CN1486968A - Air lift externally circulating bubble fower oxidation unit for producing terephthalic acid - Google Patents
Air lift externally circulating bubble fower oxidation unit for producing terephthalic acid Download PDFInfo
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Abstract
The air lift externally circulation bubble tower oxidation apparatus includes cylinder bubble tower with top expanded section, outer circulating pipe, gas distributor, reflux liquid distributor and condensator. The outer circulating pipe has its upper end and lower end communicated with the upper part and the lower part of the bubble tower reaction section separately and is used to lead slurry from the upper part of the tower to the lower part via air lift effect so as to form the fluid circulation in the whole tower and complete the liquid phase catalytic oxidation of xylene. The bubble tower has relatively high height/diameter ratio and thus reinforced gas-liquid mass transfer and the air lift outer circulation pipe improves the temperature distribution and concentraion distribution inside the tower. The tower has no moving part, simple structure and low cost and is suitable for oxidizing xylene to prepare terephthalic acid via different technological processes.
Description
Technical field
The present invention relates to be used in air lift type outer circulation the bubble tower oxidation unit, 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 0.5～1.6MP, 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.Patent JP14098/1979, EP0618186A1 and the disclosed reactor of patent US5463113 have a stirring rake, are installed in the bottom at still, play loosening slurry of solids and prevent to scab.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 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.
Patent US2002/0183546A1 discloses a kind of two-stage oxidation technology of producing aromatic carboxylic acid, first step oxidation is adopted does not have the tower reactor that stirs, in lower temperature (155～165 ℃) and pressure (0.52～0.62MP) time operation, stirred reactor is adopted in second stage oxidation, in higher temperature (205～225 ℃) and pressure (6.0～18.5MP) times operations.The first step oxidation reactor of this patent introduction belongs to the bubble tower type, adopts larger ratio of height to diameter with reinforcing mass transfer.Yet, under the situation of larger ratio of height to diameter, bad problem appears mixing easily, there are bigger thermograde and concentration gradient along tower height in the reactor, and make the reactor volume utilization ratio reduce, the solvent burning consumes aggravation.
Summary of the invention
The air lift type outer circulation bubble tower oxidation unit 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.
The air lift type outer circulation bubble tower oxidation unit of production terephthalic acid of the present invention comprises the cartridge type bubble tower that has top expanded section, outer circulating tube, gas distributor, phegma sparger and condenser.The gas distributor level places the bottom of bubble tower conversion zone, link to each other with the bubble tower inlet mouth, phegma sparger level places the bubble tower upper extension section, 1/4～1/2 place of tower height is provided with material feeding tube above the gas distributor being positioned at, be provided with discharge nozzle at the bottom of the tower, top at the bubble tower expanding reach is provided with offgas duct, the top of outer circulating tube has gas-liquid separator, the gas-liquid separator inlet is communicated with the top of bubble tower conversion zone, the lower port of outer circulating tube is positioned at above or below the gas distributor 0～1 beta and directly locates, be communicated with bubble tower conversion zone bottom, be provided with the gas outlet tube that is communicated with offgas duct on the top of gas-liquid separator, offgas duct links to each other with the inlet of condenser, the liquid exit of condenser is by prolong and material feeding tube, phegma sparger and follow-up dehydration tower link to each other, and the pneumatic outlet of condenser links to each other with follow-up tail gas treating unit.
During work, add in the reactor 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 enter gas distributor from the tower inlet mouth, bubbling carries out oxidizing reaction by the liquid bed with the liquid phase reaction thing after gas distributor disperses; Reaction heat shifts out reactor by solvent acetic acid and evaporation of water through offgas duct, 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; Keep certain liquid level to make the gas-liquid separator inlet on outer circulating tube top be positioned near the liquid level below in the reactor.When bubbling in the tower is inflated, the inner gas holdup height of bubble tower, the apparent density of three-phase medium is little, and gas holdup is low in the outer circulating tube, and apparent density is big, like this, slurry in the circulation tube will spontaneously flow under the gravitational difference effect from top to bottom, bad mixing zone, the conversion zone top higher slurry of temperature constantly is transported to tower bottom good mixing, zone that temperature is lower, forms the circulation of full tower liquid, help eliminating the bad mixing zone on tower top and along the temperature of tower and density unevenness is even distributes.The terephthalic acid slurry that reaction generates outputs to follow-up separation by the bottom discharge pipe and refining step is further handled.Simultaneously, reaction heat shifts out in the tower by solvent evaporation, the tail gas that steam and outer circulation gas-liquid separator separates go out is introduced condenser, the phlegma of gained is divided into three strands: one returns in the tower in the spray mode by liquid distributor, can remove entrained solid and liquid foam in the tail gas, one mixes the back by feed-pipe and adds in the tower with raw material, one sends into follow-up dehydration tower.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, utilize outer circulating tube that tower top slurry is introduced lower region by the gas lift effect, form the circulation of fluid at full tower, simple in structure, cost and working cost are cheap, are applicable to the various reaction conditionss of p-Xylol air liquid phase catalytic oxidation.
Description of drawings
Fig. 1 is the structural representation of apparatus of the present invention.
Embodiment
With reference to Fig. 1, the air lift type outer circulation bubble tower oxidation unit of producing terephthalic acid comprises the cartridge type bubble tower 1 that has top expanded section, outer circulating tube 2, gas distributor 3, phegma sparger 4 and condenser 5.Gas distributor 3 levels place the bottom of bubble tower conversion zone, link to each other with the bubble tower inlet mouth, phegma sparger 4 levels place the bubble tower upper extension section, 1/4～1/2 place of tower height is provided with material feeding tube 6 above the gas distributor 3 being positioned at, be provided with discharge nozzle 7 at the bottom of the tower, be provided with offgas duct 8 on the top of bubble tower expanding reach, the top of outer circulating tube 2 has gas-liquid separator 2-1, the gas-liquid separator inlet is communicated with the top of bubble tower conversion zone, the lower port of outer circulating tube 2 is positioned at above or below the gas distributor 0～1 beta and directly locates, be communicated with the bubble tower conversion zone, be provided with the gas outlet tube 10 that is communicated with offgas duct 8 on the top of gas-liquid separator 2-1, offgas duct 8 links to each other with the inlet of condenser 5, the liquid exit of condenser 5 is by prolong 9 and material feeding tube 6, phegma sparger 4 links to each other with follow-up dehydration tower, partial condensation liquid is by in feed-pipe 6 and phegma sparger 4 reflux towers, part is sent into follow-up dehydration tower dehydration in addition, the pneumatic outlet of condenser 5 links to each other with follow-up tail gas treating unit, further handles so that incoagulability tail gas is sent into follow-up tail gas treating unit.
Below main points of the present invention are further described.
1. the tube structure of bubble tower and useful volume
The effect of bubble tower expanding reach is to fall low gas velocity, the splash of buffering liquid level, and reduce carrying secretly of solid and liquid in the tail gas in conjunction with the spray of phegma.The volume of conversion zone is the useful volume of bubble tower, and useful volume is to determine according to the requirement that the assurance liquid phase oxidation reaction is fully finished.Because the slow reaction of isogonic during p xylene oxidation belongs to, mainly in the liquid phase body, carry out, it is very inresponsive to the variation of reactant concn that p xylene oxidation respectively goes on foot speed of reaction, 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%).Usually making the expanding reach and the diameter ratio of conversion zone is 1.5～2: 1, and aspect ratio is 1: 10～30.Make the scope that the liquid phase residence time (=tower in liquid holdup/outlet liquid flow rate) remained on 40～120 minutes.The slurry liquid level is controlled at junction between conversion zone and the expanding reach or lower slightly position during operation.
2. bubble tower aspect ratio
Bubble tower is that the bubbling turbulence by gas promotes mass transfer, be reinforcing mass transfer, bubble tower should adopt larger ratio of height to diameter with the increase empty tower gas velocity, but the aspect ratio increase causes the inhomogeneous of interior temperature of tower and concentration distribution again easily, 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, therefore increases aspect ratio and also causes easily and mix unevenly, forms bad mixing zone on tower top.Therefore the requirement of determining to take into account mass transfer, mixing, reaction three aspects of bubble tower aspect ratio, the aspect ratio that the present invention is suitable for is 6～13, preferred aspect ratio is 7～10.
3. outer circulating tube
Among the present invention, the top of outer circulating tube has gas-liquid separator, the gas-liquid separator inlet is generally directly located apart from liquid level 0.4～2 beta below liquid level, the lower port of outer circulating tube is positioned at gas distributor top 0～1 beta directly to be located, and perhaps is positioned at sparger below 0～1 beta and directly locates (under the situation of moving on the gas distributor).Gas-liquid separator is a cylinder, and its diameter is 1.5～2.5 times of outer circulating tube diameter, aspect ratio 1.5～3.The gas of separating enters the bubble tower offgas duct to the upper edge gas outlet tube, and slurry then returns in the tower to the lower edge pipe.The diameter of outer circulating tube determines that by required circular flow the too small then circular flow of diameter is low, is not enough to improve the inhomogeneous situation of interior temperature of tower and concentration, and diameter is excessive can to increase device fabrication and installation cost again, also reduces the volume utilising efficiency simultaneously.The diameter of the outer circulating tube that the present invention provides is 1/5～1/15 of a bubble tower conversion zone diameter.In order to increase turndown ratio, flaps or valve can or be set, in outer circulating tube in the junction of gas-liquid separator and bubble tower to regulate circular flow.
4. 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 tower height above gas distributor.Material feeding tube can be single feed-pipe, also can be many feed-pipes along the bubble tower altitude distribution.
5. gas-liquid 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, and the injection direction of gas up.The phegma sparger is installed in the expanding reach of bubble tower, the acetic acid that refluxes returns in the tower in the spray mode by the liquid distributor of cat head, purpose is to remove entrained solid and liquid foam in the tail gas, and the phegma sparger can adopt porous plate-slot type spray thrower or multitube spray thrower.The tail gas that steam that evaporates in the reactor and outer circulating tube gas-liquid separator separates go out is introduced condenser, and a condensed liquid part is back in the tower, and a part is delivered to dehydration tower and dewaters.Because the gas evaporation amount is big in the tower, so condenser is general adopts 2～5 grades of serial operations increasing the heat exchange load, but the superheated vapour of by-product different pressures simultaneously.
Device of the present invention is applicable to the various processing condition of p xylene oxidation, for example, 155～205 ℃ of temperature of reaction, pressure 0.5～2.0MP, catalyzer total concn (Co+Mn+Br) 700～3500ppm, charging solvent ratio (acetic acid: PX, kg/kg) 3～10: 1, water content 3～15%, reactor residence time 40～120min will specify by following example 1～3.
Embodiment 1
Adopt low temperature oxidation technology to produce terephthalic acid, reactor separate unit yearly capacity is 200,000 tons of TA, and annual 7600 hours production times, reaction conditions is provided by table 1.1.
Table 1.1 low-temperature oxidation method processing condition
| The middle part temperature (℃) | PX treatment capacity (10 3kg/h) | Tower top pressure (Mpa, absolute pressure) | Tail oxygen concentration (v O2，％) | Catalyst concn is (to the massfraction of HAc, 10 -6) | ??H 2O/HAc (mass percent) | Charging HAc/PX mass ratio | ||
| ??Co | ??Mn | ??Br | ||||||
| ??165 | ??17.72 | ??0.7190 | ??4.40 | ?942.9 | ?87.9 | ?942.9 | ????7.0 | ????10∶1 |
Corresponding structure of reactor and size are provided by table 1.2.
Table 1.2 structure of reactor and size
| Diameter (m) | Aspect ratio (m/m) | Circulation tube diameter (m) | Useful volume (m 3) | The PX feed entrance point |
| ???3.68 | ????H/D＝8 | ????0.368 | ????312.1 | ????0.40H |
D is a tower diameter in the table, determines that according to production capacity H is the conversion zone height.For the separate unit air lift type outer circulation bubbling column reactor (ALECBCR) of producing 200000 tons of terephthalic acids per year, when selecting aspect ratio to be 8, D=3.68m, reaction result and relevant index are provided by table 1.3, give indicator reaction under bubbling column reactor (BCR) similarity condition that does not add outer circulating tube in the table simultaneously to contrast.
Table 1.3 BCR and ALECBCR performance are relatively
| PX transformation efficiency (%) | TA yield (%) | PT concentration (10 -6kg/kgsol) | 4-CBA concentration (10 -6kg/kgsol) | Tail gas CO 2Concentration (v CO2，％) | Maximum temperature difference (℃) | The PX concentration difference (minimum/maximum, %) | The residence time (min) | |
| BCR | 99.9 | 96.9 | 8058 | 1808 | 1.14 | 5.55 | 7.54 | 100 |
| ALECBCR | 99.9 | 97.5 | 7315 | 1506 | 1.13 | 2.88 | 10.40 | 100 |
PT that provides in the table and 4-CBA be respectively the reaction intermediates p-methylbenzoic acid with 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), the PX concentration difference is the relative ratio of near Cmin of liquid level and near the peak concentration the feed points, is the inhomogeneity a kind of tolerance of concentration distribution in the tower.The result who is provided by table 1.3 can see, adopt bubble tower and air lift type outer circulation bubble tower can both finish the process that p xylene oxidation is produced terephthalic acid, but air lift type outer circulation bubbling reactor ALECBCR temperature and concentration distribution under same reaction conditions is more even, therefore the yield that obtains than bubble tower BCR is higher, and reaction intermediates PT and 4-CBA concentration are lower.Make that TA yield, PT in its discharging are consistent with 4-CBA concentration and bubble tower if increase the PX flow of outer circulation bubble tower, then adopt ALECBCR can increase production capacity 4.5% than BCR.
Warm oxidizing process is produced terephthalic acid in the employing, and reactor separate unit yearly capacity still is 200,000 tons of TA, and annual 7600 hours production times, reaction conditions is provided by table 2.1.
Warm oxidation style processing condition in the table 2.1
| The middle part temperature (℃) | PX treatment capacity (10 3kg/h) | Tower top pressure (Mpa, absolute pressure) | Tail oxygen concentration (v O2，％) | Catalyst concn is (to the massfraction of HAc, 10 -6) | H 2O/HAc (mass percent) | Charging HAc/PX mass ratio | ||
| ??Co | ??Mn | ????Br | ||||||
| ??185.0 | ??17.72 | ??1.168 | ??3.50 | ??691 | ??406 | ??892 | ????7.52 | ??4.66∶1 |
For middle temperature oxidizing process, when selecting aspect ratio to be 8, D=3.19m, structure of reactor and size are provided by table 2.2
Table 2.2 structure of reactor and size
| Diameter (m) | Aspect ratio (m/m) | Circulation tube diameter (m) | Useful volume (m 3) | The PX feed entrance point |
| ????3.19 | ????H/D＝8 | ????0.319 | ????203.3 | ????1/2H |
Reactor output under these conditions the results are shown in table 2.3.As can be seen, the outer circulation bubbling reactor still has better processing property and reaction effect, is keeping under TA yield, the sour situation identical with 4-CBA content of PT, and the bubbling column reactor of the comparable routine of outer circulation reactor that the present invention provides increases production capacity 3.8%
Table 2.3 BCR and ALECBCR performance are relatively
| PX transformation efficiency (%) | TA yield (%) | PT concentration (10 -6kg/kg ??sol) | 4-CBA concentration (10 -6kg/kgsol | Tail gas CO 2Concentration (v CO2，％) | Maximum temperature difference (℃) | The PX concentration difference (minimum/maximum, %) | The residence time (min) | |
| ????BCR | ??99.9 | ?97.4 | ??5280 | ????1333 | ???1.60 | ???6.61 | ????1.72 | ???50.3 |
| ?ALECBCR | ??99.9 | ?97.8 | ??4773 | ????1221 | ???1.58 | ???3.41 | ????2.80 | ???50.2 |
Adopt high temperature oxidation process to produce terephthalic acid, reactor separate unit yearly capacity still is 200,000 tons of TA, and annual 7600 hours production times, reaction conditions is provided by table 3.1.Structure of reactor and size are shown in table 3.2, and reactor output the results are shown in table 3.3, under same reaction conditions and output result, adopt the outer circulation bubbling reactor than conventional bubbling column reactor increase-volume 3.2%.The effect of outer circulating tube is slightly different in above-mentioned three examples, and this mainly is because reactor is different with the outer circulating tube size, causes due to the circular flow difference.
Table 3.1 high-temperature oxidation processing condition
| The middle part temperature (℃) | PX treatment capacity (10 3kg/h) | Tower top pressure (Mpa, absolute pressure) | Tail oxygen concentration (v O2，％) | Catalyst concn is (to the massfraction of HAc, 10 -6) | H 2O/HAc (mass percent) | Charging HAc/ PX mass ratio | ||
| Co | ?Mn | ?Br | ||||||
| 196.2 | 17.72 | 1.570 | 3.60 | 342 | 526 | 949 | 14.77 | 3.34∶1 |
Table 3.2 structure of reactor and size
| Diameter (m) | Aspect ratio (m/m) | Circulation tube diameter (m) | Useful volume (m 3) | The PX feed entrance point |
| ???2.97 | ????H/D＝8 | ??0.297 | ????165.0 | ??1/3H |
Table 3.3 BCR and ALECBCR performance are relatively
| PX transformation efficiency (%) | TA yield (%) | PT concentration (10 -6kg/kg sol) | 4-CBA concentration (10 -6kg/kgsol) | Tail gas CO 2Concentration (v CO2，％) | Maximum temperature difference (℃) | The PX concentration difference (minimum/maximum, %) | The residence time (min) | |
| BCR | 99.5 | 95.4 | 10339 | 2588 | 1.80 | 6.47 | 12.0 | 49.3 |
| ALECBCR | 99.7 | 96.5 | 9537 | 2330 | 1.80 | 4.49 | 17.3 | 49.1 |
Claims (9)
1. produce the air lift type outer circulation bubble tower oxidation unit that terephthalic acid is used for one kind, it is characterized in that comprising the cartridge type bubble tower (1) that has top expanded section, outer circulating tube (2), gas distributor (3), phegma sparger (4) and condenser (5), gas distributor (3) level places the bottom of bubble tower conversion zone, link to each other with the bubble tower inlet mouth, phegma sparger (4) level places the bubble tower upper extension section, be provided with material feeding tube (6) at 1/4～1/2 place that is positioned at gas distributor (3) top tower height, be provided with discharge nozzle (7) at the bottom of the tower, be provided with offgas duct (8) on the top of bubble tower expanding reach, the top of outer circulating tube (2) has gas-liquid separator (2-1), the gas-liquid separator inlet is communicated with the top of bubble tower conversion zone, the lower port of outer circulating tube (2) is positioned at above or below the gas distributor 0～1 beta and directly locates, be communicated with the bubble tower conversion zone, be provided with the gas outlet tube (10) that is communicated with offgas duct (8) on the top of gas-liquid separator (2-1), offgas duct (8) links to each other with the inlet of condenser (5), the liquid exit of condenser (5) is by prolong (9) and material feeding tube (6), phegma sparger (4) and follow-up dehydration tower link to each other, and the pneumatic outlet of condenser (5) links to each other with follow-up tail gas treating unit.
2. air lift type outer circulation bubble tower oxidation unit according to claim 1, the conversion zone height and the diameter ratio that it is characterized in that bubble tower (1) are 6～13, the diameter ratio of bubble tower (1) top expanding reach and lower reaction section is 1.5～2: 1, and aspect ratio is 1: 10～30.
3. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that the conversion zone height of bubble tower (1) and diameter ratio are 7～10.
4. air lift type outer circulation bubble tower oxidation unit according to claim 1, the diameter that it is characterized in that outer circulating tube (2) is 1/5～1/15 of a bubble tower conversion zone diameter.
5. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that the gas-liquid separator that outer circulating tube connects is a cylinder, and its diameter is 1.5～2.5 times of outer circulating tube diameter, aspect ratio 1.5～3.
6. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that in the junction of gas-liquid separator and bubble tower or be provided with flaps or the valve of regulating circular flow in outer circulating tube.
7. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that gas distributor (3) is annular, sexangle perforated-plate distributor or multitube sparger or other industrial gasses sparger.
8. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that phegma sparger (4) is porous plate-slot type spray thrower or multitube spray thrower.
9. air lift type outer circulation bubble tower oxidation unit according to claim 1 is characterized in that material feeding tube (6) is for single feed-pipe or along many feed-pipes of bubble tower altitude distribution.
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| CN116063260A (en) * | 2021-10-29 | 2023-05-05 | 中化学科学技术研究有限公司 | Continuous oxidation process of chloro-o-xylene |
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2003
- 2003-08-08 CN CN 03142246 patent/CN1208301C/en not_active Expired - Lifetime
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