CN102892742A - Purification of carboxylic acids by catalytic hydrogenation - Google Patents
Purification of carboxylic acids by catalytic hydrogenation Download PDFInfo
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- CN102892742A CN102892742A CN2011800097590A CN201180009759A CN102892742A CN 102892742 A CN102892742 A CN 102892742A CN 2011800097590 A CN2011800097590 A CN 2011800097590A CN 201180009759 A CN201180009759 A CN 201180009759A CN 102892742 A CN102892742 A CN 102892742A
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- 238000000746 purification Methods 0.000 title claims abstract description 84
- 150000001735 carboxylic acids Chemical class 0.000 title abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
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- 238000000034 method Methods 0.000 claims abstract description 43
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- 230000008569 process Effects 0.000 claims abstract description 25
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/0061—Controlling the level
Abstract
The present invention relates to a process for the production of an aromatic carboxylic acid comprising: a) introducing a crude aromatic carboxylic acid solution into a purification reactor vessel, wherein the purification reactor vessel is operating under pressure, b) introducing hydrogen gas into the purification reactor vessel, c) dissolving the hydrogen gas in the crude aromatic polycarboxylic acid solution as the solution flows down a wall of a vertical conduit onto a distributor, wherein the purification reactor vessel has a gas-liquid contact area to plant throughput (capacity) ratio of at least 0.55 m2/ te/h of carboxylic acid for dissolving the hydrogen gas in the crude aromatic polycarboxylic acid solution to produce a reaction solution, and d) contacting the reaction solution with a supported catalyst bed to produce a purified aromatic carboxylic acid,; wherein the supported catalyst bed is submerged in the reaction solution and a liquid level of the reaction solution is maintained above the supported catalyst bed.
Description
The cross reference of related application
The application requires the rights and interests of the right of priority of the U.S. Provisional Application submitted on February 15th, 2010 number 61/304567.
Invention field
The present invention relates to the method for purifying aromatics polycarboxylic acid, and be particularly related to the catalytic hydrogenation reaction for the preparation of the aromatics polycarboxylic acid of purifying.
Background of invention
The aromatics polycarboxylic acid is commercially important chemical intermediate, and particularly as polyester raw material, it is for the manufacture of fiber, bottle, film and electronic application.
The aromatics polycarboxylic acid, terephthalic acid for example, the preparation of m-phthalic acid and naphthalic acid generally includes oxidation step and purification step subsequently.This oxidation step comprises a kind of method, polyoxyethylene alkyl aryl family hydrocarbon precursor dimethylbenzene for example wherein, trialkyl benzene or dialkyl group naphthalene, at high temperature and high pressure and heavy metal for example in the presence of cobalt, manganese and the bromine compounds, in the aqueous acetic acid solvent by molecular oxygen oxidation.Comprise impurity such as monocarboxylic acid and aldehyde among the thick aromatics polycarboxylic acid who obtains by above-mentioned oxidizing reaction, they are intermediate products of oxidizing reaction, bromine adducts and derive from the metal component of catalyzer, and the coloring material with unknown structure.Be enough to and the purification step of glycol direct esterification with the aromatics polycarboxylic acid of the purity of production polyester polymers for the production of having, relate to a kind of method, wherein thick aromatics polycarboxylic acid is in High Temperature High Pressure with in the presence of catalyzer (for example at the VIII group 4 transition metal on the carbon support), in the water as solvent, be hydrogenated, for example such as U.S. Patent number 3, disclosed in 584,039.Purifying aromatics polycarboxylic acid after the hydrogenation reaction can be directly used in and produce polymkeric substance or usually adopt following method to make itself and separated from solvent: make aromatics polycarboxylic acid crystallization, crystallized product is separated with water solvent and dry to obtain dry crystallized product.
Summary of the invention
Traditional method purifying aromatics polycarboxylic acid's problem comprises: the required number of containers of working liquid stock (inventory) that i) is used for dissolving aromatics polycarboxylic acid and holds solution, and ii) is used for dissolving hydrogen, the liquid that contains thick aromatics polycarboxylic acid is contacted with catalyzer with hydrogen and provides enough residence time to finish the reactor size of purification reaction.Usually, because the solubleness of hydrogen in aromatics polycarboxylic acid solution is limited, need to keeps high reactor pressure and be dissolved in the purifying of finishing thick aromatics polycarboxylic acid in the aqueous solvent to guarantee sufficient hydrogen.The another one problem is the shortening of the catalyzer operation life due to solid support material destroys, and it results from and use heterogeneous catalyst in purification reaction.
The consequence of these combinatorial problems, or be because equipment cost is higher or catalyst life reduces the running cost increase that causes, or be that the purified product that relatively poor operation control brings changes larger.
One object of the present invention is to reduce or avoid one or more in the problems referred to above.Particularly, an object of the present invention is to provide improved continuation method, it is used for contacting with supported catalyst under high temperature and high pressure, with the hydrogen purification aromatics polycarboxylic acid aqueous solution.Have been found that a kind of method of carrying out purification reaction, it comprises that the reaction intermediate from aromatic aldehyde is converted into corresponding one dollar aromatic carboxylic acid.The present invention relates to the method for the production of the aromatic carboxylic acid, comprise: a) thick aromatic carboxylic acid's solution is incorporated in the purification reaction container, wherein this purification reaction container operates under pressure, b) hydrogen is introduced in this purification reaction container, c) when solution flows on the divider downwards along the vertical ducting wall, hydrogen is dissolved in the thick aromatics polycarboxylic acid solution, and wherein the ratio of the gas-to-liquid contact area of this purification reaction container and device processes amount (plant throughput) (capacity) is 0.55m at least
2/ te/h carboxylic acid, it is processed for hydrogen being dissolved in thick aromatics polycarboxylic acid solution to produce reaction soln, and d) reaction soln is contacted with the supported catalyst bed, produce the aromatic carboxylic acid of purifying, wherein the supported catalyst bed is immersed in the reaction solution, and keeps the liquid level of reaction solution to be higher than the supported catalyst bed.This catalyst bed is completely submerged, and the thick polycarboxylic acid of dissolving (thick acid) solution level remains on the supported catalyst.The benefit of this working method is by guaranteeing that gaseous hydrogen does not directly contact to prolong the operation life of supported catalyst bed with the granules of catalyst of load, and by keeping thick acid solution level stability to be higher than the supported catalyst bed to reduce the variation of product quality.Another object of the present invention is when hydrogen enters purification reactor, improve its solvability in thick acid solution by increasing the liquid surface area that contacts with gaseous hydrogen, with the quick variation that reduces working pressure and the fluctuation of purification reactor liquid level, and this fluctuation causes the variation of polycarboxylic acid's (purifying acid) product quality of purifying.Another purpose is to reduce the quantity of container and the total residence time of aromatic carboxylic acid's solution, thereby significantly reduces the required equipment cost of purification step in the manufacturing processed.
The accompanying drawing summary
Fig. 1 illustrates one embodiment of the invention schematic diagram of (having shown purification reactor).
Fig. 2 illustrates one embodiment of the invention schematic diagram of (having shown liquid dispenser).
Fig. 3 is the schematic diagram of conventional purification reactor.
Describe in detail
The present invention relates to the method for the production of the aromatic carboxylic acid, comprise: a) thick aromatic carboxylic acid's solution is incorporated in the purification reaction container, wherein this purification reaction container operates under pressure, b) hydrogen is incorporated in this purification reaction container, c) when solution flows on the divider downwards along the vertical ducting wall, hydrogen is dissolved in the thick aromatics polycarboxylic acid solution, and wherein the ratio of the gas-to-liquid contact area of this purification reaction container and device processes amount (capacity) is 0.55m at least
2/ te/h carboxylic acid, hydrogen is dissolved in the thick aromatics polycarboxylic acid solution to produce reaction soln, and d) reaction soln and supported catalyst bench grafting are touched, produce the aromatic carboxylic acid of purifying, wherein the supported catalyst bed is immersed in the reaction solution, and keeps the liquid level of reaction solution to be higher than the supported catalyst bed.The ratio of the gas-to-liquid contact area step c) and device processes amount (capacity) can be about 0.65m
2/ te/h carboxylic acid or more, for example about 0.75m
2/ te/h carboxylic acid or more, or 1.2m
2/ te/h carboxylic acid or more.Divider can comprise i) diameter be the purification reaction container diameter approximately 0.3 to about 0.7 perforated disc (circular disc), ii) around the notched weir opening (notched weir openings) of edge placement of dish (plate), so that thick acid solution is remained on the dish; And iii) at least one hole, reaction soln flows on the fluid surface of divider below through it.Divider also can comprise i) diameter be the purification reaction container diameter approximately 0.3 to approximately 0.7 perforation annular open tube or groove (channel), the notched weir opening of ii) arranging around pipe or groove edge is to remain on thick acid solution on the dish; And iii) at least one hole, reaction soln flows on the fluid surface of divider below through it.Divider can be positioned at the position that is higher than 0.5 to 2 meter of thick acid solution liquid level, and for example 0.5 to 1.0 meter, and flow through this hole and cross the notched weir opening of thick acid solution.Increase is provided in the time of randomly, can using alternative liquid dispenser configuration with the liquid volume that flows to catalyst bed top when thick acid solution and keep with the contacted liquid surface area of gas.The aromatics polycarboxylic acid can be terephthalic acid.
One embodiment of the invention comprise dissolving part (dissolution section) bottom that thick acid solution is fed to purification reactor by entrance, wherein all thick acid solutions are along the flow path of extending, overflow to the vertical ducting of plate distributor top, and stop surpasses the minimum residence time (approximately 3.0 minutes or longer) (to comprise dissolver or dissolving part) on the gas-to-liquid contact area of purification reactor.For example, can be approximately 3.5 minutes or longer in the minimum residence time of dissolving part, or approximately 4.0 minutes or longer.The minimum residence time in dissolving part and the total of the liquid level above catalyzer can be approximately 3.5 minutes or longer, or 4.0 minutes or longer.The configuration of inlet tube comprises bend pipe, the opening of aligning or other device that becomes known for draining into dissolver or dissolve part.
In another embodiment, extra liquid dispenser is positioned at the top of downtake, so that liquid can be sprayed so that extra Surface Contact area to be provided downwards along the inside of downtake.In this case, liquid dispenser can be pipe or groove (trough), and it is across the top orientation of downtake, the substrate of each groove or pipe has a plurality of holes, liquid flows into groove or pipe by this, these holes of then flowing through, and this produces liquid spray effectively in downtake.
Another embodiment of the invention relates to the control of the gaseous tension in thick acid solution liquid level and the purification reactor.The control of these two parameters comprises by regulating from the flow velocity of purification reactor purifying acid solution out keeps gaseous tension in the setting pressure of about 0.5 bar.Change in flow is restricted to keep the minimum liquid level of catalyst bed top, and this is in-50% to+100% scope of normal flow usually.In this way, Controlling System keeps stable liquid level and purification reactor pressure.Also can control liquid level by the flow hydrogen gas that adjusting enters purification reactor.The present invention can be described to further comprise step e) by regulating the reaction soln liquid level of controlling supported catalyst bed top reactor pressure and the purification reaction container from purification reaction container liquid-flow out; Or e) by regulating the reaction soln liquid level of controlling supported catalyst bed top reactor pressure and the purification reaction container from purification reaction container liquid-flow out and the flow hydrogen gas that enters the purification reaction container; Or e) flow hydrogen gas that enters the purification reaction container by adjusting is controlled the reaction soln liquid level of supported catalyst bed top in reactor pressure and the purification reaction container, and wherein the hydrogen pressure in the purification reaction container is greater than 60barA.
Another embodiment of the invention can be wherein step a) further be included in enter the purification reaction container before, thick aromatics polycarboxylic acid solution is heated to approximately 275 ℃ of temperature in about 291 ℃ of scopes, for example, entering 280 ℃ to approximately 289 ℃ of purification reaction container precontracts, or than the temperature that thick aromatics polycarboxylic acid is dissolved at least 3 ℃ of temperature height required in the water.
All embodiments of the present invention may further include following content.Purification reactor comprises four parts: top dissolving part; Downtake and distribution plate; The liquid volume of control, it is located immediately at last part, i.e. the top of supported catalyst bed and it is flooded fully.The depth-width ratio of purification reactor is defined as the ratio of the diameter of the length of container column part and catalyst bed, approximately 2 to approximately 4.5, for example approximately 3 to about 3.5 scope.The hydrogen that is fed to purification reactor comprises that approximately 90%v/v arrives approximately 99.9%v/v, and particularly approximately 95%v/v arrives the approximately interior hydrogen of 99.9%v/v scope.The gas that is fed to purification reactor can comprise not condensable component or the inert component with thick acid or supported catalyst reaction.The gas temperature that is fed to purification reactor can be approximately 40 ℃ to approximately 290 ℃.This gas is the gas of supercharging, enters the front pressure at least 70 bar of purification reactor, and usually than the high 1-5 bar of the air pressure in the purification reactor, can accurately control the gaseous tension of purification reactor inside.Hydrogen can be used as the hydrogen source in the inventive method, with the catalyzer associating, makes the impurity hydrogenation in the thick acid.Before touching with the supported catalyst bench grafting, hydrogen/thick acid solution (reaction soln) is even liquid phase.
Reactor of the present invention is continuous flow reactor." continuous flow reactor " used herein is defined as such reactor, wherein in a continuous manner simultaneously introducing and mixed reactant and discharge product, and this is opposite with batch reactor.Although a kind of suitable configuration of purification reactor is the vertical cylindrical vessel with constant diameter, each part of purification reactor can have different diameters.
Reaction times is defined as the free volume in the catalyst bed is passed through catalyst bed divided by reaction soln the corresponding time of volumetric flow rate, thick polycarboxylic acid can control this reaction times so that can be converted into the polycarboxylic acid of purifying efficiently, be no more than approximately 25ppm so that the polycarboxylic acid of the purifying that is precipitated out comprises from reaction medium after finishing purification reaction, the conduct that for example is no more than about 15ppm in oxidising process intermediate and the aldehyde (for example 4-CBA in the Production of Terephthalic Acid) that produces.Usually, will there be at least some aldehyde after the reaction, and be generally at least 5ppm.Similarly, the aldehyde intermediate that produces in the oxidation reaction process can be converted into corresponding monobasic aromatic carboxylic acid (for example in the Production of Terephthalic Acid to toluic acid) efficiently, be no more than approximately 200ppm so that the purifying acid that is precipitated out comprises after finishing purification reaction, for example be no more than the approximately monobasic aromatic carboxylic acid of 150ppm from reaction medium.Usually, will there be at least some monobasic aromatic carboxylic acids after the reaction, and be generally at least 140ppm.
The present invention may be better understood with reference to Fig. 1 and 2.Comprise that Fig. 3 is to compare with the present invention.
With reference to figure 1, the incoming flow 1 that enters purification reactor project A can be included in as the thick acid solution of the heating in the water of solvent.The composition of incoming flow 1 can comprise the thick acid/water of 20%w/w-35%w/w, for example 27%w/w-33%w/w.Incoming flow 1 can from slurry mix tank, be heated slurry to dissolve thick acid by preheater.Incoming flow 1 is heated to approximately 275 ℃ of temperature in about 291 ℃ of scopes, for example approximately 280 ℃ to approximately 289 ℃.Depend on that in the required temperature in this position needs obtain to exceed with the carboxylic acid temperature required limit of temperature (margin) that is dissolved in the water.Usually use 3-10 ℃, for example 4-7 ℃ limit of temperature.Incoming flow 1 is fed to purification reactor project A by entrance project B.The outlet of entrance project B is positioned at the bottom that approaches dissolving some projects C.When the inlet tube B of this configuration leaned against purification reaction container textural, then Fig. 1 showed as the downtake project D at the tube axial of container cross section central authorities.An embodiment comprises the dissolver part that is constructed to the cylinder sealed can and the cup dolly with second cylinder, the second cylinder also with purification reaction container co-axial orientation,, and link to each other with distribution tray project E at its bottom opening place as downtake at purification reaction container upper section.Downtake can form pipe or ring.
The outlet of entrance project B is near the bottom of dissolver some projects C, to guarantee that the residence time of all thick acid in dissolver some projects C surpasses approximately 3 minutes minimum time length to about 10 minutes scopes, for example approximately 3.5 minutes to approximately 5.5 minutes, and guarantee not have cycling stream to hinder (short-circuit) to overflow to flowing-path the downtake from entrance.The advantage of this configuration is the solid of guaranteeing in any water insoluble solvent, and behind the preheater of flowing through, before entering the purification reactor entrance, enough time length of stop dissolve fully in the dissolver part, to avoid the blocking catalyst bed.
Thick acid solution arrives shown in Figure 2 divider project E from the dissolver some projects C downtake project D that flows through downwards.Divider project E collects thick acid solution, makes its distributed uniform, and this moment, it continued to flow to the next section of purification reactor, and increased the surface-area of liquid, is beneficial to improve the solubleness of hydrogen in thick acid solution.Fig. 2 shows circular divider project E, comprises the perforation pallet (formation substrate) with a plurality of holes and has a plurality of vertical edges that the otch of (space) is set around the divider spaced around.
The thick acid solution that comprises dissolved hydrogen flows on the surface of the liquor capacity that is retained in supported catalyst bed project F top as many independently flow (flow stream) from divider project E.The degree of depth of liquid volume is measured by the liquid level instrument, described liquid level instrument is nucleometer (nucleonic gauge) for example, can be from Tracerco, Johnson Mttehey plc, Pavilion 11, Belasis Hall Technology Park, Coxwold Way, Billingham, Cleveland TS23 4EA obtains; Buoy; Conducting probe or other suitable instrument.The hydrogen stream that also can enter container by adjustment with the severity control of thick acid solution volume to the level of setting.The degree of depth of thick acid solution volume is being higher than approximately 0.5 meter to approximately 2.0 meters of catalyst bed project F upper surface, for example approximately 0.8 meter extremely approximately in 1.5 meters the scope.Strictly control reaction pressure by regulating the liquid flow rate that flows out purification reactor.Two controllers are set to keep the purification reactor internal pressure to change less than liquid level change, to avoid unsettled interaction between each control loop.
Keep liquid level and be higher than catalyst bed project F, the liquid stream of supported catalyst bed project F of having guaranteed to flow through evenly distributes, and advantageously reduces thick acid solution by being converted into the volume of the required supported catalyst bed project F of the acid solution of purifying with hydrogen and supported catalyst contact reacts.Fig. 3 shows the conventional purification reactor with Fig. 1 contrast.
The outer process of Fig. 1 middle outlet project G can comprise pipe, and it is connected to flow director with purification reactor export project G, flowrate control valve for example, and flow to product crystallization and the recovery part in downstream.Can be by causing in one or more stages or allowing crystallization from solution, solid-liquid separation and reclaim required product, i.e. the acid of purifying in one or more stages then.
The regulation and control stream of the acid solution of purifying can flow to the product recovery part, can be settled out from solution at this carboxylic acid.Can adopt any appropriate method that reclaims product.The product recovery part can comprise cooling or the evaporative crystallization in one or more stages, so that the acid product crystallization of purifying is formed on the crystal slurry in the aqueous mother liquor.When the product recovery part comprised one or more flash evaporation crystallizer, the flash streams that obtains from crystallizer can be used for indirectly by the heat exchanger of routine or directly flash streams is expelled to other stream in the preheating manufacturing processed the process.The slurry that obtains after the crystallization can stand the solid-liquid separation process, and example operates under normal atmosphere or the subatmospheric condition as at super-atmospheric pressure, is with or without the filter plant of washing device, and for example Andritz or Bokela or MKK provide.Therefore, solid-liquid separation can use any device that is applicable to this purpose to carry out, and is arranged as under the condition of the pressure that depends on final crystallisation stage and operates.Solid-liquid separation can use integrated solid to separate and washing equipment carries out, band filter unit for example, rotatable drumfilter unit, or the rotary drum filter unit (for example, the BHS-Fest filter drum that is formed by a plurality of chambers (cell) receives slurry, and wherein by the hydraulic pressure that is provided to the water in these chambers mother liquor is separated from filter cake).Behind the slurries filtration, the carboxylic acid product of recovery can be directly used in the production polyester, for example is used for packing, for example bottle or fiber.Equally also can be dried.If not yet reach normal atmosphere, then the filter cake of carboxylic acid product can be transferred to low pressure area (for example normal atmosphere), to carry out drying by suitable decompression device.
After the acid product of purifying reclaims, at least part of aqueous mother liquor can recirculation in order in purge process, recycle, for example by mixing with fresh water and/or reactant.Yet, also comprise the valuable reaction intermediate that can be recovered in the mother liquor, to improve the products collection efficiency of manufacturing processed.With regard to the manufacturing of terephthalic acid, these intermediates comprise P-phenylformic acid and 4-carboxyl benzaldehyde.But, also contain the material and precursor and reaction and the degradation by-products that form color in the mother liquor, and can clean during the course to reduce the residual concentration of these components.Purge flow can be sent to effluent and process, for example aerobic and/or anaerobic treatment or other removal process.
Although main present invention is described with reference to the p-Xylol as terephthaldehyde's acid precursor, it should be understood that and also can utilize other precursor replacement p-Xylol or except p-Xylol, also can utilize other precursor to produce corresponding carboxylic acid.These precursors comprise for example m-xylene of polyoxyethylene alkyl aryl family hydrocarbon, and trialkyl benzene or dialkyl group naphthalene are respectively applied to produce aromatic carboxylic acid for example m-phthalic acid and naphthalic acid.The below will further specify the present invention by following unrestricted embodiment.
Embodiment
The following examples comprise from the data of the purification reactor of isomorphism type not.Comparative example has shown the design of popular response device, as disclosed among Fig. 3.Embodiment 1 and 2 is embodiments of purification reactor of the present invention, to show the improvement of catalyst life and catalyst productivity.
Although describe the present invention in conjunction with specific embodiments of the present invention, according to the above description, a lot of replacements, modifications and variations are cheer and bright for those skilled in the art.Therefore, this invention is intended to comprise that all fall into this replacement, modifications and variations in claims spirit and scope.
Claims (16)
1. for the production of aromatic carboxylic acid's method, it comprises:
A) thick aromatic carboxylic acid's solution is incorporated in the purification reaction container, wherein said purification reaction container operates under pressure,
B) hydrogen is introduced in the described purification reaction container,
C) when solution flows on the divider downwards along the vertical ducting wall, hydrogen is dissolved in the thick aromatics polycarboxylic acid solution, the gas-to-liquid contact area of wherein said purification reaction container and the ratio of device processes amount are 0.55m at least
2/ te/h carboxylic acid is used for hydrogen is dissolved in thick aromatics polycarboxylic acid solution with the generation reaction soln, and
D) reaction soln and supported catalyst bench grafting are touched to produce the aromatic carboxylic acid of purifying, wherein said supported catalyst bed is immersed in the reaction soln, and keeps the liquid level of reaction soln to be higher than the supported catalyst bed.
2. the process of claim 1 wherein step c) in gas-to-liquid contact area and the ratio of device processes amount be about 0.65m
2/ te/h carboxylic acid or more.
3. the process of claim 1 wherein step c) in gas-to-liquid contact area and the ratio of device processes amount be about 0.75m
2/ te/h carboxylic acid or more.
4. the process of claim 1 wherein step c) in gas-to-liquid contact area and the ratio of device processes amount be about 1m
2/ te/h carboxylic acid or more.
5. the process of claim 1 wherein that described divider comprises i) diameter be the purification reactor container diameter approximately 0.3 to about 0.7 perforated disc, ii) around the notched weir opening of the edge placement of dish, so that thick acid solution is remained on the dish; And iii) at least one hole, thick aromatics polycarboxylic acid solution flow on the fluid surface of divider below through it.
6. the process of claim 1 wherein that described divider comprises i) diameter be the purification reaction container diameter approximately 0.5 to approximately 0.9 perforation annular open tube or groove, ii) around the notched weir opening of the edge placement of ring, so that thick acid solution is remained on the dish; And iii) at least one hole, thick aromatics polycarboxylic acid solution flow on the fluid surface of divider below through it.
7. claim 5 or 6 method, wherein said divider about 0.5 Mi-Yue between 2.0 meters above the reaction soln liquid level on the supported catalyst bed.
8. claim 5 or 6 method, wherein said divider about 0.5 Mi-Yue between 1 meter above the reaction soln liquid level on the supported catalyst bed.
9. the process of claim 1 wherein that the residence time of described solution on the gas-to-liquid contact area is approximately 3 minutes or longer.
10. the method for claim 1 further comprises step e) by regulating the reaction soln liquid level that flows to control supported catalyst bed top reactor pressure and the purification reaction container from purification reaction container liquid out.
11. the method for claim 1 further comprises step e) by regulating the reaction soln liquid level that flows to control supported catalyst bed top reactor pressure and the purification reaction container that flows and enter the hydrogen of purification reaction container from purification reaction container liquid out.
12. the method for claim 1, further comprise step e) the reaction soln liquid level that flows to control the top of supported catalyst bed in reactor pressure and the purification reaction container that enters the hydrogen of purification reaction container by adjusting, wherein the hydrogen pressure in the purification reaction container is greater than 60barA.
13. the process of claim 1 wherein step a) further be included in enter the purification reaction container before, thick aromatics polycarboxylic acid solution is heated to the approximately 275 ℃-temperature in 291 ℃ of scopes Yue.
14. the process of claim 1 wherein step a) further be included in enter the purification reaction container before, thick aromatics polycarboxylic acid solution is heated to the approximately 280 ℃-temperature in 289 ℃ of scopes Yue.
15. the process of claim 1 wherein that step a) further comprises thick aromatics polycarboxylic acid solution is heated to than the temperature that thick aromatics polycarboxylic acid is dissolved in 3 ℃ of temperature height required in the water at least.
16. the process of claim 1 wherein that described aromatics polycarboxylic acid is terephthalic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30456710P | 2010-02-15 | 2010-02-15 | |
| US61/304,567 | 2010-02-15 | ||
| PCT/US2011/024746 WO2011100682A2 (en) | 2010-02-15 | 2011-02-14 | Purification of carboxylic acids by catalytic hydrogenation |
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| CN102892742B CN102892742B (en) | 2014-11-19 |
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| GB201219983D0 (en) | 2012-11-06 | 2012-12-19 | Davy Process Techn Ltd | Apparatus and process |
| KR102185028B1 (en) * | 2013-12-30 | 2020-12-01 | 비피 코포레이션 노쓰 아메리카 인코포레이티드 | Purification of aromatic carboxylic acids |
Citations (8)
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|---|---|---|---|---|
| US3546285A (en) * | 1967-06-20 | 1970-12-08 | Celanese Corp | Process of purifying aromatic dicarboxylic acids |
| US3639465A (en) * | 1968-06-18 | 1972-02-01 | Standard Oil Co | Purification of aromatic polycarboxylic acids by catalytic reduction using prehumidified hydrogen |
| CN86106988A (en) * | 1985-10-07 | 1987-04-08 | 阿莫科公司 | Reduce the purification process of 4-carboxyl benzaldehyde content in the terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1396901A (en) * | 2000-02-03 | 2003-02-12 | Bp北美公司 | Low temp. purification of naphthalene dicarboxylic acids |
| CN101115705A (en) * | 2004-12-13 | 2008-01-30 | Bp北美公司 | Process for purification of aromatic carboxylic acids |
| CN101146756A (en) * | 2005-03-21 | 2008-03-19 | Bp北美公司 | Process and apparatus for manufacturing pure forms of aromatic carboxylic acids |
| US20080159926A1 (en) * | 2004-09-02 | 2008-07-03 | Eastman Chemical Company | Optimized Production of Aromatic Dicarboxylic Acids |
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2011
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|---|---|---|---|---|
| US3546285A (en) * | 1967-06-20 | 1970-12-08 | Celanese Corp | Process of purifying aromatic dicarboxylic acids |
| US3639465A (en) * | 1968-06-18 | 1972-02-01 | Standard Oil Co | Purification of aromatic polycarboxylic acids by catalytic reduction using prehumidified hydrogen |
| CN86106988A (en) * | 1985-10-07 | 1987-04-08 | 阿莫科公司 | Reduce the purification process of 4-carboxyl benzaldehyde content in the terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1396901A (en) * | 2000-02-03 | 2003-02-12 | Bp北美公司 | Low temp. purification of naphthalene dicarboxylic acids |
| US20080159926A1 (en) * | 2004-09-02 | 2008-07-03 | Eastman Chemical Company | Optimized Production of Aromatic Dicarboxylic Acids |
| CN101115705A (en) * | 2004-12-13 | 2008-01-30 | Bp北美公司 | Process for purification of aromatic carboxylic acids |
| CN101146756A (en) * | 2005-03-21 | 2008-03-19 | Bp北美公司 | Process and apparatus for manufacturing pure forms of aromatic carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102892742B (en) | 2014-11-19 |
| WO2011100682A2 (en) | 2011-08-18 |
| WO2011100682A3 (en) | 2011-12-15 |
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