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    • 专利摘要:
    A method for oxidizing a dimethyl aromatic compound includes reacting the dimethyl aromatic compound and an oxidant in the presence of a catalyst and a co-catalyst in a solvent to produce a reaction product comprising an aromatic dicarboxylic acid. The catalyst comprises cobalt, manganese, and bromine. A weight ratio of cobalt to manganese is equal to or greater than 1:1. The co-catalyst comprises at least one of cerium or iron. The co-catalyst is present in an amount in a range of 10 ppm to 200 ppm, based on a total weight of the dimethyl aromatic compound and the solvent. The aromatic dicarboxylic acid is present in the reaction product in an amount equal to or greater than 70 wt.%, or equal to or greater than 90 wt.%, based on a total weight of solids in the reaction product.
    公开号:ES2848325A2
    申请号:ES202190038
    申请日:2019-12-18
    公开日:2021-08-06
    发明作者:Selvakumar Subramanian；Naveen K Sathu；Suman Kumar Jana；Debasish Das；Syed Azhar Hashmi；Prasanna Kumar Pathath
    申请人:SABIC Global Technologies BV；
    IPC主号:
    专利说明:

    [0003] CROSS REFERENCE TO THE RELATED APPLICATION
    [0004] The present international application claims priority to US Provisional Application No. 62 / 789,583, filed January 8, 2019, which is incorporated herein by reference.
    [0005] BACKGROUND
    [0006] Aromatic dicarboxylic acids (eg, terephthalic acid) can be produced by oxidation of aromatic dimethyl compounds (eg, para-xylene) in the presence of a catalyst. The reaction is normally carried out in the presence of a solvent, for example acetic acid. The oxidation of dimethyl aromatics to the corresponding dicarboxylic acids proceeds through several intermediate steps. The inefficient catalyst and / or the oxidation process leads to the formation of intermediate products as impurities in the product. Furthermore, the oxidation process carried out at high pressures and temperatures leads to the formation of COx due to the excessive oxidation of the end products (i.e. aromatic dicarboxylic acid) and also to the combustion of the solvent, for example acetic acid. . As a result of by-product formation and / or excessive oxidation, the consumption of dimethyl aromatics and solvent is undesirably increased.
    [0007] US Patent No. 5,453,538 discloses a process for the manufacture of aromatic dicarboxylic acids that uses a low bromine to metal ratio facilitated by the use of cerium in conjunction with the catalyst of cobalt and manganese.
    [0008] BRIEF DESCRIPTION OF THE DRAWINGS
    [0009] The following figures are exemplary embodiments where similar elements are similarly numbered.
    [0010] FIG. 1 is a process flow diagram of one embodiment of a para-xylene oxidation method to obtain terephthalic acid.
    [0011] FIG. 2A is a graphical illustration of the mole percent carbon monoxide and carbon dioxide (collectively "COx") formed as by-products, based on total moles of reaction product, in Comparative Example A and Example 1; and the percent reduction in moles of COx in Example 1 compared to Comparative Example A.
    [0012] FIG. 2B is a graphic illustration of mole percent COx formed as by-products, based on total moles of reaction product, in Comparative Example B and Example 2; and the percent reduction in moles of COx in Example 2 compared to Comparative Example B.
    [0013] FIG. 3 is a graphic illustration of percent by weight of C 10 + hydrocarbons formed as by-products, based on total weight of reaction product, in Comparative Examples AB and Examples 1-2; and the percentage reduction in the amount of C 10 + hydrocarbons in Comparative Examples B and Examples 1-2 compared with Comparative Example A.
    [0014] The above-described features and other features are exemplified by the following detailed description, examples, and claims. DETAILED DESCRIPTION
    [0015] It would be desirable to provide improved methods of oxidation of dimethyl aromatic compounds that selectively produce aromatic dicarboxylic acids, particularly methods that mitigate the aforementioned disadvantages. Accordingly, methods of oxidation of aromatic dimethyl compounds to obtain aromatic dicarboxylic acids are disclosed herein. Desirably, the methods reduce undesirable side reactions that consume the dimethyl aromatics and solvent to form by-products by oxidizing the dimethyl aromatics in the presence of a catalyst that includes cobalt and manganese in a weight ratio equal to or greater than 1: 1. and a cocatalyst including cerium. Previous methods of oxidation of aromatic dimethyl compounds suffered side reactions, such as oxidation of solvents or excessive oxidation of aromatic dimethyl compounds to form by-products, such as carbon monoxide, carbon dioxide, or C 10 + hydrocarbons ( (eg, intermediate or "heavy" products). These side reactions resulted in high consumption of the dimethyl aromatics and solvent. For example, the previous methods may consume about 0.010 mole% more of the dimethyl aromatics and about 0.016 mole% more solvent compared to the methods of the present disclosure.
    [0016] As used herein, the term "excessive oxidation" refers to the oxidation of terephthalic acid and acetic acid to COx.
    [0017] In the methods of the present disclosure, aromatic dimethyl compounds are oxidized in the presence of a catalyst including cobalt and manganese in a weight ratio equal to or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1, and a cocatalyst including cerium. Surprisingly, it was found that said catalyst and cocatalyst reduce the loss of reactant and solvent, increase selectivity for aromatic dicarboxylic acids, reduce the amount of at least one of carbon monoxide, carbon dioxide and C 10 + hydrocarbons in the product of reaction and increases the purity of aromatic dicarboxylic acids compared to previous methods of oxidation of aromatic dimethyl compounds without the presence of said catalyst and cocatalyst (for example, including a cobalt to manganese weight ratio of less than 1: 1 and without cerium cocatalyst).
    [0018] For example, the methods of the present disclosure can achieve at least one of: (i) a reduction in total moles of carbon dioxide and carbon monoxide formed equal to or greater than 5 % by mole, or equal to or greater than 10% in moles, preferably equal to or greater than 15% in moles, compared to the total moles of carbon monoxide and carbon dioxide present in a reaction product obtained from an oxidation method of a dimethyl aromatic compound without the presence of said catalyst and cocatalyst; (ii) a reduction in the amount of C 10 + hydrocarbons formed equal to or greater than 10 percent by weight (% by weight), or equal to or greater than 20% by weight, preferably equal to or greater than 30% by weight, in comparison with the total amount of C 10 + hydrocarbons present in a reaction product obtained from an oxidation method of a dimethyl aromatic compound without the presence of said catalyst and cocatalyst; and (iii) an increase in the moles of aromatic dicarboxylic acid produced equal to or greater than 0.5 % by moles, or equal to or greater than 1.0 % by moles, preferably equal to or greater than 1.5% by moles, compared to the moles of aromatic dicarboxylic acid present in a product of reaction obtained from the previous methods of oxidation of dimethyl aromatic compounds without the presence of said catalyst and cocatalyst.
    [0019] Furthermore, it was surprisingly found that the amount of catalyst could be reduced compared to the previous methods that do not use the catalyst and cocatalyst as described in the present disclosure. For example, the present methods allow the use of lower amounts of at least one manganese and bromine in the catalyst, while maintaining the moles of aromatic dicarboxylic acid produced per milligram of catalyst. A reduction in the amount of manganese present can be equal to or greater than 25% by weight, or equal to or greater than 50% by weight, or equal to or greater than 75% by weight, compared to the moles of manganese present in the methods. previous oxidation of dimethyl aromatic compounds without the presence of said catalyst and cocatalyst. Desirably, a reduction in the amount of bromine present can reduce, mitigate or prevent corrosion of the equipment used for oxidation or allow the use of different materials of construction for the equipment. A reduction in the amount of bromine present can be equal to or greater than 25% by weight, or equal to or greater than 50% by weight, or equal to or greater than 75% by weight, compared to the moles of bromine present in the methods. previous oxidation of dimethyl aromatic compounds without the presence of said catalyst and cocatalyst.
    [0020] As noted above, a method of oxidation of a dimethyl aromatic compound may include reacting the compound aromatic dimethyl and an oxidant in the presence of a catalyst and a cocatalyst in a solvent to produce a reaction product comprising an aromatic dicarboxylic acid.
    [0021] The aromatic dimethyl compound may include at least one of xylene (eg, at least one of para-xylene, meta-xylene and / or to-xylene) and 2,6-dimethylnaphthalene; preferably para-xylene.
    [0022] To catalyze the oxidation of the aromatic dimethyl compound, a catalyst is used. The catalyst can include cobalt, manganese, and bromine. The catalyst may be unsupported and sources of cobalt, manganese, and bromine may be combined to form the catalyst as a mixture of catalysts. The sources of cobalt and manganese used for the catalyst may include salts of cobalt (eg, cobalt (II) acetate tetrahydrate) and manganese (eg, manganese (II) acetate tetrahydrate), respectively. A source of bromine can be hydrobromic acid, sodium bromide, ammonium bromide, tetrabromoethane, or a combination comprising at least one of the above. Other sources of catalyst can include metal bromides (eg, MnBr 2 , CoBr 2 , etc.) and salts of metal nitrate. Desirably, the bromine can be at least one of a solid or dissolved in the solvent.
    [0023] Desirably, the catalyst may include a cobalt to manganese weight ratio equal to or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1. A total amount of cobalt and manganese can be equal to or less than 1,000 parts per million by weight (ppm), or equal to or less than 900 ppm, preferably equal to or less than 800 ppm, based on the total weight of the reactant mixture that includes aromatics from dimethyl, acetic acid, and water.
    [0024] Bromine may be present in an amount equal to or less than 800 ppm, or equal to or less than 400 ppm, preferably equal to or less than 200 ppm, based on the total weight of the reactant mixture including dimethyl aromatics, acetic acid and Water. The catalyst may include a molar ratio between bromine and (cobalt and manganese) in a range of 0.3: 1 to 3: 1, or 0.3: 1 to 2: 1, preferably 0.3: 1 to 1: 1 .
    [0025] Desirably, in various embodiments, during the reaction, a reaction mixture (eg, comprising the aromatic dimethyl compound, oxidant, catalyst, cocatalyst, and solvent) is substantially free of ammonium acetate, meta-xylene, and ionic liquid comprising at least one of a bromide anion or an iodide anion; substantially free of ammonium acetate, meta-xylene, and ionic liquid comprising a bromide anion. As used herein, the term "substantially free of" allows for the presence of impurities in the aromatic dimethyl compound, oxidant, catalyst, cocatalyst, and solvent. In other words, during the reaction, no ammonium acetate, meta- xylene, or ionic liquid that includes at least one of a bromide anion and an iodide anion is present, in addition to trace impurities. They are not deliberately added compounds.
    [0026] In addition to the catalyst, the method uses a cocatalyst. Desirably, the cocatalyst includes cerium. Cerium may be present in an amount ranging from 10 ppm to 200 ppm, or 20 ppm to 190 ppm, preferably 30 ppm to 180 ppm, based on the total weight of the aromatic dimethyl compound and solvent.
    [0027] The solvent may include at least one of: water, a C 1 -C 7 aliphatic carboxylic acid, an aromatic acid, and supercritical CO 2 , preferably acetic acid. The solvent can be an aqueous solution. Desirably, a weight ratio of solvent to dimethyl aromatic may be in a range of 15: 1 to 1: 1, or 10: 1 to 1: 1, preferably 5: 1 to 1: 1.
    [0028] To oxidize the aromatic dimethyl compound, the method uses an oxidant. The oxidant may include hydrogen peroxide, dioxygen, ozone, an anthraquinone, a C 2-32 alkyl peroxide, a C 2- alkyl hydroperoxide
    [0029] 32 a C 2-32 ketone peroxide, a diacyl peroxide C 2-32, C 3-22 diperoxy one, a ketal, one peroxyester C 2-32, C 2-32 peroxydicarbonate one, a peroxyacid C 2-32 , a C 6-32 perbenzoic acid, a C 2-32 peracid, a periodinane, a periodate, or a combination comprising at least one of the above, preferably dioxygen (eg, in air).
    [0030] Desirably, the reaction of the aromatic dimethyl compound and the oxidant can be at a temperature in a range of 170 ° C to 200 ° C, or 180 ° C to 200 ° C, or 190 ° C to 200 ° C.
    [0031] The reaction of the aromatic dimethyl compound and the oxidant can be at a pressure in a range of 1 MegaPascal (mPa) to 1.8 mPa, or 1 mPa to 1.7 mPa, preferably 1 mPa to 1.6 mPa.
    [0032] A residence time of the reaction of the dimethyl aromatic compound and the oxidant in a reactor may be in a range of 20 minutes to 200 minutes, or 40 minutes to 150 minutes, preferably 60 minutes to 100 minutes.
    [0033] The reaction of the aromatic dimethyl compound can be carried out in any reactor capable of operating under the conditions described in The present disclosure, such as a batch reactor, a continuous reactor, or a semi-continuous one. The reactor may include an inlet for feeding at least one of the aromatic dimethyl compound, the solvent, the catalyst and the cocatalyst continuously over a period of time and an outlet for removing the reaction product continuously over a period of time or at specific time (s). Desirably, the reaction of the dimethyl aromatic compound and the oxidant can be in a continuous stirred tank reactor.
    [0034] The aromatic dicarboxylic acid can be present in the reaction product in an amount equal to or greater than 70 % by weight, or equal to or greater than 90% by weight, preferably equal to or greater than 92% by weight, more preferably equal to or greater than 94% by weight, based on the total weight of solids in the reaction product, for example, measured by high pressure liquid chromatography (HPLC) at room temperature.
    [0035] Desirably, the present methods result in C 10 + hydrocarbons which are present in the reaction product in an amount equal to or less than 1.5% by weight, or equal to or less than 1.0% by weight, preferably equal to or less 0.5% by weight, based on the total weight of solids in the reaction product, for example, measured by HPLC at room temperature. The catalyst and cocatalyst as described in the present disclosure can help prevent the formation of C 10 + hydrocarbons. As used herein, "hydrocarbon C 10 +" refers to a hydrocarbon including 10 or more carbon atoms. It may be present any number of hydrocarbon C 10 + in a reaction product, such as the least five hydrocarbons C 10+ different, or less fifteen different C 10 + hydrocarbons, or at least twenty different C 10 + hydrocarbons.
    [0036] The method may further include removing the solvent, catalyst, and cocatalyst from the reaction product, and recycling the solvent, catalyst, and cocatalyst to the dimethyl aromatic compound reaction step. For example, the separation step may include crystallization of the aromatic dicarboxylic acid to obtain an aromatic dicarboxylic acid crystal. The aromatic dicarboxylic acid crystal can then be separated from the solvent, the catalyst, and the cocatalyst. For example, the catalyst and cocatalyst can be in solution in the solvent and the separation can be by filtration or any other solid-liquid separation method. The aromatic dicarboxylic acid crystallization stage can be in at least one stage, or at least two stages, preferably at least three stages.
    [0037] The method may further include the reaction of the reaction product and hydrogen in the presence of a hydrogenation catalyst. For example, the method may include reacting the aromatic dicarboxylic acid crystals and hydrogen in the presence of a hydrogenation catalyst to purify the aromatic dicarboxylic acid crystals. The hydrogenation catalyst can include palladium, ruthenium, rhodium, osmium, iridium, platinum, or a combination comprising at least one of the above. The hydrogenation catalyst can be on a support, such as silicon dioxide, diatomaceous earth, titanium dioxide, carbon, thorium oxide, zirconium oxide, silicic carbide, aluminum oxides, or a combination comprising at least one of the above. Desirably, the hydrogenation catalyst it can be palladium on a carbon support. Thus, the purity of the aromatic dicarboxylic acid crystals and the yield of the aromatic dicarboxylic acid can be improved.
    [0038] A reaction mixture for the oxidation of a dimethyl aromatic compound by the above-described methods may include the dimethyl aromatic compound, the oxidant, the catalyst, the cocatalyst, water, and the solvent.
    [0039] A reaction product can be produced by the methods described above, or by using the reaction mixture described above.
    [0040] A more complete understanding of the components, processes, and apparatus disclosed herein can be obtained by reference to the accompanying drawings. These figures (also referred to herein as "FIG.") Are merely schematic representations based on convenience and ease of demonstrating the present disclosure and, therefore, are not intended to indicate relative size or dimensions of the devices or components of the devices. themselves and / or define or limit the scope of exemplary embodiments. Although specific terms are used in the following description for the sake of clarity, these terms are only intended to refer to the particular structure of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it should be understood that similar numerical designations refer to components of similar function.
    [0041] As illustrated in FIG. 1, a terephthalic acid production facility may include a reactor 10. The reaction mixture 6 which includes Para-xylene, solvent, catalyst and cocatalyst can be fed into reactor 10. An oxidant 8 can also be fed into reactor 10. After the reaction of the para-xylene and oxidant 8, the product of reaction 12 that includes terephthalic acid. The reaction product 12 can be fed into the first crystallizer 20 to produce the first crystallizer stream 22. The first crystallizer stream 22 can be fed into the second crystallizer 30 to produce the second crystallizer stream 32. The second crystallizer stream 32 can be feeding into the third crystallizer 40 to produce the third crystallized stream 42 which includes crystallized terephthalic acid. The solvent, catalyst, and cocatalyst stream 44 can be separated from the third crystallized stream 42 and recirculated to reaction mixture 6.
    [0042] The present disclosure is further illustrated by the following examples, which are not limiting.
    [0043] EXAMPLES
    [0044] The following components listed in Table 1 were used in the examples. Unless specifically indicated otherwise, the amount of each component is in percent by weight in the following examples, based on l l l m i i n.
    [0049] Examples 1-2 and Comparative Examples A-B
    [0050] In Examples 1-2 and Comparative Examples A-B, para-xylene was oxidized in the presence of different catalyst and cocatalyst compositions in acetic acid. The oxidation reactions were carried out in a semi-continuous flow stirred tank reactor in the presence of air. In Examples 1-2 cerium was used in an amount of 50 ppm, based on the total weight of para-xylene, water, and acetic acid. Cerium cocatalyst was not used in Comparative Examples A-B. In Example 2 and Comparative Example B a smaller amount of catalyst was included than in Example 1 and Comparative Example A. The amounts of catalyst, cocatalyst and solvent used are summarized in Table 2, the weight ratio between solvent and para-xylene and the reaction conditions in the examples ymlmr iv.
    [0052]
    [0053] As shown in FIG. 2A, a reduction in the total amount of carbon monoxide and carbon dioxide (COx) produced of about 10% by mole was observed in Example 1 compared to Comparative Example A. As shown in FIG. 2B, a reduction in the total amount of carbon monoxide and carbon dioxide (COx) produced of about 8 mol% was observed in Example 2 compared to Comparative Example B. Thus, the catalyst and cerium reduced the oxidation of solvent and terephthalic acid product to carbon monoxide and carbon dioxide. Therefore, the presence of the catalyst and cerium during the oxidation reaction did not significantly affect the selectivity for terephthalic acid, which can be measured by high pressure liquid chromatography (HPLC) and is calculated based only on the solid products, i.e. , non-gaseous products. For example, the methods of the present disclosure can achieve a terephthalic acid purity of about 96.5% by weight.
    [0054] As shown in Fig. 3, a reduction in the amount of catalyst and the use of cocatalyst reduced the formation of C 10 + hydrocarbons. This decrease in the production of C 10 + hydrocarbons reduces the specific consumption of para-xylene.
    [0055] In Examples 3-27, para-xylene was oxidized in the presence of different catalyst and cocatalyst compositions in acetic acid. The oxidation reactions were carried out in a semi-continuous flow stirred tank reactor in the presence of air. The amounts of the metals in the catalyst were based on the total weight of para-xylene, water, and acetic acid. The reaction for Examples 3-10 was carried out at a temperature of 170 ° C, and for Examples 11-26 it was carried out at 190 ° C. All examples were carried out at a pressure of 1.3 mPa.
    [0056] The composition of Co and Mn was tested at two levels Co: Mn of 400: 400 and Co: Mn of 300: 100, but the Br ranged from 166 to 730 ppm. The results show the yield of the cocatalyst compared to the yield of the reaction without a cocatalyst (nothing).
    [0057] Initial experiments are carried out at the temperature of 170 ° C using 50 ppm each of Zr, Pd, Mo, Ce or Ag as a cocatalyst in the p-xylene oxidation process. The results showed a decrease in the amount of COx formation with the use of Ce as a cocatalyst. Among all the metals, Zr presented the least amount of 4-CBA, but has presented the highest amount of COx. 4-CBA, which is an unwanted impurity, is about 4 % by weight for reactions carried out at 170 ° C. A lower amount of 4-CBA was found to be produced for reactions performed at 190 ° C. Therefore, higher reaction temperatures are beneficial in reducing 4-CBA production.
    [0058] As reported in Table 3, 50 ppm of Fe, Ag, Ce and Cu were tested as joint metals along with Co-Mn-Br at 190 ° C. Among the different metals studied, the experiment carried out using copper as a cocatalyst showed incomplete oxidation, that is, the product distribution analysis shows more intermediate products, such as p-toluic acid and 4-CBA, than the desired final product, the terephthalic acid (TPA).
    [0059] Fe and Ce are found to be promising candidates as a cocatalyst for p-xylene oxidation in terms of reduced COx formation, particularly at a reaction temperature of 190 ° C. When use these materials as a cocatalyst:
    [0060] • Fe presented reduced COx and heavy formation, but 4-CBA formation is higher.
    [0061] • The Ce presented reduced formation of COx and 4-CBA, but the formation of heavy ones is higher.
    [0062] The function of the cocatalyst was evaluated at reduced amounts of Co, Mn and Br using Fe, Ce, Zr and Ru. The combination of Fe + Ce and Fe + Zr was also studied in the distribution of oxidation products of p-xylene, in reduced amounts of Co-Mn-Br of 300-100-332, respectively. All the results showed that the presence of Fe and Ce was able to reduce the formation of COx and heavy. The formation of 4-CBA is reduced with the use of Zr as a cocatalyst, but the formation of COx and heavy was higher.
    [0063]
    [0064]
    [0065]
    [0066] Therefore, the presence of small amounts of cocatalysts in the Co-Mn-Br catalyst presented wide ranges of yields. The improvement of specific consumption and the reduction of impurities by the incorporation of the cocatalyst in the Co-Mn-Br catalytic system for the oxidation of para-xylene is clearly shown. This study also shows that the reaction temperature has more influence on the quality of TPA and on the formation of heavy. Cu as a cocatalyst showed an inhibitory function in the para-xylene formation process. Among the various cocatalysts tested, Fe and Ce showed promising performance, increasing product quality.
    [0067] As shown in the examples, the present methods using a catalyst that includes cobalt and manganese in a weight ratio equal to or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1, and a cocatalyst including cerium can reduce the amount of reactant and solvent used, increase selectivity for aromatic dicarboxylic acids, reduce the amount of at least one carbon monoxide, carbon dioxide, and C 10 + hydrocarbons in the reaction product, and increase the purity of aromatic dicarboxylic acids compared to previous methods of oxidation of aromatic dimethyl compounds without the presence of said catalyst and cocatalyst. In addition, the amount of catalyst, preferably the amount of bromine, can be reduced compared to said previous methods.
    [0068] The present disclosure further encompasses the following aspects.
    [0069] Aspect 1. A method of oxidation of a dimethyl aromatic compound comprising: reacting the dimethyl aromatic compound and an oxidant in the presence of a catalyst and a cocatalyst in a solvent to produce a reaction product comprising an aromatic dicarboxylic acid, wherein the catalyst comprises cobalt, manganese, and bromine, and wherein a weight ratio of cobalt to manganese is equal. or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1, and wherein the cocatalyst comprises at least one of cerium or iron, preferably comprises cerium, and wherein the cocatalyst is present in an amount in a range of 10 ppm to 200 ppm, or 20 ppm to 190 ppm, preferably 30 ppm to 180 ppm, based on the total weight of the aromatic dimethyl compound and solvent, and wherein the aromatic dicarboxylic acid is present in the reaction product in an amount equal to or greater than 70 % by weight, or equal to or greater than 90 % by weight, preferably equal to or greater than 92% by weight, more preferably equal to or greater than 94% by weight, based on the weight total solids in the reaction product.
    [0070] Aspect 2. The method of aspect 1, wherein the aromatic dimethyl compound comprises para-xylene, meta-xylene, ortho-xylene, 2,6-dimethylnaphthalene, or a combination comprising at least one of the foregoing, preferably para- xylene.
    [0071] Aspect 3. The method of any one or more of the preceding aspects, wherein a total amount of cobalt and manganese is equal to or less than 1,000 ppm, or equal to or less than 900 ppm, preferably equal to or less than 800 ppm, based on the total weight of aromatic dimethyl compound and solvent.
    [0072] Aspect 4. The method of any one or more of the preceding aspects, wherein the bromine is present in an equal or less amount at 800 ppm, or equal to or less than 600 ppm, preferably equal to or less than 400 ppm, based on the total weight of aromatic dimethyl compound and solvent.
    [0073] Aspect 5. The method of any one or more of the preceding aspects, wherein the bromine comprises hydrobromic acid.
    [0074] Aspect 6. The method of any one or more of the preceding aspects, wherein the total moles of carbon monoxide and carbon dioxide present in the reaction product are reduced by equal to or greater than 5% by moles, or equal to or greater at 10% by moles, preferably equal to or greater than 15 % by moles, compared to the total moles of carbon monoxide and carbon dioxide present in a reaction product obtained from an oxidation method of a dimethyl aromatic compound without the presence of the catalyst and the cocatalyst.
    [0075] Aspect 7. The method of any one or more of the preceding aspects, wherein C 10+ hydrocarbons are present in the reaction product in an amount equal to or less than 1.5% by weight, or equal to or less than 1.0 % by weight, preferably equal to or less than 0.5% by weight, based on the total weight of solids in the reaction product.
    [0076] Aspect 8. The method of any one or more of the preceding aspects, wherein the oxidant comprises air.
    [0077] Aspect 9. The method of any one or more of the preceding aspects, wherein the solvent comprises at least one of water and a C 1 -C 7 aliphatic carboxylic acid, preferably acetic acid.
    [0078] Aspect 10. The method of any one or more of the preceding aspects, wherein the weight ratio of solvent to compound Dimethyl aromatic is in a range of 15: 1 to 1: 1, or 10: 1 to 1: 1, preferably 5: 1 to 1: 1.
    [0079] Aspect 11. The method of any one or more of the preceding aspects, wherein a molar ratio of bromine to cobalt and manganese is in a range of 0.3: 1 to 3: 1, or 0.3: 1 to 2: 1, preferably 0.3: 1 to 1: 1.
    [0080] Aspect 12. The method of any one or more of the foregoing aspects, wherein the reaction is at a temperature in a range of 170 ° C to 200 ° C, or 180 ° C to 200 ° C, preferably 190 ° C to 200 ° C.
    [0081] Aspect 13. The method of any one or more of the preceding aspects, wherein the reaction is at a pressure in the range of 1 MegaPascal to 1.8 MegaPascals, or 1 MegaPascal to 1.7 MegaPascals, preferably 1 MegaPascal to 1, 6 MegaPascales.
    [0082] Aspect 14. The method of any one or more of the preceding aspects, wherein the reaction is a continuous stirred tank reactor and a residence time is in a range of 20 minutes to 200 minutes, or 40 minutes to 150 minutes, preferably 60 minutes to 100 minutes.
    [0083] Aspect 15. The method of any one or more of the preceding aspects, wherein during the reaction, a reaction mixture comprising the aromatic dimethyl compound, the oxidant, the catalyst, the cocatalyst, and the solvent is substantially free of acetate. ammonium, meta-xylene and ionic liquid comprising at least one of a bromide anion or an iodide anion; preferably the reaction mixture is substantially free of ammonium acetate, meta-xylene and ionic liquid comprising a bromide anion; more preferably, without ammonium acetate, meta-xylene and ionic liquid comprising a bromide anion.
    [0084] Aspect 16. The method of any one or more of the preceding aspects, further comprising crystallizing the reaction product.
    [0085] Aspect 17. The method of any one or more of the preceding aspects, further comprising removing the solvent, catalyst, and cocatalyst from the reaction product, and recirculating the solvent, catalyst, and cocatalyst to the reaction step.
    [0086] Aspect 18. The method of any one or more of the preceding aspects, further comprising reacting the aromatic dimethyl compound and hydrogen in the presence of a hydrogenation catalyst.
    [0087] Aspect 19. The method of any one or more of the preceding aspects, wherein the reaction mixture (comprising the aromatic dimethyl compound, oxidant, catalyst, cocatalyst, and solvent) comprises a total amount of cobalt and manganese equal to or less than 1,000 ppm, preferably equal to or less than 900 ppm, more preferably equal to or less than 800 ppm, based on the total weight of the reactant mixture.
    [0088] Aspect 20. The method of any one or more of the preceding aspects, wherein the catalyst comprises a molar ratio between bromine and (cobalt and manganese) in a range of 0.3: 1 to 3: 1, preferably 0.3: 1 to 2: 1, more preferably 0.3: 1 to 1: 1.
    [0089] Aspect 21. The method of any one or more of the preceding aspects, wherein the catalyst is free of Cu.
    [0090] Aspect 22. A reaction mixture for the oxidation of dimethyl aromatic compound by the method of any one or more of the preceding aspects, wherein the reaction mixture comprises: the compound dimethyl aromatic; the oxidant; the catalyst; the cocatalyst; and the solvent.
    [0091] Aspect 23. A reaction product produced by the method of any one or more of aspects 1-21, or using the reaction mixture of aspect 22.
    [0092] Aspect 24. A catalyst system for the oxidation of a dimethyl aromatic compound, the catalyst system comprising: a catalyst comprising cobalt, manganese and bromine, wherein a weight ratio between cobalt and manganese is equal to or greater than 1: 1 , or equal to or greater than 2: 1, preferably equal to or greater than 3: 1; and a cocatalyst comprising at least one of cerium or iron, preferably comprising cerium.
    [0093] Aspect 25. A reaction mixture for the oxidation of a dimethyl aromatic compound, the reaction mixture comprising: the catalyst system of aspect 24; the aromatic dimethyl compound; an oxidant; and a solvent, wherein the cocatalyst is present in an amount ranging from 10 ppm to 200 ppm, or 20 ppm to 190 ppm, preferably 30 ppm to 180 ppm, based on the total weight of the aromatic dimethyl compound and solvent, wherein a total amount of cobalt and manganese is equal to or less than 1,000 ppm, or equal to or less than 900 ppm, preferably equal to or less than 800 ppm, based on the total weight of the aromatic dimethyl compound and solvent, where the bromine is present in an amount equal to or less than 800 ppm, or equal to or less than 600 ppm, preferably equal to or less than 400 ppm, based on the total weight of aromatic dimethyl compound and solvent, and wherein a molar ratio between bromine and Cobalt and manganese is in a range of 0.3: 1 to 3: 1, or 0.3: 1 to 2: 1, preferably 0.3: 1 to 1: 1.
    [0094] Compositions, methods, and articles may alternatively comprise, consist of, or consist essentially of any appropriate step or component disclosed herein. The compositions, methods, and articles may be formulated in addition, or alternatively, so that they lack, or are substantially free, of any step, component, material, ingredient, adjuvant, or species that is not otherwise necessary for the achievement of the function or objectives of the compositions, methods and articles.
    [0095] The singular forms "a", "an", "the" and "the" include plural referents, unless the context clearly indicates otherwise. "Or" means "and / or", unless the context clearly indicates otherwise. The terms "first," "second," and the like, "primary," "secondary," and the like, as used herein, do not indicate any order, quantity, or importance, but are used to distinguish one item from another.
    [0096] The end points of all ranges referring to the same component or property are inclusive and independently combinable (for example, ranges of "less than or equal to 25 % by weight, or 5 % by weight to 20% by weight" include the end points and all intermediate values in the ranges of "5% by weight to 25% by weight," etc.). Disclosure of a narrower range or more specific group, in addition to a broader range, is not a waiver of the broader range or larger group.
    [0097] The suffix "(s)" is intended to include both the singular and plural of the term it modifies, thus including at least one of that term (eg, the colorant (s) include at least one colorant). "Optional ”Or“ optionally ”means that the event or circumstance described below may or may it cannot occur, and that the description includes cases where the event occurs and cases where it does not. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this disclosure belongs. A "combination" includes mixtures, alloys, reaction products, and the like.
    [0098] Although typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be construed as limiting the scope herein. Accordingly, various modifications, adaptations, and alternatives may occur to one of ordinary skill in the art without departing from the spirit and scope herein.
    权利要求:
    Claims (20)
    [1]
    1. A method of oxidation of a dimethyl aromatic compound comprising:
    reacting the aromatic dimethyl compound and an oxidant in the presence of a catalyst and a cocatalyst in a solvent to produce a reaction product comprising an aromatic dicarboxylic acid, wherein the catalyst comprises cobalt, manganese, and bromine, and wherein a ratio weight between cobalt and manganese is equal to or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1, and wherein the cocatalyst comprises at least one of cerium or iron, preferably it comprises cerium, and
    wherein the cocatalyst is present in an amount ranging from 10ppm to 200ppm, or 20ppm to 190ppm, preferably 30ppm to 180ppm, based on the total weight of the aromatic dimethyl compound and solvent, and
    preferably wherein the aromatic dicarboxylic acid is present in the reaction product in an amount equal to or greater than 70 % by weight, or equal to or greater than 90% by weight, preferably equal to or greater than 92% by weight, more preferably equal to or greater than 94% by weight, based on the total weight of solids in the reaction product.
    [2]
    The method of claim 1, wherein the aromatic dimethyl compound comprises para-xylene, meta-xylene, ortho-xylene, 2,6-dimethylnaphthalene, or a combination comprising at least one of the foregoing, preferably para-xylene.
    [3]
    3. The method of any one or more of the preceding claims, wherein a total amount of cobalt and manganese is equal to or less than 1,000 ppm, or equal to or less than 900 ppm, preferably equal to or less than 800 ppm, based on the total weight of aromatic dimethyl compound and solvent; and / or where the bromine is present in an amount equal to or less than 800 ppm, or equal to or less than 600 ppm, preferably equal to or less than 400 ppm, based on the total weight of the aromatic dimethyl compound and solvent.
    [4]
    4. The method of any one or more of the preceding claims, wherein the cocatalyst comprises cerium, preferably wherein the cocatalyst is cerium.
    [5]
    5. The method of any one or more of the preceding claims, wherein the bromine comprises hydrobromic acid.
    [6]
    6. The method of any one or more of the preceding claims, wherein the total moles of carbon monoxide and carbon dioxide present in the reaction product are reduced by equal to or greater than 5 % by moles, or equal to or greater than 10% by moles, preferably equal to or greater than 15% by moles, compared to the total moles of carbon monoxide and carbon dioxide present in a reaction product obtained from an oxidation method of an aromatic dimethyl compound without the presence of the catalyst and the cocatalyst.
    [7]
    7. The method of any one or more of the preceding claims, wherein the C 10 + hydrocarbons are present in the reaction product in an amount equal to or less than 1.5 % by weight, or equal to or less than 1.0 % by weight, preferably equal to or less than 0.5% by weight, based on the total weight of solids in the reaction product.
    [8]
    8. The method of any one or more of the preceding claims, wherein the catalyst is free of copper.
    [9]
    The method of any one or more of the preceding claims, wherein the solvent comprises at least one of water and a C 1 -C 7 aliphatic carboxylic acid, preferably acetic acid.
    [10]
    The method of any one or more of the preceding claims, wherein the weight ratio of solvent to aromatic dimethyl compound is in a range of 15: 1 to 1: 1, or 10: 1 to 1: 1, preferably 5 : 1 to 1: 1.
    [11]
    The method of any one or more of the preceding claims, wherein a molar ratio of bromine to cobalt and manganese is in a range of 0.3: 1 to 3: 1, or 0.3: 1 to 2: 1 , preferably 0.3: 1 to 1: 1.
    [12]
    12. The method of any one or more of the preceding claims, wherein the reaction is at a temperature in a range of 170 ° C to 200 ° C, 0 180 ° C to 200 ° C, preferably 190 ° C to 200 ° C.
    [13]
    The method of any one or more of the preceding claims, wherein the reaction is at a pressure in a range of 1 MegaPascal to 1.8 MegaPascal, or 1 MegaPascal to 1.7 MegaPascal, preferably 1 MegaPascal to 1.6 MegaPascales.
    [14]
    The method of any one or more of the preceding claims, wherein the reaction is in a continuous stirred tank reactor and a residence time is in a range of 20 minutes to 200 minutes, or 40 minutes to 150 minutes, preferably 60 minutes to 100 minutes.
    [15]
    The method of any one or more of the preceding claims, wherein during the reaction, a reaction mixture comprising the aromatic dimethyl compound, the oxidant, the catalyst, the cocatalyst, and the solvent is substantially free of ammonium acetate. , meta-xylene and ionic liquid comprising a bromide anion and an iodide anion.
    [16]
    16. The method of any one or more of the preceding claims, further comprising crystallizing the reaction product.
    [17]
    17. The method of any one or more of the preceding claims, further comprising removing the solvent, the catalyst, and the cocatalyst from the reaction product, and recirculating the solvent, the catalyst and cocatalyst to the reaction stage.
    [18]
    18. The method of any one or more of the preceding claims, further comprising reacting the aromatic dimethyl compound and hydrogen in the presence of a hydrogenation catalyst.
    [19]
    19. A catalyst system for the oxidation of a dimethyl aromatic compound, the catalyst system comprising:
    a catalyst comprising cobalt, manganese and bromine, wherein a weight ratio between cobalt and manganese is equal to or greater than 1: 1, or equal to or greater than 2: 1, preferably equal to or greater than 3: 1; and
    a cocatalyst comprising at least one of cerium or iron, preferably comprising cerium.
    [20]
    20. A reaction mixture for the oxidation of a dimethyl aromatic compound, the reaction mixture comprising:
    the catalyst system of claim 19;
    the aromatic dimethyl compound;
    an oxidant; and
    a solvent;
    wherein the cocatalyst is present in an amount ranging from 10ppm to 200ppm, or 20ppm to 190ppm, preferably 30ppm to 180ppm, based on the total weight of the aromatic dimethyl compound and solvent;
    where a total amount of cobalt and manganese is equal to or less than 1,000 ppm, or equal to or less than 900 ppm, preferably equal to or less than 800 ppm, based on the total weight of aromatic dimethyl compound and solvent;
    wherein the bromine is present in an amount equal to or less than 800 ppm, or equal to or less than 600 ppm, preferably equal to or less than 400 ppm, based on the total weight of aromatic dimethyl compound and solvent; and
    wherein a molar ratio of bromine to cobalt and manganese is in a range of 0.3: 1 to 3: 1, or 0.3: 1 to 2: 1, preferably 0.3: 1 to 1: 1.
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    同族专利:
    公开号 | 公开日
    WO2020144517A1|2020-07-16|
    CN113286654A|2021-08-20|
    JP2022516354A|2022-02-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5453538A|1994-02-14|1995-09-26|Amoco Corporation|Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio|
    US9212121B2|2013-09-24|2015-12-15|Eastman Chemical Company|Processes for producing terephthalic acid|WO2021255671A1|2020-06-16|2021-12-23|Sabic Global Technologies B.V.|Method for producing aromatic dicarboxylic acid using iron co‑catalyst|
    法律状态:
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    US201962789583P| true| 2019-01-08|2019-01-08|
    PCT/IB2019/061047|WO2020144517A1|2019-01-08|2019-12-18|Method for producing dicarboxylic acid using cerium co-catalyst|
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