CN100447124C - Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers - Google Patents
Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers Download PDFInfo
- Publication number
- CN100447124C CN100447124C CNB2006100861241A CN200610086124A CN100447124C CN 100447124 C CN100447124 C CN 100447124C CN B2006100861241 A CNB2006100861241 A CN B2006100861241A CN 200610086124 A CN200610086124 A CN 200610086124A CN 100447124 C CN100447124 C CN 100447124C
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- tower
- water
- oxidizing
- oxidizing tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a method for preparing trimellitic acid with series intermediate bubble oxidization columns by continuous oxidation. The method comprises: (1) mixing 1,2,4-trimethylbenzene with solvent and catalyst in a kettle, heating for mixing, and sending to a series of three oxidization columns for reaction; (2) introducing the reaction products into a crystallization kettle, crystallizing to obtain mixed slurry of trimellitic acid crystal, acetic acid and water, sending to a centrifugation separator for separation, and sending the w trimellitic acid granules to the anhydridization process; (3) sending the mixture of acetic acid and water to a concentration column, and recovering acetic acid for recycling; (4) recovering trimellitic acid from the concentration column bottom product in a flash evaporation column. The series oxidization columns have such advantages as low investment, no leakage, no blockage at the inlet/outlet, continuous operation, high productivity, high yield, low raw material consumption and low energy consumption.
Description
Technical field
The present invention relates to a kind of utilize the intermediate bubble oxidization column multitower to connect method that continuous oxidation produces trimellitic acid.Belong to field of chemical technology.
Background technology
Trimellitic acid is the important source material of producing trimellitic acid 1,2-anhydride.Trimellitic acid 1,2-anhydride is the important Organic Chemicals of modern type material, and very high reactive behavior is arranged, and can generate a series of fine chemicals that high added value is arranged, and is mainly used in industries such as engineering plastics, high-quality softening agent, heatproof insullac, high grade paint.Owing to have excellent electrical insulating property, resistance to elevated temperatures and mechanical property with its made resin material, also be widely used in industrial circles such as electromechanics, electronics and space flight.
At present, the method of producing trimellitic acid mainly adopts the intermittent type liquid-phase air oxidation, being about to the raw material unsym-trimethyl benzene is dissolved in the acetate solvate, with Cobaltous diacetate, manganese acetate and tetrabromoethane is catalyzer, through batching, preheating, intensification, feed pressurized air and boost, carry out oxidizing reaction under 170～240 ℃, 1.8～2.8MPa condition, oxidation generates trimellitic acid.
This method mainly has the following disadvantages:
1, long reaction time, reaction is incomplete, by product is many, quality is unstable, the product recovery rate is low, at present, interrupter method is produced the molar yield of trimellitic acid handicraft product 65～80%.
2, in the batch production process, reactor needs repeatedly voltage raising and reducing, the cooling that heats up, and equipment is tired easily, and shorten work-ing life.
3, oxidation step be because each increasing temperature and pressure all might enter explosion-risk area, careless slightlyly just has the danger of blasting, and the security of production is very low.
Above characteristic determines this technology to be difficult to carry out large-scale production.
Have four about the patent application of continuous oxidation production trimellitic acid of unsym-trimethyl benzene or trimellitic acid 1,2-anhydride is at present domestic.Wherein, Chinese patent application CN1485304A discloses " one-step production of high-purity trimellitic acid from pseudocumene ", and the production method that this application relates to is one step of gaseous oxidation to generate trimellitic acid 1,2-anhydride, and is different with present method.Chinese patent application CN1401642A disclosed " the continuous processing oxidizing process is produced the method for trimellitic acid 1,2-anhydride ", Chinese patent application CN1594302A disclosed " a kind of method of the continuous production of catalyzed oxidation step by step trimellitic acid 1,2-anhydride ", Chinese patent application CN1634907A disclosed " method of stirring type multi-kettle continuous oxidation preparation of trimellitic anhydride ", they and present method are the continuous oxidation style of unsym-trimethyl benzene liquid-phase catalysis, generate trimellitic acid earlier, be dehydrated into the refining trimellitic acid 1,2-anhydride of producing of acid anhydride again.They are the continuous oxidation of stirring tank formula, wherein patent application CN1401642A is disclosed be single still serialization, patent application CN1594302A disclosed be two still serializations, patent application CN1634907A is disclosed is three stills or four still serializations.There is the facility investment costliness in stirred-tank reactor, dynamic seal parts leakiness is fragile, oxidation reactor discharging gas-liquid separation is insufficient, and high solidifying point material easily is brought into condenser, influences condenser heat exchange effect.In the above several method, a large amount of reaction heat energy that oxidizing reaction generates all do not obtain utilizing, and cause significant wastage.The crystallization method that relates among Chinese patent application CN1401642A and the Chinese patent application CN1634907A is the crystallization of single groove (still) continous way, and the crystallization method that relates among the Chinese patent application CN1594302A is the progressively step-down cooling continous way crystallizations of many stills.Band is pressed the clean still facility investment of stirring-type costliness, has the problem of motion sealing element leakiness rapid wear.Serialization operation can not alternating temperature, is unfavorable for crystal growth, and crystallization effect is poor, the incomplete Recycling Mother Solution of crystallization must be utilized again, can reach the Crystallization Separation purpose.And, each easy blockage problem of crystallizer ingress when there is punishment in advance in multi-still continuous crystallization.Single groove (still) serialization operation, because temperature can not change, crystallization effect is poorer.
The principles of chemistry and the atmospheric oxidation kinetics mechanism that generate trimellitic acid according to the unsym-trimethyl benzene oxidation are analyzed, and this reaction process is an exothermal reaction process; Be reflected at inclined to one side benzene one formic acid of generation and can emit very big heat, can under the temperature of reaction that is lower than the generation trimellitic acid, carry out, need in time shift out reaction heat with the inclined to one side phthalic acid stage.Trimellitic acid elementary reaction thermal discharge is less generating, and reaction activity is the highest, improves temperature of reaction and will improve speed of reaction, in order to keep and finish reaction, must guarantee temperature of reaction, replenishes certain heat energy.From unsym-trimethyl benzene oxidation reaction kinetics principle, improve the impellent that reactant concn will strengthen reaction.
Summary of the invention:
The objective of the invention is to overcome above-mentioned deficiency, a kind of oxidation furnaces reduced investment is provided, leakage and damage, crystallizer feed inlet and outlet be difficult for to take place is difficult for low utilize the intermediate bubble oxidization column multitower to connect the method that continuous oxidation produces trimellitic acid of serialization operation, production capacity height, product yield height, raw material consumption and energy consumption stifled, that can guarantee preceding road oxidation operation and subsequent handling.
The object of the present invention is achieved like this: a kind of utilize the intermediate bubble oxidization column multitower to connect method that continuous oxidation produces trimellitic acid, it is characterized in that it is is raw material with the unsym-trimethyl benzene, acetic acid is solvent, Cobaltous diacetate, manganese acetate are that catalyzer, tetrabromoethane are promotor, the tertiary oxidation tower will be added after the above-mentioned mixing of materials continuously, and feed pressurized air respectively continuously and carry out oxidizing reaction, this method comprises following processing step:
A) with after raw material unsym-trimethyl benzene and solvent acetic acid, catalyst acetic acid cobalt, manganese acetate, the metering of promotor tetrabromoethane, drop into the heating of batching still and mix, temperature is controlled at 60 ℃～110 ℃,
B) said mixture is sent into continuously in the 1# oxidizing tower of three placed in-line oxidizing towers with pump, temperature is at 180 ℃～220 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, feed pressurized air continuously, control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the gas house steward≤8% (V/V)
C) by pump 1# oxidizing tower reaction product is imported the 2# oxidizing tower continuously, temperature is at 180 ℃～240 ℃ in the control tower, and pressure feeds pressurized air continuously at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold;
D) 1#, 2# oxidizing tower dispose respectively and waste heat boiler are set as overhead condenser, the steam of reacted oxygen-denuded air and acetic acid and water passes through condenser, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber, and tail gas up to standard enters atmosphere;
E) by pump 2# oxidizing tower reaction product is imported the 3# oxidizing tower continuously, temperature is at 180 ℃～250 ℃ in the control tower, pressure is at 1.8MPa～3.5Mpa, feed pressurized air continuously, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower top is provided with flashing tower, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flash distillation Tata still, remove the acetic acid upgrading system after containing most of water and seldom the steam of part acetic acid being condensed, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber, and tail gas up to standard enters atmosphere;
F) the 3# oxidizing tower reaction product of coming out and the mixture of solvent acetic acid and water import in 2～4 crystallization kettles in turn, when reaching the setting liquid level, a crystallization kettle charging promptly switches to another crystallization kettle, the mixture of oxidation products and solvent acetic acid in crystallization kettle under the normal pressure by a decrease temperature crystalline, part acetic acid and water are steamed, after condenser condenses, remove the acetic acid upgrading system, crystallization control still temperature is 60 ℃～180 ℃, through the trimellitic acid crystal after the crystallization, the mixed slurry of acetic acid and water is delivered to centrifuge separator and is separated, acetic acid, water and most of catalyzer remove the acetic acid upgrading system by liquid phase separation, and the wet thing of trimellitic acid solid particulate send into anhydridization process;
G) mixture of the acetic acid that produces in oxidation, the Crystallization Procedure and water is delivered to carried out continuous still battery in the concentration tower, water steams from cat head, and waste water up to standard send the water treatment post after the condensation, and the acetic acid of content 〉=98% reclaims from the tower bottom, uses as solvent cycle;
H) acetic acid concentration tower tower still feed liquid is delivered to the flash distillation still in batches, acetic acid steams from flash distillation still top, delivers to the acetic acid jar after condensation, uses as solvent cycle, steams slurry that thing contains trimellitic acid 〉=60% at the bottom of the still and delivers to crystallization kettle and recycle.
Catalyst acetic acid cobalt described in the step a) of the present invention, manganese acetate and promotor tetrabromoethane can be by in the described 1# oxidizing towers of disposable adding step b), also can be separated to add in described 1# oxidizing tower of step b) and the described 2# oxidizing tower of step c), separately add fashionable, with Cobaltous diacetate, manganese acetate, the tetrabromoethane total amount is respectively under 1 the situation: Cobaltous diacetate add-on in the 1# oxidizing tower is 0.6～0.8, add-on is 0.2～0.4 in the 2# oxidizing tower, manganese acetate add-on in the 1# oxidizing tower is 0.2～0.4, add-on is 0.6～0.8 in the 2# oxidizing tower, tetrabromoethane add-on in the 1# oxidizing tower is 0.4～0.6, and add-on is 0.4～0.6 in the 2# oxidizing tower.
Compare with batch process, the present invention embodies many-sided advantage, adopt tertiary oxidation can realize the operational condition of differential responses stage enforcement differing temps preferably, each stage is implemented the differential responses residence time, can meet the unsym-trimethyl benzene oxidation kinetics better, avoid reacting too concentrating and cause the out of control of temperature, realize the recycling of reaction heat energy preferably, both alleviate the burden of thermal energy source, also alleviated the burden of circulating cooling system; Present method stable equipment operation is reliable, technic index is stable, be easy to control, basic for moving under constant temperature, the constant voltage, avoided in the batch process lifting temperature and pressure repeatedly, made the shortcoming of the easy fatigue damage of equipment, reaction process is stable, reduced corrosion, prolonged the work-ing life of equipment equipment pipe.Because the reaction controlling index is stabilized in the safety zone, and device can be moved safely and reliably, has improved the security of technology greatly.This technological design is reasonable, can successfully manage power failure, cut off the water, stops the supple of gas or steam, stops emergency case such as thermal source.Because this continuous process flow process makes the every index of technology meet the oxidation kinetics principle, makes device be in optimal operational condition, produce adaptation intensity height, complete assembly throughput is greatly improved, and is particularly suitable for large-scale production.Characteristics such as this technology has stable production process safety, and constant product quality, content height, recovery rate height, plant factor height, catalyzer and energy consumption are low.The high pressure exhaust gas of oxidizing reaction and self-produced steam can be directly used in the promotion tail gas turbine and the steam turbine air compressor produces pressurized air, will improve energy conversion efficiency, and the self-produced energy of use device reduces production costs to a greater degree.Finish the crystalline mixture and carry out solid-liquid separation by centrifugal method, the catalyzer that is dissolved in acetic acid and water finally returns the oxidation system recycling by liquid phase separation, has both saved catalyst levels, also reduces the promotion Decomposition of catalyzer in the subsequent handling.
With above several continuation method contrasts, reactor is a tower reactor in present method, utilize reaction raw materials pressurized air as stirring power, avoided investment, the sealing element of expensive high pressure zone whipping device easily to leak causing improper driving and problem such as parking maintenance more continually; Tower reactor has: low equipment investment, stationary seal parts are difficult for taking place to leak and damage.Tower top has enough spaces that gas-liquid is fully separated mutually, and liquid phase material can not be brought into condenser, the condenser good effect of heat exchange.The heat energy that 1#, 2# oxidizing tower internal reaction generate among the present invention is used in the mode of producing water vapor, has also alleviated the load of circulating cooling system simultaneously greatly.Crystallization mode is that many crystallizers take turns periodic running in present method, and material is carried out crystallization by disposable cooling under normal pressure, has avoided the easily stifled problem of equipment importation, and progressively cooling helps the good growth of crystal grain.Finish the crystalline mixture and carry out solid-liquid separation by centrifugal method, the catalyzer that is dissolved in acetic acid and water finally returns the oxidation system recycling by liquid phase separation.Because crystallization operation carries out under normal pressure, and is not high to equipment requirements, avoided expensive facility investment.By the operation in turn of many crystallizers, can guarantee the serialization operation of preceding road oxidation operation and subsequent handling.The 3# oxidation is provided with flashing tower, utilizes the heat energy of reaction itself to isolate unnecessary moisture content in the tower, and the assurance oxidizing reaction is fully finished.Catalyzer enforcement adds in batches, makes reaction control more be tending towards rationally both having reduced catalyst levels, has also reduced by product generation in the oxidising process, has improved quality product and product yield.Propose trimellitic acid recovery in the dense operation, avoid causing the trimellitic acid over oxidation to decompose, increase the trimellitic acid recovery rate.
In the inventive method, the adding mode of catalyzer is preferably in batches and adds, and helps oxidizing reaction like this and more reasonably carries out, and can save the part catalyzer.The high pressure exhaust gas and the by-product steam of oxidizing reaction are used in the compressed-air actuated mode of turbocompressor, make system's control more be tending towards independent, and improve the utilising efficiency of energy.
The present invention adopts the liquid-phase oxidation of continuous processing air to produce the technology of trimellitic acid, compare with existing batch process, raw material, catalyzer are identical, and quality product and material consumption energy consumption all make moderate progress, the average single tower ability of oxidizing tower is greatly improved, and lists the contrast table of two kinds of methods below.
Table 1: the present invention and batch production method unit product consumption contrast
| Project | The multitower continuous process | Existing discontinuous method |
| Unsym-trimethyl benzene (ton/ton product) | 0.62～0.68 | 0.81～0.95 |
| Acetic acid (ton/ton product) | 0.1～0.2 | 0.3～0.4 |
| Cobaltous diacetate (kilogram/ton product | 1.7～3.8 | 5.7～9.5 |
| Manganese acetate (kilogram/ton product | 1.7～3.8 | 5.7～9.5 |
| Tetrabromoethane (kilogram/ton product | 2.0～5.2 | 5.1～9.5 |
| Coal (ton/ton product) | 1.～1.5 | 2～3 |
| (kilowatt-hour/ton produces electricity | ≤850 | 1150～1900 |
| Produce steam (ton/ton product) | 3.5～4.5(0.4～0.5MPa) | 0 |
Table 2: the single tower output contrast of the present invention and batch production method
| Project | The multitower continuous process | Existing discontinuous method |
| Product yield % (mol/mol) | 85～90 | 65～80 |
| Average single tower trimellitic acid output ton/sky | 17.85～20.5 | 8.74～10.75 |
The present invention and existing continuous processing air liquid-phase oxidation are produced the technology of trimellitic acid and are distinguished to some extent, list the contrast table with other method below.
Table 3: the present invention and continuous production method contrast
| The contrast project | Present method | Other serialization |
| Reactor | Tower reactor | Stirred-tank reactor |
| Crystallization method | Many intermittent types | Separate unit or many continous ways |
| Total energy approach | Reclaim reaction heat and produce steam | Do not utilize |
| The material comprehensive utilization | Reclaim material in the solvent | Do not reclaim |
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Among the figure: head tank 1, transferpump 2, solvent tank 3, solvent pump 4, scale tank 5 and 6, the 1# still 7 of preparing burden, charge pump 8, the 2# still 9 of preparing burden, charge pump 10, pressurized air 11,1# oxidation condenser 12,1# oxidizing tower 13, recycle pump 14,2# oxidation condenser 15,2# oxidizing tower 16, recycle pump 17, flashing tower 18,3# oxidation condenser 19,3# oxidizing tower 20, crystallization condenser 21 and 22, crystallization kettle 23,24 and 25, centrifuge separator 26, tail gas absorber 27, recycle pump 28, dilture acid jar 29, dilture acid pump 30, carry dense condenser 31, waste water tank 32, concentration tower 33, carry dense reboiler 34, softened water pump 35, water softening tank 36, carry concentrated acid jar 37, carry concentrated acid pump 38, flash condenser 39, flash distillation charge pump 40, flash distillation still 41, pump 42 is reclaimed in flash distillation.
Embodiment
Embodiment 1:
A) the 1000Kg unsym-trimethyl benzene is beaten respectively through scale tank 6 and 5 from solvent tank 3 usefulness transferpumps 2 and solvent pump 4 from head tank 1,4000Kg acetate solvate sent into 1# batching still 7, weighing Cobaltous diacetate, manganese acetate, each 4.5Kg of tetrabromoethane drop into 1# batching still 7 respectively again, be heated to 80 ℃, be stirred well to catalyzer simultaneously and dissolve fully;
B) open softened water pump 35 and add soft water, keep the soft water liquid level 60%～80% to 1# condenser 12 and 2# oxidation condenser 15; With charge pump 8 1# is prepared burden mixture in the still 7 with 4M
3/ h sends into 1# oxidizing tower 13, reach and set liquid level 50%～60% and o'clock stop charging, open recycle pump 14 material in the 1# oxidizing tower 13 is played circulation, and, in tower, feed progressively increasing temperature and pressure of pressurized air 11 simultaneously continuously with the heating of the material in the tower, carry out the initiation of oxidizing reaction, the interior temperature of control tower is at 190 ℃～200 ℃ after causing successfully, pressure is at 1.8MPa～3.5MPa, and the reaction process stable state is carried out, with 8.0M
3/ h flow is to 13 continuously feedings of 1# oxidizing tower, and control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 1# oxidation condenser 12 soft water liquid levels 40%～60%, water vapour pressure 0.3MPa～0.4MPa;
C) reach when setting liquid level 90%～100% when 1# oxidizing tower 13 tower bottoms positions, open the control valve of recycle pump 14 loop exits to 2# oxidizing tower 16, charging with 1# oxidizing tower 13 tower bottoms positions control 2# oxidizing tower 16, reach and set liquid level 50%～60%, open recycle pump 17 material in the 2# oxidizing tower 16 is played circulation, in tower, feed pressurized air 11 simultaneously continuously continuously and carry out oxidizing reaction, temperature is at 210 ℃～220 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 2# oxidation condenser 15 soft water liquid levels 60%～80%, water vapour pressure 0.4MPa～0.5MPa;
D) steam of 1#, the reacted oxygen-denuded air of 2# oxidizing tower and acetic acid and water is by 1# oxidation condenser 12 and 2# oxidation condenser 15, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
E) reach when setting liquid level 90%～100% when 2# oxidizing tower 16 tower bottoms positions, open the control valve of recycle pump 17 loop exits to 3# oxidizing tower 20, with the charging of 2# oxidizing tower tower bottoms position control 3# oxidizing tower, in 3# oxidizing tower 20, feed pressurized air simultaneously continuously and carry out oxidizing reaction, temperature is at 220 ℃～240 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower 20 tops are provided with flashing tower 18, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flashing tower 18 tower stills, the steam that contains most of water and few part acetic acid removes the acetic acid upgrading system after by 19 condensations of 3# oxidation condenser, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
F) reach when setting liquid level 90%～100% when 3# oxidizing tower 20 tower bottoms positions, open the bleeder valve of 3# oxidizing tower to a crystallization kettle 23 (24,25), the crystallization kettle charging reaches to be set liquid level and promptly switches to another crystallization kettle; The mixture of oxidation products and solvent acetic acid in crystallization kettle under the normal pressure by disposable continuous cooling, part acetic acid and water are steamed, after crystallization condenser condenses 21,22, remove the acetic acid upgrading system, crystallization control still temperature is 60 ℃～180 ℃, delivering to centrifuge separator 26 through the mixed slurry of trimellitic acid crystal, acetic acid and water after the crystallization separates, acetic acid after the separation, water and most of catalyzer remove dilture acid jar 29 by liquid phase separation, obtain the trimellitic acid solid materials simultaneously, deduction foreign material conversion trimellitic acid yield is the 1400Kg/1000Kg unsym-trimethyl benzene; The trimellitic acid yield is 80% (mol).
G) mixture of acetic acid in the dilture acid jar 29 and water is delivered to dilture acid pump 31 carried out continuous still battery in the concentration tower 33, water steams from cat head, carry after dense condenser 31 condensations waste water up to standard and advance waste water tank 32 and send the water treatment post, the acetic acid of content 〉=98% reclaims from the tower bottom, uses as solvent cycle;
H) acetic acid concentration tower tower still feed liquid is delivered to flash distillation still 41 with flash distillation charge pump 40 in batches, acetic acid steams from flash distillation still 41 tops, after flash condenser 39 condensations, deliver to acetic acid jar 3, use as solvent cycle, steam slurry that thing contains trimellitic acid 〉=60% at the bottom of the still and reclaim pump 42 with the pump flash distillation and deliver to crystallization kettle 23,24,25 recyclings.
Embodiment 2:
A) the 1500Kg unsym-trimethyl benzene is beaten respectively through scale tank 6 and 5 from solvent tank 3 usefulness transferpumps 2 and solvent pump 4 from head tank 1,7500Kg acetate solvate sent into 1# batching still 7, weighing Cobaltous diacetate 4.5kg, manganese acetate 2.5kg, tetrabromoethane 3.8Kg drop into 1# batching still 7 respectively again, drop into 2# batching still 9 through test tank 5 metering acetic acid 300kg, difference weighing Cobaltous diacetate 2.5kg, manganese acetate 4.5kg, tetrabromoethane 3.8Kg, be heated to 80 ℃ respectively, be stirred well to catalyzer simultaneously and dissolve fully;
B) open softened water pump 35 and add soft water, keep the soft water liquid level 60%～80% to 1# condenser 12 and 2# oxidation condenser 15; With charge pump 8 1# is prepared burden mixture in the still 7 with 4M
3/ h sends into 1# oxidizing tower 13, reach and set liquid level 50%～60% and o'clock stop charging, open recycle pump 14 material in the 1# oxidizing tower 13 is played circulation, and, in tower, feed progressively increasing temperature and pressure of pressurized air 11 simultaneously continuously with the heating of the material in the tower, carry out the initiation of oxidizing reaction, the interior temperature of control tower is at 190 ℃～200 ℃ after causing successfully, pressure is at 1.8MPa～3.5MPa, and the reaction process stable state is carried out, with 9.5M
3/ h flow is to 13 continuously feedings of 1# oxidizing tower, and control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 1# oxidation condenser 12 soft water liquid levels 40%～60%, water vapour pressure 0.3MPa～0.4MPa;
C) reach when setting liquid level 90%～100% when 1# oxidizing tower 13 tower bottoms positions, open the control valve of recycle pump 14 loop exits to 2# oxidizing tower 16, with the charging of 1# oxidizing tower 13 tower bottoms positions control 2# oxidizing tower 16, with charge pump 10 2# is prepared burden still 9 inner catalyst solution with 0.31M simultaneously
3/ h flow is to 16 continuously feedings of 2# oxidizing tower, material reaches and sets liquid level 50%～60% in tower, open recycle pump 17 material in the 2# oxidizing tower 16 is played circulation, in tower, feed pressurized air 11 simultaneously continuously continuously and carry out oxidizing reaction, temperature is at 220 ℃～230 ℃ in the control 2# oxidizing tower 16, pressure is at 1.8MPa～3.5MPa, cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 2# oxidation condenser 15 soft water liquid levels 60%～80%, water vapour pressure 0.4MPa～0.5MPa;
D) steam of 1#, the reacted oxygen-denuded air of 2# oxidizing tower and acetic acid and water is by 1# oxidation condenser 12 and 2# oxidation condenser 15, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
E) reach when setting liquid level 90%～100% when 2# oxidizing tower 16 tower bottoms positions, open the control valve of recycle pump 17 loop exits to 3# oxidizing tower 20, with the charging of 2# oxidizing tower tower bottoms position control 3# oxidizing tower, in 3# oxidizing tower 20, feed pressurized air simultaneously continuously and carry out oxidizing reaction, temperature is at 225 ℃～235 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower 20 tops are provided with flashing tower 18, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flashing tower 18 tower stills, the steam that contains most of water and few part acetic acid removes the acetic acid upgrading system after by 19 condensations of 3# oxidation condenser, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
F) when 3# oxidizing tower 20 tower bottoms positions reach design liquid level 90%～100%, open the bleeder valve of 3# oxidizing tower to a crystallization kettle 23 (24,25), the crystallization kettle charging reaches the design liquid level and promptly switches to another crystallization kettle; The mixture of oxidation products and solvent acetic acid in crystallization kettle under the normal pressure by disposable cooling, part acetic acid and water are steamed, after crystallization condenser condenses 21,22, remove the acetic acid upgrading system, crystallization control still temperature is 80 ℃～150 ℃, delivering to centrifuge separator 26 through the mixed slurry of trimellitic acid crystal, acetic acid and water after the crystallization separates, acetic acid after the separation, water and most of catalyzer remove dilture acid jar 29 by liquid phase separation, obtain the trimellitic acid solid materials simultaneously, deduction foreign material conversion trimellitic acid yield is the 1490Kg/1000Kg unsym-trimethyl benzene; The trimellitic acid yield is 85.1% (mol).
All the other are with example 1.
Embodiment 3:
A) the 1000Kg unsym-trimethyl benzene is beaten respectively through scale tank 6 and 5 from solvent tank 3 usefulness transferpumps 2 and solvent pump 4 from head tank 1,6000Kg acetate solvate sent into 1# batching still 7, weighing Cobaltous diacetate 4.0kg, manganese acetate 1.1kg, tetrabromoethane 2.4Kg drop into 1# batching still 7 respectively again, drop into 2# batching still 9 through test tank 5 metering acetic acid 300kg, difference weighing Cobaltous diacetate 1.1kg, manganese acetate 4.0kg, tetrabromoethane 3.0Kg, be heated to 80 ℃ respectively, be stirred well to catalyzer simultaneously and dissolve fully;
B) open softened water pump 35 and add soft water, keep the soft water liquid level 60%～80% to 1# condenser 12 and 2# oxidation condenser 15; With charge pump 8 1# is prepared burden mixture in the still 7 with 4M
3/ h sends into 1# oxidizing tower 13, reach and set liquid level 50%～60% and o'clock stop charging, open recycle pump 14 material in the 1# oxidizing tower 13 is played circulation, and, in tower, feed progressively increasing temperature and pressure of pressurized air 11 simultaneously continuously with the heating of the material in the tower, carry out the initiation of oxidizing reaction, the interior temperature of control tower is at 180 ℃～190 ℃ after causing successfully, pressure is at 1.8MPa～3.5MPa, and the reaction process stable state is carried out, with 11M
3/ h flow is to 13 continuously feedings of 1# oxidizing tower, and control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 1# oxidation condenser 12 soft water liquid levels 40%～60%, water vapour pressure 0.3MPa～0.4MPa;
C) reach when setting liquid level 90%～100% when 1# oxidizing tower 13 tower bottoms positions, open the control valve of recycle pump 14 loop exits to 2# oxidizing tower 16, with the charging of 1# oxidizing tower 13 tower bottoms positions control 2# oxidizing tower 16, with charge pump 10 2# is prepared burden still 9 inner catalyst solution with 0.46M simultaneously
3/ h flow is to 16 continuously feedings of 2# oxidizing tower, material reaches and sets liquid level 50%～60% in tower, open recycle pump 17 material in the 2# oxidizing tower 16 is played circulation, in tower, feed pressurized air 11 simultaneously continuously continuously and carry out oxidizing reaction, temperature is at 220 ℃～235 ℃ in the control 2# oxidizing tower 16, pressure is at 1.8MPa～3.5MPa, cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 2# oxidation condenser 15 soft water liquid levels 60%～80%, water vapour pressure 0.4MPa～0.5MPa;
D) steam of 1#, the reacted oxygen-denuded air of 2# oxidizing tower and acetic acid and water is by 1# oxidation condenser 12 and 2# oxidation condenser 15, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
E) reach when setting liquid level 90%～100% when 2# oxidizing tower 16 tower bottoms positions, open the control valve of recycle pump 17 loop exits to 3# oxidizing tower 20, with the charging of 2# oxidizing tower tower bottoms position control 3# oxidizing tower, in 3# oxidizing tower 20, feed pressurized air simultaneously continuously and carry out oxidizing reaction, temperature is at 230 ℃～235 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower 20 tops are provided with flashing tower 18, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flashing tower 18 tower stills, the steam that contains most of water and few part acetic acid removes the acetic acid upgrading system after by 19 condensations of 3# oxidation condenser, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
F) when 3# oxidizing tower 20 tower bottoms positions reach design liquid level 90%～100%, open the bleeder valve of 3# oxidizing tower to a crystallization kettle 23 (24,25), the crystallization kettle charging reaches to be set liquid level and promptly switches to another crystallization kettle; The mixture of oxidation products and solvent acetic acid in crystallization kettle under the normal pressure by disposable cooling, part acetic acid and water are steamed, after crystallization condenser condenses 21,22, remove the acetic acid upgrading system, crystallization control still temperature is 80 ℃～150 ℃, delivering to centrifuge separator 26 through the mixed slurry of trimellitic acid crystal, acetic acid and water after the crystallization separates, acetic acid after the separation, water and most of catalyzer remove dilture acid jar 29 by liquid phase separation, obtain the trimellitic acid solid materials simultaneously, deduction foreign material conversion trimellitic acid yield is the 1580Kg/1000Kg unsym-trimethyl benzene; The trimellitic acid yield is 90% (mol).
All the other are with example 1.
Embodiment 4:
A) the 1000Kg unsym-trimethyl benzene is beaten respectively through scale tank 6 and 5 from solvent tank 3 usefulness transferpumps 2 and solvent pump 4 from head tank 1,6000Kg acetate solvate sent into 1# batching still 7, weighing Cobaltous diacetate 4.0kg, manganese acetate 1.0kg, tetrabromoethane 2.7Kg drop into 1# batching still 7 respectively again, drop into 2# batching still 9 through test tank 5 metering acetic acid 300kg, difference weighing Cobaltous diacetate 1.0kg, manganese acetate 4.0kg, tetrabromoethane 2.7Kg, be heated to 80 ℃ respectively, be stirred well to catalyzer simultaneously and dissolve fully;
B) open softened water pump 35 and add soft water, keep the soft water liquid level 60%～80% to 1# condenser 12 and 2# oxidation condenser 15; With charge pump 8 1# is prepared burden mixture in the still 7 with 4M
3/ h sends into 1# oxidizing tower 13, reach and set liquid level 50%～60% and o'clock stop charging, open recycle pump 14 material in the 1# oxidizing tower 13 is played circulation, and, in tower, feed progressively increasing temperature and pressure of pressurized air 11 simultaneously continuously with the heating of the material in the tower, carry out the initiation of oxidizing reaction, the interior temperature of control tower is at 180 ℃～190 ℃ after causing successfully, pressure is at 1.8MPa～3.5MPa, and the reaction process stable state is carried out, with 11M
3/ h flow is to 13 continuously feedings of 1# oxidizing tower, and control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 1# oxidation condenser 12 soft water liquid levels 40%～60%, water vapour pressure 0.3MPa～0.4MPa;
C) reach when setting liquid level 90%～100% when 1# oxidizing tower 13 tower bottoms positions, open the control valve of recycle pump 14 loop exits to 2# oxidizing tower 16, with the charging of 1# oxidizing tower 13 tower bottoms positions control 2# oxidizing tower 16, with charge pump 10 2# is prepared burden still 9 inner catalyst solution with 0.46M simultaneously
3/ h flow is to 16 continuously feedings of 2# oxidizing tower, material reaches and sets liquid level 50%～60% in tower, open recycle pump 17 material in the 2# oxidizing tower 16 is played circulation, in tower, feed pressurized air 11 simultaneously continuously continuously and carry out oxidizing reaction, temperature is at 220 ℃～230 ℃ in the control 2# oxidizing tower 16, pressure is at 1.8MPa～3.5MPa, cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V), 2# oxidation condenser 15 soft water liquid levels 60%～80%, water vapour pressure 0.4MPa～0.5MPa;
D) steam of 1#, the reacted oxygen-denuded air of 2# oxidizing tower and acetic acid and water is by 1# oxidation condenser 12 and 2# oxidation condenser 15, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
E) reach when setting liquid level 90%～100% when 2# oxidizing tower 16 tower bottoms positions, open the control valve of recycle pump 17 loop exits to 3# oxidizing tower 20, with the charging of 2# oxidizing tower tower bottoms position control 3# oxidizing tower, in 3# oxidizing tower 20, feed pressurized air simultaneously continuously and carry out oxidizing reaction, temperature is at 225 ℃～240 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower 20 tops are provided with flashing tower 18, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flashing tower 18 tower stills, the steam that contains most of water and few part acetic acid removes the acetic acid upgrading system after by 19 condensations of 3# oxidation condenser, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber 27, and tail gas up to standard enters atmosphere;
F) when 3# oxidizing tower 20 tower bottoms positions reach design liquid level 90%～100%, open the bleeder valve of 3# oxidizing tower to a crystallization kettle 23 (24,25), the crystallization kettle charging reaches the design liquid level and promptly switches to another crystallization kettle; The mixture of oxidation products and solvent acetic acid in crystallization kettle under the normal pressure by disposable cooling, part acetic acid and water are steamed, after crystallization condenser condenses 21,22, remove the acetic acid upgrading system, crystallization control still temperature is 80 ℃～150 ℃, delivering to centrifuge separator 26 through the mixed slurry of trimellitic acid crystal, acetic acid and water after the crystallization separates, acetic acid after the separation, water and most of catalyzer remove dilture acid jar 29 by liquid phase separation, obtain the trimellitic acid solid materials simultaneously, deduction foreign material conversion trimellitic acid yield is the 1560Kg/1000Kg unsym-trimethyl benzene; The trimellitic acid yield is 89% (mol).
All the other are with example 1.
The present invention is together in series original intermittent type oxidizing tower and carries out serialization production.Through facts have proved: single tower, double tower serialization are produced and are difficult to realize optimizing reaction conditions, not even as the intermittent reaction effect; Same reaction reaches target conversion and product yield under the time, and three towers and the placed in-line effect of four towers are approaching.By the residence time of each tower material of properly distributed, can avoid the exothermic heat of reaction amount too concentrated, optimize the product recovery rate.
Unsym-trimethyl benzene of the present invention is 1: 1～12 (wt) with the ratio that cooperates of acetic acid, is that 1: 0.00003～0.002 (wt), manganese acetate proportioning are that 1: 0.00003～0.003 (wt), promotor tetrabromoethane proportioning are 1: 0.00003～0.004 (wt) based on the catalyst acetic acid cobalt proportioning of unsym-trimethyl benzene and acetic acid mixed solution total amount.
Claims (3)
1, a kind of utilize the intermediate bubble oxidization column multitower to connect method that continuous oxidation produces trimellitic acid, it is characterized in that it is is raw material with the unsym-trimethyl benzene, acetic acid is solvent, Cobaltous diacetate, manganese acetate are that catalyzer, tetrabromoethane are promotor, the tertiary oxidation tower will be added after the above-mentioned mixing of materials continuously, and feed pressurized air respectively continuously and carry out oxidizing reaction, this method comprises following processing step:
A) with after raw material unsym-trimethyl benzene and solvent acetic acid, catalyst acetic acid cobalt, manganese acetate, the metering of promotor tetrabromoethane, drop into the heating of batching still and mix, temperature is controlled at 60 ℃～110 ℃;
B) said mixture is sent into continuously in the 1# oxidizing tower of three placed in-line oxidizing towers with pump, temperature is at 180 ℃～220 ℃ in the control tower, pressure is at 1.8MPa～3.5MPa, feed pressurized air continuously, control cat head tail gas contains oxygen at 0.5%～6% (V/V), oxygen level in the engine manifold≤8% (V/V);
C) by pump 1# oxidizing tower reaction product is imported the 2# oxidizing tower continuously, temperature is at 180 ℃～240 ℃ in the control tower, and pressure feeds pressurized air continuously at 1.8MPa～3.5MPa, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold;
D) 1#, 2# oxidizing tower dispose respectively and waste heat boiler are set as overhead condenser, the steam of reacted oxygen-denuded air and acetic acid and water passes through condenser, after being condensed, acetic acid and water returns in the tower, produce a certain amount of steam simultaneously, steam advances steam pipe system, noncondensable gas reclaims the acetic acid that the end is condensed by tail gas absorber, and tail gas up to standard enters atmosphere;
E) by pump 2# oxidizing tower reaction product is imported the 3# oxidizing tower continuously, temperature is at 180 ℃～250 ℃ in the control tower, pressure is at 1.8MPa～3.5Mpa, feed pressurized air continuously, control cat head tail gas contains oxygen at 0.5%～6% (V/V), and oxygen level≤8% (V/V) in the control engine manifold, 3# oxidizing tower top is provided with flashing tower, after containing most of acetic acid and seldom the steam of portion water being liquefied, return the 3# oxidizing tower from flash distillation Tata still, remove the acetic acid upgrading system after containing most of water and seldom the steam of part acetic acid being condensed, noncondensable gas reclaims the acetic acid that is not condensed by tail gas absorber, and tail gas up to standard enters atmosphere;
F) the 3# oxidizing tower reaction product of coming out and the mixture of solvent acetic acid and water import in 2～4 crystallization kettles in turn, when reaching the setting liquid level, a crystallization kettle charging promptly switches to another crystallization kettle, the mixture of oxidation products and solvent acetic acid is decrease temperature crystalline of normal pressure in crystallization kettle, part acetic acid and water are steamed, after condenser condenses, remove the acetic acid upgrading system, crystallization control still temperature is 60 ℃～180 ℃, through the trimellitic acid crystal after the crystallization, the mixed slurry of acetic acid and water is delivered to centrifuge separator and is separated, acetic acid, water and most of catalyzer remove the acetic acid upgrading system by liquid phase separation, and the wet thing of trimellitic acid solid particulate send into anhydridization process;
G) mixture of the acetic acid that produces in oxidation, the Crystallization Procedure and water is delivered to carried out continuous still battery in the concentration tower, water steams from cat head, and waste water up to standard send the water treatment post after the condensation, and the acetic acid of content 〉=98% reclaims from the tower bottom, uses as solvent cycle;
H) acetic acid concentration tower tower still feed liquid is delivered to the flash distillation still in batches, acetic acid steams from flash distillation still top, delivers to the acetic acid jar after condensation, uses as solvent cycle, steams slurry that thing contains trimellitic acid 〉=60% at the bottom of the still and delivers to crystallization kettle and recycle.
2, according to described a kind of utilize the intermediate bubble oxidization column multitower to connect the method that continuous oxidation produces trimellitic acid of claim 1, it is characterized in that the cobalt of catalyst acetic acid described in the step a), manganese acetate and promotor tetrabromoethane are by in the described 1# oxidizing tower of disposable adding step b).
3, according to described a kind of utilize the intermediate bubble oxidization column multitower to connect the method that continuous oxidation produces trimellitic acid of claim 1, it is characterized in that the cobalt of catalyst acetic acid described in the step a), manganese acetate and promotor tetrabromoethane are separated to add in described 1# oxidizing tower of step b) and the described 2# oxidizing tower of step c), separately add fashionable, with Cobaltous diacetate, manganese acetate, the tetrabromoethane total amount is under 1 the situation: Cobaltous diacetate add-on in the 1# oxidizing tower is 0.6～0.8, add-on is 0.2～0.4 in the 2# oxidizing tower, manganese acetate add-on in the 1# oxidizing tower is 0.2～0.4, add-on is 0.6～0.8 in the 2# oxidizing tower, tetrabromoethane add-on in the 1# oxidizing tower is 0.4～0.6, and add-on is 0.4～0.6 in the 2# oxidizing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100861241A CN100447124C (en) | 2006-08-31 | 2006-08-31 | Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100861241A CN100447124C (en) | 2006-08-31 | 2006-08-31 | Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1915960A CN1915960A (en) | 2007-02-21 |
| CN100447124C true CN100447124C (en) | 2008-12-31 |
Family
ID=37737058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100861241A Active CN100447124C (en) | 2006-08-31 | 2006-08-31 | Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100447124C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471404A (en) * | 2022-01-19 | 2022-05-13 | 南京延长反应技术研究院有限公司 | Micro-interface preparation system and preparation method of trimellitic acid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788296A (en) * | 1987-05-29 | 1988-11-29 | Amoco Corporation | Process for the production and recovery of trimellitic anhydride |
| US5068406A (en) * | 1989-09-06 | 1991-11-26 | Amoco Corporation | Compartmented oxidation method |
| CN1472188A (en) * | 2002-07-30 | 2004-02-04 | SK��ѧ��ʽ���� | Preparation of dimellitic acid |
| JP2004331585A (en) * | 2003-05-08 | 2004-11-25 | Mitsubishi Gas Chem Co Inc | High-purity trimellitic anhydride and method for producing the same |
| CN1594302A (en) * | 2004-07-15 | 2005-03-16 | 中国石油化工股份有限公司 | Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process |
| CN1634907A (en) * | 2004-11-26 | 2005-07-06 | 天津大学北方化工新技术开发公司 | Process for stirring type multi-kettle continuous oxidation preparation of trimellitic anhydride |
| US20060128987A1 (en) * | 2002-12-09 | 2006-06-15 | Sheppard Ronald B | Process for the oxidative purification of terephthalic acid |
-
2006
- 2006-08-31 CN CNB2006100861241A patent/CN100447124C/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788296A (en) * | 1987-05-29 | 1988-11-29 | Amoco Corporation | Process for the production and recovery of trimellitic anhydride |
| US5068406A (en) * | 1989-09-06 | 1991-11-26 | Amoco Corporation | Compartmented oxidation method |
| CN1472188A (en) * | 2002-07-30 | 2004-02-04 | SK��ѧ��ʽ���� | Preparation of dimellitic acid |
| US20060128987A1 (en) * | 2002-12-09 | 2006-06-15 | Sheppard Ronald B | Process for the oxidative purification of terephthalic acid |
| JP2004331585A (en) * | 2003-05-08 | 2004-11-25 | Mitsubishi Gas Chem Co Inc | High-purity trimellitic anhydride and method for producing the same |
| CN1594302A (en) * | 2004-07-15 | 2005-03-16 | 中国石油化工股份有限公司 | Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process |
| CN1634907A (en) * | 2004-11-26 | 2005-07-06 | 天津大学北方化工新技术开发公司 | Process for stirring type multi-kettle continuous oxidation preparation of trimellitic anhydride |
Non-Patent Citations (10)
| Title |
|---|
| 偏苯三酸酐工业技术探讨. 王化淳.现代化工，第12期. 1997 |
| 偏苯三酸酐工业技术探讨. 王化淳.现代化工，第12期. 1997 * |
| 偏苯三酸酐技术改进的探讨. 屈威等.当代化工，第34卷第1期. 2005 |
| 偏苯三酸酐技术改进的探讨. 屈威等.当代化工，第34卷第1期. 2005 * |
| 偏苯三酸酐技术进展. 杨林森.石油化工技术经济，第10卷第3期. 1994 |
| 偏苯三酸酐技术进展. 杨林森.石油化工技术经济，第10卷第3期. 1994 * |
| 偏苯三酸酐的生产. 史立新等.沈阳化工，第4期. 1994 |
| 偏苯三酸酐的生产. 史立新等.沈阳化工，第4期. 1994 * |
| 偏苯三酸酐的生产应用及市场前景. 燕丰.化工中间体，第1卷第6期. 2004 |
| 偏苯三酸酐的生产应用及市场前景. 燕丰.化工中间体，第1卷第6期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1915960A (en) | 2007-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101575284B (en) | Novel method for manufacturing PIA | |
| CN101531588B (en) | The manufacture method of a kind of new pure terephthalic acid | |
| CN1594302A (en) | Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process | |
| CN102775274A (en) | System and method for preparing ethylene glycol through oxalate hydrogenation | |
| CN101302285B (en) | production process of polyethylene glycol terephthalate | |
| CN104961630B (en) | Preparation method of 2, 5-dichlorophenol | |
| CN100447124C (en) | Method for producing meta benzene tricarbonic acid through sequential oxidation by using intermittent multiple cascaded Bubbling oxidation towers | |
| CN106179135B (en) | A kind of reactor and its application for liquid phase successive reaction | |
| CN101475463B (en) | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid | |
| CN1951900A (en) | Low-energy consumption preparation method of terephthalic acid | |
| CN109748791A (en) | Produce the power-economizing method of dimethyl adipate | |
| CN101990531A (en) | Oxidation reactor for manufacturing of crude terephthalic acid | |
| CN105601520A (en) | Device for synthesizing nitromethane and separating products | |
| CN100460400C (en) | Continuous production process of high purity trimellitic anhydride with trimellitic acid | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN1401642A (en) | Process for production of trimellitic anhydride by continuous oxidizing process | |
| CN212375203U (en) | Device for continuously producing polyester polyol | |
| CN1166616C (en) | Process and apparatus for purifying raw lactic acid | |
| CN101747177A (en) | Device and method for preparing butane diacid by continuously hydrolyzing dialkyl succinate ester | |
| KR100539285B1 (en) | Recovery system of waste polyester oligomer using hybrid process of methanolysis reactor and distillation | |
| CN111153787B (en) | Preparation method of 1-naphthylacetic acid | |
| CN221207986U (en) | Production system of chlorophthalic anhydride | |
| KR100365023B1 (en) | A process for recovering acetic acid from methylacetate | |
| CN109280040A (en) | A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride | |
| CN101691325B (en) | Preparation method and device of raw materials needed in preparing acetic anhydride by carbonylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BAICHUAN CHEMICAL INDUSTRIAL (RUGAO) CO., LTD. Free format text: FORMER OWNER: WUXI BAICHUAN CHEMICAL CO., LTD. Effective date: 20131015 Owner name: WUXI BAICHUAN CHEMICAL CO., LTD. Effective date: 20131015 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 214422 WUXI, JIANGSU PROVINCE TO: 226532 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20131015 Address after: 226532 No. 6 Xiangjiang Road, Changjiang town (Rugao port area), Jiangsu, Rugao, China Patentee after: Baichuan Chemical (Rugao) Co., Ltd. Patentee after: Wuxi Baichuan Chemical Industrial Co., Ltd. Address before: 214422, Jianshe Road, Jiangsu Province, Jiangyin Town, No. 55 Patentee before: Wuxi Baichuan Chemical Industrial Co., Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 226200 Changjiang Town, Rugao City, Rugao, Nantong, Jiangsu, No. 6, Xiangjiang Road Co-patentee after: Jiangsu hundred Sichuan high science and technology new materials Limited by Share Ltd Patentee after: Nantong hundred Sichuan new materials Co., Ltd. Address before: 226532 No. 6 Xiangjiang Road, Changjiang town (Rugao port area), Rugao, Jiangsu. Co-patentee before: Wuxi Baichuan Chemical Industrial Co., Ltd. Patentee before: Baichuan Chemical (Rugao) Co., Ltd. |