Patent Application
20110040121
This invention belongs to petrochemical industry field, is a new method for producing petrochemical product.
Purified terephthalic acid (English ab. PTA) product is the raw material of polyethylene glycol terephthalate (polyester for short, English ab. PET).
Prepare the purified terephthalic acid (PTA) with paraxylene (PX) as raw material, compressed air or other oxygen-containing gases (oxygen for instance) as assistant material, acetic acid as solvent, cobalt acetate and manganese acetate as catalyst, and hydrobromic acid as assistant catalyst, carry out the oxidation reaction at the relatively gentle temperature to obtain terephthalic acid (TA). The ion content of cobalt, manganese and bromine of effective ingredients from catalyst and assistant catalyst is general 900 ppm to 2000 ppm, the proportion range between cobalt, manganese and bromine is wide, and the general proportion is 1:1:1 or 1:2:3 or 1:2:2 and so on.
After the processes of oxidation reaction, terephthalic acid (TA) crystallization, separation, and desiccation etc., obtain the crude terephthalic acid (CTA), then dissolve the CTA with heat water, and send it into hydrogenation reactor in high temperature and high pressure, carry out the hydrogenation reaction in the use of Pd/C catalyst, reduce the 4-CBA into P-methyl benzoic acid (PT acid), the water solubility of PT acid is significantly higher than TA, so the TA and PT acid can be basically separated by the re-crystallizing of TA in aqueous solution. Then the purified terephthalic acid (PTA) is obtained by water washing, centrifugal separating, filtering and drying the TA. The PT acid and a little of TA in aqueous solution are returned into the oxidation reactor after which are concentrated and dehydrated.
The known research indicated that the oxidation reaction from paraxylene (PX) to terephthalic acid (TA) was a tandem reaction, it mainly underwent four reaction processes, firstly it was from PX to P-methyl benzaldehyde (TALD), secondly it was from TALD to PT acid, thirdly it was from PT acid to 4-CBA, fourthly it was from 4-CBA to TA. Four of the oxidation reactions were Irreversible reactions. Wherein the reaction velocity from PT acid to 4-CBA was the slowest in the same condition, this reaction was the control step of the whole tandem reaction (Reference: Weizheng Sun, etc. Kinetics of Liquid-Phase Catalytic Oxidation of p-Toluic Acid. Chemical Reaction Engineering and Technology. February, 2007. Vol. 23 No. 1, p 8-12).
The design philosophy of this invention is as follows:
1. As to the different reaction steps, offer the different reaction conditions, decrease the oxidation reaction temperatures from PX to P-methyl benzaldehyde (TALD) and from P-methyl benzaldehyde (TALD) to PT acid whose oxidation reaction conditions are not too rigorous, reduce the side reaction in which the solvent acetic acid is oxidized into carbon dioxide or carbon monoxide at high temperature as much as possible;
2. Increase the oxidation reaction temperature of control step of tandem oxidation reaction (from PT acid to 4-CBA), so as to increase the reaction velocity of this control step, then achieve the aim of increasing the whole oxidation reaction velocity;
3. Make sure that TA can not form crystal inside oxidation reaction, choose water as the assistant solvent during the oxidation processes from PT acid to 4-CBA and to TA, increase the temperature to enhance the TA solubility, but never enhance the acetic acid consumption.
According to this design philosophy, this invention innovated designs new processes of reaction materials, separate the final oxidation product TA from PX and other intermediate products as much as possible, so that the main reaction materials form the up-stream to down-stream flow and processes from entering into reactor to leaving reactor. Instead of the current PX oxidation reactor inside, various materials, intermediate products and final product are mixed together, and be a mixed oxidation reaction. This invention is a step oxidation reaction (or step by step reaction), in this way, not only the aim that TA crystal having no the impurities of 4-CBA and PT acid can be achieved, but also the residence time of produced TA inside the oxidation reactor can be deceased, and also the raw materials consumption resulted from TA over-oxidizing and acetic acid consumption are reduced.
This invention applies a new oxidation process for paraxylene (PX), which makes the major impurities of 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid) that can not be avoided in current production process are hardly contained in the intermediate product crude terephthalic acid (CTA) obtained from oxidation reaction, thereby, the “purified” production process for removing two of the impurities can be predigested or omitted, as a result, the consumptions of materials and fuel and power energy, acetic acid solvent, and water can be reduced, and the production cost can be saved. The quality of this product can exceed the current PTA product. Furthermore, the contents of 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid) contained in new terephthalic acid product can nearly be closed to zero, this product is called purified purified terephthalic acid, abbreviation is PPTA.
The perfect oxidation reaction design of this invention is that the oxidation reaction is carried out in the sequence of tandem oxidation reaction from PX to TA—step by step oxidation reaction or step oxidation reaction.
During the design of specific reaction processes, this invention designs the local and approximative plug-flow reaction processes, the oxidation reaction in plug-flow process stage is carried out in the successively sequence of tandem reaction from PX to TA, that is, the raw material PX newly added into reactor can not enter into the latter stage of the tandem reaction. Consequently, the target product TA obtained from oxidation reaction can be effectively separated with reaction material PX and intermediate products of oxidation reaction.
Due to the difference from mixed oxidation, the material flows inside reactor has the upstream and downstream relationship, the outlet area of target oxidation product TA can be effectively separated with the inlet area of raw materials, this kind of separation is not completely blocked out in space, but the materials at two of the areas can not directly be mixed because of the presence of materials flowing during the reaction.
This invention has designed the oxidation reactor with the structure of internal and external chambers; the oxidation reactor with the structure of internal, medium, and external chambers; horizontal plug-flow oxidation reactor; tower type plunger-flow oxidation reactor; and the tandem oxidation reactor combination of multi-reactor. Inside these reactors or reactor combinations, the materials are similar with that in the plunger-flow or plug-flow process, the oxidation reactor is basically carried out in the sequence of tandem oxidation reaction.
The function of these reactors or reactor combinations is that the materials earlier entered into reactor can carry out the oxidation reaction earlier, and the materials latter entered into reactor can carry out the oxidation reaction latter, the PX material and the final oxidation product TA staying at two end of liquid phase materials flow inside the reactor can not be mixed, so that a TA solution buffer area where the residual p-TA and 4-CBA can be oxidized into TA can exist at the end of liquid phase material flow inside the reactor, and make sure that the materials come out from the oxidation reactor outlet (or from the end oxidation reactor outlet of oxidation reactor combination)and the PX, TLAD, p-TA, and 4-CBA etc. materials and intermediates are not contained in oxidation reaction materials entering into crystallizer, and the organic material phase of reactant only has TA. The organic material phase from PX to TA liquid phase materials (including PX, TALD, p-TA, 4-CBA, and TA etc.) for oxidation reaction materials forms a material flow relationship from upstream process to downstream, Which is different to current PX oxidation process.
Current PX oxidation process applies mixed oxidation process, the liquid phase materials inside reactor—various materials, production and oxidized intermediates are mixed together.
Compressed air or oxygen as assistant material, oxidation reactor with the structure of internal, external chambers for instance, PX is fed from the internal chamber of the oxidation reactor, in the external chamber of the oxidation reactor, the compressed air or other oxygen-containing gas is excessively supplied, the concentration of liquid phase oxygen is higher, and PX do not participate in the reaction to contest the oxygen, the oxygen concentration using for PT acid oxidation is high, so the reaction velocity of control step of tandem oxidation reaction from PT acid to 4-CBA is quicker, therefore, the reaction velocity of whole tandem oxidation reaction is quickened and the total consumption of acetic acid solvent is reduced. The throughput per capacity is enhanced. The reaction temperature from PT acid to 4-CBA can be increased, and so the whole oxidation reaction velocity is increased.
Compressed air or other oxygen-containing gas enters into the reactor from the internal chamber in multi-blast, and the air or oxygen-containing gas is sent into the external chamber from bottom by using a circle distributor. Or send the compressed air or other oxygen-containing gas into internal and external chambers respectively by using a circle distributor. The total flow rate of air or oxygen-containing gas shall be set according to the PX flow rate and oxygen concentration in reactor tail gas, so as to the oxygen concentration in tail gas discharged from tail gas condenser of reactor is less than 2-4%.
The precondition that directly using oxygen as assistant material is that the water proportion in solution in the oxygen added area is more than 40%, and in this condition, the oxidation reaction velocity may be very quick, but the phenomena of acute oxidation reaction and reaction out of control do not occur.
Control the flow rate of the PX, compressed air or other oxygen-containing gas entered into oxidation reaction to ensure the TA solution discharged from reactor without 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid). The 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid) are oxidized into terephthalic acid (TA) step by step in the oxidation reactor.
The oxidation reaction pressure of this invention is about 0.1-8.0 MPaG, and the reaction temperatures are about 90° to 210° C. and 210° to 350° C. respectively by stage control.
As a single oxidation reactor (tower type oxidation reactor for instance), the temperature of low temperature stage (up stage) is 120°-246° C., and the typical temperature of low temperature stage (up stage) is 160° C.; The temperature and pressure of high temperature stage (down stage) are 180°-350° C. and 1.3-8.5 MPaG respectively, and the typical temperature and pressure of high temperature stage (down stage) are 288° C. and 7.5 MPaG respectively.
As a oxidation reactor combination, the temperature and pressure of low temperature reactor (first oxidation reactor) is 90°-210° C. and 0.1-1.8 MPaG,and the typical temperature of low temperature reactor is 130° C., the pressure depends on temperature, the pressure is the saturated vapor pressure of liquid phase materials at this temperature. The temperature and pressure of high temperature reactor are 180°-350° C. and 1.3-8.5 MPaG respectively, and the typical temperature and pressure of high temperature reactor are 288° C. and 7.5 MPaG respectively.
Control the reactor pressure by controlling the gas throughput of compressed air or other oxygen-containing gas and the outlet control valve for non-condensable gas from condensation system of reactor, tail gas. Oxidation reactor temperature control is the main control parameter, the reactor pressure changes as the saturated vapor pressure corresponding to the temperature.
The catalysts of cobalt acetate and manganese acetate and the assistant catalyst of hydrobromic acid can be combined in many proportions, such as 1:1:1, 1:2:3, or 1:2.5:1, etc.
The typical proportion is 1:1:1. The proportion of single ion mass content of cobalt, manganese, bromine to total ion mass content of catalyst is 1:30. The concentration range of catalyst (total ion mass content) is 50-3000 ppm (catalysts/ (organic material phase+solvent)), the typical concentration is 1050 ppm. The general method for feeding catalyst is that three of the catalysts and assistant catalyst, raw material, and solvent (including the recovered catalyst and solvent) are mixed and added into oxidation reactor together.
As an optimized method, add the catalysts of cobalt acetate and manganese acetate into the oxidation reaction area from PX to PT acid, then add the hydrobromic acid as assistant catalyst when the second methyl starts to be oxidized.
Start solvent is acetic acid, assistant solvent is water. Along with the processes of tandem oxidation reaction, acetic acid proportion in mixed solvent consisted of acetic acid and water decreases step by step, forms grads, but water proportion increases step by step. In solvent, acetic acid proportion decreases from 100% to 0%. The water proportion increases from 0% to 100%. The typical solvent gradient is that acetic acid proportion decreases from 94% to 20% step by step, and water proportion increases from 6% to 80%.
Add a great deal of water into reactor as the solvents of terephthalic acid (TA), 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid), so that the target product terephthalic acid (TA) obtained from oxidation reaction can be dissolved sufficiently, the intermediate product 4-CBA can be dissolved sufficiently, and can be further oxidized into terephthalic acid.
During the oxidation processes from PX to TALD and from TALD to PT acid, acetic acid is the major solvent, the water content as assistant solvent is 3-20%, and the typical water content is 6%.
During the oxidation processes from PT acid to 4-CBA and from 4-CBA to TA, water instead of acetic acid is the major solvent, the proportion of water to acetic acid is from 100:0 to 20:80, the typical proportion is 80:20. in the typical condition of mixed solvent consisted of water and acetic acid, the liquid phase temperature of oxidation reactor can be increased to 288° C., at this time, 40-45% of TA can be dissolved into solution, if choosing 30% to be the typical concentration of TA, there is no TA crystal, and still the consumption of acetic acid is very low.
1. Apply the oxidation reactor with the structure which can separate the raw material PX and target product TA from oxidation reaction, so that the liquid phase materials for oxidation reaction can form the upstream and downstream relationship in the sequence of the tandem oxidation reaction. Control the condition of oxidation reaction to meet the crystallization system demand, make sure that, the paraxylene (PX), P-methyl benzaldehyde (TALD), P-methyl benzoic acid (PT acid) and 4-carboxyl benzaldehyde (4-CBA) of these reaction materials at this area have been all oxidized into terephthalic acid (TA) when target product terephthalic acid (TA) of oxidation reaction is being crystallized into solid, so there are no two impurities of 4-carboxyl benzaldehyde (4-CBA) and P-methyl benzoic acid (PT acid) in the intermediate product crude terephthalic acid (CTA) obtained from crystallization
Inside oxidation reactor, add water into liquid phase materials in the oxidation reaction area from 4-CBA to TA as assistant solvent of TA, properly increase the reaction temperature, enhance the TA solubility in mixed solvent consisted of water and acetic acid, so that the TA obtained from reaction can be completely dissolved in solvent.
Also, the temperature in the reaction area from PT acid to 4-CBA can be properly increased, so as to increase the reaction velocity of control step of tandem oxidation reaction, the water as solvent can be added into oxidation reaction area from PT acid to 4-CBA step by step, also can be added into the reaction area before producing PT acid.
Although the local reaction temperature will be high, the water content is also high at this area, so acute oxidation reaction does not occur.
2. Respectively control the quantities of compressed air of different areas inside oxidation reactor, increase the supply quantity of compressed air per liquid phase capability in the oxidation reaction area from PT acid to 4-CBA. Respectively control the quantity of compressed air or other oxygen-containing gas to keep the oxygen content in tail gas is less than 2-4%.
3. By the methods of controlling the feeding quantities of PX, solvents of acetic acid and water, the vaporizing quantities and the recovering quantities of solvents, control the reaction product terephthalic acid (TA) concentration in liquid phase at oxidation reactor, make sure that this concentration is closed to, but less than the saturated solubility of terephthalic acid in the oxidation reaction condition, so that the terephthalic acid (TA) can not be crystallized inside oxidation reactor.
4. As an oxidation reactor with the structure of internal and external chambers, the bottom of external chamber is effectively separated with outlet of material at internal chamber, the quantity of compressed air per liquid phase capability at external chamber is larger than internal chamber.
5. As an oxidation reactor with the structure of internal, medium, and external chambers, the liquid phase at top of external chamber is effectively separated with the liquid phase at top of medium chamber, the bottom of medium chamber is effectively separated with the inlet of materials at internal chamber, and the outlet of liquid phase materials at top of external chamber is effectively separated with the inlet of materials at internal chamber.
6. As a horizontal oxidation reactor with the plug-flow reaction processes, the liquid phase at the end of reaction can not be mixed at will with liquid phase at the material inlet, from inlet of raw material to outlet of reaction material inside reactor, the oxidation reaction is basically carried out in the sequence of tandem oxidation reaction.
7. The tower type oxidation reactor with the approximative plunger-flow reaction processes.
8. Oxidation reactor combination with two or three or more tandem reactors can keep the oxidation reaction materials in approximative plug-flow state;
Two normal oxidation reactors are hardly to keep the oxidation reaction materials in an approximative plug-flow state, but the combination of “oxidation reactor with the structure of internal and external chambers”, or “oxidation reactor with the structure of internal, medium, and external chambers”, or “horizontal oxidation reactor with the plug-flow reaction processes”, or “tower type oxidation reactor with the approximative plunger-flow reaction processes” can commendably keep the oxidation reaction materials in approximative plug-flow state.
9. The solvent water added into liquid phase materials inside oxidation reactor can be heated by the method of tube heat exchange, add water into tubes, the tube outlet is the place to adding water to liquid phase at reactor as assistant solvent, and the end surface of water inlet of tubes is closed, but add water from the side. The tubes are buried at the upstream of liquid phase material flow of reactants, the liquid phase materials of reactants are at outside, and fetch the heat from reaction heat of upstream materials.
As a substitute for water supply by tubes, drill holes on the reactor wall, and supply water (or mixed solvent of acetic acid with high water content) to liquid phase at reactor, increase the water proportion in solvent.
Control the reaction product terephthalic acid (TA) concentration in liquid phase at oxidation reactor, make sure that this concentration is closed to, but less than the saturated solubility of terephthalic acid (TA) in the oxidation reaction condition, so that the terephthalic acid (TA) can not be crystallized inside oxidation reactor. Increase the concentration of terephthalic acid (TA) as much as possible (precondition is that TA does not crystallized during this process), the aim is to decrease the residence time of solvent per product output, and decrease the loss of acetic acid solvent resulted from oxidation.
By comparison with the current PTA production technology, under the precondition of the same reactor capability, the reaction velocity of oxidation reactor applying this invention can be quickened, total residence time of materials are shortened, output is increased, and the consumptions of organic materials, solvent, and fuel and power are reduced.
Terephthalic acid (TA) obtained from oxidation reactor is only crystallized in crystallizer, and the solid of relatively purified terephthalic acid (TA) can be obtained in crystallizer.
There are no paraxylene (PX), P-methyl benzaldehyde (TALD), 4-carboxyl benzaldehyde (4-CBA), and P-methyl benzoic acid (PT acid) in the oxidation reaction materials entering into crystallizer, they are oxidized into terephthalic acid (TA) before they leaving oxidation reactor.
Inside reactor, part of the reaction heat is removed by flash vaporization of solvent and water, the condenser on top of reactor exchange and recycle heat. A great deal of reaction heat are removed by flash vaporization of solvent in crystallization system, the solvent vaporized recovers heat by crystallizer.
In the crystallizer, solvent is continuously flash vaporized by decreasing pressure and temperature, the TA concentration is increased but the saturated solubility coefficient is decreased along with the decreasing temperature, and TA is continuously crystallized out from solution, crystal particles are slowly accreting. Equip with stirrer on the crystallizer to keep the dimensions of crystal particles in a relatively uniformity. There are no 4-carboxyl benzaldehyde (4-CBA), and P-methyl benzoic acid (PT acid) in the solution, so the TA crystal does not contain 4-carboxyl benzaldehyde (4-CBA), and P-methyl benzoic acid (PT acid).
by the methods of multi-level crystallization and decreasing temperature step by step, most of the TA solid is separated with solvent, catalyst, and other impurities, by the methods of centrifugal separation, filtration, and dryness, remove the residual solvent, then water washing it to remove the water soluble impurities, finally, by the methods of centrifugal separation, filtration, and dryness again, obtain PPTA product.
The purified purified terephthalic acid (PPTA) product is suitable as the materials for food packaging, beverage bottle, pharmaceutical packaging, and as the polymer material of medical equipments, due to the lowest formaldehyde group content and the less than 5-15 ppm of 4-CBA and PT acid contents, it has the advantages of a more secure without poison.
If relaxing the requirement for the product quality, that is, produce it according to the current product quality standards of PTA, the consumption index of PX in this invention will be further decreased.
Apply a built-in cylinder with the same axis to oxidation reactor to separate the internal and external chambers, and the bottom of cylinder is connected with the internal wall of the bottom of main body of oxidation reactor. The interstice between the cylinder outside and internal wall of oxidation reactor main body is external chamber, but the cylinder inside is the internal chamber of reactor. The height of cylinder is lower than the design standard level of reactor, so as to keep the liquid phase materials at the internal and external chambers connected at the top of the reactor during the normal production processes. The supply quantity of compressed air or other oxygen-containing gas at the internal and external chambers can be designed to be the same, and also can be designed that the quantity of compressed air or other oxygen-containing gas per liquid phase capacity at external chamber is larger than that at internal chamber.
Set up one or two circle distributors at the bottom of external chamber of reactor to supply the required compressed air or other oxygen-containing gas to external chamber. The capacity of external chamber is ¼ to ½ of that of internal chamber.
Set up stirrer in the internal chamber of reactor, but the stirring intensity is depressed a lot compared to that in the condition of TA crystal occurring inside reactor formerly, but now the aim is to disperse the materials of PX, acetic acid, and catalyst etc. from inlet into liquid phase materials inside reactor as soon as possible, and so that a little of TA crystal can not deposit, but enter into the external chamber from the upside of cylinder.
Use the distributor to supply water to reactor from the upside of external chamber of reactor to ensure that the produced TA can be completely dissolved into the mixed solvent of water and acetic acid. The downside temperature of external chamber is up to 246° to 288° C.
The conditions of material flow are: at internal chamber, compressed air or other oxygen-containing gas comes in from the bottom in multi-entry (four-entry for instance), the fresh materials come in from bottom of internal chamber and enter into reactor, and after the mixed reaction, enter into the external chamber. The produced water and carbon dioxide disperse upwards. At external chamber, the liquid materials move from up to down, and the compressed air or other oxygen-containing gas disperse from downwards to upwards, and the produced water and carbon dioxide disperse upwards. The reaction heat is removed by the flash vaporization of solvent which enters into condenser on the top of reactor. The condenser recycles the heat by heat exchange. The condenser can be combined with the structure of segregation tower to separate the acetic acid and water entering into condensation tower. Water and acetic acid are sent into tanks respectively. Part of water return into the external chamber to increase the proportion of water in solvent phase. Part of condensation water and acetic acid are mixed and sent into internal chamber to decrease the temperature of internal chamber. The production TA dissolves into the mixed solvent consisted of water and acetic acid, discharge from the bottom of external chamber, and sent into the crystallization system.
As a substitute, there is no stirrer in the oxidation reactor.
As a substitute, the materials can come in from the bottom of external chamber, but come out from the bottom of internal chamber.
The proportion of external chamber space to internal chamber space can be 4:1, or 3:1, or 2:1; and also can be 1:4, or 1:3, or 1:2.
An oxidation reactor with the structure of internal, medium, and external chambers
Apply two built-in cylinders with the same axis to oxidation reactor to separate the oxidation reactor into the three chambers of internal, medium, and external. The bottom of small cylinder is connected with the internal wall of bottom of main body of oxidation reactor, and upside of small cylinder is immerged below design level. The small cylinder separates the oxidation reactor into internal and medium chambers. The bottom of big cylinder is hung in the air, its upside height is higher than the design level, the inside and outside of big cylinder are respectively fixed in the side walls of small cylinder and main body of reactor, also they can be fixed on the bottom of main body of reactor by the method of point supports on the bottom. The big cylinder separates the oxidation reactor into medium and external chambers.
The gas phases in internal, medium and external chambers are connected, where the liquid phase capacities are the same (calculate as the liquid phase capacity completely separated by extended faces of cylinder).
Set up there of circle distributors at the bottom of internal, medium and external chambers for compressed air or other oxygen-containing gas, the place for compressed air or other oxygen-containing gas at external and medium chambers is slightly higher than the height of bottom of big cylinder. The flow rates of compressed air or other oxygen-containing gas at the three chambers are the same. The distributor at internal chamber blows downwards, but the distributors for compressed air or other oxygen-containing gas at medium and external chambers blow upwards. The conditions of material flow are: after mixed, the PX, acetic acid, and catalyst etc. come in from the bottom of external chamber at reactor, and come out from bottom of internal chamber. The gas phases at internal, medium and external chambers are connected, the reaction heat is removed from reactor by the flash vaporization of solvent.
The condenser on top of reactor can be combined with the structure of segregation tower to separate the acetic acid and water entering into condensation tower. Water and acetic acid are sent into tanks respectively. Part of water return into the upside of medium chamber to increase the proportion of water in solvent phase. Part of condensation water and acetic acid are mixed and sent into external chamber to decrease the temperature of external chamber.
Use the distributor to supply water to reactor from the upside and mid-side of internal chamber of reactor to ensure that the produced TA can be completely dissolved into the mixed solvent of water and acetic acid. The temperature of internal chamber is up to 246° to 350° C., and the typical temperature is 288° C.
The materials come in from one end of reactor and come out from the other end, set up several row and straight tube distributors for compressed air or other oxygen-containing gas. This reactor is approximative to plug-flow reactor. Set up spiral sheet propeller shaft in the reactor to slowly propel the materials along with the flowing direction of liquid phase, the spiral sheet propeller shaft do not need to contact with reactor internal wall, the materials propelling is only token, the main aim is to separate the chambers by dynamic method inside reactor, and decrease the disorder fluidity of liquid phase materials to ensure that the material flowing direction of liquid phase materials is basically carried out in the sequence of tandem oxidation reaction from PX to TA.
The gas phases at the upside of reactor are connected, part of solvent and water are vaporized, water, carbon dioxide, and nitrogen etc. are volatilized, then all enter into the gas condensation system, and the heat is recycled and removed from reactor. A great deal of reaction heat are removed by flash vaporization of solvent in crystallizer, and recycled by heat exchange or removed by flash vaporization of solvent and entering into condenser (exchanger)on the top of reactor.
Use the distributor to supply water to reactor from the midstream and downstream of material flow (gas phase) of reactor to ensure that the produced TA can be completely dissolved into the mixed solvent of water and acetic acid. The end temperature of reactor is up to 246° to 350° C., and the typical temperature is 288° C.
A set of tower type reactor with a high aspect ratio (increase the aspect ratio of reactor with the structure of internal and external chambers or of reactor with internal, medium, and external chambers, the reactor having the property of tower type oxidation reactor), inside set up the distributor for compressed air or other oxygen-containing gas in subsection, the carbon dioxide and nitrogen etc. inside reaction materials are removed by volatilization from the top of reactor, when it is used as a single oxidation reactor, avoid the solvent flash vaporization as much as possible, so as to ensure that the top of reactor is in low temperature oxidation area (exchange and fetch heat by water solvent tubes to keep the low temperature and decrease the consumption of acetic acid). The heat is removed by the flash vaporization of a great deal of solvent in crystallizer and the heat is recycled by heat exchange. Set up water inlet tubes inside reactor, fetch the heat from upstream materials, and use the heat to heat up the solvent water inside tubes as the solvent of downstream TA. Along with the adding of solvent water, the reaction temperature in the corresponding area is continuously increased to overcome the trend of reaction velocity deceasing resulted from the deceasing of reactant concentration, the temperature in high temperature stage is up to 246° to 350° C., and the typical temperature is 288°.
Also, this is another way to exchange heat by tangling tubes on the external wall of reactor, and using cooling medium.
The raw materials, solvents and catalysts (including the solvent and catalyst recycled) which are mixed together come into the top of liquid phase of reactor, and use the circle air distributor to blow into compressed air or other oxygen-containing gas (or blow into oxygen-containing gas from the drilled holes on the reactor wall) from the bottom and middle place. Inside the reactor, the materials travels from up to down, and come out from the bottom of reactor by level control. Basically, the material flow is a plunger-flow.
The control principle of reaction is also that: increase the concentration of TA inside oxidation reactor as high as possible without forming crystal by the method of controlling the feeding quantity and discharge quantity of PX, acetic acid and water. TA forms crystal in crystallization system only.
If TA forms crystal at the low temperature area on the top of reactor, the crystal will deposit at the high temperature area and completely dissolve, and also the 4-CBA inside TA crystal will be quickly oxidized into TA.
A. Apply a general oxidation reactor (mixed oxidation) as the first oxidation reactor, Oxidation processes includes: 1) pressure oxidation; 2) atmospheric oxidation.
B. Apply the oxidation reactor with the structure of internal and external chambers (or the oxidation reactor with the structure of internal, medium and external chambers) as the first oxidation reactor,
Oxidation processes includes: 1) pressure oxidation; 2) atmospheric oxidation.
C. Apply a tower type plunger-flow oxidation reactor (including horizontal plug-flow oxidation reactor) as the first oxidation reactor,
Oxidation processes includes: 1) pressure oxidation; 2) atmospheric oxidation.
The major process of the first oxidation reactor is low temperature process, the main aim is to obtain the PT acid, and decrease the consumption of acetic acid. The production of a little of TA crystal is permitted. The hydrobromic acid is not added into the first oxidation reactor, the bromide ion plays an important part as assistant catalyst for the oxidation of the second methyl.
Atmospheric oxidation is that the heat from oxidation reaction tail gas is recycled by the method of tail gas going through condensation tower, then obtain the crude acetic acid and water by segregation, after this process, the tail gas is directly blow to air to decrease the rating of compressed air and the rating of pressure resistance of oxidation reactor.
A. Apply tower type oxidation reactor as the second oxidation reactor, the heat removing method can be solvent flash vaporization, and also can be firstly the decalescence of low temperature deionized water, then flash vaporization in crystallizer.
Oxidation processes includes:
1) Apply compressed air as assistant material (the oxygen in the air is oxidant)
2) Apply oxygen as assistant material (the oxygen is oxidant)
B. Apply oxidation reactor with the structure of internal and external chambers (or the oxidation reactor with the structure of internal, medium and external chambers) as the second oxidation reactor, the advantage is that the reaction heat can be removed by solvent flash vaporization, and finally the concentration of TA solution is relatively higher, and the load of crystallization equipment can be decreased.
Oxidation processes includes:
1) Apply compressed air as assistant material (the oxygen in the air is oxidant)
2) Apply oxygen as assistant material (the oxygen is oxidant)
Set up 3-5 sets of tandem crystallizers in the crystallization system, the crystallization temperatures are decreased in turn. The heat from solvent after flash vaporization through condenser and the solvent are all recycled. After removing the floating solid impurities, the mother liquor separated from crystal coming from the last crystallizer is sent back to recycle systems for solvent and catalyst. Set up stirrer in the crystallizer, so as to distribute the crystal particles in a uniformity dimension to the design demand.
The discharge from oxidation reaction enters into the first crystallizer by level control.
The heat from oxidation reaction is removed by solvent and water in tail gas after flash vaporization. More reaction heat is removed from reaction by the method of solvent flash vaporization in crystallizer, which is different to current processes. Also, the new solvent for crystallization includes acetic acid which results in the high quality demand for materials made of crystallizer, which is different to current processes too.
The recycled water and acetic acid from crystallization system are sent back to recycle system for water and acetic acid respectively.
Inside oxidation reactor, add water into liquid phase materials in the oxidation reaction area from PT acid to TA as assistant solvent of TA, properly increase the reaction temperature, enhance the TA solubility in mixed solvent consisted of water and acetic acid, so that the TA obtained from reaction can be completely dissolved in solvent. Also, the temperature in the reaction area from PT acid to 4-CBA can be properly increased, so as to increase the reaction velocity of control step of tandem oxidation reaction.
The pressure of this invention has two cases:
1) As a single oxidation reactor, the reaction pressure is about 7.2 to 8.0 MPaG, the reaction temperature is about 150° to 210° C. and 210° to 350° C. respectively by stage control. The typical temperature of low temperature stage is 160° C., the pressure is the same to that in high temperature stage, and this pressure is significantly higher than the saturated vapor pressure of liquid phase materials in low temperature stage. The typical temperature of high temperature stage is 288° C. and about 7.5 MPaG respectively. The temperature control is achieved by the overall balance of the heat of coming in and out of the reactor from solvent flash vaporization in crystallizer and the reaction heat etc.
As the tower type oxidation reactor whose temperature is controlled by stage, the heat can not be removed by solvent flash vaporization, but only add the cold mixed solvent consisted of deionized water and acetic acid to absorb the heat, then remove the heat by the solvent flash vaporization in crystallizer.
Control the reactor pressure by controlling the gas throughput of compressed air or other oxygen-containing gas and the outlet control valve for non-condensable gas from condensation system of reactor tail gas. The pressure is the corresponding saturated vapor pressure at the high temperature area in reactor, or is slightly higher than this saturated vapor pressure, but the vaporization of liquid phase solvent inside oxidation reactor is not allowed.
Except the oxidation reactor with the structure of internal and external chambers (or oxidation reactor with the structure of internal, medium and external chambers), the heat can be removed by the solvent flash vaporization inside reactor.
2) As a oxidation reactor combination, apply low temperature in oxidation reactor with low temperature, and oxidize the PX into PT acid in the presence of acetic acid solvent (containing a little of water, such as, the water content is 6% or 8%), the reaction temperature is 120° to 210° C., typical temperature is 130° C., and pressure is 0.1 to 0.5 MPaG respectively; The temperature for oxidation reactor with high temperature is 210° to 350° C., typical temperature is 288° C., and pressure is about 7.5 MPaG. The reaction heat in oxidation reactor with low temperature can be removed by solvent flash vaporization, and the reaction heat in oxidation reactor with high temperature can be removed by solvent flash vaporization in crystallizer.
For a tower type oxidation reactor, apply compressed air as assistant material instance:
Apply a tower type oxidation reactor with the diameter of 4500 mm, and with the height of 28000 mm, apply paraxylene (PX) as material, acetic acid as start solvent, cobalt acetate, manganese acetate as catalyst, and hydrobromic acid as assistant catalyst, the ion content (the sum of ion mass) of cobalt, manganese and bromine of effective ingredients in catalyst and assistant catalyst is 1050 ppm, the proportion of cobalt to manganese to bromine is 1:1:1. The feed-in proportions (as mass) of start materials of PX, acetic acid, and water are respectively 28%, 66%, and 6%. The prepared materials and catalysts are fed from the top of oxidation reactor, and the liquid phase materials go downwards.
Feed the compressed air from the bottom and the middle of ⅘ of liquid phase height from upwards to downwards, apply the circle air distributor, the air distributor on the bottom has three circles with the diameters of 2000 mm, 3200 mm, and 4000 mm respectively. Add a crossed distributor in the cirque of 2000 mm. The air distributor in the middle also has three circles with the diameters of 1800 mm, 3000 mm, and 3800 mm respectively. The content of gas quantity of bottom distributor to the total gas quantity is 30%. This design for gas feeding can make sure that the disturbance from bottom liquid phase is little, and the material flow process from upwards to downwards is relatively stable as much as possible, and the materials on the top and intermediates are unable to settle to the bottom.
The inlet pressure of compressed air is 8.5 MPaG. The pressure inside reactor is 7.3 MPaG.
The temperature of liquid phase in oxidation reactor is controlled in four stages.
1) The temperature of liquid phase materials from top to the downwards place in ⅕ is controlled at 130-180° C., preferably 160° C. Apply the tube heat exchanger to remove heat, feed the deionized water with low temperature inside tubes, the water flow direction is from upwards to downwards, the water inside tubes is respectively sent to the various areas with high temperature inside reactor. Apply tubes to heat exchange and heat removed to keep the temperature of the first temperature control area in 160° C.
2) The temperature of liquid phase materials from the place in ⅕ to the downwards place in ⅖ is controlled at 160-246° C., preferably 200° C. Also apply the method of heat exchanger with the cold water tubes to remove heat at this area, at the same time, take out a little of water from tubes, on the one hand, limit the temperature, on the other hand, control the total water content in liquid phase materials to be less than 20% by calculating the feeding quantity of PX and acetic acid, and calculating the inflow quantity of deionized cold water.
If control the quantity of compressed air, the place where liquid phase oxidation reaction is completed can move downwards, so the temperatures at the two areas mentioned above is unable to be out of control, and increased uncontrolled.
Because the conditions are not rigor at the two areas, a little of oxygen can be snatched by organic materials to carry out the oxidation reaction, so the oxygen content of oxidized tail gas on the top of reactor is less than 1.5% to 2%. Compared to the current mixed oxidation technology for PX, the utilization rate of compressed air is increased by 10%.
3) The temperature of liquid phase materials from the place in ⅖ to the downwards place in ⅘ is controlled at 210-300° C., preferably 288° C. At this area, balance the increasing trend of temperature of liquid phase materials resulted from exothermic oxidation reaction by adding deionized water with high temperature of 100-250° C. to stabilize the liquid temperature. The deionized water with high temperature can be sprayed from the reactor side wall or sprayed using a circle distributor. Apply the nozzle of deionized water or circle distributor by the method of one for use and one for standby alternatively (or one for use and two for standby) to make sure that the TA crystal which is deposited and crystallized near the nozzle or crystallized on the circle distributor is dissolved.
The method that spraying water by circle distributor and from nozzle of reactor side wall can be quit, but apply the uniformity spraying water by tubes at this area to absorb the heat from oxidation reaction to maintain the reaction temperature.
The oxidation reaction from PT acid to TA is completed at this area.
4) The temperature of liquid phase materials from the place in ⅘ to the bottom is controlled at 285-300° C., preferably 288° C. Actually control it in the range of 288-289° C. Set up four test points from up to down at this area, that the temperature of the second test point is 0.1° C. higher than the first test point is permitted, and the temperature of the third test point is the same to the temperature of the second test point. When the temperature at this area has the increasing trend, make sure that the completion process of oxidation reaction move upwards by increasing the supply of compressed air bottom and the total supply of compressed air, or decreasing the feed-in velocity of PX material, so as to ensure that the reactant of organic material phase are all oxidized into TA at this area.
The main ingredient of oxidized tail gas is nitrogen, a little of carbon dioxide, carbon monoxide, and trace acetic acid and other organic ingredients. The pressure is 7.3 MPaG, a great deal of inertia tail gas can be used in power recycle.
The process is different from the current PX oxidation process, in which there is no heat withdraw by a great deal of solvent flash vaporization on the top of reactor, the temperatures of liquid phase from up to down at the reactor forms gradient, except that part of the heat are taken out by inert gases on the top of reactor, most of the reaction heat are removed by heating deionized water and the exothermic flash vaporization of deionized water in crystallizer.
The outlet from oxidation reactor bottom is TA solution, wherein the TA is 17.3%, acetic acid is 24.1%, and water is 57.6%. The TA solution is sent into the first crystallizer and flash vaporized and crystallized at 255° C., about 10% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Refine the acetic acid, then use it as solvent of preparing PX material, add the water which is used as deionized cooling water for the third temperature control area into reactor to control temperature.
The residual solution from the first crystallizer is sent into the second crystallizer, and flash vaporized and crystallized at 200° C., about 7% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily.
The residual solution from the second crystallizer is sent into the third crystallizer, and flash vaporized and crystallized at 150° C., about 0.8% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily.
The residual solution from the third crystallizer is filtered to remove the solid impurities, a part of it is sent into recycle system for mother liquor to recycle the catalyst and remove the soluble impurities, the other mother liquor are used as the cooling medium of liquid phase materials inside oxidation reactor—deionized cooling water (the actual temperature is much higher, but compare with the liquid phase materials inside reactor, the temperature is lower).
Acetic acid wash (remove the catalyst and assistant catalyst of cobalt, manganese, and bromine, also this process can be omitted), separate, and dry the CTA crystal obtained from crystallization system, and then water wash, separate, and dry it, obtain the PPTA production wherein the contents of 4-CBA and PT acid are all less than 15 ppm.
PPTA yield per hour is 120 t. The consumption of PX per PPTA product is 652 kg/t, the consumption of fuel and power is 100 kg standard oil per ton. the consumption of acetic acid is 20 kg/t.
For a tower type oxidation reactor applying oxygen as assistant material instance:
Except that the assistant material is oxygen and compressed air, other reactor structure and reaction processes are similar to example 1.
In order to avoid using a large flow rate of air compressor with high pressure, this device applies the liquid oxygen supplied by air separation unit as oxidant material. The liquid oxygen is sent into evaporator by a high-pressure pump (or high-velocity pump), the cooling energy is recycled in the evaporator, and the gasified oxygen is fed into oxidation reactor from bottom. Because the total quantity of oxygen gas is relatively less than compressed air, the disturbance to liquid phase at bottom resulted from gas travelling upwards can be very little, make sure that the flow of liquid phase materials is relatively more stable as much as possible, and it is more closed to plunger-flow, the materials on the top and the intermediate products are unable to deposit to the bottom quickly.
Also because the water content in liquid phase materials at the place of feeding oxygen is up to 59%, the sum of organic phase is about 41%, the condition of acute oxidation reaction does not occur. Along with the oxygen-containing gas travelling upwards, the water content in liquid phase decreases, and the oxygen concentration in oxygen-containing gas reduces step by step. Control the oxygen content in tail gas from reactor to be less than 1-2%, so as to ensure the safety of oxidation reactor and increase the utilization rate of oxygen.
As a substitute, instead of adding cooling water into reactor by the circle distributor and by the water nozzle on the side wall of reactor, set up the tube heat exchanger where the water flows from up to down inside reactor, add the deionized cooling water at the temperature of 36° C. into tubes, the water outlets inside tubes are dispersed at different heights of liquid phase at reactor, the water quantity is large where the reaction heat is large, so as to keep the temperatures at different areas stable. The advantages of this project are: 1. Get the heat from the liquid phase materials from upside to downside in turn to keep the increasing temperature gradient from up to down of liquid phase materials; 2. Decrease the temperature differences between water outlet of tubes and the liquid phase materials at the places of water outlets to avoid the TA depositing on exchanger wall. The quantity of deionized water entering into tubes is 133 t/h.
Wherein there is no water discharged at the first temperature control area, it absolutely depends on the tube exchanger to get heat; there is 48 t/h of water discharged in uniformity from up to down at the second temperature control area, it depends on the tube exchanger to get heat and absorb reaction heat by neutralizing and diluting the liquid phase materials with low temperature water; there is 85 t/h of water discharged in uniformity at the third temperature control area, it depends on the exchanger to get heat and absorb reaction heat by diluting the liquid phase materials with a relative low temperature water (actual temperature is 200-280° C.) to keep the liquid phase temperature at 288°. The water outlet locations and the water quantities at the outlet locations depend on the amount of holes on the different outlet locations of tubes.
The outlet from oxidation reactor bottom is TA solution, wherein the TA is 17.5%, acetic acid is 23.5%, and water is 58.2%. The TA solution is sent into the first crystallizer and flash vaporized and crystallized at 255° C., about 10% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Refine the acetic acid, then use it as solvent of preparing PX material, add the water which is used as deionized cooling water for the third temperature control area into reactor to control temperature or send it to the water tanks.
for the combination with two oxidation reactors instance: wherein the first oxidation reactor apply tower type reactor with the assistant material of compressed air; Apply a tower type reactor with the assistant material of oxygen at the second oxidation reactor.
Apply a tower type oxidation reactor with the diameter of 4000 mm, and with the height of 24000 mm as the first oxidation reactor, apply paraxylene (PX) as material, acetic acid as start solvent, cobalt acetate, manganese acetate as catalyst, the ion content (the sum of ion mass) of cobalt and manganese of effective ingredients in catalyst is 700 ppm, the proportion of cobalt to manganese is 1:1. The feed-in proportions (as mass) of start materials of PX, acetic acid, and water are respectively 30%, 64%, and 6%. The prepared materials and catalysts are fed from the top of oxidation reactor, and the liquid phase materials go downwards. The feed-in flow rate of PX is 128 t/h.
Blow into compressed air from the bottom of reactor, the reaction heat is removed from the top of reactor by solvent flash vaporization, then recycle the heat by heat exchanger which can be a condensation tower, after removing a little of acetic acid, part of the water is sent back to the oxidation reactor. The water content inside reactor is 8-20%, the typical water content is 12%. Control the oxygen content in tail gas from reactor to be less than 1-3%, so as to ensure the safety of oxidation reactor and increase the utilization rate of compressed air.
The inlet pressure of compressed air is 0.5 MPaG The pressure inside reactor is 0.1-0.3 MPaG. The reaction temperature is 120-160° C., the typical temperature is 128-130° C. Because it is difficult to oxidize PT acid further, and without the assistant catalyst of hydrobromic acid inside system, in this condition, the PX is mainly oxidized into PT acid, and a little of PT acid can be further oxidized into TA and deposit in the form of crystal.
There is no PX near the outlet area at the bottom of reactor. The materials come out from bottom, and are vaporized and concentrated to remove the acetic acid, water, and a little of PX to obtain the mixture consisted of 73% PT acid, 15% TA, 8% acetic acid, and 4% water. In the proportion of 1:2.5, mix and beat this mixture with deionized water into slurry, add the hydrobromic acid as assistant catalyst according to the PX content of 350 ppm (ion mass concentration), and the cobalt and manganese catalysts added in the first stage still exist and are available. Send the slurry into the upside of liquid phase at the reactor with a high velocity pump.
The second oxidation reactor applies a set of tower type oxidation reactor (or oxidation reactor with the structure of internal and external chambers, or oxidation reactor with the structure of internal, medium, and external chambers, or horizontal plug-flow oxidation reactor) with the diameter of 4500 mm, and the height of 28000 mm. Apply oxygen (or compressed air) as assistant material.
The liquid phase temperature at the second oxidation reactor is 285-300° C., the typical temperature is 288° C. Temperature is the first control factor, pressure is the second. Apply solvent flash vaporization to remove heat that the vapor comes out of the reactor from the top of reactor, the solvent consisted of water and acetic acid is segregated by condensation tower on the top of oxidation reactor, then the water and acetic acid are respectively enter into tanks. Heat up the vapor by segregation tower to recycle the heat. Part of condensation water is sent back into oxidation reactor to make sure that the proportion of acetic acid and water of solvent phase inside reactor is 1:4 to 1:99, and the typical proportion is 3:17.
Because the water content in liquid phase materials at the place of feeding oxygen is up to 61%, the sum of organic phase is about 39%, the condition of acute oxidation reaction does not occur. Control the oxygen content in tail gas from reactor to be less than 1-2%, so as to ensure the safety of oxidation reactor and increase the utilization rate of oxygen.
Because of the exothermic reaction of liquid phase materials at the bottom of reactor, result in the local warming (or trend), and the water and acetic acid is gasified and ascended, then the water and acetic acid vapors arrive into the gas phase at the top of reactor, enter into segregation tower, so that the heat is removed. The ascending process of vapors has a disturbance effect on the plunger-flow travelling downwards of liquid phase materials, but it is unable to result in the top material containing PT acid quickly depositing into bottom. The TA crystal in the slurry added from the top of liquid phase at the reactor dissolves very quickly during the deposition process, and the 4-CBA contained in TA crystal is also oxidized into TA very quickly.
The inlet pressure of oxygen is 8.1 MPaG. The pressure inside reactor is 7.3-7.5 MPaG.
The main ingredient of oxidized tail gas is a little of oxygen, carbon dioxide, carbon monoxide, and trace acetic acid and other organic ingredients. The pressure is 7.5 MPaG.
The outlet from oxidation reactor bottom is TA solution, wherein the TA is 27%, acetic acid is 11%, and water is 72%. The TA solution is sent into the first crystallizer and flash vaporized and crystallized at 255° C., about 19.5% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Refine the acetic acid, then use it as solvent of preparing PX material, add the water which is used as deionized water for the second oxidation reactor into reactor to complement the assistant solvent water, decrease the concentration of acetic acid and reduce the consumption of acetic acid.
The residual solution from the first crystallizer is sent into the second crystallizer, and flash vaporized and crystallized at 200° C., about 7% of TA is crystallized into crystal. Set up distillation tower on the top of crystallizer to recycle the residual heat, and separate the acetic acid and water preliminarily. Crude acetic acid and water are respectively sent into tanks.
The residual solution from the second crystallizer is sent into the third crystallizer, and flash vaporized and crystallized at 150° C., about 0.8% of TA is crystallized into crystal.
The residual solution from the third crystallizer is filtered to remove the solid impurities, a part of it is sent into recycle system for mother liquor to recycle the catalyst and remove the soluble impurities, the other mother liquor are used for the beating of PT acid.
Acetic acid wash (remove the catalyst and assistant catalyst of cobalt, manganese, and bromine, also this process can be omitted), separate, and dry the CTA crystal obtained from crystallization system, and then water wash, separate, and dry it, obtain the PPTA production wherein the contents of 4-CBA is less than 10 ppm, and the PT acid is less than 5 ppm.
PPTA yield per hour is 200 t. The consumption of PX per PPTA product is 652 kg/t, the consumption of fuel and power is 99 kg standard oil per ton. The consumption of acetic acid is 9 kg/t.
| Number | Date | Country | Kind |
|---|---|---|---|
| 200810085014.2 | Mar 2008 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN2009/000264 | 3/12/2009 | WO | 00 | 10/25/2010 |
