CN1528732A - Bubble tower oxidation reaction unit for producing terephthalic acid - Google Patents
Bubble tower oxidation reaction unit for producing terephthalic acid Download PDFInfo
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Abstract
The invention discloses a bubbling column oxidizing reaction device to produce p-phthalic acid, including a uniform straight-cylindrical bubbling column, where there are gas processing segment, free space segment and three phase reaction segment in turn form top to bottom in the bubbling column, there are liquid distributor and filling or liquor-holding board installed in the gas processing segment, there is a gas distributor installed at the bottom of the three phase reaction segment, there is a raw material feeding pipe set at 1/4-1/2 of the height of reaction segment, there is a discharge pipe set at the bottom of the bubbling column, there is a tail-gas pipe and a liquor condensate reflux pipe on the top of the bubbling column, the inlet of the condenser is linked with the tail-gas pipe, the gas outlet is linked with the follow-up tail-gas processing unit, the liquid outlet of the condenser is linked with raw material feeding pipe, liquor condensate reflux pipe and follow-up dehydration tower. It is applied to the process of preparing p-phthalic acid by high temperature oxidization.
Description
Technical field
The present invention relates to be used in the bubble tower oxidation reaction apparatus, particularly production process of a kind of production terephthalic acid (TA) usefulness the device of p-Xylol (PX) air liquid phase catalytic oxidation.
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.
Oxidation reactor is the core apparatus that PTA produces, and DESIGN OF REACTOR need satisfy the requirement that gas-liquid mass transfer, liquid phase reaction and crystallization, evaporation move heat, four aspects of mixing of materials.Present industrialized oxidation reactor mainly adopts the still formula structure of band stirring rake, stirred-tank reactor as patent US5211924 and patent US5102630 introduction has two-layer stirring rake, the function of lower floor's oar is to realize liquid mixing and solid suspension, the upper strata oar is used to disperse bubble, reaches the requirement that promotes liquid circulation in gas-liquid mass transfer and the still.The subject matter of the reactor that this class band stirs is that equipment manufacturing cost and working cost are higher, because the dynamic seal of stirring rake and vibration problems need special Machine Manufacturing Technology to solve, in addition, current consumption is big during the equipment operation, and maintenance cost is also higher.
Patent JP14098/1979, EP0618186A1 and the disclosed reactor of patent US5463113 are made up of two portions, and top is rectifying tower, diameter is less, has polylith column plate or filler, is used for separating the acetic acid and the water of tail gas, the bottom is a reactor, and diameter is bigger, and aspect ratio is little.This reactor is because upper rectifying section is too elongated, and the lower reaction section height is restricted.Because the conversion zone aspect ratio is little, is difficult to adopt the bubble tower configuration, often need be during industrial implementation at stirring rake of bottom-up installation to promote to mix and strengthen solid suspension, this just makes such reactor still belong to the tank reactor that band stirs on feature.
Patent CN1293184A discloses a kind of oxidation unit that does not have the production aromatic carboxylic acid of stirring, it is characterized in that installing in the reactor shell multilayer vertical and horizontal diaphragm space segmentation has been become a plurality of sub-districts that link to each other up and down, each sub-district is equivalent to a perfectly mixed reactor, raw material and air add from the tower bottom, reacted slurry is discharged from top, material flows in the mode near horizontal sliding, reaches higher transformation efficiency and yield with this.But this inside reactor complex structure easily forms local gas bag when a large amount of solvent evaporation, be unfavorable for gas and contain flowing of solid slurry.
Summary of the invention
The bubble tower oxidation reaction apparatus that the object of the invention is to provide a kind of simple in structure, cost and the cheap production terephthalic acid of working cost to use is to overcome the defective of above-mentioned all kinds of reactors.
Technical solution of the present invention is to adopt the bubbling column reactor that does not have stirring to replace existing all kinds of stirring tank formula oxidation reactor, to reduce equipment manufacturing cost and running cost.This change of reactor configuration is to be based upon on the deep chemical engineering research basis that the p xylene oxidation process is carried out.According to research, the maximum speed of reaction of p-Xylol liquid-phase oxidation is slower than maximum gas-liquid mass transfer speed, for example, for stirring tank, the ratio of the two speed is 0.2～0.3, and to bubble tower, this ratio is between 0.3～0.4, therefore, industrial oxidising process is essentially liquid phase reaction and controls, and the configuration of employing bubble tower can satisfy the requirement of reaction pair gas-liquid mass transfer.Simultaneously, suitably adjust the residence time, aspect ratio and distributor designs parameter after, distribute at liquid-phase mixing, solid suspension, solvent evaporation, liquid phase oxygen concn and also can satisfy the requirement of oxidation reaction process aspect several, obtain and the similar reaction effect of stirring tank.In addition, 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 0.4～1.0 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 and part acetic acid.
The bubble tower oxidation reaction apparatus that production terephthalic acid of the present invention is used comprises even straight-cylindrical bubble tower, be followed successively by the gas processing section in the tower from top to bottom, free space segment and three phase reaction section, the gas processing section accounts for 10～20% of bubble tower total height, three phase reaction section accounts for 60～85% of bubble tower total height, the free space segment height is 1～3 meter, in the gas processing section, liquid distributor is installed, filler or supporting liquid column plate, lower horizontal at three phase reaction section is equipped with gas distributor, gas distributor links to each other with the bubble tower inlet mouth, 1/4～1/2 place that is positioned at the three phase reaction section height above gas distributor is 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, offgas duct links to each other with the inlet of condenser, the liquid exit of condenser respectively with material feeding tube, the phlegma return line links to each other with follow-up dehydration tower, and the pneumatic outlet of condenser links to each other with follow-up tail gas treating unit.
During work, add in the three phase reaction section of bubble tower oxidation unit from feed-pipe behind raw material p-Xylol, solvent comprises water acetic acid, the catalyst cobalt-manganese-bromine uniform mixing, air or oxygen rich gas inlet mouth at the bottom of the tower enters gas distributor, bubbling is by the liquid bed after gas distributor disperses, carry out oxidizing reaction with the liquid phase reaction thing, generate the product terephthalic acid solid; Reaction heat shifts out by solvent acetic acid and evaporation of water gas, and tail gas and solvent vapo(u)r at first by the gas processing section on tower top, with the overhead condensation liquid counter current contact that refluxes, reclaim entrained solid particle, liquid foam and part acetic acid in the tail gas.The tail gas that leaves the gas processing section shifts out reactor through offgas duct and enters overhead condenser, and the solvent in the tail gas is by in the reflux tower of condenser condenses rear section, and part is delivered to follow-up dehydration tower dehydration in addition; The terephthalic acid slurry that reaction generates outputs to follow-up separation by the bottom discharge pipe and refining step is further handled, and condensed incoagulability tail gas is sent into follow-up cell processing.
No stirring rake and other moving parts in the device tower of the present invention, simple in structure, cost and working cost are cheap, are applicable to the reaction conditions of p-Xylol high-temperature liquid-phase catalyzed oxidation.
Description of drawings
Fig. 1 is the structural representation of apparatus of the present invention.
Embodiment
With reference to Fig. 1, the bubble tower oxidation reaction apparatus that the production terephthalic acid is used comprises uniformly straight up and down tubular bubble tower, be followed successively by gas processing section 3 in the tower from top to bottom, free space segment 11 and three phase reaction section 1, gas processing section 3 accounts for 10～20% of bubble tower total height, three phase reaction section 1 accounts for 60～85% of bubble tower total height, the free space segment height is 1～3 meter, liquid distributor 9 is installed in gas processing section 3, filler or supporting liquid column plate 10, be used for reclaiming tail gas entrained solid particle and part acetic acid, lower horizontal at three phase reaction section 1 is equipped with gas distributor 2, gas distributor 2 links to each other with the bubble tower inlet mouth, 1/4～1/2 place that is positioned at the three phase reaction section height above gas distributor 2 is provided with material feeding tube 5, be provided with discharge nozzle 6 at the bottom of the tower, cat head is provided with offgas duct 7 and phlegma return line 8, offgas duct 7 links to each other with the inlet of condenser 4, the liquid exit of condenser 4 respectively with material feeding tube 5, phlegma return line 8 links to each other with follow-up dehydration tower, and the pneumatic outlet of condenser 4 links to each other with follow-up tail gas treating unit.Partial condensation liquid is by in return line 8 and feed-pipe 5 reflux towers, and part is sent into follow-up dehydration tower dehydration in addition, and incoagulability tail gas is sent into follow-up tail gas treating unit and further handled.
The principle of work of bubble tower oxidation reaction apparatus shown in Figure 1 is as follows: raw material p-Xylol, solvent comprises water acetic acid and catalyzer Cobalt diacetate tetrahydrate, four water acetic acid manganese, hydrogen bromide (or tetrabromoethane) add in the tower by feed-pipe 5 from the conversion zone middle and lower part continuously, oxygen-containing gas or air are blown in the tower by the gas distributor bubbling of tower bottom, gas is that disperse phase, liquid are external phase in the tower, gas-liquid fully contacts, under catalyst action oxidizing reaction taking place, generates product terephthalic acid solid particle.Because the p xylene oxidation process is liquid-phase chemical reaction control, the bubble tower liquid holdup is big, can guarantee that liquid phase has the abundant oxidation of enough residence time.Simultaneously, the oxidizing reaction oxygen-consumption is big, go into tower air or oxygen-containing gas gas speed higher (air inlet empty tower gas velocity generally at per second more than 0.1 meter), solvent acetic acid and evaporation of water amount also very big (steam flow is generally 2～4 times into the tower air flow quantity), so empty tower gas velocity very high (0.4～1.0 meter per second) in the tower, can greatly strengthen gas-liquid mass transfer and liquid-phase mixing, also can satisfy the requirement of solid suspension simultaneously.Reaction paste is discharged continuously by discharge nozzle 6 at the bottom of the tower, is input to follow-up operation and further handles, and discharging flow is controlled according to liquid level.The water of reaction liberated heat and generation shifts out by solvent evaporation.Because gas flow is big, carrying part liquid foam and solid particulate in the tail gas secretly, traditional bubbling column reactor generally adopts the top expanding reach to slow down gas speed, parting liquid foam and solid particulate, the present invention then is provided with a gas processing section on tower top, filler or supporting liquid column plate are installed, the gas that the phlegma of trim the top of column and Ta Nei rise carries out counter current contact in the gas processing section, one side collecting granules and liquid foam, on the one hand separating acetic acid and water, with back flow reaction section after the part acetic acid separated with water content in the control tower.The reaction end gas that is rich in moisture and non-condensable gases enters overhead condenser by offgas duct 7, and condensed gas send next procedure to handle, and in the phlegma partial reflux tower, part send follow-up dehydration tower further to dewater.
Below main points of the present invention are further described.
1. the tube structure of bubble tower and useful volume
General bubbling column reactor mostly has an expanding reach with separating particles and liquid foam on top, the present invention just need not be provided with expanding reach again owing to be provided with the gas processing section that liquid distributor 9, filler or supporting liquid column plate 10 are installed.The gas processing section highly accounts for 10～20% of bubble tower total height, and during operation, the control of conversion zone liquid level makes in position and leaves 1～3 meter freeboard between liquid level and the gas processing section.
The useful volume of bubble tower refers to the volume of conversion zone, and it is to determine according to the requirement that the assurance liquid phase oxidation reaction is fully finished.Research according to the chemical engineering aspect, p xylene oxidation belongs to the middle slow reaction of isogonic, mainly in the liquid phase body, carry out, and p xylene oxidation respectively to go on foot speed of reaction very responsive to the variation of reactant concn, therefore as long as keep liquid phase that enough residence time are arranged, just can reach high p-Xylol transformation efficiency (more than 99%) and terephthalic acid yield (more than 95%).Compare with stirring tank, the bubble tower gas Liquid Mass Transfer Coefficient will be hanged down, and gas holdup is then slightly higher, and for example, under industrial oxidizing condition, the bubble tower mass transfer coefficient is about 60% of stirring tank, and Gas Hold-Up in Bubble Columns is 0.4～0.5, and stirring tank gas holdup 0.3～0.4.But because the bubble tower aspect ratio is greater than stirring tank, the tower bottom is in the higher zone of oxygen concn, helps eliminating the influence that oxygen transmits, and therefore amid all these factors considers, the bubble tower useful volume need be bigger by about 30% than stirring tank under same production capacity.The bubbling column reactor useful volume that the present invention provides was determined according to the liquid phase residence time, and liquid holdup in the liquid phase residence time=tower/outlet liquid flow rate should remain on 40～120 minutes scope.
2. conversion zone aspect ratio and reaction conditions
The three phase reaction section aspect ratio distributes and determines according to desired gas speed, gas Liquid Mass Transfer Coefficient, gas holdup, gas-liquid mixed speed, solid suspension requirement, dissolved oxygen concentration.At first, bubble tower is that the bubbling turbulence by gas promotes mass transfer, be reinforcing mass transfer, bubble tower should adopt bigger aspect ratio to increase empty tower gas velocity, cause the inhomogeneous of temperature and concentration distribution in the tower again easily but aspect ratio is excessive, gas holdup is increased, and the liquid phase residence time reduces.P-Xylol (PX) oxidation reactor is an evaporation reaction device, reaction heat shifts out by solvent evaporation, like this, near the gas inlet of bubble tower bottom, solvent evaporation is violent, and temperature is lower, and is less at middle part and top evaporation, temperature is higher, and the Lower Half of tower exists significant non-uniform temperature to distribute.In addition, because the feed entrance point of PX is in the middle and lower part of tower, the slurry discharge port is nearer from the bottom, increasing aspect ratio also causes mixing uneven easily, form bad mixing zone on tower top, therefore from mass transfer with mix the consideration of two aspects, should have a suitable aspect ratio to take into account two aspect requirements.Secondly, the aspect ratio of bubble tower is also relevant with temperature of reaction and pressure, consider the requirement of liquid phase dissolved oxygen concn.According to the research of oxidation reaction kinetics, there is a threshold value in the influence of liquid phase oxygen concn in the p xylene oxidation process, about 1.4～1.8mol/m
3Between, surpass this scope then oxygen concn reaction is no longer had a significant effect, then oxygen concn is on the low side to be lower than this scope, causes main reaction to slow down, by-product impurities increases.For the consideration of secure context, the oxygen in the tail gas/nitrogen ratio can not surpass 5%, therefore increases the liquid phase oxyty and only takes to improve reaction pressure and increase by two kinds of measures of height for reactor.In order to keep certain steam output, the variation of pressure and variation of temperature are carried out synchronously.For low-temperature oxidation process (temperature＜170 ℃, tower top pressure＜0.8MPa), partial pressure of gaseous oxygen and liquid phase dissolved oxygen concn are all lower, the bubble tower conversion zone requires to have bigger aspect ratio (6～13) to increase height for reactor, form necessarily, make that most of zone (middle and lower part) can be by oxygen saturation in the tower along the tower oxygen concentration gradient; And for high-temperature oxidation process (temperature＞180 ℃, pressure＞1.0MPa) because partial pressure of gaseous oxygen and liquid phase oxyty are higher, oxygen concn near or reach the saturated requirement of reaction, therefore can adopt lower aspect ratio to increase tower diameter, improve and mix.The height of the bubble tower three phase reaction section that the present invention is suitable for and diameter ratio are 3～7.Corresponding temperature, pressure condition is: 180～205 ℃ of temperature, pressure 1～2MPa.
4. the structure of gas processing section
The gas processing section of setting of the present invention is positioned at bubble tower cylindrical shell top, is made up of liquid distributor, packing section or supporting liquid column plate, and it highly accounts for 10～20% of bubble tower height overall.Liquid distributor is positioned at the top, and its form can adopt porous plate one slot type spray thrower or multitube spray thrower, its function be with the phegma behind the overhead condensation along the tower section uniform distribution, avoid the liquid bias current.The liquid distributor below is packing section or supporting liquid column plate, and its function mainly provides a gas-liquid counter current osculating element, reclaims solid particulate, liquid foam and part acetic acid in the upstream, makes in its reflux tower.Filler generally adopts structured packing to stop up to reduce air resistance and to prevent, supporting liquid column plate can adopt the porous turbogrid tray, also can adopt other board-like column plate commonly used.
5. gas distributor
Gas distributor among the present invention is installed in the bubble tower bottom, can adopt conventional annular, sexangle perforated-plate distributor or multitube sparger, also can be other common used in industry gas distributor.When adopting the porous sparger, stop up in order to guarantee all even solid that prevents of gas distribution, the upper surface of sparger circulation duct and lower surface all have gas orifice, and the ratio of upper and lower surface percentage of open area is 1: 0.05～0.5.Most of gas (account for add gas 60～90%) upwards sprays, and small part gas (about 10～30%) sprays downwards.
6. p-Xylol feed entrance point
Add the bubble tower conversion zone behind raw material p-Xylol and solvent, the catalyzer uniform mixing, reactant concn is higher near opening for feed, and oxidation is also more violent.Because the boiling point of p-Xylol and acetic acid is close, so feed entrance point can not be provided with too highly, otherwise damage is run in the evaporation that will increase PX, and the while can not be provided with low, in order to avoid PX runs off from the short circuit of bottom discharge mouth.1/4～1/2 place of the suitable feed entrance point that the present invention provides conversion zone height above gas distributor.Material feeding tube can be single feed-pipe, also can be many feed-pipes along the bubble tower altitude distribution.
Device of the present invention is applicable to the various processing condition of p-Xylol high temperature oxidation, for example, 180～205 ℃ of temperature of reaction, pressure 1.0～2.0MPa, catalyzer total concn (Co+Mn+Br) 1000～3000ppm, charging solvent ratio (acetic acid: PX, kg/kg) 3～10: 1, water content 6～18% in the tower, reactor residence time 40～120min will specify by following example 1～2.
Embodiment 1
High temperature oxidation process is produced terephthalic acid in the employing, and establishing reaction unit separate unit yearly capacity is 300,000 tons of TA, and annual 7600 hours production times, reaction conditions is provided by table 1.1.
Table 1.1
| Temperature (℃) | PX treatment capacity (10 3kg/h) | Tower top pressure (Mpa, absolute pressure) | Tail oxygen concentration (v O2，％) | Catalyst concn (ppmHAc) | Water content (H 2O/H ? ?Ac％) | Charging HAc/PX mass ratio | ||
| ??Co | ??Mn | ??Br | ||||||
| ??185 | ??26.60 | ??1.13 | ??3.52 | ??691 | ??406 | ??892 | ??7.5 | ??4.66∶1 |
The scantlings of the structure of device is provided by table 1.2.
Table 1.2
| Diameter (m) | Aspect ratio (m/m) | Useful volume (m 3) | The PX feed entrance point |
| ??4.60 | ????H/D＝4 | ????305.3 | ????1/2H |
D is a tower diameter in the table, determines that according to production capacity H is the conversion zone height.For the bubbling column reactor of producing 300000 tons of terephthalic acids per year, when selecting aspect ratio to be 4, D=4.60m, reaction result and relevant index are provided by table 1.3.
Table 1.3
| PX transformation efficiency (%) | TA yield (%) | PT concentration (ppm) | 4-CBA concentration (ppm) | Tail gas CO 2Concentration (%) | Maximum temperature difference (℃) | The residence time (min) |
| ??99.9 | ??97.2 | ??5412 | ??1343 | ??1.58 | ??1.6 | ??52.3 |
PT that provides in the table and 4-CBA are respectively the reaction intermediates p-methylbenzoic acid and to the liquid concentration (quality of=constituent mass/solvent acetic acid and water) of carboxyl benzaldehyde in the reactor discharging, maximum temperature difference is the temperature head of interior temperature vertex (tower middle and upper part) of tower and lower-most point (at the bottom of the tower).
Adopt high temperature oxidation process to produce terephthalic acid, establishing reaction unit separate unit yearly capacity still is 300,000 tons of TA, and annual 7600 hours production times, reaction conditions is provided by table 2.1.Reaction unit structure and size are shown in table 2.2, and reactor output the results are shown in table 2.3.
Table 2.1
| Temperature (℃) | PX treatment capacity (10 3kg/h) | Tower top pressure (Mpa, absolute pressure) | Tail oxygen concentration (v O2，％) | Catalyst concn (ppmHAc) | Water content (H 2O/HAc ? ????％) | Charging HAc/ PX mass ratio | ||
| ?Co | ?Mn | ??Br | ||||||
| ?196.0 | ??26.57 | ??1.524 | ??3.51 | ?342 | ?526 | ??949 | ????14.8 | ??3.34∶1 |
Table 2.2
| Diameter (m) | Aspect ratio (m/m) | Useful volume (m 3) | The PX feed entrance point |
| ??4.31 | ????H/D＝4 | ????250.8 | ????1/3H |
Table 2.3
| PX transformation efficiency (%) | TA yield (%) | PT concentration (ppm) | 4-CBA concentration (ppm) | Tail gas CO 2Concentration (%) | Maximum temperature difference (℃) | The residence time (min) |
| ??99.4 | ??95.6 | ??9931 | ??2627 | ??1.69 | ??1.8 | ??53.3 |
Claims (3)
1. produce the bubble tower oxidation reaction apparatus that terephthalic acid is used for one kind, it is characterized in that comprising even straight-cylindrical bubble tower, be followed successively by gas processing section (3) in the tower from top to bottom, free space segment (11) and three phase reaction section (1), the gas processing section accounts for 10～20% of bubble tower total height, three phase reaction section accounts for 60～85% of bubble tower total height, the free space segment height is 1～3 meter, liquid distributor (9) is installed in gas processing section (3), filler or supporting liquid column plate (10), lower horizontal at three phase reaction section (1) is equipped with gas distributor (2), gas distributor (2) links to each other with the bubble tower inlet mouth, 1/4～1/2 place that is positioned at the three phase reaction section height in gas distributor (2) top is provided with material feeding tube (5), be provided with discharge nozzle (6) at the bottom of the tower, cat head is provided with offgas duct (7) and phlegma return line (8), offgas duct (7) links to each other with the inlet of condenser (4), the liquid exit of condenser (4) respectively with material feeding tube (5), phlegma return line (8) links to each other with follow-up dehydration tower, and the pneumatic outlet of condenser (4) links to each other with follow-up tail gas treating unit.
2. the bubble tower oxidation reaction apparatus that production terephthalic acid according to claim 1 is used is characterized in that the height of bubble tower three phase reaction section and diameter ratio are 3～7.
3. the bubble tower oxidation reaction apparatus that production terephthalic acid according to claim 1 is used, it is characterized in that gas distributor (2) is annular, sexangle perforated-plate distributor or multitube sparger or other industrial gasses sparger, wherein, the ratio of the gas orifice percentage of open area of the upper surface of perforated-plate distributor airflow line and lower surface is 1: 0.05～0.5.
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| US7683210B2 (en) | 2004-09-02 | 2010-03-23 | Eastman Chemical Company | Optimized liquid-phase oxidation |
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| US8114356B2 (en) | 2004-09-02 | 2012-02-14 | Grupo Pretrotemex, S.A. de C.V. | Optimized liquid-phase oxidation |
| US8470257B2 (en) | 2004-09-02 | 2013-06-25 | Grupo Petrotemex, S.A. De C.V. | Optimized liquid-phase oxidation |
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| US8178054B2 (en) | 2004-09-02 | 2012-05-15 | Grupo Petrotemex, S. A. DE C. V. | Optimized liquid-phase oxidation |
| US7910769B2 (en) | 2004-09-02 | 2011-03-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7960581B2 (en) | 2004-09-02 | 2011-06-14 | Grupo Petrotemex, S.A. De C.V. | Optimized liquid-phase oxidation |
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| US7659427B2 (en) | 2004-09-02 | 2010-02-09 | Eastman Chemical Company | Optimized liquid-phase oxidation |
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| US8470257B2 (en) | 2004-09-02 | 2013-06-25 | Grupo Petrotemex, S.A. De C.V. | Optimized liquid-phase oxidation |
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| US8114356B2 (en) | 2004-09-02 | 2012-02-14 | Grupo Pretrotemex, S.A. de C.V. | Optimized liquid-phase oxidation |
| US7692036B2 (en) | 2004-11-29 | 2010-04-06 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US8501986B2 (en) | 2004-11-29 | 2013-08-06 | Grupo Petrotemex, S.A. De C.V. | Optimized liquid-phase oxidation |
| US7884232B2 (en) | 2005-06-16 | 2011-02-08 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| CN111054278A (en) * | 2019-12-02 | 2020-04-24 | 河南金鹏化工有限公司 | Continuous production process and device for thiodicarb synthesis reaction |
| WO2021196383A1 (en) * | 2020-03-31 | 2021-10-07 | 南京延长反应技术研究院有限公司 | External micro-interface unit enhanced reaction system and process for production of pta from px |
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| CN1228302C (en) | 2005-11-23 |
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