CN1634848A - Process for producing terephthalic acid and device therefor - Google Patents

Process for producing terephthalic acid and device therefor Download PDF

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CN1634848A
CN1634848A CNA2004100673582A CN200410067358A CN1634848A CN 1634848 A CN1634848 A CN 1634848A CN A2004100673582 A CNA2004100673582 A CN A2004100673582A CN 200410067358 A CN200410067358 A CN 200410067358A CN 1634848 A CN1634848 A CN 1634848A
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gas
tail gas
tower
acetic acid
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CN1257146C (en
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李希
王丽军
成有为
肖咸江
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Zhejiang University ZJU
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Abstract

The invention discloses a method for producing terephthalic acid (TA) and its device. The device is composed of three parts: bubble column reactor, slurry treating device, and exhaust gas treating device. The method is provided as follows: Adopting bubble column reactor with gas separating zone for liquid phase catalytic oxidation of xylene; adopting multistage vaporization, filtering and drying in slurry treating device for recovering solid TA; adopting multistage condensation of byproduced steam for recovering reaction heat in the exhaust gas treating device and recovering solvent by using azeotropy rectification method; determining related process conditions according to the demand of minimum production cost.

Description

The production method of terephthalic acid and device
Technical field
The present invention relates to the production method and the device of a kind of production terephthalic acid (TA).
Background technology
Terephthalic acid is the important source material of producing polyester (PET) fiber and resin, main at present employing p-Xylol air oxidation process is produced, this method is dissolved in the raw material p-Xylol in the acetate solvate that contains catalyst acetic acid cobalt, manganese acetate, hydrogen bromide (or tetrabromoethane), bubbling air or oxygen rich air are carried out oxidation, generate the solid product terephthalic acid.Typical temperature of reaction is 155～205 ℃, pressure 0.5～1.6MPa, the residence time 40～120min, reaction heat shifts out by solvent evaporation, in the Returning reactor, the slurry of generation obtains pure terephthalic acid (PTA) product through follow-up separation and refining step again behind the vapor condensation.
The Production Flow Chart of TA comprises reaction member, tail gas treating unit and three major portions of slurry processing unit, and each unitary task and function can be represented with the functional diagram of Fig. 1.Raw material p-Xylol and air add bubbling column reactor, under the effect of catalyzer liquid-phase oxidation take place, and generate solid terephthalic acid.Slurry enters the slurry processing unit after reactor bottom is discharged, this unitary main task is to separate mother liquor and TA solid, reclaims the energy in the slurry, and mother liquor is carried out purifying treatment with the control impurity concentration, reclaims catalyzer simultaneously.Reaction heat is taken out of by the evaporation of solvent acetic acid, and acetic acid steam shifts out reactor with tail gas from the top, enters tail gas treating unit.This unitary main task is to reclaim reaction heat, recovery acetate solvate, cleaning of off-gas.
Because p xylene oxidation process thermal discharge is very big (emits 1.26 * 10 behind every kilogram of p xylene oxidation 7J reaction heat), each unit of process and plant capacity consumption simultaneously is also very high, so the comprehensive utilization of energy is exactly a very important problem, need carry out mature consideration aspect reactor design and flow scheme design.At first, aspect reactor design, present industrialized bubbling column reactor mainly adopts the still formula structure of band stirring rake, has two-layer stirring rake as the stirred-tank reactor of patent US5211924 and patent US5102630 introduction.This class reactor apparatus cost height, (every cubic capacity power consumption 2～3kw), reaction heat does not obtain directly and effectively utilization current consumption yet simultaneously greatly during operation.Patent ZL94103145.4 and the disclosed reactor of patent US5463113 are provided with a rectifying tower above oxidizer, utilize reaction heat as the rectifying thermal source, make the energy utilization more reasonable.But this reactor upper rectifying section is too elongated, make the lower reaction section height be restricted, the conversion zone aspect ratio is little, often need be at stirring rake of bottom-up installation to promote mixing and to strengthen solid suspension that this has just strengthened capital cost of reactor and working cost during industrial implementation.
Secondly, aspect flow scheme design, the steam that existing processes generally all adopts the method for tail gas multi-stage condensing to produce different energy levels reclaims reaction heat, and phlegma is extracted a part again out and carried out rectifying and dewatering recovery acetate solvate; For the processing of reaction paste, the process using multistage evaporation that has carries out liquid-solid the separation with filter method, and the employing multistage centrifugal method that has is separated.The energy expenditure index of different process has nothing in common with each other, but all also has very big potentiality aspect energy-conservation.For further energy-conservation taping the latent power, patent US5723656 discloses a kind of method, and bubbling column reactor cat head tail gas is directly introduced a rectifying tower, then rectifying tower top tail gas is carried out the multi-stage condensing heat exchange and reclaims its energy, and tail gas enters the decompressor acting again.The method that patent US6143925 introduces is that a high-efficient spiral-screen column is set above reactor, separating acetic acid and water, and tail gas produces the steam of different energy levels by multi-stage condensing, then steam is introduced the turbine acting.The method that patent ZL99108695.3 ZL99109477.8 introduces is with electric motor, compressor, steam turbine, the coaxial connection of decompressor, by the byproduct steam driving steam turbine of different energy levels, introduces the decompressor acting after the reaction end gas heating again.But, aforesaid method is difficult to carry out a bit, for example patent US5723656 just requires separating device very huge with the task that the rectifying tower that passes through to link to each other with bubbling column reactor that US6143925 introduces is finished whole acetic acid dehydrations, because the temperature, pressure of reaction end gas is higher, also contain a large amount of rare gas elementes simultaneously.On the other hand, disclosed various patented technologies all are a kind of partial conservation measuress at present, though might produce certain energy-saving effect to some unit and equipment after implementing, are difficult to reach the minimum purpose of whole process energy consumption.Therefore, be necessary to adopt the method for systems engineering to take all factors into consideration and optimization design, form best process design plan system-wide energy is integrated.
Summary of the invention
The object of the invention is to provide that a kind of cost is lower, the better terephthalic acid production method of energy-saving effect and equipment, and the design and processes that is used for process flow improves.To achieve these goals, this device is made up of three parts: bubbling column reactor, slurry treatment unit, exhaust gas processing device; The whole thinking of method is: adopt the bubbling column reactor that has gas fallaway section to realize the liquid phase catalytic oxidation of p-Xylol; The slurry treatment unit adopts multistage evaporation, filtration, drying step to reclaim solid terephthalic acid; Exhaust gas processing device adopts the multi-stage condensing byproduct steam to reclaim reaction heat, adopts the azeotropic distillation method to reclaim solvent; The configuration of each unit, equipment, stream thigh and associated process conditions are optimized definite according to the requirement of products production cost minimum in the flow process.
The invention provides a kind of terephthalic acid production plant, comprise bubbling column reactor, slurry treatment unit, exhaust gas processing device, bubbling column reactor is straight tubular, inside is followed successively by the gas processing section from top to bottom, free space segment and three phase reaction section, the gas processing section accounts for 10～30% of bubbling column reactor height overall, and three phase reaction section accounts for 60～85% of bubbling column reactor height overall; Filler or supporting liquid column plate are installed in the gas processing section, lower horizontal at three phase reaction section is equipped with gas distributor, gas distributor links to each other with the bubble tower inlet mouth, on the three phase reaction section above the gas distributor, be provided with material feeding tube, be provided with discharge nozzle at the bottom of the tower, cat head is provided with offgas duct and phlegma return line; The bubble tower inlet mouth links to each other with air compressor pump.The slurry treatment unit comprises the multi-step evaporator that links to each other with discharge nozzle, the upper outlet of multi-step evaporator by behind the heat exchanger, link to each other with acetic acid tank, tail gas absorber respectively, rectifying tower links to each other, the following outlet of multi-step evaporator links to each other with filter, and the outlet of filter links to each other with material feeding tube, mother liquor purification device, drying machine respectively; The outlet of mother liquor purification device links to each other with acetic acid tank.Exhaust gas processing device comprises the multi-stage condensing device, and the shell side of multi-stage condensing device links to each other with steam turbine, thermal source, and the tube side of multi-stage condensing device links to each other with phlegma return line, rectifying tower, tail gas absorber respectively through behind the vapour liquid separator; Rectifying tower links to each other with the outlet of heat exchanger, the following outlet of rectifying tower links to each other with material feeding tube, acetic acid tank respectively, the upper outlet of rectifying tower links to each other with phlegma return line, water-and-oil separator respectively, and the outlet of water-and-oil separator links to each other with entrainer recovery tower, p-Xylol recovery tower respectively; The outlet of tail gas absorber links to each other with exhaust purifier.
Adopt said apparatus production method of terephthalic acid, comprise the steps:
1), oxidizing reaction: through behind the gas distributor, the three phase reaction section that enters respectively in the bubbling column reactor carries out oxidizing reaction from the bubble tower inlet mouth from material feeding tube, oxygen-containing gas for p-Xylol and solvent acetic acid; After the reaction gained gas process gas processing section, from the offgas duct discharge, the slurry of reaction gained is discharged from discharge nozzle;
2), slurry is handled: the slurry of discharging from the discharge nozzle cooling of reducing pressure in multi-step evaporator, enter heat exchanger from multi-step evaporator upper outlet expellant gas and carry out heat exchange, the phlegma of gained is introduced acetic acid tank, non-condensable gases is introduced tail gas absorber and is handled, and steam introducing rectifying tower dewaters and part of heat energy is provided; The slurry of discharging from the following outlet of multi-step evaporator is divided into mother liquor and solid through the filtration of filter, solid enters in the drying machine dry to reclaim acetic acid, most mother liquor is got back to three phase reaction section through material feeding tube, the mother liquor of small part carries out purifying treatment through the mother liquor purification device, reclaim the metal catalyst composition in the mother liquor simultaneously, the mother liquor after the purification enters acetic acid tank;
3), vent gas treatment: after the processing of tail gas through the multi-stage condensing device of offgas duct discharge, the steam of generation drives steam turbine and provides thermal source to rectifying tower by shell side, and the water coolant of generation is by shell side condensation tail gas; Described condensation tail gas from the tube side of multi-stage condensing device come out, through behind the vapour liquid separator, tail gas purifies by tail gas absorber, exhaust purifier successively, a phlegma part turns back to bubbling column reactor inside, part introducing rectifying tower separating acetic acid and water, also introducing rectifying tower separating acetic acid and water that heat exchanger comes out by the phlegma return line; Acetic acid part after the separation enters bubbling column reactor inside by material feeding tube, and part enters acetic acid tank; The phlegma of the gas condensation gained that comes out from the rectifying tower upper outlet, part enters bubbling column reactor inside through return line, the part extraction enters water-and-oil separator and separates, separating obtained oil phase is introduced entrainer recovery tower entrainer recovery tower again and is carried out rectifying and dewatering, and entrainer enters the p-Xylol recovery tower to purify entrainer.
Below main points of the present invention are elaborated:
One. the oxidizing reaction unit
The bubbling column reactor structure that the present invention provides is shown in Fig. 2, reactor is the bubbling column reactor that has gas fallaway section of tubular always, inside is formed by three sections from top to bottom: top is the gas processing section, and the middle and lower part is a three phase reaction section, is free space segment between the two.During work, add in the reactor from material feeding tube after raw material p-Xylol, solvent acetic acid and the catalyst mix, oxygen-containing gas feeds through the gas distributor bubbling from the bubble tower inlet mouth, reacts with p-Xylol, generates solid terephthalic acid.The slurry of solids that reaction is produced is discharged from discharge nozzle, enters the slurry processing unit, and major part is back in the reactor after the mother liquor filtering separation, and small part is extracted out and purified and catalyst recovery.Reaction heat shifts out by the evaporation of solvent acetic acid, solvent vapo(u)r and tail gas enter the tail gas recycle unit by the offgas duct outflow reactor, acetic acid steam major part after condensation in the tail gas is back in the reactor, small part is extracted processed out to shift out the water that generates in the reaction, the water content in the controlling reactor.
About the key points in design of bubbling column reactor structure and processing condition comprises following aspect:
1. bubbling column reactor three phase reaction section
Three phase reaction section is the main part of bubbling column reactor, at this gas-to-liquid contact and chemical reaction takes place.The bubbling column reactor that the present invention adopts is the bubble tower configuration, is different from the stirring tank configuration that existing most of technology adopts.Why select bubble tower, be because of research according to chemical engineering, the maximum speed of reaction of p-Xylol liquid-phase oxidation is slower than maximum gas-liquid mass transfer speed, for example, and for stirring tank, the ratio of the two speed is 0.2～0.3, and to bubble tower, therefore this ratio is between 0.3～0.4,, the industry oxidising process is essentially liquid-phase chemical reaction and controls, and the configuration of employing bubble tower can satisfy the requirement of reaction pair gas-liquid mass transfer.Simultaneously, turbulence is violent in the bubble tower under reaction conditions, and good mixing distributes at liquid-phase mixing, solid suspension, solvent evaporation, liquid phase oxygen concn and also can satisfy the requirement of oxidation reaction process aspect several, obtains and the similar reaction effect of stirring tank.In addition, bubble tower is simple in structure, and is cheap, do not have moving partss such as stirring rake, more energy saving during operation.
The height of three phase reaction section is exactly the liquid level of reaction paste, accounts for 60～85% of bubbling column reactor total height, has the enough volumes and the slurry residence time to guarantee conversion zone.Gas distributor is installed in the bottom of tower.P-Xylol mix with solvent acetic acid, catalyzer and backflow mother liquor the back from gas distributor top, 1/4～1/2 the adding of conversion zone height by feed-pipe, the slurry that reaction generates is discharged from the slurry pipe of tower bottom.
Gas distributor is the even distribution device that feeds gas, and its form can be varied.As adopting conventional perforated-plate distributor, circle distributor or multitube sparger.
2. gas fallaway section
Be provided with gas fallaway section on bubbling column reactor top, its function mainly is to impel the water-containing acetic acid that refluxes behind steam that lower reaction section rises and tail gas and the overhead condensation fully to contact, reclaim entrained solid particle in the tail gas on the one hand, carry out the rectifying of solvent, separating acetic acid and water on the one hand.The structure of gas fallaway section is similar to general rectifying tower, can adopt high efficiency packing tower, also can adopt sieve-tray tower or valve tray column, or the array configuration of several column plate, filler.The phlegma that refluxes flows downward from cat head, and reaction end gas and steam upwards flow, and the two counter current contact realizes separating of solid recovery and solvent.
Conventional bubbling column reactor is provided with an expanding reach separate solid particles and liquid foam usually on top, but but be difficult to prove effective for this scheme of p xylene oxidation process, because this process gas treatment capacity and solvent evaporation amount are very big, empty tower gas velocity high (reaching 0.3～1.0 meter per second), adopt expanding reach to be difficult to effective separate solid particles and minimizing liquid foam entrainment, therefore the present invention has adopted up and down bubble tower cylindrical shell uniformly, be provided with by holding the gas processing section that liquid tower tray or filler are formed on top simultaneously, be used for separate solid.On the other hand, rectifying section is set above bubbling column reactor can directly utilizes reaction heat to carry out separating of solvent acetic acid and water, favourable energy-conservation.In theory, the stage number that gas fallaway section had is many more, energy recovery rate is just high more, therefore patent US5723656 proposes to adopt a high-efficient spiral-screen column that links to each other with reactor to finish the task of reclaiming whole acetic acid from tail gas with US6143925, but this is the comparison difficulty, because temperature and the pressure of reaction also contain a large amount of non-condensable gasess all than higher in the tail gas, be difficult to accomplish separating fully of acetic acid and water.Therefore, consider from the optimization of total system that should adopt multistage rectifying to distribute the dehydration load, promptly a part of dehydration task is finished at the gas fallaway section of reactor, a part is finished in follow-up tail gas recycle unit.The theoretical plate number of the suitable reactor segregation section that the present invention provides is 5～15 theoretical stages, and the height of corresponding gas fallaway section accounts for 10～30% of total tower height.
To the liquid level of three phase reaction section, is the freeboard of reactor from column plate in below of gas fallaway section, and it highly accounts for 5～15% of total tower height, mainly is that fluctuation and the splash for liquid level makes allowances, and prevents that it from exerting an influence to gas fallaway section.
3. reactor aspect ratio
The aspect ratio of reactor (i.e. height and diameter ratio) is an important design variable, and when reactor production capacity and given volume, different aspect ratio correspondences different reactor diameters and height, causes empty tower gas velocity and bottom pressure to have nothing in common with each other.Definite needs of aspect ratio take into account that flowing of gas fallaway section requires with mass transfer, the gas-liquid mass transfer of three phase reaction section and many-sided factors such as the fast radial distribution of gas, gas holdup and reactor residence time.The aspect ratio of the suitable three phase reaction section that the present invention provides can calculate the corresponding height of gas fallaway section and free space segment according to this parameter between 3～7.
4. oxidation reaction condition
Temperature of reaction is most important process design variable.According to the principle of chemical engineering, adopt higher temperature of reaction can improve the energy grade of byproduct steam, favourable energy-conservation; The pyroreaction condition also helps the TA crystal and grows up, and is convenient to filtration drying; Simultaneously, catalyst levels and impurity growing amount are also less under the high temperature, help mother liquor purification.But too high temperature will make the burning reaction aggravation of raw material and solvent, and material loss increases, and facility investment is increased.Take all factors into consideration above-mentioned pros and cons, according to total system energy consumption and the minimized requirement of material consumption, the suitable reactions temperature that the present invention provides is 185～195 ℃, and corresponding pressure is 1.0～1.8MPa.
Reactor residence time (being defined as the liquid phase volume/outlet liquid volume flow in the reactor) mainly influences the degree of depth, crystal particle diameter and the reactor production capacity of oxidizing reaction.The suitable reactor residence time that the present invention provides is 50～120 minutes.
Other reaction conditions is:
The charging solvent ratio---promptly adding the raw material p-Xylol of reactor and the mass ratio of solvent comprises water acetic acid, is 1: 3～1: 10.
Cobalt, manganese, the total concn of three kinds of ions of bromine in liquid phase are 1000～3000ppm in catalyst concn and proportioning---the reactor, and wherein the atomic ratio of cobalt/manganese is 3: 1～1: 3, and metal catalyst (cobalt+manganese) is 0.5～2.0: 1 with the atomic ratio of bromine.
The liquid phase water content is 6～15% (w/w) in water content---the reactor.
The tail gas oxygen concn---the volume ratio of oxygen and nitrogen is 3～6% in the tail gas.
Two, slurry processing unit
The solid terephthalic acid that generates in the bubbling column reactor is discharged from the reactor bottom slurry pipe together with mother liquor, enters the slurry processing unit, as shown in Figure 3.The slurry processing unit comprises multi-step evaporator 301,302,303, filter 304, drying machine 305 and mother liquor purification device 306, and relevant auxiliary facility.Its function be carry out liquid-solid Separation and Recovery terephthalic acid, reclaim slurry stream strand energy, mother liquor is purified with foreign matter content in the control liquid phase.Be respectively described below:
1. multi-step evaporator
Higher from slurry temperature and pressure that bubbling column reactor is discharged, for ease of carrying out liquid-solid separation, the while also makes in the liquid phase dissolved small part TA crystallization separate out, need be to the slurry cooling of reducing pressure.Though adopt the one-level flash evaporation also can achieve the goal, be difficult to reclaim the energy in the slurry.In addition, also have partial reaction intermediate such as p-methylbenzoic acid, p-tolyl aldehyde etc. all not to be converted into terephthalic acid in the reaction mother liquor, need supplemental.Therefore, the steam energy that multi-step evaporator can reclaim different energy levels on the one hand is set, can also feed the part oxygen-containing gas in vaporizer carries out supplemental on the one hand, improves the TA yield.
Multi-step evaporator 301～303 is made up of the stirring tank of 3 polyphones, and each kettle is long-pending identical with structure.The temperature of first vaporizer 301 is lower 2～5 ℃ than bubbling column reactor, and the low 0.1～0.3MP of pressure is so that slurry enters evaporating pot automatically by slurry pipe under pressure reduction promotes.The residence time of slurry is 20～40 minutes in first vaporizer.Oxygen-containing gas carries out with the degree of depth of promotes oxidn reaction from the bottom feeding of first vaporizer, and the gas gross of feeding accounts for 2～8% of bubbling column reactor gas feeding amount, the O in the tail gas 2/ N 2Be controlled at 3～6% than (volume ratio).Steam that evaporates after the step-down and reaction end gas flow out from the still top, introduce acetic acid tank through the phlegma that reclaims after the heat exchanger condensation, incoagulability tail gas is incorporated into tail gas treating unit and absorbs and purify, and the steam of heat exchanger by-product is used to miscellaneous equipment that thermal source or power are provided.Second vaporizer, 302 temperature and pressures further reduce to impel more solvent evaporation, and steam is introduced directly into the rectifying tower G16 bottom of tail gas treating unit and dewaters, and also provide part of heat energy for this rectifying tower simultaneously.Last step vaporizer 303 is reduced to normal pressure or negative pressure so that slurries filtration with pressure.
2. filtration, drying and mother liquor purification
The slurry that comes out from multistage slurry vaporizer enters filter 304 filtering separation mother liquor and solids, feeds a certain amount of acetic acid simultaneously and washs to reduce impurity and the catalyst content in the solid.Solid Conveying and Melting after the filtration is carried out drying to reclaim acetic acid in drying machine 305.The filtrated stock major part is back in the bubbling column reactor, and small part is retracted to mother liquor purification device 306 and carries out purifying treatment with the foreign matter content in the Control Circulation mother liquor, reclaims the metal catalyst composition in the mother liquor simultaneously.
The purification of mother liquor adopts the method for evaporation concentration to reclaim solvent acetic acid, and resulting impurity residue water dissolution extraction reclaims catalyzer, and also available oxalate precipitation method reclaims catalyzer.
Three, tail gas recycle unit
The steam, the part non-condensable gases (N that contain a large amount of acetic acid and water from bubbling column reactor cat head effluent air 2, CO 2, CO) and on a small quantity other organic constituent (p-Xylol, monobromethane, ritalin etc.) need be handled by the tail gas recycle unit, and recovered energy and solvent acetic acid carry out tail gas clean-up, subsequently discharging.The flowage structure of tail gas treating unit also is shown in Fig. 3, comprises multi-stage condensing device 205,206,207,208, azeotropy rectification column group 216,219,220, and tail gas absorbs and refining plant 213,214, and equipment such as steam turbine and decompressor, is described as follows:
1. multi-stage condensing device
The multi-stage condensing device 205～208 at bubbling column reactor top also is a vapour generator simultaneously, is made up of the shell and tube heat exchanger of several polyphones, and wherein reaction end gas is by tube side, and water coolant and byproduct steam pass through shell side.The function of condenser is condensation reaction tail gas on the one hand, will be back in the reactor after the condensation of solvent acetic acid, and byproduct steam reclaims reaction heat on the one hand.3～4 grades of steam of multi-stage condensing device operated by rotary motion with generation different-energy grade.A phlegma part from the trim the top of column to the reactor in, a part is extracted out and to be dewatered to remove the water that dereaction generates, the water content in the controlling reactor.The middle pressure steam that high pressure steam that first condenser generates and the 3rd condenser generate is mainly used in the driving steam turbine, and the middle pressure steam that second stage condenser generates is mainly used in to azeotropy rectification column the reboiler thermal source is provided.The later condenser of the third stage condenses to tail gas to fixed temperature, byproduct steam no longer with water coolant.
2. rectifying tower group
The condensed lime set of tail gas need be extracted a part out and be dewatered with the water content in the controlling reactor.Extract is introduced rectifying tower 216 separating acetic acids and water.The rectifying tower that the present invention provides adopts azeotropic distillation method and multiply charging measure in order to energy-conservation.Phlegma to be separated (moisture and acetic acid) is from tower middle part charging, another strand adds from the tower bottom from the water-containing acetic acid steam of slurry processing unit second vaporizer, acetic acid after the separation goes out from tower bottom flow, and partial reflux is to bubbling column reactor, and part offers miscellaneous equipment as washing lotion.Water vapor flows out from cat head, extracts the partial reflux cat head out through the condensation rear section.Reflux ratio generally remains on 1.5～4.5 with the acetate concentration in the control cat head tail gas.Reboiler thermal source part is from the steam of the bubbling column reactor cat head second condenser by-product, the water-containing acetic acid steam that part is sent here from the second slurry vaporizer.Entrainer can be selected n-butyl acetate, or n-propyl acetate.The tower bottom reboiler temperature is 110～130 ℃, and the cat head exhaust temperature is 80～100 ℃.
Except water, also be rich in entrainer in the rectifying tower overhead condensation liquid, the part lime set is extracted to carries out layering in the water-and-oil separator 218, and upper oil phase is introduced entrainer recovery tower 219 again and carried out rectifying and dewatering.In addition, also contain a spot of p-Xylol in the charging of dehydration tower 216, be enriched in easily during rectifying in the entrainer, therefore a p-Xylol recovery tower 220 also need be set to purify entrainer.Like this, the rectifying tower of bearing the solvent dehydration load just is made up of three towers: azeotropy rectification column 216, entrainer recovery tower 219 and p-Xylol recovery tower 220.
3. tail gas absorbs and refining plant
Through after the multi-stage condensing, also contain little acetic acid, p-Xylol and other organic constituent from the reactor tail gas discharged, should further reclaim and purify.Tail gas absorbs p-Xylol and acetic acid by absorption tower 213 earlier, and the tail gas after absorbing enters refining plant 214 and carries out catalyzed oxidation or burning, removes organic substance on the one hand, improves exhaust temperature on the one hand.Tail gas after the purification enters the acting of tail gas decompressor, reclaims the expansion energy of gas, subsequently discharging.Compressor 202, decompressor 204, steam turbine 203 adopt coaxial mode to connect in order to energy-conservation with starter motor 201.
Four. the integrated and process optimization of system capacity
P xylene oxidation is a strong exothermal reaction, and effective utilization of reaction heat is the energy-conservation major measure of process.Most of oxidation reaction heat reclaims by reactor tail gas condensers at different levels, produces the steam of different energy levels, and part is used to drive steam turbine, and for compressor provides power, part is used to equipment such as dehydration tower, drying machine, mother liquor purification device that thermal source is provided.The vapor recovery that another part energy produces by multistage slurry vaporizer.The present invention considers that according to the method synthesis of systems engineering energy that reaction produces and each unit equipment are used for the balance between supply and demand between the isolating energy.Heat exchange between the distribution of steam and the stream strand is distributed rationally according to the system capacity integrated approach, makes the heating and the cooling load minimum of the required general facilities of system.According to flow scheme design shown in Figure 3 and typical reaction conditions, the energy of each unit stream thigh of system is supplied with the energy requirement load and is listed in Fig. 4, wherein the steam of bubbling column reactor, condenser at different levels, vaporizers at different levels and tail gas are for providing the hot-fluid thigh of energy, rectifying tower group, drying machine, the required thermal source of mother liquor purification device are the cold flow thigh, and energy level coupling and energy distribution between the stream thigh are represented with arrow on figure.Among the figure in the hot-fluid thigh on the left side, what production capacity was maximum, energy level is the highest is the steam of tail gas condenser by-products at different levels, the energy that is provided is except that a part is used for the heating of the right cold flow thigh, and quite a few also is used to drive the steam turbine acting, for compressor provides power.This part energy that does work is represented with the block diagram and the arrow of figure middle portion.Temperature is lower than 115 ℃ hot-fluid thigh, as dehydration column overhead steam and condensed reaction end gas, and low utility value, the water quench that this part used heat needs outer boundary to provide of having no longer included of its energy level.Temperature is higher than 135 ℃ cold flow thigh, as the required thermal source of drying machine, can't adopt the heating of hot-fluid thigh, need the external common engineering to provide, but this part energy requirement is less.Except that compressor, (do not mark) in the system power consumption maximum be dehydration tower, its energy by be lower than 135 ℃ the cold flow thigh can with the steam heat-exchanging of hot-fluid thigh by-product or directly and the hot-fluid thigh mate heat exchange.
Each unit that the present invention provides, the processing condition of equipment and energy matching scheme all determine that according to total system material consumption and the minimum principle of energy consumption the related process parameter will be illustrated by embodiment 1.
Description of drawings
Fig. 1 is the unit module and the process task figure of terephthalic acid generative process;
Fig. 2 is the structure for amplifying synoptic diagram of bubbling column reactor 100 provided by the invention;
Fig. 3 is a process flow diagram of the present invention;
Fig. 4 is the energy energy level and the stream burst match map of each unit stream thigh of Production of Terephthalic Acid process.
Embodiment
As shown in Figure 1: production process comprises three unit: oxidizing reaction unit, slurry processing unit and air processing unit.Raw material p-Xylol and oxygen-containing gas react at bubbling column reactor 100, generate solid terephthalic acid; Reaction paste enters the slurry processing unit, this unitary task and function are to carry out liquid-solid Separation and Recovery terephthalic acid, mother liquor is purified the control foreign matter content, reclaims the portion of energy in the slurry, and resulting crude terephthalic acid is sent into refining step and further made the pure terephthalic acid; Steam and tail gas that bubbling column reactor 100 comes out enter tail gas treating unit, and this unitary task and function are to reclaim reaction heat and gas expansion energy, reclaim solvent acetic acid, carry out gas sweetening to reach emission standard.
As shown in Figure 2, the bubble tower oxidation unit of producing terephthalic acid comprises up and down bubbling column reactor 100 uniformly, is followed successively by gas processing section 101 in the bubbling column reactor 100 from top to bottom, free space segment 102 and three phase reaction section 103.Gas processing section 101 accounts for 10～30% of bubbling column reactor 100 total heights, three phase reaction section 103 accounts for 60～85% of bubbling column reactor 100 total heights, free space segment 102 accounts for 5～15%, filler or supporting liquid column plate 108 are installed in gas processing section 101, be used for reclaiming tail gas entrained solid particle and part acetic acid, lower horizontal at three phase reaction section 103 is equipped with gas distributor 107, gas distributor 107 links to each other with bubble tower inlet mouth 105,1/4～1/2 place that is positioned at three phase reaction section 103 height above gas distributor 107 is provided with material feeding tube 104, be provided with discharge nozzle 106 at the bottom of the tower, cat head is provided with offgas duct 110 and phlegma return line 109, offgas duct 110 links to each other with the inlet of multi-stage condensing device, the liquid exit of condenser links to each other with follow-up rectifying tower 216 with phlegma return line 109 respectively, and the pneumatic outlet of condenser links to each other with follow-up tail gas treating unit.Partial condensation liquid is by in the return line 109 backflow bubbling column reactors 100, and part is sent into follow-up rectifying tower 216 dehydrations in addition, and incoagulability tail gas is sent into follow-up tail gas treating unit and further handled.
As shown in Figure 3, the Production Flow Chart of terephthalic acid is implemented as follows: (wherein 301～306 is slurry processing unit main device, and 201～221 is the air processing unit main device, and 1～48 is main process line and stream burst numbering)
Pipeline 1 adds cobalts, manganese metal and the bromide catalyzer as oxidizing reaction to the bubbling column reactor p-Xylol (PX) of supplying raw materials through pipeline 2, and simultaneously, pipeline 3 and 5 provides oxidation required solvent acetic acid.Air compressor 202 is compressed to (than the high about 0.2MPa of the pressure in the bubbling column reactor R1) about 1.2～2.0MPa with atmospheric air, feeds in the bubbling column reactor 100 through pipeline 4, and the oxygen in the high-pressure air is as the oxygenant of reaction.Temperature of reaction is 185～195 ℃, and pressure is 1.0～1.8MPa.PX generates solid terephthalic acid (TA), the slurry residence time 50～120min through liquid-phase oxidation in reactor.
Steam that produces in the three phase reaction section 103 and tail gas enter gas fallaway section 101 through free space segment 102, phlegma counter current contact with trim the top of column, entrained solid terephthaldehyde granulates is recovered in the gas, arrive bottom three phase reaction section 103 with liquid return, acetic acid and water carry out rectifying separation in gas fallaway section 101 simultaneously, light constituent water is discharged from offgas duct 110 with steam, carry out multi-stage condensing via pipeline 8 to condenser, solvent acetic acid is then concentrated and solid matter is back in the bottom three phase reaction section 103 together.
The effusive tail gas of reactor cat head enters the tube side of multi-stage condensing device 205～208 through pipeline 8, and the condenser shell side is walked water coolant and steam.The first～three grade of condenser 205～207 will produce the saturated vapor of differing temps and pressure, be respectively applied for the power of steam turbine 203 and the thermal source of other processing unit by certain proportioning.Wherein the water vapor about 2/3 of first condenser, 205 generations is used to drive steam turbine 203, and all the other are used for the heat supply of miscellaneous equipment; The steam that second condenser 206 produces is mainly used in to rectifying tower 216 the reboiler thermal source is provided; The steam that the 3rd condenser 207 produces also is mainly used in and drives steam turbine 203.
100～110 ℃ have been reduced to from the fluid temperature (F.T.) of last step tail gas condenser 208 outlets, deliver in the gas-liquid separator 209, the isolated liquid phase overwhelming majority is in pipeline 7 is back to bubbling column reactor 100, and small part liquid is sent into rectifying tower 216 through pipeline 13 and carried out the solvent acetic acid dehydration.And send into further condensation and flash distillation in the condenser 210 through pipeline 10 by vapour liquid separator 209 isolated gases, liquid portion is passed into separating acetic acid and water in the rectifying tower 216 by pipeline 12, gas then is passed into tail gas absorber 213 bottoms via pipeline 11, the p-Xylol that reclaims acetic acid and wherein carry secretly.
In tail gas absorber 213, tail gas respectively with acetic acid and water counter current contact, p-Xylol of carrying secretly in the tail gas and acetic acid are absorbed by liquid phase acetic acid and water respectively.Vinegar pickle is respectively from acetic acid tank 215 and condensation flasher 212, and this washing lotion absorbs p-Xylol after pipeline 23 is sent bubbling column reactor 100 back to.Tail gas after pickling enters top, absorption tower again, and water absorbs the acetic acid in the gas phase.Water lotion is sent here through pipeline 21 by entrainer recovery tower 219, discharges from side line behind the absorption acetic acid, feeds rectifying tower 216 middle parts, separating acetic acid and water by pipeline 24.
The tail gas of discharging from the top, absorption tower enters exhaust purifier 214, carries out oxidation and intensification, introduces tail gas decompressor 204 subsequently and reclaims expansion energy.Decompressor 204 is coaxial with air compressor 202, steam turbine 203 and starter motor 201.Steam turbine 203 is by the steam driven of tail gas condenser 205～207 by-products, the heat energy of steam is converted into mechanical energy and decompressor provides compressor required energy together.The steam dump energy then is converted into electric energy through turbine, can carry to the outside.When device is driven, at first drive air compressor and start the total system operation by electric motor 201, after production process reaches steady state, then electric motor driving is switched to steam turbine and decompressor and drive, the energy of recovery also has electric power output more than needed except that system's self-sufficiency.
The tail gas phlegma major part that obtains from gas-liquid separator 209 is back to bubbling column reactor 100 through pipeline 7, and small part is extracted out and dewatered to shift out the water that reaction generates.Extract is delivered to rectifying tower 216 middle part chargings with the lime set of condenser 210 and the water lotion of tail gas absorber 213 through pipeline 28, carries out rectifying and dewatering.Simultaneously, the steam that is produced by slurry processing unit second vaporizer 302 provides dehydration required portion of energy from rectifying tower 216 bottom feeds, and its complementary energy is provided by the reboiler interchanger by the water vapor that second condenser 206 produces.Entrainer (N-BUTYL ACETATE or propyl acetate) is added by cat head through pipeline 36 with water, and the vapor phase product after the rectifying is rich in water and entrainer, flows out from cat head, to condenser 217 condensations, is separated into water and oil phase via pipeline 35 in water-and-oil separator 218.The part oil phase (moisture 4～10%wt), be back in the rectifying tower 216 by pipeline 36.Water (contains entrainer 1～5%wt) and delivers to 219 rectifying of entrainer recovery tower by pipeline 39, reclaim the entrainer that obtains and (contain entrainer 45～60%wt) and deliver to water-and-oil separator 218 separation and azeotropic agent and water via pipeline 38, entrainer is recycled.Also contain a spot of p-Xylol in the oil phase of water-and-oil separator 218, part oil phase is delivered in the p-Xylol recovery tower 220 by pipeline 47, its liquid product is rich in p-Xylol, be transmitted back to bubbling column reactor 100 by pipeline 44, its gas-phase product is rich in entrainer, sends back to water-and-oil separator 218 by pipeline 37.
Acetic acid concentrates back (concentration＞90%wt), from bottom discharge, deliver to acetic acid tank 215 by pipeline 29 in rectifying tower 216.An acetic acid part that reclaims is sent bubbling column reactor 100 back to through pipeline 33, and a part is as the scavenging solution of slurries filtration and tail gas absorption.
The slurry of discharging from the bubbling column reactor bottom enters the first slurry vaporizer 301 through pipeline 6, and reduction vaporization carries out supplemental on the one hand on the one hand.Oxygen-containing gas feeds slurry vaporizer 301 bottoms by pipeline 14, and the steam of generation and tail gas enter heat exchanger 211 by pipeline 16, separates obtaining liquid and vapor capacity.Liquid phase is directly delivered to acetic acid tank 215 by pipeline 18, vapour phase is sent into condensation flash tank 212 through pipeline 17 and is further separated, the liquid phase that obtains is delivered to tail gas absorber 213 as scavenging solution through pipeline 20, and vapour phase is also delivered to tail gas absorber 213 tops recovery acetic acid wherein through pipeline 19.
Deliver to the second slurry vaporizer, 302 further reduction vaporizations from the first slurry vaporizer, 301 effusive slurries through pipeline 15, the steam that produces is sent into rectifying tower 216 bottoms by pipeline 30, provide dehydration required portion of energy, slurry after concentrating is delivered directly to the 3rd slurry vaporizer 303 through pipeline 31, this evaporator pressure is reduced to normal pressure, the steam that produces refluxes after by condenser condenses, makes temperature reduce to 85～95 ℃, so that follow-up filtration and drying.
Deliver to filter 304 from the 3rd slurry vaporizer 303 effusive slurries by pipeline 32 and separate mother liquor and solid, simultaneously, wash to 304 pairs of solids of filter through pipeline 34 transport portion acetic acid by acetic acid jar 215.Filter 304 mother liquor major parts are back to bubbling column reactor 100 by pipeline 42, and small part (5～10%) is extracted out and carried out mother liquor purification and catalyst recovery, and the acetic acid of recovery is delivered to acetic acid tank 215 via pipeline 27.Solid behind the filtration washing is delivered to drying machine 305 dryings through pipeline 40, makes moisture percentage reduce to 0.05～1% by 10～15%.Dried thick TA will deliver to the further hydrogen treatment of refined unit, obtain the pure terephthalic acid.
As shown in Figure 4, the energy of each stream thigh is arranged in order from top to bottom by the temperature height.Left-hand component is for providing the hot-fluid thigh of energy, and its length is provided by the energy values size that can provide, and its temperature is represented the rank of energy, is the tolerance of available energy.Right-hand component is for needing the cold flow thigh of heating, and its length is represented the power consumption size, and temperature is represented the energy needed rank.Arrow among the figure is represented energy distribution or the coupling between the specified stream thigh, and each stream thigh of the numeral on the arrow provides the number of energy, and the block diagram of middle portion and arrow are represented to be converted into the mechanical energy acting by heat energy.
Below will further specify advantage of the present invention and implementation detail by embodiment 1 and Comparative Examples.
Embodiment 1.
The method and apparatus that adopts the present invention to provide is produced 600000 tons terephthalic acid flow process and device design per year, 7600 hours production times of year, each Elementary Function and the task determined by Fig. 1 obtain flow process shown in Figure 3 through system in combination optimization, the processing condition of each unit equipment determine that according to material consumption and energy consumption minimized principle the energy between each stream thigh is flux matched to be optimized according to the integrated principle of system capacity.Gained related process parameter is enumerated as follows according to sequence of unit:
1. bubbling column reactor
Adopt two bubble tower bubbling column reactors parallel operation shown in Figure 2, the throughput of separate unit reactor is 300,000 tons/year, and slurry is handled and vent gas treatment adopts single covering device.Reactor size and processing parameter are listed in table 1, and reaction result and index of correlation are listed in table 2.
Table 1 bubbling column reactor size and processing condition
The tower top pressure catalyst concn
Diameter height overall conversion zone precursor reactant section temperature PX treatment capacity
(MPa, exhausted (ppmHAc)
(m) long-pending (m of degree (m) 3) (℃) (10 3Kg/h)
Press) Co Mn Br
4.70????32??????360?????????190???????????1.24????????51.1???????????380????380????760
Tail gas separates
Charging HAc/PX air rate phlegma refluxer refluxes
The theoretical tower of section
Mass ratio (mark m 3/ h) than temperature (℃)
The plate number
4∶1???????????9.9×10 4???22????????????102??????????7
Table 2 bubbling column reactor output-index
PX transformation efficiency TA yield (%) conversion zone gas holdup conversion zone solid holdup TA crystal particle diameter mother liquor water content
(%) (%) (%) (um) (quality %)
99.5????????96???????????46??????????????27.8???????????87???????????9.2
Mother liquor 4-CBA solid phase 4-CBA tail gas CO XDense tail gas acetate concentration tail gas PX concentration tail gas oxygen concn
Concentration (ppm) concentration (ppm) degree (CO X/ N 2%) (HAC/N 2%) (PX/N 2%) (O 2/ N 2%)
2584????????4773?????????1.67????????????0.93??????????7.7×10 -5????3.5
In table 1 and the table 2, PX refers to p-Xylol, and TA refers to terephthalic acid, CO XConcentration refers to CO 2With CO concentration sum, 4-CBA refers to that HAC refers to acetic acid to carboxyl benzaldehyde (in the following table all with).The quality of mother liquor 4-CBA concentration=liquid phase 4-CBA quality/solvent acetic acid and water, solid phase 4-CBA concentration=solid phase 4-CBA quality/solid phase t A quality.
2. slurry processing unit
Adopt three grades of slurry vaporizers reduction vaporization step by step, the first slurry vaporizer feeds the little air deep oxidation, and the steam that the second slurry vaporizer produces directly feeds dehydration tower, and the 3rd evaporator outlet slurry enters filter and drying machine makes thick TA product.The processing parameter of three grades of vaporizers and filter drying apparatus is listed in table 3～6.
The table 3 first slurry vaporizer processing parameter
Slurry 4-CBA concentration
Volumetric pressure temperature solid holdup residence time air rate
(ppm)
(m 3)????(MPa)???(℃)???(％)????(min)?????(Nm 3/h)
The solid phase liquid phase
87.2?????1.095???185????32??????33????????3.1×10 3????2300?????＜100
The table 4 second slurry vaporizer processing parameter
Volumetric pressure temperature solid holdup residence time steam productive rate
(m 3)???(MPa)?????(℃)??????(％)??????(min)???????(kg/h)
66???????0.217?????136????????41???????34.6????????52996
Table 5 the 3rd slurry vaporizer processing parameter
Volumetric pressure temperature solid holdup mother liquor contains water retention time
(m 3) (MPa) (℃) (%) measure (%) (min)
66????????0.05?????96????????41????????5.9?????????34.6
Table 6 filtration drying process parameter
The filter drying machine
Filtration area area load filter cake contains wet (m 2)?????(kgTA/m 2.h) rate (%) The discharging of heat interchanging area thermal load contains the residual (m of moist catalysis 2) (KW) rate (%) stay (ppm)
38.7??????2.2×10 3????14.7 4500??????2.8×10 3?0.5???????35.4
3. tail gas treating unit
Bubbling column reactor top tail gas adopts the level Four condensation, first three grade byproduct steam, and the fourth stage condenses to 102 ℃ with water of condensation, and 95% of lime set is back to the reactor tail gas processing section, and 5% extraction causes the dehydration tower rectifying separation.Level Four condenser heat exchange load and operational condition are listed in table 7.
Table 7 reactor tail gas condenser processing parameters at different levels
First condenser, second condenser
Tail gas outlet byproduct steam heat interchanging area heat exchange load temperature (℃) temperature (℃) (m 2)????(KW) Tail gas outlet byproduct steam heat interchanging area heat exchange load temperature (℃) temperature (℃) (m 2)????(KW)
165??????140??????3200??????6.5×10 4 155???????130???????1900??????3.3×10 4
The 3rd condenser the 4th condenser
Tail gas outlet byproduct steam heat interchanging area heat exchange load temperature (℃) temperature (℃) (m 2)????(KW) Tail gas outlet heat interchanging area heat exchange load temperature (℃) (m 2)?????(KW)
130???????115???????2300??????4.4×10 4 102???????2000??????2.8×10 4
The steam of the tail gas lime set and the second slurry vaporizer adopts the dehydration of azeotropic distillation method, and entrainer is n-butyl acetate (NBA), and lime set enters from the tower middle part, and steam enters from the tower still.The reboiler thermal source adopts the steam of the reactor tail gas second condenser by-product.The processing parameter of rectifying tower group is provided by table 8～10.
Table 8 dehydration tower processing parameter
Theoretical tray liquid phase feeding vapour phase charging tower top pressure tower bottom pressure reflux ratio
Numerical digit seated position (MPa) (MPa)
30??????????15??????????30???????????0.1?????????0.12?????????2.1
The dense tower top temperature column bottom temperature of acid at the bottom of the dense tower of the negative cat head acid of the negative condenser of reboiler
Lotus (KW) lotus (KW) degree (quality %) degree (quality %) (℃) (℃)
1.7×10 4???2.2×10 4???＜0.1????????92??????????92???????????119
Table 9 entrainer recovery tower processing parameter
Theoretical tower feed position middle part go out the reboiler bottom discharge altogether the middle part discharging top discharge is altogether altogether
Reflux ratio
The plate number is put material level and is put (KW) the agent concentration agent concentration agent concentration that boils that boils that boils
21??????12??????10?????????20???????3.0×10 3????＜0.1???????86??????????＜0.1
Table 10 p-Xylol recovery tower processing parameter
The top discharge of reboiler bottom discharge
Theoretical feed entrance point reflux ratio
(KW) PX concentration (%) PX concentration (%)
20??????2???????????1.3??????????5.0×10 2???99?????????????3.5
After the condensation of reactor tail gas process level Four, enter tail gas absorber and absorb p-Xylol and acetic acid, two-stage structure is adopted on the absorption tower, and hypomere absorbs the p-Xylol that contains in the tail gas with acetum earlier, the epimere water absorbs the acetic acid that contains in the tail gas, and the related process parameter is provided by table 11.
Table 11 tail gas absorber processing parameter
Hypomere spray hypomere exit gas concentration of component epimere exit gas concentration of component
The epimere spray
The acetic acid flow rate
Water-content acetic acid content PX content rate of flow of water water-content acetic acid content PX content
(kg/h)
2.7×10 4????2.4?????0.3???????1.4×10 -4?4.2×10 3??3.3?????2.6×10 -4??1.4×10 -4
4. main material consumption and energy consumption index
According to above-mentioned embodiment, table 12 has provided supplies consumption and the energy expenditure of this technological process TA per ton, wherein the supplies consumption of main device bubbling column reactor, dehydration tower, tail gas absorber, drying machine etc. has only been considered in the consumption of acetic acid and p-Xylol, does not comprise the supplies consumption of other auxiliary facility.Energy expenditure is also only considered the major equipment energy consumption among Fig. 3, does not comprise the power consumption of auxiliary facility, instrument etc.The steam energy that reclaims is also all unified to be converted to electric energy and is considered that therefore the major equipment power consumption that provides in the table is exactly the clean consumption that system is calculated with electric energy after the consideration energy recovery.
Table 12 material consumption and energy consumption
Major equipment material consumption (kg/tTA) major equipment power consumption cooling-water consumption disappears for steam outward
P-Xylol acetic acid entrainer catalyzer (KW.h/tTA) (t/tTA) consumes (t/tTA)
648.5???????38.5????0.5???????0.2?????????41.5????????24.4????????0.05
Comparative Examples 1
For further specifying advantage of the present invention, the Production Flow Chart and the existing typical process that the present invention can be provided compare.As a comparison case 1, be to adopt conventional stirred-tank reactor to replace bubble tower bubbling column reactor of the present invention with reference to relatively flow process, the dehydration tower of tail gas treating unit is the azeotropic distillation that adopts conventional distillation to replace the present invention to adopt simultaneously, and the configuration of slurry processing unit and miscellaneous equipment is identical with condition and the present invention.
Table 13～15 have provided the major equipment processing parameter of the comparison flow process of producing 600000 tons of terephthalic acids per year, and table 16 has been listed relevant material consumption and energy consumption index.
Table 13 stirring tank bubbling column reactor processing parameter
Catalyst concn
Reactor platform separate unit reaction response section temperature tower top pressure PX treatment capacity charging HAc/
(ppmHAc)
Long-pending (the m of number segment body 3) degree (℃) (MPa, absolute pressure) (10 3Kg/h) PX mass ratio
Co????Mn????Br
2??????????286.0???????190???????1300.0???????51.1???????4∶1????????480???480???960
Table 14 bubbling column reactor output-index
PX transformation efficiency TA yield (%) conversion zone gas contains conversion zone and contains TA crystal particle diameter mother liquor water content admittedly
(%) rate (%) rate (%) (um) (quality %)
99.5???????96???????????38??????????31???????????103.0???????9.2
Mother liquor 4-CBA solid phase 4-CBA phlegma is extracted tail gas oxygen concn tail gas CO out XDense tail gas PX concentration
Concentration (ppm) concentration (ppm) flow rate (kg/h) (volume %) degree (volume %) (volume %)
2300???????4500?????????734600??????3.5??????????1.7?????????5.2×10 -4
Table 15 conventional distillation dehydration tower processing parameter
Liquid phase feeding vapour phase charging tower top pressure tower bottom pressure tower top temperature
Theoretical plate number
Position, position (MPa) (MPa) (℃)
40????????????25??????????40??????????0.1??????????0.16???????????98
Acid concentration at the bottom of the column bottom temperature reboiler condenser duty cat head acid concentration tower
Reflux ratio
(℃) (KW) (KW) (quality %) (quality %)
126???????????15??????????3.4×10 4???3.9×10 4????＜0.1??????????95
Table 16 is the major equipment material consumption and the energy consumption of flow process 1 relatively
Major equipment material consumption (kg/tTA) major equipment power consumption cooling-water consumption disappears for steam outward
P-Xylol acetate catalyst (KW.h/tTA) (t/tTA) consumes (t/tTA)
648.5?????????38.5??????????0.2??????????62.3????????26.7??????????0.05
The processing condition of above-mentioned relatively flow process and the correlated results of consumption indicators and embodiment 1 are contrasted as can be seen, adopt and compare the production that flow process also can realize terephthalic acid, but energy expenditure is higher than the index that embodiment 1 provides, its reason is mainly reflected in two aspects: the one, and the bubbling column reactor that the comparison flow process adopts is present general stirred-tank reactor, gas fallaway section is not set, makes reaction heat can not be used for separated from solvent more directly, effectively; The 2nd, solvent dehydration adopts conventional distillation, more consumes energy than azeotropic distillation.In addition, reactor stirring power consumption also makes energy consumption slightly increase.Therefore, aforesaid method and flow process obviously are not so good as method and the flow process that the present invention provides aspect energy-conservation.
Comparative Examples 2
Second reference flow process and difference of the present invention relatively is the slurry processing unit, relatively flow process adopts the one-level flash evaporation to concentrate bubbling column reactor outlet slurry, directly pressure is reduced to normal pressure, and then by two-stage centrifugal machine separation mother liquor and solid, with multistage evaporation and the filter method that replaces the present invention to adopt.The design of bubbling column reactor and tail gas treating unit is identical with the present invention.For above-mentioned relatively flow process, under same 600,000 tons/annual capacity and oxidation reaction condition, relevant material consumption and energy consumption index are listed in table 17.
Table 17 is the major equipment material consumption and the energy consumption of flow process 2 relatively
Major equipment material consumption (kg/tTA) major equipment power consumption cooling-water consumption disappears for steam outward
P-Xylol acetate catalyst entrainer (KW.h/tTA) (t/tTA) consumes (t/tTA)
648.0???????37.7????0.2??????????0.5???????73.1??????????26.2????????0.05
The flow process that provides with this patent compares, and relatively the supplies consumption of flow process 2 is lower slightly, mainly is the supplemental consumption of having saved the first slurry vaporizer.But the energy expenditure of this flow process is maximum in above-mentioned three flow processs, and its major cause is after the slurry treatment system adopts the one-level flash evaporation, and the energy in the slurry does not obtain recycling.Simultaneously, whizzer causes the TA particle fragmentation to make the solid water capacity increase, and has also increased drying load and energy expenditure.Therefore, the method that also provides aspect energy-conservation of the method that provides of Comparative Examples 2 not as the present invention
At last, it is also to be noted that what more than enumerate only is a specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (8)

1, a kind of terephthalic acid production plant comprises bubbling column reactor (100), slurry treatment unit, exhaust gas processing device, it is characterized in that:
Described bubbling column reactor (100) is straight tubular, inside is followed successively by gas processing section (101) from top to bottom, free space segment (102) and three phase reaction section (103), described gas processing section (101) accounts for 10～30% of bubbling column reactor (100) height overall, and three phase reaction section (103) accounts for 60～85% of bubbling column reactor (100) height overall; Filler or supporting liquid column plate (108) are installed in gas processing section (101), lower horizontal at three phase reaction section (103) is equipped with gas distributor (107), gas distributor (107) links to each other with bubble tower inlet mouth (105), on the three phase reaction section (103) of gas distributor (107) top, be provided with material feeding tube (104), be provided with discharge nozzle (106) at the bottom of the tower, cat head is provided with offgas duct (110) and phlegma return line (109); Described bubble tower inlet mouth (105) links to each other with air compressor pump (202);
Described slurry treatment unit comprises the multi-step evaporator that links to each other with discharge nozzle (106), the upper outlet of multi-step evaporator by heat exchanger (211) back, link to each other with acetic acid tank (215), tail gas absorber (213) respectively, rectifying tower (216) is continuous, the following outlet of multi-step evaporator links to each other with filter (304), and the outlet of filter (304) links to each other with material feeding tube (104), mother liquor purification device (306), drying machine (305) respectively; The outlet of mother liquor purification device (306) links to each other with acetic acid tank (215);
Described exhaust gas processing device comprises the multi-stage condensing device, the shell side of the byproduct steam of multi-stage condensing device, link to each other with steam turbine (203) thermal source required with processing unit is provided respectively, the tube side of described multi-stage condensing device links to each other with phlegma return line (109), rectifying tower (216), tail gas absorber (213) respectively after through vapour liquid separator (209); Rectifying tower (216) links to each other with the outlet of heat exchanger (211), the following outlet of rectifying tower (216) links to each other with material feeding tube (104), acetic acid tank (215) respectively, the upper outlet of rectifying tower (216) links to each other with phlegma return line (109), water-and-oil separator (218) respectively, and the outlet of water-and-oil separator (218) links to each other with entrainer recovery tower (219), p-Xylol recovery tower (220) respectively; The outlet of tail gas absorber (213) links to each other with exhaust purifier (214).
2, a kind of terephthalic acid production plant according to claim 1 is characterized in that: the theoretical plate number of described gas processing section (101) is 5～15, and the height of oxidation reactor three phase reaction section (103) and diameter ratio are 3～7.
3, a kind of terephthalic acid production plant according to claim 1 and 2 is characterized in that: the outlet of described exhaust purifier (214) links to each other with tail gas decompressor (204).
4, a kind of terephthalic acid production plant according to claim 3, it is characterized in that: described multi-step evaporator comprises first vaporizer (301), second vaporizer (302), the 3rd vaporizer (303) of polyphone successively, described first vaporizer (301) is provided with feeding oxygen tube (14), and described feeding oxygen tube (14) links to each other with air compressor pump (202).
5, a kind of terephthalic acid production plant according to claim 4 is characterized in that: described multi-stage condensing device comprises first condenser (205), second condenser (206), the 3rd condenser (207), the 4th condenser (208) of polyphone successively; Electric motor (201) and described air compressor pump (202), steam turbine (203), the coaxial connection of tail gas decompressor (204).
6, a kind of terephthalic acid production method is characterized in that, comprises the steps:
1), oxidizing reaction: behind bubble tower inlet mouth (105) process gas distributor (107), the three phase reaction section (103) that enters respectively in the bubbling column reactor (100) carries out oxidizing reaction from material feeding tube (104), oxygen-containing gas for p-Xylol and solvent acetic acid; Reaction gained gas is through gas processing section (101) back, from offgas duct (110) discharge, and the slurry of reaction gained is discharged from discharge nozzle (106);
2), slurry is handled: the slurry of discharging from discharge nozzle (106) cooling of reducing pressure in multi-step evaporator, enter heat exchanger (211) from the upper outlet expellant gas of multi-step evaporator and carry out heat exchange, the phlegma of gained is introduced acetic acid tank (215), non-condensable gases is introduced tail gas absorber (213) and is handled, and steam introducing rectifying tower (216) dewaters and part of heat energy is provided; The slurry of discharging from the following outlet of multi-step evaporator is divided into mother liquor and solid through the filtration of filter (304), solid enters in the drying machine (305) dry to reclaim acetic acid, most mother liquor is got back to three phase reaction section (103) through material feeding tube (104), the mother liquor of small part carries out purifying treatment through mother liquor purification device (306), reclaim the metal catalyst composition in the mother liquor simultaneously, the mother liquor after the purification enters acetic acid tank (215);
3), vent gas treatment: after the processing of tail gas through 3～4 grades of condensers of offgas duct (110) discharge, the steam of generation drives steam turbine (203) and thermal source is provided for rectifying tower (216) by shell side, and the water coolant of generation is by shell side condensation tail gas; Described condensation tail gas from the tube side of multi-stage condensing device come out, through after vapour liquid separator (209), tail gas purifies by tail gas absorber (213), exhaust purifier (214) successively, a phlegma part turns back to inner, a part of rectifying tower (216) separating acetic acid and water, also introducing rectifying tower (216) separating acetic acid and the water that heat exchanger (211) comes out introduced of bubbling column reactor (100) by phlegma return line (109); Acetic acid after the separation partly enters bubbling column reactor (100) inside by material feeding tube (104), and part enters acetic acid tank (215); The phlegma of the gas condensation gained that comes out from rectifying tower (216) upper outlet, part enters bubbling column reactor (100) inside through return line (109), the part extraction enters water-and-oil separator (218) and separates, separating obtained oil phase is introduced entrainer recovery tower entrainer recovery tower (219) again and is carried out rectifying and dewatering, and entrainer enters p-Xylol recovery tower (220) to purify entrainer.
7, a kind of terephthalic acid production method according to claim 6, it is characterized in that: described three phase reaction section (103) interior reaction temperature is 185～195 ℃, pressure 1.0～1.8MP, catalyst cobalt, manganese, three kinds of ionic total mass concentrations of bromine are 1000～3000ppm, the atomic ratio of cobalt manganese is 3.0～0.3, and the atomic ratio of metal catalyst ion and bromide anion (ratio) is 0.5～2.5.
8, a kind of terephthalic acid production method according to claim 7 is characterized in that: slurry feeds oxygen-containing gas and carries out the supplemental reaction in first vaporizer (301).
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