• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    ISO- OR TEREPHTHALIC PREPARATION IN A BENZOIC ACID-WATER SOLVENT SYSTEM The present invention relates to the preparation of iso- or terephthalic acid by the oxidation of m- or p-xylene with molecular oxygen at elevated temperatures and under liquid phase conditions in the presence of catalysis provided by a combination of one or more transition metal oxidation catalysts and a source of bromine improved by the use of a liquid solvent system consisting essentially of benzoic acid and at least 3 percent and up to about 15 percent by weight of water which provides commercially feasible control of oxidation temperature not otherwise feasible in the absence of the water component of said catalyst system when said xylenes are oxidized.
    公开号:SU793378A3
    申请号:SU772505759
    申请日:1977-07-26
    公开日:1980-12-30
    发明作者:Юджин Старк Леонард；Расселл Марш Дэвид
    申请人:Стандард Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the field of organic synthesis, specifically to a process for the production of iso or terephthalic acid, an important monomer in fiber production. Methods are known for producing isoyl terephthalic acid by oxidizing l-or p-xylene by heating to 50-275 ° C and under pressure to keep the reactants in the liquid phase, in the presence of a catalyst, consisting of transition metals, as well as a chromium ij source. Typically, acetic acid is used as a solvent in the process. The disadvantage of this method is the corrosion of the apparatus used. The closest to the invention in technical essence and the achieved results is a method of producing iso- or terephthalic acid by oxidation of Al - or p-xylene with air oxygen, at a temperature of 170 and a pressure of 21-35 kg / cm, in the presence of liquid benzoic acid the solvent, with a ratio of benzoic acid: xylene 3 10: 1, as well as in the presence of a catalyst, including cobalt and / or manganese and bromine with a total metal content of 0.1-1 per xylene and bromine in an amount of 0.2 -1.0% also based on xylene, while Removal of water forming as a by-product 2. A disadvantage of the known method is the inability to control the operating temperature of the process, carried out under a pressure of 21-35 kg / cm, when the condition of removing water as it is formed as a by-product of the reaction is fulfilled, which leads to undesirable deep oxidation of reagents - benzoic acid, xylene, as well as products of its partial oxidation. In addition, the absence of mixing in a known process leads to the occurrence of local overheating areas. The purpose of the invention is to simplify and intensify the process. The goal is achieved by the proposed method of obtaining isoil or terephthalic acid by oxidation with mixing of gl or xylene with oxygen at a temperature of usually 200-230 0 under a pressure of 14-25 kg / cm, in the presence of liquid 92-85% benzoic acid containing 8-15% water, when the ratio of the solvent system and xylene in the oxidation zone is 3-7: 1, in the presence of a catalyst comprising cobalt and / or manganese and bromine, with a total amount of metal 0.1-0.2 wt.%, And also bromine in an amount of 0.02-0.3 ve, based on the solvent, with the content air oxygen in the benzoic acid waste vapors of 3–15% by volume, followed by complete condensation of benzoic acid vapor and partial condensation of water vapor leaving the oxidation zone, and returning the condensation to the process in such quantity that The temperature fluctuations in the oxidation zone would not exceed + 5 s and the preset water content in the solvent would remain. The distinguishing features of the process are carrying out the oxidation with stirring, under a pressure of 1425 kg / cm-, using 92-85% benzoic acid containing 8-15% water, with a ratio of solvent system and xylene in the oxidation zone of 3-7: 1 and the total amount of metal in the catalyst is 0.1-0.2 wt.%, and bromine - 0.02-0.3 wt.%, calculated on the solvent and when the content of unreacted oxygen of the air in benzoic acid vapor is 3-15% by volume, the subsequent complete condensation of benzoic acid vapor and the partial condensation of water vapor emitted from the oxidation, and with the return of the condensate formed to the process in such an amount that the temperature fluctuations in the oxidation zone do not exceed + 5 ° C and the water content in the solvent is preserved, which allows to simplify and intensify the process. The proposed method consists in improving the conditions for carrying out the process according to patent No. 1088183, since it allows to prevent the temperature from rising above the set value. The process can be carried out in continuous mode, keeping the temperature at a predetermined level. Control of the working temperature can be achieved by using a solvent system consisting of 85-92% by weight of liquid benzoic acid and 15-8% by weight of water, provided that the working gauge pressure is in the range of 14-25 kg / cm with Thereby, the amount of water removed as a by-product does not exceed 15% in the system, and less than 3% does not decrease. Under such operating conditions, the operating temperature of the oxidation process can and should be in the range of 200-235 ° C. For the continuous oxidation process, a special catalyst is proposed, which is a combination of an oxide catalyst of one or more transition metals and a source of bromine obtained by dissolving suitable sources of these components in the solvent system. The process is carried out in a stirred oxidation zone to obtain sufficient air distribution and heat distribution throughout the entire liquid reaction phase in the oxidation zone. Due to the heat of reaction, a small amount of benzoic acid and mainly water from the oxidation zone evaporates. Xylene and its oxidation products practically do not evaporate under these operating conditions. Satisfactory temperature control is established for almost constant operating conditions by adjusting the water content of the reflux liquid (mainly water) in the oxidation zone after condensing these vapors to remove the heat generated in the reaction. The water content in the liquid reflux, which is usually 90-95%, can be controlled by changing the temperature of the reflux condenser. The deviation of the oxidation temperature from a given constant operating temperature can be corrected by changing the feed rate of the additional amount of water (since the condensate contains only 9-10 wt.% Of benzoic acid) returned to the oxidation zone. Thus, for example, the rate of reflux of water with a reflux liquid is increased or decreased, depending on the increase or decrease in temperature in the reaction zone, as compared with the selected constant temperature. The change in temperature in the oxidation zone can be maintained at a level of T 5 ° C compared with the selected constant temperature for the oxidation zone. A change in the rate of return of water should not lower the water content in the solvent system below 3% by weight, since under these conditions an uncontrollable strong change in temperature conditions may occur. Changes in the returned fluid should not lead to an increase in the water content of the solvent system above 15 wt.%, For example, to 18 wt.%, Since this amount of water partially or completely deactivates the catalytic system. The oxidation of l-and p-xylene is carried out at a weight ratio of the solvent system of benzoic acid: water in the range of 3-7: 1. The proposed process is carried out as follows. First, the components of the catalyst and the solvent system are loaded into the oxidation zone with mixing. The resulting solution is stirred and heated to the oxidation initiation temperature. Then AD or I-xylene is supplied to the stirred liquid in the oxidation zone, as well as air at a speed of 10001500 nl per 1 kg of xylene until the temperature in the oxidation zone reaches the working one, i.e. selected in the interval 200-230s . After that, the air supply rate is increased from 3800 to about 5900 nl per 1 kg of xylene, ensuring the oxygen content in the exhaust gas is 3-10 vol.% (Benzoic acid and anhydrous base). After the weight ratio of the initially loaded solvent system to the total amount of loaded xylene reaches a pre-selected 3–7: 1.0 solution of the catalyst components in the solvent system, benzoic acid: water is fed at a rate corresponding to a continuous supply of xylene to maintain the selected weight ratio solvent and xylene. Air is introduced at a rate of 380–5900 nl per 1 kg of xylene, ensuring the oxygen content in the exhaust gas is 3–10 vol.%. Target iso-or terephthalic acid, which is practically insoluble in the solvent system, can be separated from the resulting oxidation liquid stream using any solid-liquid phase separation method, for example, by filtration or centrifugation, at which temperature the benzoic acid remains liquid. Since the temperature of the effluent is 200-230 ° C (well above the benzoic acid cure temperature) and the gauge pressure is 14-25 kg / cm, this separation can be accomplished by decompression with accompanying cooling of the effluent. Decompression can be carried out either to atmospheric pressure or to lower pressure. The cooled, but liquid outflowing current is pumped into the specified separator of the solid and liquid phases. Preferably, this effluent is decompressed to a pressure below atmospheric to avoid impulse evaporation in devices for separating the solid and liquid phases. The separated crystalline product is washed with hot, fresh benzoic acid, and then xylene, toluene, or their mixture to remove traces of benzoic acid. The washed product is dried and xylene or a mixture of xylene and toluene is removed by drying, after which the product is ready for use. The proposed method allows to reduce the combustion of organic components of the solvent system; ventilation flows are cleaner; the possibility of corrosion in the oxidation reactor, transmission lines and devices for the purification of the product is reduced; in addition, the cost of the oxidation reactor decreases as the operating pressure decreases. Air-blown moist (315% water) boiling acid is significantly less corrosive at working temperature, even when it contains bromine as a catalyst component than with blown air wet (5-10% water) acetic acid containing the same r about ton of bromine. Examples of implementation of the invention. The following 13 examples illustrate the implementation of the method of the invention by the method of semi-continuous oxidation, in which terephthalic acid (TK) is obtained by oxidizing para-xylene (PC) with atmospheric oxygen. The oxidizer unit is a cylindrical oxidation-carrying vessel containing a stirring mixer, which, together with the solvent system used and the product suspended in it, after the final loading of paraxylplate and purging it with air is about 60% of the total vessel volume. The remaining 40% of the volume is left for the vapors and gases released from the stirred liquid during the reaction. Said oxidation vessel is also provided with separate devices for introducing air into the lower part of the oxidation zone, paraxylene and water into the upper part of the zone of diversion of the oxidized liquid stream from the bottom of the ugly vessel, discharging the mixture of i-basics and vapors from the upper part of the vessel and means for sealing the vessel d.p works with pressure at atmospheric. A top outlet fixture is connected to a reflux condenser to condense the benzoic acid into its liquid reflux and to supply uncondensed gases and vapors to a side condenser, the purpose of which is to condense water. The water vapor condenser is connected to a receiver in which water condensate collects and through which the uncondensed gases (a mixture of nitrogen, oxygen and carbon oxides together with some water vapor) are released via a pressure regulating valve. Between said pressure control valve and a device for receiving and analyzing ventilated gases, there is installed a water catch for freezing water. Para-xylene is fed to the oxidation zone by pumping from a pressurized supply tank. Means are also provided for supplying water to the oxidation zone using a combination of a supply tank (3.5 kg / cm overpressure relative to the pressure in the oxidation zone), a measuring needle valve and a rotameter with an additional bypass through a ball valve designed to add a large the amount of water in the reaction zone, for quick quenching of the reaction in the event that an accidental or any other uncontrolled increase in the reaction temperature occurs. Additional means are provided to heat or cool the stirred liquid or liquid contents in the system of the oxidation zone, initially loaded into the reaction vessel, and bring the specified solution to the operating temperature until the beginning of the introduction of para-xylene and air, and, if necessary, after Paraxylene is complete. The reflux condenser is heated with steam under a maximum pressure of 7 kg / cm, which is supplied through a pneumatic steam regulator: by regulating the air pressure, the vapor pressure is controlled in the range of about 7 kg / cm in the condenser and is controlled by its operating temperature. The specified air pressure is in turn controlled according to the temperature in the reaction zone. For such adjustment of the temperature in the condenser in accordance with the temperature of the oxidation zone, the vapor pressure is increased when the temperature in the reactor rises. The resulting increase in vapor pressure leads to a decrease in the water content of the solvent system, and a decrease in vapor pressure increases the water content in the solvent system. In the examples, the described means for controlling the reaction temperature by controlling the temperature of the reflux condenser (supply vapor pressure) were sufficiently accurate, so there was no need to add water in large quantities to quench the reaction. However, at low flow rates of outgoing steam and complex temperature control of the vented gas, more accurate temperature control is more easily accomplished with the introduction of small amounts of water.
    Oxidation of para-xylene in a solvent 218 170 153 273 Para-xylene, g Pump capacity, g / h 327 170. 166 193 Pumping time, 40 60 55 85 min. Water in dissolve 10 10 10 10 le, wt.% 81 90 90 90 Water, g Benzoic acid, g Co, calculated on solvent, wt.% Mn calculated on solvent, weight,% Br calculated on the solvent, wt.% Solvent / para-xylene, weight so3, 7 5.3 5.85 3.3 Ratio Operating temperature, C 218 216 218 205 810 0.10 0.02 0.02 Table 1 Benzoic acid- water 127127 127127 9090 9090 8585 85 85 1010 1010 9090 9090 810810 810810 0.030.03 0.060.03 0.090.09 0.090.18 0.180.18 0.180.18 7.17.1 7.17.1 215205 20520S Outlet content: 4 -Carboxybenealdehyde (4-CBL), 2700 430 610 2000 mln
    Paratoluic acid, wt.%
    Para-xylene, wt.%
    Terephthalic acid, wt. %
    Terephthalic acid, yield, mol.%
    Filter residue,
    4-carboxybenzaldehyde, million
    The complete reaction stream was obtained by decompression to atmospheric pressure. At the same time, the water contained in it instantly evaporated. Oxidation of para-xylene in reduced with fresh benzoic acid and further examples 9-14 was carried out with marg acetate tetrahydrate. ntsa In the same manner and at the same facility, accumulation of intermediate ke in the examples 1-8, but in example 40 of the product 4-carboxybenzaldehyde 14, the solvent was obtained for the reaction, and para-toluic acid, as well as its 80% solution of the increase the color of the isolated benzoic acid from example 13 with a product. Oxidation of para-xylene in benzoic acid-water solvent
    Materials and conditions
    Paraxylene, g
    Pump capacity, g / h
    Pumping time
    min
    Water in solution, wt.%
    Water, g
    Renzoic acid, g
    Continued table. one
    0,030,0131,270,0930,130,120,13
    0.0420.0330.001--0.00520, 419,330,2122,321,622,122.3
    95,795,890,795,696,695,796.3
    3700 290 490 350 1000
    390 310
    .Table 2 290 400 300 770 Co calculated on solvent, wt.% 0.015 0.030.03 Mp calculated per pa0, 090.09 fixator, wt.% 0.09 V g calculated on par0, 180.18 fixator, weight % 0.18 Solvent / para-xylene, weight so7, 17.1 ratio 7.1 Working temperature, ° С205 205205 Working pressure max 19,719, -7 nominal, kg / cm 19.7 O2 in exhaust gases, vol. 7-14 9-139-13 9090 Reaction time, min 90 Content of outgoing reaction stream: 4-CBA, MnH- 680
    Paratoluic acid, wt.% Paraxylene, wt.%
    Terephthalic acid, wt.%
    Terephthalic acid, yield, mol.%
    Filter residue
    4-kba, ppm 1000
    690
    The following examples of para-xylene oxidation illustrate the implementation of a continuous oxidation process. The continuous process is carried out in the same setup as described for the previous 14 examples, only larger. This leads to an increase in paraxylene loaded in B.1 h. The process of continuous oxidation is started in the same way, the NTO and the semi-continuous process are pumped and paraxylene is pumped.
    Continued table. 2
    1600 1400 3000
    770
    until the weight ratio of solvent (loaded at the beginning) to para-xylene reaches the desired value. Thereafter, the solution of the catalyst components in the solvent is also pumped into the reaction zone at such a rate as to maintain this ratio of solvent and xylene, and the terephthalic acid is withdrawn at a rate at which the residence time in the reactor (retention time) corresponds to the time indicated in table. 3. 000 0.20,150,16 0.30,180,13 4.94.94.9 221218218 19.718.318.3 7-128-1310-12 606060 1400 3100
    Oxidation of para-xylene in the solvent benzoic acid - water
    Materials and conditions
    Xylene feed rate, g / h Water in solvent, wt.%
    Co, based on the solvent, wt. %
    MP, based on solvent,
    weight. %
    Vg per solvent, wt. %
    Solvent / para-xylene, weight ratio
    Operating temperature, ° С
    Working gauge pressure kg / cm
    02 in waste gas, vol.% Retention time, min Mole CO / mole xylene
    Full output of the reaction stream:
    4-kba,
    Paratoluic acid, wt.%
    Para-xylene, wt.%
    Terephthalic acid, wt.%
    Terephthalic acid yield, m
    Washed filtration residue,
    4-kba, wt.%.
    When the para-xylene was oxidized in accordance with Comparative Example 1, the water formed as a by-product was not removed. The reflux cooler operated at a temperature at which all the condensate of water and benzoic acid returned to the oxidation zone. This allowed the concentration of water in the benzoic acid solvent system to be raised from 10 to 18 wt.%. when working in stationary mode. The 18% water content exceeds the upper limit (15%) allowing an acceptable oxidation rate. In addition, 225 g of para-xylene was added to the initial load of the solvent system containing the catalyst components, and the pumping of para-xylene was delayed until that time (calculated) when
    Table 3
    权利要求:
    Claims (2)
    [1]
    let the paraxylene loaded at the beginning be converted by the supplied air. Under these modified operating conditions, the temperature in the stirred oxidation zone can be controlled close to the planned, however, most likely, the temperature of the oxidation zone periodically noticeably exceeds and becomes lower than the indicated temperature. In addition, the carbon monoxide formation and oxygen content in the flue gas varies qualitatively, which indicates insufficient temperature control of the reaction and indicates that the oxygen concentration in the oxidation zone is either too high or too low, although the air supply remained constant. The cumulative effect is unfavorable. effects on control of reactivity and temperature persistence and may cause an increase in the aromatic by-products and by-products to such a high concentration that will significantly reduce the desired oxidation rate to terephthalic acid. For oxidation, in comparative mode 2, the temperature in the reverse refrigerator was increased, in order to be able to remove the water formed as a by-product in gas and vapor at 121 ° C and maintain a 10% concentration of water in the solvent system. . Xylene re-loaded in advance (908 g). However, the temperature in the oxidation zones cyclically changed again, and it was not possible to establish a constant temperature of 218 ° C, the oxygen consumption was low. The temperature of the oxidation zone reached a maximum value of 226 ,, at this moment the oxygen consumption increased sharply, which became noticeable by a 75% drop in the oxygen content in the exhaust gas. In addition, paraxylene condensate accumulated in a cold trap prior to installation for sampling and analysis of the off-gas. Thus, a significant amount of para-xylene was converted into steam as it entered the oxidation zone, the pressure in which was maintained at 14.6 kg / cm and therefore did not oxidize. Precise control of the reaction temperature was not possible, as the temperature of the reflux condenser could not be maintained. For the purpose of example 15, the operating temperature of the reflux condenser was maintained with water heated by a controlled stream of steam which was added to the hot water entering the condenser. Thus, precise control of the reflux temperature in the range of 121 + 0.5 s was achieved. With such precise control of the temperature of the reflux condenser, using the specified pressure in the reaction zone, precise control of the reaction temperature at 226, is achieved, and the oxygen consumption at the same time reaches a high stationary level. Production of isophthalic acid with similarly high yields, good color and high purity in the system of 83-95% benzoic acid and 15-5% water can be done by replacing paraxylene with methoxylene in the examples given. 1. Method for producing iso- or terephthalic acid by oxidizing mi-xylene with oxygen at elevated temperatures and pressures in the presence of liquid benzoic acid as a solvent, and also a catalyst comprising cobalt and / or manganese and bromine, so that, in order to simplify and intensify the process, the oxidation is carried out with stirring, under a pressure of 14–25 kg / cm, using 92–85% benzoic acid containing 8–15% water, with a ratio of solvent system and xylene in the zone oxidation of 3: 7: 1 and the total amount of metal 0.10, 2 wt.%, and bromine - 0.02-0.3 wt.% (based on the solvent and the content of unreacted oxygen of the air in benzoic acid waste vapors 3-15 vol.% followed by complete condensation of benzoic acid vapor and partial condensation of water vapor leaving the oxidation zone and returning the condensate to the process in such an amount that temperature fluctuations in the oxidation zone do not exceed 5 ° C and the water content remains in a solvent. 2. The method according to claim 1 is also distinguished by the fact that the oxidation is carried out at 200-230 ° C. Sources of information taken into account in the examination 1. US patent number 2833816, CL, 260-524, published. 1958.
    [2]
    2. The UK patent number 1088183, cl. C 2 C, pub. 1967 (prototype).
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    同族专利:
    公开号 | 公开日
    LU77836A1|1978-02-02|
    ES461021A1|1978-05-16|
    FR2359809B1|1980-07-11|
    AU2650077A|1979-01-04|
    MX145448A|1982-02-17|
    IE45504B1|1982-09-08|
    DK334777A|1978-01-27|
    CA1079296A|1980-06-10|
    CS197297B2|1980-04-30|
    AU510097B2|1980-06-05|
    DE2732149A1|1978-02-02|
    BE857068A|1978-01-23|
    BR7704878A|1979-07-03|
    NL7707202A|1978-01-30|
    PL199858A1|1979-01-02|
    GB1577544A|1980-10-22|
    IT1079740B|1985-05-13|
    DD132428A5|1978-09-27|
    JPS5315334A|1978-02-13|
    IE45504L|1978-01-26|
    AR211428Q|1977-12-15|
    FR2359809A1|1978-02-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL6413067A|1963-11-14|1965-05-17|JP2893860B2|1990-05-17|1999-05-24|三菱瓦斯化学株式会社|Production method of high purity isophthalic acid|
    GB9210832D0|1992-05-21|1992-07-08|Ici Plc|Bromine catalysed oxidation process|
    EP0596395B1|1992-11-04|2000-06-28|Clariant GmbH|Process for the preparation of fluorinated benzil|
    ES2104512B1|1995-09-21|1998-07-01|Interquisa|INDUSTRIAL PROCEDURE FOR THE MANUFACTURE OF AROMATIC CARBOXYL ACIDS.|
    PL389529A1|2009-11-10|2011-05-23|Fabryka Maszyn FAMUR Spółka Akcyjna|Method for mounting the arm to the body of longwall coal miner|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US70835876A| true| 1976-07-26|1976-07-26|
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