet is located at reaction
The 1st block of region column plate, propyl alcohol feed inlet are located at last block column plate of conversion zone；
The recovery tower (2) is plate column, and the recovery tower number of plates is 32~40 pieces, feed inlet in the middle part of recovery tower is located at the 20th~
At 24 blocks of column plates.
4. a kind of method that tower reactor Flash Type heat pump reactive distillation prepares propyl propionate, it is characterised in that: the method is using such as
The device that tower reactor Flash Type heat pump reactive distillation described in any one of claims 1 to 3 prepares propyl propionate is implemented, specific to wrap
Include following steps:
The propionic acid after bubble point will be preheating to and be preheating to the excessive propyl alcohol after bubble point respectively via propionic acid feed pipe (15) and third
Alcohol feed pipe (14) be sent into reactive distillation column conversion zone (17) and with the solid in the conversion zone of reactive distillation column (17)
Acid catalyst contact, carries out Reaction Separation, and generate crude product and the first vapour mixture, first vapour mixture is by anti-
Water, part propyl propionate and the unreacted propyl alcohol that should be generated are formed；
First vapour mixture is flowed out via the first steam pipe at the top of tower top separated region (16), and passes through reactive distillation
Enter the first condenser (7) after tower tower reactor heat exchanger (3) heat exchange, separator (13) are entered after condensing and isolate organic phase and water
Phase, wherein organic phase flows back to reactive distillation column tower top separated region (16)；
The crude product is the mixture of target product propyl propionate and unreacted propyl alcohol, and the crude product is from reactive distillation column
Tower reactor recovery zone (18) extraction, and it is divided into two strands, wherein one is delivered to recovery tower (2), another stock-traders' know-how throttle valve (11) drop
Enter reactive distillation column tower reactor heat exchanger (3) after pressure, and exchange heat to form the second vapour mixture with first vapour mixture,
Then via reactive distillation column tower reactor recovery zone (18) are returned after compressor (9) pressurization, for being provided again to reactive distillation column
Boiling hot amount；
Crude product into recovery tower (2) isolates unreacted propyl alcohol steam and propyl propionate object through rectifying, wherein third
Alcohol steam enter recovery tower tower reactor heat exchanger (4) heat exchange after enter the second condenser (8) condensation after is divided into two strands, wherein one with
Propyl alcohol in propyl alcohol feed pipe (14) flows into reactive distillation column conversion zone (17) after converging, and another plume Huis receives column overhead point
From region (19)；The propyl propionate object is divided into two strands after flowing out from propyl propionate recovery zone (20), wherein a plume
Enter propyl alcohol preheating heat exchanger (5) and is dropped to the propyl propionate product, another stock-traders' know-how throttle valve (12) is obtained after propyl alcohol raw material preheating
Recovery tower tower reactor heat exchanger (4) are flowed into after pressure, through compressor in recovery tower tower reactor heat exchanger (4) and after propyl alcohol steam heat-exchanging
(10) recovery tower tower reactor recovery zone (20) are returned to after pressurizeing, for providing boiling hot amount again to recovery tower (2).
5. the method that tower reactor Flash Type heat pump reactive distillation according to claim 4 prepares propyl propionate, it is characterised in that:
The reactive distillation column operating pressure is 100~150kPa, and the temperature of reactive distillation column overhead separated region is 100~120 DEG C,
The temperature of tower reactor recovery zone is 115~138 DEG C；
The operating pressure of the recovery tower is 100~120kPa, and recycling column overhead Disengagement zone operation temperature is 90~120 DEG C, is returned
Receiving tower tower reactor recovery area temperature is 120~130 DEG C；The power of first compressor (9) is 213-226kW, first throttle valve
(11) outlet pressure is 17-19kpa；The power of second compressor (10) is 82-86kW, and second throttle (12) goes out
Mouth pressure is 30-32kpa.
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| CN110483283A (en) * | 2019-09-25 | 2019-11-22 | 许兆石 | A kind of synthetic method and synthesizer of propyl propionate |
| CN110563580A (en) * | 2019-09-25 | 2019-12-13 | 许兆石 | synthesis method of high-purity propyl propionate |
| CN112052580A (en) * | 2020-08-28 | 2020-12-08 | 杭州百子尖科技股份有限公司 | Rectifying tower solving method based on dynamic mathematical model |
| CN116077965A (en) * | 2023-04-10 | 2023-05-09 | 中建安装集团有限公司 | Backpack type reaction rectification control method for preparing n-propyl propionate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483283A (en) * | 2019-09-25 | 2019-11-22 | 许兆石 | A kind of synthetic method and synthesizer of propyl propionate |
| CN110563580A (en) * | 2019-09-25 | 2019-12-13 | 许兆石 | synthesis method of high-purity propyl propionate |
| CN112052580A (en) * | 2020-08-28 | 2020-12-08 | 杭州百子尖科技股份有限公司 | Rectifying tower solving method based on dynamic mathematical model |
| CN112052580B (en) * | 2020-08-28 | 2023-12-05 | 杭州百子尖科技股份有限公司 | Rectifying tower solving method based on dynamic mathematical model |
| CN116077965A (en) * | 2023-04-10 | 2023-05-09 | 中建安装集团有限公司 | Backpack type reaction rectification control method for preparing n-propyl propionate |
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