CN101854989A - Azeotropic distillation with entrainer regeneration - Google Patents
Azeotropic distillation with entrainer regeneration Download PDFInfo
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- CN101854989A CN101854989A CN200880108239A CN200880108239A CN101854989A CN 101854989 A CN101854989 A CN 101854989A CN 200880108239 A CN200880108239 A CN 200880108239A CN 200880108239 A CN200880108239 A CN 200880108239A CN 101854989 A CN101854989 A CN 101854989A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
- C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
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Abstract
The present invention relates to a process for azeotropic distillation (Dl) of a feedstock (1), wherein the feedstock (1) comprises an aliphatic carboxylic acid and water, comprising conducting the azeotropic distillation (Dl) in the presence of an organic entrainer to produce a liquid phase component (2) comprising said aliphatic carboxylic acid having a reduced water content relative to the water content in the feedstock (1) and a vapor phase component (3) comprising the organic entrainer, an organic entrainer by-product and water, and either (i) returning a stream comprising the organic entrainer by-product to a point in the azeotropic distillation below where the feedstock is fed (9), wherein the organic entrainer by-product is converted to the organic entrainer or (ii) converting the organic entrainer by-product to the organic entrainer and then returning the organic entrainer to the azeotropic distillation.
Description
The cross reference of related application
The application requires the priority of No. the 60/950th, 426, the provisional application submitted on July 18th, 2007.
Invention field
The present invention relates to divide dried up, more especially, divide dried up from moisture and incoming flow aliphatic carboxylic acid from the liquid phase medium of moisture and at least a organic component.
Background of invention
For example, by paraxylene the aliphatic carboxylic acid solvent for example the liquid phase oxidation in the acetic acid prepare in the terephthalic acid (TPA), water and solvent are removed from oxidation reactor as vapor stream of top of the tower usually, as a kind of method of control reaction temperature.Make the vapor stream condensation to reclaim condensate, some of them can the backflow form be recycled to oxidation reactor, and make other condensate enter separation process, and this separation process allows for example acetic acid of aliphatic carboxylic acid solvent that recycle-water content reduces again.
A kind of separation method of convenient form of clamp comprises azeotropic distillation, and it is preferred that this azeotropic distillation is compared with fractionation, because the operation of the energy efficiency of its improvement.Yet for finishing azeotropic distillation, the existence of entrainer causes for example formation of alcohol of entrainer accessory substance.Accessory substance under the condition in being present in destilling tower, by the decomposition of entrainer, especially forms by hydrolysis usually.During azeotropic distillation, these accessory substances trend towards resting on the destilling tower top area of the more water of dissolving, the tower diameter that this increases energy consumption again and needs.In addition, when entrainer degraded and formation accessory substance, more entrainer must be added into azeotrope tower, to realize separation, this has increased the cost of operation.
Therefore, in the art, need to handle the method for entrainer accessory substance, to guarantee to be used for the cheapness of aliphatic carboxylic acid solvent dehydration and the effectively operation of azeotrope tower.
Summary of the invention
According to the present invention, found to handle and therefore reduce the method for entrainer accessory substance, this entrainer accessory substance produces in the azeotrope tower that is used for the aliphatic carboxylic acid solvent dehydration.In the method, the minimizing of entrainer accessory substance causes in the azeotropic distillation system or externally entrainer regeneration in the container of conversion by the entrainer accessory substance.Feature of the present invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water; With
Perhaps
(b) make the stream that contains organic entrainer accessory substance be back to the point in the azeotropic distillation below charging place of described raw material, wherein said organic entrainer accessory substance changes into organic entrainer.
Perhaps
(c) organic entrainer accessory substance is changed into organic entrainer; With
(d) make organic entrainer be back to azeotropic distillation.
The accompanying drawing summary
Fig. 1 is the method flow diagram that illustrates one embodiment of the invention, wherein divides dried uply from aliphatic carboxylic acid through azeotropic distillation, and makes the recirculation of organic entrainer accessory substance.
Fig. 2 is the flow chart of standby embodiment of the present invention.
Fig. 3 is the flow chart of another standby embodiment of the present invention.
Fig. 4 is the flow chart of another standby embodiment of the present invention, and wherein the esterification of entrainer accessory substance occurs in the external reactors container.
Fig. 5 is a flow chart of arranging (configuration) as pilot-scale as described in the comparing embodiment 1.
Fig. 6 is the flow chart of another standby embodiment of the present invention, and wherein the esterification of entrainer accessory substance occurs in the external reactors container.
Fig. 7 is the flow chart of another standby embodiment of the present invention, and wherein the esterification of entrainer accessory substance occurs in the external reactors container.
Fig. 8 is the flow chart of another standby embodiment of the present invention, and wherein the esterification of entrainer accessory substance occurs in the external reactors container.
Fig. 9 is the flow chart of another standby embodiment of the present invention, and wherein the esterification of entrainer accessory substance occurs in the external reactors container.
Describe in detail
Feature of the present invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and the method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, have the water content of reduction with respect to the water content in the raw material, described gaseous component comprises organic entrainer, organic entrainer accessory substance and water; With
(b) make the stream that contains organic entrainer accessory substance be back to the point in the azeotropic distillation below raw material charging place, wherein organic entrainer accessory substance changes into organic entrainer.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and the method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, have the water content of reduction with respect to the water content in the raw material, described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) make organic entrainer accessory substance change into organic entrainer; With
(c) make organic entrainer be back to azeotropic distillation.
In all above-mentioned embodiments of the present invention, step (a) can also comprise that (i) removes the gaseous component of the step of distillating method (a); (ii), form organic liquid phase and aqueous liquid phase with its condensation; (iii) make organic facies be recycled to distillating method; (iv) stripping (stripping) water reclaiming organic entrainer and organic entrainer accessory substance, and forms second gas phase.In addition, in all above-mentioned embodiments, step (a) can also comprise (v) with second vapor condensation; (vi) make at least some steps (condensate recirculation v) to described stripping step (iv).
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) therefore organic entrainer, organic entrainer accessory substance and water-cooled coalescence be formed with machine mutually with the condition of water under, with described gaseous component condensation;
(c) organic facies that makes step (b) is back to the top of azeotropic distillation with the form that refluxes.
(d) carry out the purifying of step (b) water, from water, to remove organic entrainer and organic entrainer accessory substance; With
(e) make organic entrainer and organic entrainer accessory substance be back to the point in the azeotropic distillation below raw material charging place, wherein organic entrainer accessory substance changes into organic entrainer.
In above-mentioned embodiment of the present invention, step (b) can comprise also that (i) makes organic facies and aqueous phase separation; And the purifying that carries out step (d) can comprise that (i) formation contains the stream of organic entrainer, organic entrainer accessory substance and water and (ii) stream is separated into the organic aqeous water that contains organic entrainer and organic entrainer accessory substance.Perhaps, the purifying that carries out step (d) can comprise the water of (i) stripping step (b), the gas phase that contains organic entrainer, organic entrainer accessory substance and water with generation, (ii) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with vapor condensation with (iii) organic entrainer, organic entrainer accessory substance and water are separated into the organic aqeous water that contains organic entrainer and organic entrainer accessory substance.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the gaseous component condensation of step (a);
(c) organic entrainer of step (b), organic entrainer accessory substance and water condensate are separated into organic facies and water;
(d) organic facies that makes step (c) is back to the top of azeotropic distillation with the form that refluxes;
(e) carry out the purifying of step (c) water, contain the stream of organic entrainer, organic entrainer accessory substance and water with generation;
(f) organic entrainer of step (e), organic entrainer accessory substance and current are separated into organic facies and water; With
(g) make the organic facies of step (f) be back to the point in the azeotropic distillation below raw material charging place, wherein organic entrainer accessory substance changes into organic entrainer.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the gaseous component condensation of step (a);
(c) organic entrainer of step (b), organic entrainer accessory substance and water condensate are separated into organic facies and water;
(d) organic facies that makes step (c) is back to the top of azeotropic distillation with the form that refluxes;
(e) water of stripping step (c) contains the gas phase of organic entrainer, organic entrainer accessory substance and water with generation;
(f) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the vapor condensation of step (e);
(g) organic entrainer of step (f), organic entrainer accessory substance and water condensate are separated into organic facies and water; With
(h) make the organic facies of step (g) be back to the point in the azeotropic distillation below raw material charging place, wherein organic entrainer accessory substance changes into organic entrainer.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) therefore organic entrainer, organic entrainer accessory substance and water-cooled coalescence be formed with machine mutually with the condition of water under, with described gaseous component condensation;
(c) make the organic facies of step (b) be back to azeotropic distillation;
(d) carry out the purifying of step (b) water, from water, to remove organic entrainer and organic entrainer accessory substance;
(e) make organic entrainer accessory substance change into organic entrainer; With
(f) make organic entrainer be back to azeotropic distillation.
In above-mentioned embodiment of the present invention, step (b) can comprise also that (i) makes organic facies and aqueous phase separation; And the purifying that carries out step (d) can comprise that (i) formation contains the stream of organic entrainer, organic entrainer accessory substance and water and (ii) stream is separated into the organic aqeous water that contains organic entrainer and organic entrainer accessory substance.Perhaps, the purifying that carries out step (d) can comprise the water of (i) stripping step (b), the gas phase that contains organic entrainer, organic entrainer accessory substance and water with generation, (ii) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with vapor condensation with (iii) organic entrainer, organic entrainer accessory substance and water are separated into the organic aqeous water that contains organic entrainer and organic entrainer accessory substance.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the gaseous component condensation of step (a);
(c) organic entrainer of step (b), organic entrainer accessory substance and water condensate are separated into organic facies and water;
(d) organic facies that makes step (c) is back to the top of azeotropic distillation with the form that refluxes;
(e) carry out the purifying of step (c) water, contain the stream of organic entrainer, organic entrainer accessory substance and water with generation;
(f) organic entrainer of step (e), organic entrainer accessory substance and current are separated into organic facies and water;
(g) make the organic entrainer accessory substance in the organic facies change into organic entrainer; With
(h) make organic entrainer be back to azeotropic distillation.
The feature of another embodiment of the invention can be the Azotropic distillation method of raw material, and wherein raw material comprises aliphatic carboxylic acid and water, and this method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the gaseous component condensation of step (a);
(c) organic entrainer of step (b), organic entrainer accessory substance and water condensate are separated into organic facies and water;
(d) organic facies that makes step (c) is back to the top of azeotropic distillation with the form that refluxes;
(e) water of stripping step (c) contains the gas phase of organic entrainer, organic entrainer accessory substance and water with generation;
(f) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with the vapor condensation of step (e);
(g) organic entrainer of step (f), organic entrainer accessory substance and water condensate are separated into organic facies and water;
(h) make the organic entrainer accessory substance in the organic facies change into organic entrainer; With
(i) make organic entrainer be back to azeotropic distillation.
In all embodiments, the gaseous component that comprises organic entrainer, organic entrainer accessory substance and water of step (a) is for example removed from still-process as the vapor stream of top of the tower of destilling tower as top product, and can be condensed into the liquid stream and first vapor stream.First vapor stream can be delivered to after-fractionating tower, first vapor stream that wherein comprises organic entrainer, organic entrainer accessory substance and water enters into Ta Nei and further distillation of process, so organic entrainer, organic entrainer accessory substance and water condensation, and reclaim from tower as liquid phase, and any other impurity is retained in the gas phase.The liquid phase of the organic entrainer/organic entrainer accessory substance/water that reclaims can allow to be separated into organic facies and water then.
In all embodiments of the present invention, organic entrainer can be to be selected from following at least a ester: n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate or its mixture, for example isobutyl acetate, n-propyl acetate or isopropyl acetate; N-propyl acetate or isopropyl acetate; Or n-propyl acetate.Organic entrainer can be a boiling point the boiling point of the about isopropyl acetate scope to the boiling point of about n-butyl acetate, for example about 88 ℃-Yue 126 ℃ entrainer.Organic entrainer accessory substance can be to be selected from least one following member: propyl alcohol, butanols, corresponding to alcohol or its mixture of organic ester entrainer.
In all embodiments of the present invention, organic entrainer accessory substance changes into the esterification that organic entrainer can comprise organic entrainer accessory substance and aliphatic carboxylic acid.For this purpose, aliphatic carboxylic acid should be high relatively concentration, is beneficial to esterification rather than hydrolysis.Aliphatic carboxylic acid is present in below the input of column point with such concentration.Esterification can use existing aliphatic carboxylic acid to occur in the destilling tower, otherwise in the reactor vessel that separates of tower outside.The reactant aliphatic carboxylic acid can be fresh or derive from bottoms product.The stream of question response can be the entrainer accessory substance that is easy to the relative high concentration of its esterification.
In all embodiments of the present invention, be recycled to the organic facies of azeotrope tower or reflux and to comprise organic entrainer accessory substance of following concentration: in total composition, about 1% weight-Yue 15% weight, for example about 2% weight-Yue 15% weight or about 1% weight-Yue 10% weight or about 2% weight-Yue 10% weight or about 2% weight-Yue 8% weight or about 2% weight-Yue 6% weight.
Wherein the present invention can the most suitable aromatic carboxylic acid preparation method be preparation terephthalic acid (TPA) and employed those methods of M-phthalic acid on the commercial size, and wherein the aliphatic carboxylic acid solvent is generally acetic acid.
Can understand the present invention better by with reference to figure 1,2,3,4,6,7,8 and 9, these figure illustrate the Azotropic distillation method that separates aliphatic carboxylic acid and water.
With reference to figure 1, feeding line 1 comprises the dehydration that obtains from oxidation reactor overhead condenser system to dehydrating tower D1 (it can be the destilling tower of filling or tower tray (tray) type), and this overhead condenser system is connected with the oxidation reactor of preparation terephthalic acid (TPA).Such as but not limited to, the composition of feeding line 1 can comprise 1% weight-40% weight water and 99% weight-60% weight acetic acid.Other charging also can be supplied to tower, for example the crystallizer vapor stream.Heat to tower D1 provides through reboiler E1.The organic entrainer of low boiling, for example n-propyl acetate, isopropyl acetate, isobutyl acetate or n-butyl acetate can be supplied to tower through reflux pipeline 5, and operational tower infiltrate into the level that is lower than charging 1 to guarantee entrainer, so charging 1 enters tower in the zone of being rich in entrainer.
The bottom product that takes out from the bottom of tower D1 through pipeline 2 comprises the acetic acid that for example has relative low water content with respect to the feeding line 1 of coming in, and is applicable to and is recycled to oxidation reaction.Such as but not limited to, bottom product can comprise 1% weight-20% weight water and 99% weight-80% weight acetic acid.In column overhead condenser system E2, adopt suitable medium such as but not limited to cooling water, steam or heat transfer fluid, cooling is at the top product of tower D1 head.Condensate is supplied to elementary decanter F1, wherein condensate separation is become organic facies (mainly being to contain a small amount of organic entrainer accessory substance, water and some methyl acetates, paraxylene and other organic organic entrainer) and contain the water of organic entrainer accessory substance and a small amount of organic entrainer.The organic facies that consists predominantly of the machine entrainer is imported destilling tower again through pipeline 5.In order to reclaim organic entrainer and organic entrainer accessory substance through pipeline 8, water is sent to recovery tower D2 through pipeline 6 to recycling decanter F2.Elementary decanter F1 also can be used for the required any other entrainer of the system that is introduced in.By steam (by direct injection or pass reboiler) heating recovery tower D2, and steam pipe line 8 leaves tower and enters condenser E3.Recovery tower D2 comprises filling or tray section.The bottom product that takes out from recovery tower D2 bottom through pipeline 7 comprises the water that has low relatively content of organics (such as but not limited to being lower than about 1% weight) with respect to the incoming flow 6 of coming in.
Recirculation decanter F2 is through pipeline 8 chargings, and this pipeline 8 passes condenser E3 from recovery tower D2.Incoming flow 8 consists predominantly of machine entrainer and organic entrainer accessory substance.Any water in the incoming flow 8 can be separated in recirculation decanter F2, and is back to elementary decanter F1 or to recovery tower D2 through pipeline 10 chargings.Organic entrainer and the dehydrating tower D1 of organic entrainer accessory substance below pipeline 9 is fed to feeding line 1.Organic entrainer accessory substance is got back to organic entrainer by the esterification conversion in dehydrating tower D1.
Fig. 2 illustrates the standby layout of Fig. 1, and wherein condenser E3 is in recovery tower D2 inside.Uncondensable light materials can be fed to recovery tower D2 through pipeline 11, this pipeline 11 fill from the upper and lower of E2 to the tower D2 or tray section between feed points.Separator can provide above upper and lower filling or tray section in recovery tower D2.The point of feeding line 6 between bottom separator and under-filled or tray section from elementary decanter F1 is fed to recovery tower D2.The pipeline 8 that is fed to recirculation decanter F2 leaves recovery tower D2 at lucky point below filling of above the separator of bottom and top or tray section.
Fig. 3 illustrates the standby layout of Fig. 2, wherein recycles decanter F2 in recovery tower D2 inside.
Fig. 4 illustrates the standby layout of Fig. 1-3, and wherein the esterification of entrainer accessory substance can occur in the esterifier R1, rather than in azeotrope tower D1.The inside decanter of Fig. 3 also can be used for this layout, with the function that is separated.
Fig. 6 illustrates the standby layout of Fig. 4, and wherein pipeline 8 can be by other heat exchanger E4 cooling.
Fig. 7 illustrates the standby layout of Fig. 4, and the point of pipeline 8 in top filling or tray section that wherein is fed to recirculation decanter F2 leaves recovery tower D2.In addition, the pipeline 15 that is fed to elementary decanter F1 leaves recovery tower D2 on the top of tower D2 and the point between under-filled or the tray section.
Fig. 8 illustrates the standby layout of Fig. 7, and wherein pipeline 8 is by other heat exchanger E4 cooling.
Fig. 9 illustrates the standby layout of Fig. 4, and wherein pipeline 16 can be fed to the entrainer accessory substance in the pipeline 9 of esterifier R1 front.
Following examples further illustrate the present invention.
Comparing embodiment 1
The dehydrating tower system of pilot-scale moves in the layout of Fig. 5, gathers in that cat head is debatable to prove organic entrainer accessory substance.Pilot test system is several days time of operation under the tower top pressure of 4 crust.Fetch from SP1, enter the sample of dehydrating tower D1, increase at cat head to prove organic entrainer accessory substance.The organic entrainer that uses is to have the 99% pure n-propyl acetate that is lower than 1% propyl alcohol impurity.In result's table 1 below.
Table 1
| My god | Propyl alcohol (% weight) at SP1 |
| ??1 | ??2.3 |
| ??2 | ??4.6 |
| ??3 | ??6.5 |
| ??4 | ??5.3 |
| ??5 | ??7.2 |
| ??6 | ??9.2 |
The autoclave in batches of running experiment chamber scale repeatedly proves that organic entrainer accessory substance transforms to get back to organic entrainer.Condition in the autoclave is designed to similar to the bottom part of azeotrope tower.In order to prove conversion, in the charging to autoclave in batches, as entrainer, propyl alcohol (PrOH) is as the entrainer accessory substance with n-propyl acetate (nPA).Describe in detail as table 2, water and acetic acid also are fed to autoclave in batches.By after each run from the liquid sampling of autoclave, detect the concentration of propyl alcohol.The percentage that feed composition in the register system, propyl alcohol reduce, the time of staying and the temperature of autoclave in batches.In result's table 2 below.
Table 2
Use the validity of Aspen simulation and kinetic model proof esterifier R1.Esterification device input concentration produces by the Aspen simulation, and is applied to the kinetic model of n-propyl acetate hydrolysis/esterification.According to this model, measure the speed that normal propyl alcohol transforms.As shown in Figure 4, the layout scope of Aspen simulation that is used to produce esterifier R1 feed composition is very wide, has following difference:
By two divided portion (top and bottom), set up the model of methyl acetate recovery tower D2.
Only a part enters the esterification device from the organic matter of recirculation decanter (pipeline 9).Remainder mixed with pipeline 5 before getting back to tower with the form that refluxes.
PX purifying column (purge column) is arranged in the ASPEN model.
Hydrolysis module in the hydrolysis of all places simulation entrainer is arranged.By the value that the classification of stipulating in esterification device module transforms, the control propyl alcohol leaves standstill concentration in reflux (pipeline 5).
The Aspen simulation is made up of following formant operation:
Dehydrating tower D1 and reboiler E1: standard: top P=3.8 crust, P=4 crust in bottom is by " design specification " control bottom product
Dehydrating tower condenser E2: standard: T=115-116C
Methyl acetate recovery tower: P=3.65-4 crust
Esterification device R1: standard: P=7 crust, T=160C
Use following formula to calculate esterification rate:
In result's table 3 below of simulation and kinetic model.
Table 3
Use the validity of Aspen simulation and kinetic model proof esterifier R1.Operation Aspen simulation in the layout of Fig. 6, and produce the esterification device input concentration that is used for as the kinetic model of embodiment 3.Simulation arrangements difference, unit operations description and rate calculations are identical with embodiment 3.In result's table 4 below.
Table 4
Use the validity of Aspen simulation and kinetic model proof esterifier R1.Operation Aspen simulation in the layout of Fig. 7, and produce the esterification device input concentration that is used for as the kinetic model of embodiment 3.Simulation arrangements difference, unit operations description and rate calculations are identical with embodiment 3.In result's table 5 below.
Table 5
Use the validity of Aspen simulation and kinetic model proof esterifier R1.Operation Aspen simulation in the layout of Fig. 8, and produce the esterification device input concentration that is used for as the kinetic model of embodiment 3.Simulation arrangements difference, unit operations description and rate calculations are identical with embodiment 3.In result's table 6 below.
Table 6
The tubular reactor system of running experiment chamber scale proves the validity of esterifier R1, and verifies the result of embodiment 3-6Aspen simulation and kinetic model.Laboratory scale tubular reactor system has the pump of 10ml head, feed composition is pumped into 1/16 " O.D. preheater coil pipe; then to be furnished with the HITRAN insert 1/2 " the O.D. tubular reactor, " the O.D. coil pipe in cooler enters in the shuttle at last to 1/16 then.Preheater coil pipe and tubular reactor are in being set in about 160 ℃ oil bath.Coil pipe in cooler is being set in about 20 ℃
Cooling bath in.This system has the back pressure regulator that is positioned at just before the shuttle, and pressure is set in about 11 crust (suppressing boiling).Reactor residence time is about 25 minutes.
In the beginning of each test, send the system of passing with water pump, and oil bath is set to required temperature.When reaching design temperature, use the feeding liquid place of water.Before sampling, operation unit time enough be the representative of feeding liquid with the liquid of guaranteeing to flow through the unit, and all water is pumped out.Collect 3 samples of each experiment, each 7-8ml.On gas chromatograph, analyze the sample of charging and product.Based on 10 l injected sample,, use standard K F volumetric soiutions to measure water concentration by Karl Fischer test.In result's table 7 below of propyl alcohol (PrOH) conversion ratio.
Table 7
Though the present invention is described in conjunction with its specific embodiment, obviously,, manyly substitute, modifications and variations will be conspicuous to those skilled in the art according to the description of front.Therefore, the present invention will comprise all these type of alternative, the modifications and variations in the spirit and scope that drop on claim.
Claims (43)
1. the Azotropic distillation method of a raw material, wherein said raw material comprises aliphatic carboxylic acid and water, and described method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water; With
(b) make the stream that contains organic entrainer accessory substance be back to the point in the azeotropic distillation below charging place of described raw material, wherein said organic entrainer accessory substance changes into organic entrainer.
2. the process of claim 1 wherein that described organic entrainer has at the boiling point of the about isopropyl acetate boiling point to the boiling spread of about n-butyl acetate.
3. the process of claim 1 wherein that described organic entrainer has the boiling point in about 88 ℃-Yue 126 ℃ of scopes.
4. the process of claim 1 wherein that described organic entrainer is to be selected from following at least a ester: n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate and composition thereof.
5. the process of claim 1 wherein that described organic entrainer accessory substance is to be selected from least one following member: propyl alcohol, butanols, corresponding to alcohol of described organic entrainer and composition thereof.
6. the method for claim 1, described method comprises following other step: the gaseous component of (i) removing the step (a) of distillating method; (ii), form organic facies and water with its condensation; (iii) make described organic facies be recycled to distillating method; The (iv) described water of stripping reclaiming organic entrainer and organic entrainer accessory substance, and forms second gas phase.
7. the method for claim 6, wherein step organic facies (iii) comprises organic entrainer accessory substance that concentration is about 1% weight-Yue 15% weight.
8. the method for claim 6, described method comprises following other step: (v) with second vapor condensation; (vi) make at least some steps (condensate recirculation v) to described stripping step (iv).
9. the process of claim 1 wherein that the conversion of step (b) comprises the esterification of organic entrainer accessory substance.
10. the Azotropic distillation method of a raw material, wherein said raw material comprises aliphatic carboxylic acid and water, and described method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) make organic entrainer accessory substance change into organic entrainer; With
(c) make described organic entrainer be back to azeotropic distillation.
11. the method for claim 10, wherein said organic entrainer have at the boiling point of the about isopropyl acetate boiling point to the boiling spread of about n-butyl acetate.
12. the method for claim 10, wherein said organic entrainer have the boiling point in about 88 ℃-Yue 126 ℃ of scopes.
13. the method for claim 10, wherein said organic entrainer are to be selected from following at least a ester: n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate and composition thereof.
14. the method for claim 10, wherein said organic entrainer accessory substance is to be selected from least one following member: propyl alcohol, butanols, corresponding to alcohol of described organic entrainer and composition thereof.
15. the method for claim 10, described method comprise following other step: the gaseous component of (i) removing the step (a) of distillating method; (ii), form organic facies and water with its condensation; (iii) make described organic facies be recycled to distillating method; (iv) stripping water reclaiming organic entrainer and organic entrainer accessory substance, and forms second gas phase.
16. the method for claim 15, wherein step organic facies (iii) comprises organic entrainer accessory substance that concentration is about 2% weight-Yue 15% weight.
17. the method for claim 15, described method comprise following other step: (v) with second vapor condensation; (vi) make at least some steps (condensate recirculation v) to described stripping step (iv).
18. the method for claim 10, wherein the conversion of step (b) comprises the esterification of described organic entrainer accessory substance.
19. the Azotropic distillation method of a raw material, wherein said raw material comprises aliphatic carboxylic acid and water, and described method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) therefore organic entrainer, organic entrainer accessory substance and water-cooled coalescence be formed with machine mutually with the condition of water under, with described gaseous component condensation;
(c) make the organic facies of step (b) be back to azeotropic distillation.
(d) carry out the purifying of step (b) water, from water, to remove organic entrainer and organic entrainer accessory substance; With
(e) make described organic entrainer and organic entrainer accessory substance be back to the point in the azeotropic distillation below charging place of described raw material, wherein organic entrainer accessory substance changes into organic entrainer.
20. the method for claim 19, wherein said organic entrainer have at the boiling point of the about isopropyl acetate boiling point to the boiling spread of about n-butyl acetate.
21. the method for claim 19, wherein said organic entrainer have the boiling point in about 88 ℃-Yue 126 ℃ of scopes.
22. the method for claim 19, wherein said organic entrainer are to be selected from following at least a ester: n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate and composition thereof.
23. the method for claim 19, wherein said organic entrainer accessory substance is to be selected from least one following member: propyl alcohol, butanols, corresponding to alcohol of described organic entrainer and composition thereof.
24. the method for claim 19, wherein the conversion of step (e) comprises the esterification of described organic entrainer accessory substance.
25. the method for claim 19, wherein the organic facies of step (c) comprises organic entrainer accessory substance that concentration is about 1% weight-Yue 15% weight.
26. the method for claim 19, wherein step (b) comprises that also (i) makes described organic facies and aqueous phase separation; And the wherein said purifying that carries out step (d) comprises that (i) formation contains the stream of organic entrainer, organic entrainer accessory substance and water and (ii) described stream is separated into organic facies and the water that contains organic entrainer and organic entrainer accessory substance.
27. the method for claim 19, wherein step (b) comprises that also (i) makes described organic facies and aqueous phase separation; And the wherein said purifying that carries out step (d) comprises the water of (i) stripping step (b), the gas phase that contains organic entrainer, organic entrainer accessory substance and water with generation, (ii) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with vapor condensation with (iii) described organic entrainer, organic entrainer accessory substance and water are separated into organic facies and the water that contains organic entrainer and organic entrainer accessory substance.
28. the Azotropic distillation method of a raw material, wherein said raw material comprises aliphatic carboxylic acid and water, and described method comprises:
(a) in the presence of organic entrainer, carry out azeotropic distillation, to produce liquid phase component and gaseous component, described liquid phase component comprises described aliphatic carboxylic acid, has the water content of reduction with respect to the water content in the raw material, and described gaseous component comprises organic entrainer, organic entrainer accessory substance and water;
(b) therefore organic entrainer, organic entrainer accessory substance and water-cooled coalescence be formed with machine mutually with the condition of water under, with described gaseous component condensation;
(c) make the organic facies of step (b) be back to azeotropic distillation.
(d) carry out the purifying of step (b) water, from water, to remove organic entrainer and organic entrainer accessory substance;
(e) make described organic entrainer accessory substance change into organic entrainer; With
(f) make described organic entrainer be back to azeotropic distillation.
29. the method for claim 28, wherein said organic entrainer have at the boiling point of the about isopropyl acetate boiling point to the boiling spread of about n-butyl acetate.
30. the method for claim 28, wherein said organic entrainer have the boiling point in about 88 ℃-Yue 126 ℃ of scopes.
31. the method for claim 28, wherein said organic entrainer are to be selected from following at least a ester: n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate and composition thereof.
32. the method for claim 28, wherein said organic entrainer accessory substance is to be selected from least one following member: propyl alcohol, butanols, corresponding to alcohol of described organic entrainer and composition thereof.
33. the method for claim 28, wherein the conversion of step (e) comprises the esterification of described organic entrainer accessory substance.
34. the method for claim 28, wherein the organic facies of step (c) comprises organic entrainer accessory substance that concentration is about 2% weight-Yue 15% weight.
35. the method for claim 28, wherein step (b) comprises that also (i) makes organic facies and aqueous phase separation; And the wherein said purifying that carries out step (d) comprises that (i) formation contains the stream of organic entrainer, organic entrainer accessory substance and water and (ii) described stream is separated into organic facies and the water that contains organic entrainer and organic entrainer accessory substance.
36. the method for claim 35, wherein step (d) also is included in before the separation, makes described stream cooling.
37. the method for claim 35, wherein the point of the described stream of step (d) in top filling or tray section leaves recovery tower.
38. the method for claim 35 wherein is added into step (d) organic facies (ii) with other organic entrainer accessory substance.
39. the method for claim 28, wherein step (b) comprises that also (i) makes organic facies and aqueous phase separation; And the wherein said purifying that carries out step (d) comprises the water of (i) stripping step (b), the gas phase that contains organic entrainer, organic entrainer accessory substance and water with generation, (ii) under the condition of therefore organic entrainer, organic entrainer accessory substance and water condensation, with vapor condensation with (iii) described organic entrainer, organic entrainer accessory substance and water are separated into organic facies and the water that contains organic entrainer and organic entrainer accessory substance.
40. the method for claim 39, wherein step (d) (ii) also is included in after their condensations, with organic entrainer, organic entrainer accessory substance and water cooling.
41. the method for claim 39, wherein the point of step (d) described organic entrainer, organic entrainer accessory substance and water (ii) in top filling or tray section leaves recovery tower.
42. the method for claim 39 wherein is added into step (d) organic facies (iii) with other organic entrainer accessory substance.
43. each method in the claim 1,10,19 or 28, wherein said aliphatic carboxylic acid is an acetic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US95042607P | 2007-07-18 | 2007-07-18 | |
| US60/950426 | 2007-07-18 | ||
| PCT/IB2008/002698 WO2009013623A2 (en) | 2007-07-18 | 2008-06-27 | Azeotropic distillation with entrainer regeneration |
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| Publication Number | Publication Date |
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| CN101854989A true CN101854989A (en) | 2010-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200880108239A Pending CN101854989A (en) | 2007-07-18 | 2008-06-27 | Azeotropic distillation with entrainer regeneration |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN101854989A (en) |
| AR (1) | AR067614A1 (en) |
| SA (1) | SA08290441B1 (en) |
| TW (1) | TW200909408A (en) |
| WO (1) | WO2009013623A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328432A (en) * | 2010-12-10 | 2013-09-25 | 陶氏环球技术有限责任公司 | Apparatus and process for using a nitroalkane as an entrainer for azeotropic removal of water from aqueous acid solution |
| CN103827076A (en) * | 2011-04-18 | 2014-05-28 | 陶氏环球技术有限责任公司 | Apparatus and process for nitration selectivity flexibility enabled by azeotropic distillation |
| CN105381624A (en) * | 2015-11-24 | 2016-03-09 | 肥城金威机械有限公司 | Azeotropy rectification method-based acetic acid recovery device and method |
| CN103827076B (en) * | 2011-04-18 | 2016-11-30 | 安格斯化学公司 | Equipment and the method for nitrification selectivity motility is given by azeotropic distillation |
| CN109467501A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | Acetic acid refining and entrainer regeneration technology and device in polyvinyl alcohol disposing mother liquor unit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8382961B2 (en) * | 2010-06-07 | 2013-02-26 | Amt International, Inc. | System and method for reduction of water consumption in purified terephthalic acid production |
| GB201015986D0 (en) | 2010-09-23 | 2010-11-03 | Davy Process Techn Ltd | Process and apparatus |
| EP2461613A1 (en) * | 2010-12-06 | 2012-06-06 | Gemalto SA | Methods and system for handling UICC data |
| EP2649030A1 (en) | 2010-12-10 | 2013-10-16 | Dow Global Technologies LLC | Apparatus and process for using olefin as an azeotropic entrainer for isolating 1,3-dichloro-2-propanol from a 2,2'-oxybis (1-chloropropane) waste stream |
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| CN1492850A (en) * | 2001-02-27 | 2004-04-28 | 三菱化学株式会社 | Azeotropic distillation process |
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| JPS53116314A (en) * | 1977-03-19 | 1978-10-11 | Mitsui Petrochem Ind Ltd | Separation of acetic acid and water |
| JPS61109750A (en) * | 1984-11-02 | 1986-05-28 | Shinetsu Sakusan Vinyl Kk | Dehydrative distillation of aqueous solution of carboxylic acid |
| BR9508815A (en) * | 1994-08-23 | 1997-11-18 | Ici Plc | Processes for producing an aromatic dicarboxylic acid and for carrying out the water separation of a liquid phase vehicle containing at least one component body by azeotropic distillation |
| EP0973717B1 (en) * | 1997-04-09 | 2003-10-01 | E.I. Du Pont De Nemours And Company | Water separation process |
| US7048835B2 (en) * | 2002-02-12 | 2006-05-23 | Amt International, Inc. | System and method for acetic acid recovery during terephthalic acid production |
| AU2003262636A1 (en) * | 2003-08-12 | 2005-03-10 | Amt International, Inc. | System and method for acetic acid recovery during terephthalic acid production |
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2008
- 2008-06-27 CN CN200880108239A patent/CN101854989A/en active Pending
- 2008-06-27 WO PCT/IB2008/002698 patent/WO2009013623A2/en active Application Filing
- 2008-07-04 TW TW097125461A patent/TW200909408A/en unknown
- 2008-07-16 SA SA8290441A patent/SA08290441B1/en unknown
- 2008-07-18 AR ARP080103125A patent/AR067614A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1492850A (en) * | 2001-02-27 | 2004-04-28 | 三菱化学株式会社 | Azeotropic distillation process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328432A (en) * | 2010-12-10 | 2013-09-25 | 陶氏环球技术有限责任公司 | Apparatus and process for using a nitroalkane as an entrainer for azeotropic removal of water from aqueous acid solution |
| CN103328432B (en) * | 2010-12-10 | 2015-07-22 | 安格斯化学公司 | Apparatus and process for using a nitroalkane as an entrainer for azeotropic removal of water from aqueous acid solution |
| CN103827076A (en) * | 2011-04-18 | 2014-05-28 | 陶氏环球技术有限责任公司 | Apparatus and process for nitration selectivity flexibility enabled by azeotropic distillation |
| CN103827076B (en) * | 2011-04-18 | 2016-11-30 | 安格斯化学公司 | Equipment and the method for nitrification selectivity motility is given by azeotropic distillation |
| CN105381624A (en) * | 2015-11-24 | 2016-03-09 | 肥城金威机械有限公司 | Azeotropy rectification method-based acetic acid recovery device and method |
| CN109467501A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | Acetic acid refining and entrainer regeneration technology and device in polyvinyl alcohol disposing mother liquor unit |
| CN109467501B (en) * | 2018-08-03 | 2024-02-20 | 内蒙古蒙维科技有限公司 | Process and device for refining acetic acid and regenerating entrainer in polyvinyl alcohol mother liquor recovery unit |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009013623A2 (en) | 2009-01-29 |
| TW200909408A (en) | 2009-03-01 |
| AR067614A1 (en) | 2009-10-14 |
| WO2009013623A3 (en) | 2009-08-06 |
| SA08290441B1 (en) | 2012-02-07 |
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