• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    There is disclosed a process for preparing terephthalic acid by oxidizing p-xylene which comprises contacting a substantially liquid mixture of p-xylene with p-toluic acid and water wherein the molar ratio of p-toluic acid to p-xylene is between about 0.01 and about 100 and the molar ratio of water to p-toluic acid is between about 0.4 and about 60, with a molecular oxygen-containing gas in the presence of an oxidation catalyst.
    公开号:SU791221A3
    申请号:SU772535148
    申请日:1977-10-26
    公开日:1980-12-23
    发明作者:Даниель Виктор Анотье Жак
    申请人:Лябофина С.А. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to organic (cic) synthesis, in particular, to a method for producing terephthalic acid, which is an important monomer for the synthesis of 5 5 polyester fibers.
    Known are the methods for producing terephthalic acid by liquid phase oxidation of p-xylene with atmospheric oxygen in the presence of a metal catalyst and an activator or promoter and a lower fatty acid.
    The disadvantages of the known methods are the high consumption of fatty acid, for example, acetic acid, as well as the presence of intensive corrosion of equipment.
    The closest to the proposed technical essence and the achieved results is the method of producing 20 terephthalic acid by liquid phase oxidation of p-c4 ylol and p-toluic acid with oxygen in the presence of a catalyst, in which nickel and 25 manganese are used in a ratio of 95: 5 and 0.5:: 99.5, at a temperature of 16 ° C-280 ° C under pressure sufficient to maintain the reaction mass in the liquid state.-JQ
    The yield of the target product is not more than 60% by weight (or not more than 150 g / h per 1 kg of p-xylene. The optical density at 340 µm, 380 µm and 400 µm is 0.726, 0.183 and 0.111, respectively.
    The disadvantage of this method, carried out without solvent, is the need to maintain the content of the target terephthalic acid in the reaction mass at a certain level, because exceeding this level complicates the process of separating the solid target product from other reaction products and does not allow a high degree of its purity to be achieved. -
    The purpose of the invention is to increase the yield and quality of the target product.
    This goal is achieved by the fact that in the method of producing terephthalic acid by liquid-phase oxidation of p-xylene and p-toluic acid with oxygen in the presence of a metal catalyst at a temperature of 165-185 ° C under sufficient pressure to maintain the reaction mass in a liquid state, oxidation is carried out in the presence of water at a molar ratio of p-toluic acid; rj-xylene O, 05-87 and water: P-then luyl acid 0.97-38, and the catalyst used is a cobalt salt or manganese salt, or their mixture in an amount of 0.025-0.075 mol per 1 liter of organic compound. In addition, naphtecate or acetate is used as the salt of manganese or cobalt. It was previously believed that the presence of iodine in the oxidation process is undesirable. In all cases, its content should not exceed 5 Unce.%. The presence of water was considered possible only if there was bromine in the reaction mass. However, in accordance with the proposed method, it is possible to use water in a concentration exceeding 50 wt. The amount of water used depends mainly on the temperature and composition of the reaction mixture. In this case, the amount of water should be sufficient so that P-toluic acid is practically in solution at the operating temperature. Since the solubility of p-toluic acid in water increases rapidly with increasing temperature, the amount of water used may be the smaller, the higher the temperature. Typically, the amount of water should not be below 0.9 mol per 1 mol of p-toluic acid present in the reaction mixture. However, it is often expedient to work with quantities of water in excess of those needed to keep P-toluic acid in solution. For example, if relatively large amounts of terephthalic acid (the target product) are present in the systems, then some amount of water can be added to obtain a suspension suitable for treatment. However, it is impractical to use an amount of water that is 10% more than the amount of terephthalic acid dissolved at the operating temperature. The influence of other factors has been established. Thus, the presence of too much water with respect to P-toluic acid may have a detrimental effect on the reaction rate if the amount of: P-xylene in the system is relatively small. The amount of water should be less than 60 mol per 1 mol of P-toluic acid present in the system. The oxidation reaction temperature is IGS-ISS.C. Below 1 to 5, the solubility of p-toluic acid in water is too low to make it possible to use the advantages of using water in accordance with the proposed method. At temperatures above, secondary reactions are undesirable and corrosion occurs. The catalyst used in the method may be a salt of manganese or cobalt, usually using a salt that is soluble in the reaction medium. Salts of aliphatic carboxylic acids, such as acetates, stearates, naphthenates, can be used. When these salts are added to a system containing large amounts of P-toluic acid, anion exchange takes place with the formation of the corresponding toluylate, which is an effective catalyst. A feature of the proposed method is that P-xylene is oxidized only in the presence of P-toluic acid. At the same time, the acid content must be strictly defined, since when its amount decreases below a certain level, the oxidation process stops. The proposed method allows the heat generated by oxidation to be removed by regulating the evaporation of water. o As the reaction progresses, oxygen absorption decreases, in which case P-xylene must be additionally introduced into the system. To obtain high yields of terephthalic acid, the presence of P-xylene in the system is necessary in such an amount that the molar ratio of P-toluic acid: P-xylene does not exceed 87. The process is carried out either periodically or continuously. The process is carried out periodically until the absorption of oxygen ceases, after which the tereft. The left acid is separated by filtration at the reaction temperature or at the temperature at which P-toluic acid remains in solution. The filtrate contains a catalyst as well as intermediate oxidation products and can be reused. With continuous process control, the reaction is carried out in a reactor into which fresh P-xylene, air and recycled products are introduced. The reaction heat released is removed by evaporation of water. The oxidate obtained in the reactor is fed to an extraction column in which the unreacted P-xylene is sampled by extraction with water. Terephthalic acid is separated in a separator, washed in a wash column fed with hot water. The filtrate, the washings, and the catalyst are recycled to the reactor. The water used as the washing solvent of terephthalic acid can be heated and evaporated, at least partially, due to the heat generated during the oxidation itself, without the aid of an external energy source.
    The yield of terephthalic acid is determined by the rate of its formation (g / h) per 1 kg of p-xylene.
    Example ... A 100 l P-xylene, 180 g p-toluic acid, 50 g water and 7.5 mmol are placed in a corrosion-resistant 1 liter autoclave equipped with a mechanical stirrer, a heating jacket, a condenser, a gas supply and air intake pipe. (0.025 mole per liter of organic compound) cobalt naphthenate.
    The molar compounds P-toluic acid: P-xylene and water: H-toluic acid are 1.4 and 2.1, respectively. The pressure in the reactor is 20 kg / cm. The mixture is heated with stirring and with air at a flow rate of 300 l / h. Oxygen absorption begins as soon as the temperature exceeds 100 ° C. The temperature quickly rises and is kept equal. The rate of oxygen absorption increases greatly during the first 20 minutes of the reaction, and then gradually decreases. Upon completion of the process, the reaction mass is cooled. The resulting residue is washed with water, filtered and dried under vacuum at 80 ° C. The filtrate is treated with a cation exchange resin to remove metal catalysts and dried.
    A variety of different fractions are produced using combinations of acidometry, polarography, and gas phase chromatography. The reaction mixture consists of 137 g terephthalic acid, 177 g P-toluic acid and 7 g P-carboxybenzaldehyde
    Example 2. In the autoclave described in example 1, 100 g of P-xylene, 180 g of P-toluic acid, 150 g of water, 7.5 mmol of cobalt naphthenate and 0.75 mmol of manganese naphthenate are placed.
    The molar ratio of P-toluic acid: P-xylene is 1.4, the molar ratio of water: P-toluic acid is 6.3. Oxygen absorption begins as soon as the temperature reaches 140 ° C. The temperature is maintained at 185 ° C. After 295 min after the absorption of 106 l of oxygen, the reaction is stopped, the reaction mass is cooled and processed, and then the reaction mixture is analyzed as in Example 1. A reaction mixture is obtained containing 182 g of terephthalic acid, 118 g of p-toluic acid and 7 g of p- carboxybenzaldehyde The yield of terephthalic acid is 370 g / h per kg of P-xylene.
    When carrying out the process without manganese naphthenate, oxygen absorption begins as described above, but drops sharply after 80 minutes of reaction. Total oxygen absorption does not exceed
    58 liters, and the amount of terephthalic acid in the reaction medium is only 68 g.
    Example 3. The process is carried out analogously to example 2. The reaction is stopped 120 minutes after heating to 185 seconds. The reaction mixture is discharged to a filter press heated to a temperature that allows the separation of terephthalic acid from other
    Q oxidation products. Twice washed the resulting cake with water, heated to, and dried it. After cooling to room temperature, the filtrate and the washings are filtered again. To separate the precipitated
     P-toluic acid, which is also washed with water. The final filtrate, containing almost all of the catalyst and a small amount of P-toluic acid, is dried.
    0 The resulting residue is loaded into the autoclave together with precipitated P-toluic acid and the same amount of fresh P-xylene and water as during the initial loading. Then, the resulting mixture is oxidized as described.
    The operation is repeated nine times. By analysis it is established that the yield of terephthalic acid is
    Q 87 mol.% Based on the amount of reacted P-xylene.
    Example 4. The process is carried out analogously to example 2, but 7.5 mmol of manganese naphthenate is used as cattigitating agent. Through
    5 30 minutes of reaction is absorbed by 95 liters of oxygen. The reaction mixture is cooled, treated and analyzed as in example 1. Receive 150 g of terephthalic acid (290 g / h per
    0 .1 kg of L-xylene), 146 g of P-toluic acid and 7 g of P-carboxybenzaldehyde,
    Example 5. The process is carried out analogously to example 2, but loading 75 ml of water and using 7.5 mmol
    five
    manganese toluylate as a catalyst. After 20 minutes of reaction, 81 liters of oxygen are absorbed. According to the analysis, the reaction mixture consists of 111 g of terephthalic acid.
    0 (277 g / h per kg P-xylene, 179 g
    P-toluic acid, 7 g of p-carboxybenzaldehyde and a small amount of unreacted P-xylene. Example 6. P-xylene, p-toluic acid and water are placed in the autoclave in the amounts indicated in Example 2, while adding 3.75 mmol of cobalt naphthenate and manganese naphthenate. The oxidation was carried out with air under conditions of example 2, but at a temperature of 170 ° C. After 230 minutes, 74 liters of oxygen are absorbed. The reaction mixture is cooled, treated and analyzed as in Example 1. 98 g of terephthalic acid are obtained (255 g / h per 1 kg of P-xylene, 179 g of fl-toluic acid, 7 g of P-carboxybenzaldehyde to a small} {unreacted I-xy lol A. Example 7. Under the conditions of example 6, 13 successive operations were performed with recycling of catalysts and intermediate products as in example 3. Terephthalic acid is obtained as a white powder with an average yield of 87 mol.%. Analysis of the various fractions shows that the residue composed of carbon dioxide, slightly an amount of unrecycled p-toluene-aldehyde and a small amount of light acids. Example 8. In an autoclave, p xylene, P-toluic acid and water are placed in the amounts indicated in Example 2, as well as 3.9 moles of cobalt acetate and manganese acetate. air is carried out under the conditions of example 2, but at a temperature of 165 ° C. After 300 minutes the reaction absorbs 61 liters of oxygen and, as the analysis shows, the reaction mixture contains 91 g of terephthalic acid (182 g / h per 1 kg of p-xylene). Example 9. The process is carried out with stirring under the influence of an air stream at a flow rate of 300 l / h and a pressure of 20 kg / cm. 68 g of P-xylene, 120 g of P-toluic acid, 250 g of water, 2.5 mmol of naphtha are loaded. Nata cobalt and 10.0 mmol manganese naphthenate. The molar ratio of water: p-toluene acid is 15.6. The absorption of oxygen begins as soon as the temperature reaches 125 ° C. The temperature is maintained at 170 ° C. After 300 minutes of reaction, 43 liters of oxygen are absorbed. The reaction is stopped, the reaction mixture is cooled, processed and analyzed as in the example. 49 g of terephthalic acid (144 g / h per 1 kg of p-toluene), 139 g of P-toluic acid and 5 g of P-carboxylic bendehyde are obtained. Example 10. Process wire with stirring under the influence of air flow at a flow rate of 200 l / h and a pressure of 20 kg / cm. Load 155 g of P-xylene, 10 g of L-toluic acid, 50 g of water, 2.5 mmol of manganese naphtha and Cobalt naphthenate 2.5 mmol. P-Toluic acid: p-xylene and water: I-Toluic acid molar ratios are 0.05 and 38, respectively. Intensive oxygen absorption begins as soon as the temperature reaches 180 s. Oxygen absorption is 92 92 over 245 min at, after which the reaction is stopped. The reaction mass is cooled. According to the English version, the reaction mixture contains 96 g of terephthalic acid (152 g / h per 1 kg of P-xylene, 08 g of L-toluic acid and 5 g of carboxybenzaldehyde. Example 11. A 700 ml corrosion-resistant autoclave equipped with a mechanical mesh double heated a wall, condensate, gas inlet and outlet were charged, 9 g of p-xylene, 213.9 g of p-toluic acid, 27.5 g of water and 0.75 mmol (0.0035 mol per 1 l of organic substance) of manganese acetate. The molar ratio of p-toluyl acid: P-xylene is 87, the water: P-toluyl acid ratio is 0.97. p serves air at a pressure of 20 kg / cm 2 and the mixture is heated with stirring while maintaining an air flow rate of 90 l / h to 157 ° C. The reaction temperature is maintained at 170 ° C. by controlled cooling of the reaction mixture 300 minutes after the start of the reaction, oxygen absorption reaches 23.2 L and the reaction is interrupted, and the reaction mixture is cooled. The analysis shows that 95% of the introduced P-xylene and 29% of the introduced P-toluic acid are converted into the following products, g: Terephthalic acid 54.8 4-Carboxybenzaldehyde 5, 8 Decomposition products (co2 and lungs kitty lots) 12.1 Other products 6.7 The optical density is determined as follows. 1 g of terephthalic acid is dissolved in 25 ml of an aqueous solution obtained by dissolving concentrated ammonium hydroxide (density 0.880) in the same amount of distilled water. The optical density of the solution is determined in a chamber from 5 cm to 340, 380 and 400 microns. Optical density in Examples 1-10 is shown in the table.
    Continuation taol
    权利要求:
    Claims (2)
    [1]
    1. A method for producing terephthalic acid by liquid-phase oxidation of p-xylene and p-toluic acid with oxygen in the presence of a metal catalyst at a temperature of 165-185 ° C under a pressure sufficient to maintain the reaction mass in a liquid state, characterized by increasing the yield and quality of the target product / oxidation is carried out in the presence of water at molar ratios of P-toluic acid: L-xylene 0 / 05-87 and water: P-toluic acid 0 / 97-38 / and the salt is used as a catalyst or salt argantsa / or a mixture thereof in an amount of 0/0250, 075 mol per 1 liter of the organic compound.
    "
    five
    [2]
    2. Method POP.1, characterized in that naphthenate or acetate is used as the salt of manganese or cobalt.
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    同族专利:
    公开号 | 公开日
    PL120521B1|1982-03-31|
    PL201671A1|1979-04-09|
    IN146937B|1979-10-20|
    CS194694B2|1979-12-31|
    US4278810A|1981-07-14|
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    引用文献:
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    US3883584A|1971-11-25|1975-05-13|Teijin Ltd|Process for the preparation of terephthalic acid|IN152155B|1978-10-02|1983-11-05|Labofina Sa|
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    法律状态:
    优先权:
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