CN111068790B - Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof - Google Patents
Catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing 2,6-naphthalene dicarboxylic acid, which mainly solves the problem of lower activity and selectivity of the catalyst for synthesizing 2,6-naphthalene dicarboxylic acid in the prior art, and comprises a main catalyst and a cocatalyst, wherein the main catalyst comprises Co, mn and at least one selected from the group consisting of IIA metal elements and IVA metal elements; the cocatalyst adopts a technical scheme of bromide, better solves the technical problem, and can be used in the industrial production of polyethylene 2, 6-naphthalate.
Description
Technical Field
The present invention relates to a catalyst for synthesizing 2,6-naphthalene dicarboxylic acid and a method for synthesizing 2,6-naphthalene dicarboxylic acid.
Background
2,6-naphthalene dicarboxylic acid (2, 6-NDA) is known as a novel functional material in the 21 st century, and is an important monomer for synthesizing high-performance plastics and liquid crystal polyester resins. In recent years, due to the excellent properties of polyethylene 2, 6-naphthalate (PEN), the use of polyethylene terephthalate (PET) instead of it has been a trend. The synthesis of 2,6-NDA becomes the bottleneck and key of PEN production, and how to research and develop industrially feasible 2,6-NDA synthesis process route is favored by domestic and foreign scientific research units.
Examples of the method for synthesizing 2,6-NDA include Henke method, oxidation method and carbonyl transfer method. The Henke process is similar to the process for preparing terephthalic acid by synthesis of 2,6-NDA, and mainly includes both disproportionation and isomerization. Naphthalene carboxylation or beta-methylnaphthalene direct oxidation is adopted in the disproportionation method to obtain naphthoic acid, then the naphthoic acid reacts with potassium hydroxide to obtain potassium salt, and then the Henkel method is adopted to prepare 2,6-NDA. The isomerization method is to extract or alkylate naphthalene (methylnaphthalene) to obtain disubstituted naphthalene, oxidize the disubstituted naphthalene into naphthalene dicarboxylic acid, and isomerize potassium naphthalene diacid into 2,6-NDA by a Henkel method.
The carbonyl transfer method mainly uses diiodonaphthalene as a raw material, and carries out carbonylation reaction in an acetic acid environment to obtain 2,6-NDA. U.S. Pat. No. 3,3779 (titled: carbonylation processfor production of aromatic) discloses that a mixture of 2, 6-diiodonaphthalene and 2, 7-diiodonaphthalene is used as a starting material, a mixture of naphthalene dicarboxylic acids is obtained by carbonylation with Rh-containing material as a catalyst in the presence of acetic acid as a solvent, and the 2,6-NDA is separated from the naphthalene dicarboxylic acid isomers by crystallization.
The 2, 6-dialkyl naphthalene liquid phase oxidation method is gradually the key point of research and development at home and abroad because of the milder reaction conditions and relatively simple process route. The oxidation method mainly prepares 2,6-NDA by 2, 6-dialkyl naphthalene oxidation, adopts a Co-Mn-Br catalyst system, takes acetic acid as a solvent, and has the reaction temperature of about 200 ℃ and the reaction pressure of about 3MPa. The 2, 6-dialkylnaphthalene oxidation process includes 2, 6-dimethylnaphthalene oxidation process, 2, 6-isopropylnaphthalene oxidation process, 2, 6-alkylacylnaphthalene oxidation process and 2, 6-diethylnaphthalene oxidation process. In the different 2, 6-dialkyl naphthalene liquid-phase oxidation methods, the separation is difficult and the operation cost is high because the physical and chemical properties of the 2, 6-dimethylnaphthalene and the 2, 7-dimethylnaphthalene are similar (such as the melting point and the boiling point differ less); and 2,6-diisopropyl naphthalene (2, 6-DIPN) is easy to separate and purify from raw materials (isomer mixture), and the operation cost is lower. Therefore, 2,6-diisopropylnaphthalene oxidation may be a very competitive process route in the long run. The liquid phase oxidation of 2,6-diisopropylnaphthalene to 2,6-NDA was earlier studied in japan and the united states, focusing mainly on 3 aspects: (1) the proportion of the Co-Mn-Br main catalyst system and the reaction conditions; (2) a cocatalyst system; (3) a reaction solvent system. Guo Xia et al, in Liquid phase catalytic oxidation of.6-diisopropylnaphthalene to.2.6-naphthalenedicarboxyIic acid over Co-Mn-B catalyst, teach that at a temperature of 185℃and a pressure of 2.0MPa, a mass ratio of Co-Mn to Br of 5:1, a mass ratio of Co-Mn to 2,6-DIPN of 15:1, a mass ratio of 2,6-DIPN to HOAc of 1:80 gives a pale yellow product with a 2,6-NDA yield of 62.9%.
The method has the problems of low yield and low selectivity of the 2,6-NDA in the process of preparing the 2,6-NDA.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low yield and low selectivity of 2,6-naphthalene dicarboxylic acid, and the catalyst for synthesizing 2,6-naphthalene dicarboxylic acid is provided, and has the characteristics of high yield of 2,6-naphthalene dicarboxylic acid and high selectivity of 2,6-naphthalene dicarboxylic acid.
The second technical problem to be solved by the invention is a method for synthesizing 2,6-naphthalene dicarboxylic acid by adopting the catalyst in one of the technical problems.
In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows:
a catalyst for 2,6-naphthalene dicarboxylic acid synthesis, the catalyst comprising a main catalyst, a cocatalyst, the main catalyst comprising Co, mn and at least one selected from the group consisting of IIA metal elements and IVA metal elements; the cocatalyst is bromide.
The IIA metal element or the IVA metal element improves the selectivity and the yield of the 2,6-naphthalene dicarboxylic acid.
In the above technical scheme, the main catalyst preferably comprises both IIA metal element and IV metal element. At this time, the IIA metal element and the IVA metal element have a synergistic effect in improving the selectivity and the yield of the 2,6-naphthalene dicarboxylic acid. The ratio between the IIA metal element and the IVA metal element is not particularly limited, so long as the IIA metal element and the IVA metal element exist in the catalyst at the same time, and can obtain a comparable synergistic effect. For example, but not limited to, the weight ratio of IIA metal element to IVA metal element is from 0.10 to 10.00, more specific weight ratios within this range can be 0.15, 0.35, 0.45, 0.65, 0.85, 1.00, 1.3, 1.5, 1.9, 2.4, 2.8, 3.2, 3.6, 3.8, 4.2, 5.00, 5.4, 5.8, 6.00, 6.4, 6.8, 7.00, 7.4, 7.6, 7.8, 8.5, 9.0, etc.
In the above technical solution, the IVA metal is preferably at least one selected from the group consisting of Ge, sn, and Pb. It is still more preferable to include both Sn and Pb. Sn and Pb have synergistic effects in improving the yield of 2, 6-naphthalenedicarboxylic acid and the selectivity of 2, 6-naphthalenedicarboxylic acid. The ratio of Sn to Pb is not particularly limited as long as both are present in the catalyst to achieve comparable synergistic effects, for example, but not limited to, a weight ratio of Sn to Pb of 0.10 to 10.00, and more specific examples of weight ratios within this range may be 0.20, 0.40, 0.50, 0.60, 0.80, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, etc.
In the above technical solution, the IIA metal element is preferably at least one of the group consisting of Be, mg, ca, sr and Ba. It is even more preferred to include both Mg and Sr. Mg and Sr have a synergistic effect in improving the yield of 2, 6-naphthalenedicarboxylic acid and the selectivity of 2, 6-naphthalenedicarboxylic acid. The ratio of Mg to Sr is not particularly limited as long as both are present in the catalyst at the same time, and both can achieve comparable synergistic effects. For example, but not limited to, a weight ratio of Mg to Sr of 0.10 to 10.00, non-limiting examples of more specific weight ratios within this range may be 0.20, 0.40, 0.50, 0.60, 0.80, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, etc.
In the above technical solution, the promoter is preferably at least one of the group consisting of alkali metal bromide, HBr and organic bromide, more preferably potassium bromide.
In the above technical scheme, as the most preferable technical scheme, the main catalyst comprises Co element, mn element, IIA metal element and IVA metal element, and the components have a combined effect in improving the yield of 2,6-naphthalene dicarboxylic acid and the selectivity of 2,6-naphthalene dicarboxylic acid; for example, the main catalyst is composed of Co, mn, sn and Pb, or the main catalyst is composed of Co, mn, sr and Mg, or is composed of Co, mn, sn, pb and Sr (or Mg). Most preferably the active component consists of Co, mn, sn, pb, sr and Mg.
In the above technical solution, the weight part of Co element in the catalyst is preferably 50 to 100 parts, for example, but not limited to, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, etc., more preferably 85 to 100 parts, based on 100 parts of Mn element.
In the above technical solution, the weight part of Co element in the catalyst is preferably 1 to 20 parts, for example, but not limited to, 1 part, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts, 13 parts, 14 parts, 15 parts, 17 parts, 18 parts, 20 parts, etc., and more preferably 8 to 18 parts, based on 100 parts by weight of the Co element in the catalyst.
In the above technical solution, the weight part of Co element in the catalyst is preferably 1 to 20 parts, for example, but not limited to, 1 part, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts, 13 parts, 14 parts, 15 parts, 17 parts, 18 parts, 20 parts, etc., more preferably 8 to 18 parts, based on 100 parts of the weight part of IVA metal element.
In the above technical solution, the weight part of Co element in the catalyst is preferably 50 to 250 parts by weight calculated as bromine based on 100 parts, for example, but not limited to, 50 parts, 55 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 130 parts, 150 parts, 170 parts, 190 parts, 200 parts, 210 parts, 230 parts, 240 parts, 250 parts, etc., more preferably 170 to 210 parts.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the synthesis method of the 2,6-naphthalene dicarboxylic acid comprises the following steps: 2,6-diisopropyl naphthalene and air are used as raw materials, acetic acid is used as a solvent, and the 2,6-naphthalene dicarboxylic acid is generated by reaction in the presence of the catalyst according to any one of the technical schemes.
The key point of the invention is the selection of the catalyst, and the person skilled in the art knows how to determine the proper reaction temperature, reaction time, reaction pressure and material proportion according to actual needs. However:
the reaction temperature in the technical scheme is preferably 120-200 ℃;
the pressure of the reaction in the technical proposal is preferably 1.5-3.0 MPa;
in the technical scheme, the reaction time is preferably 2.0-5.0 h.
In the technical scheme, the molar ratio of acetic acid is 2, 6-diisopropylnaphthalene=1 (0.02-0.10).
In the specific embodiment, the number of moles of the catalyst means the sum of the number of moles of all metal element atoms in the main catalyst.
The product of the invention is cooled, decompressed and separated, the crude product is washed by hot distilled water after centrifugal separation, then dried, dissolved by ammonia water and analyzed by high performance liquid chromatography, and the conversion rate of 2,6-diisopropylnaphthalene and the yield and selectivity of 2,6-naphthalene dicarboxylic acid are calculated according to the following formula:
compared with the prior art, one of the key points of the invention is that the catalyst comprises Co element, mn element and at least one metal element selected from IIA metal element and IVA metal element, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield and selectivity of 2,6-naphthalene dicarboxylic acid.
Experimental results show that the yield of the 2,6-naphthalene dicarboxylic acid prepared by the method can reach 80.45%, the selectivity can reach 94.53%, and a better technical effect is achieved, particularly when the catalyst comprises Co element, mn element, at least one metal element selected from IIA metal elements and at least one metal element selected from IVA, a more outstanding technical effect is achieved, and the catalyst can be used in the industrial production of polyethylene 2,6-naphthalene dicarboxylic acid. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 12 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 80.45% and the selectivity was 94.53%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 2 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Pb(OAc) 2 ·3H 2 O, KBr the weight portions of Co element are 100 portions, mn element are 90 portions, pb element are 12 portions, and bromide is 200 portions calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was 80.63% and the selectivity was 94.48%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ comparative example 1 ]
Comparative examples are [ example 1 ] and [ example 2 ].
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.04mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was 67.85% and the selectivity was 85.73%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
As can be seen from comparison with examples 1 to 2, the catalyst used in the present invention has better performance than the catalyst containing Co, mn and Sr at the same time, and Co, mn and Pb at the same time, and the selectivity and yield of 2,6-naphthalene dicarboxylic acid are both high.
[ example 3 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Be(OAc) 2 ·H 2 O, KBr it is weighed. Wherein the weight part of Co element is 100 partsThe Mn element is 85 parts by weight, the Be element is 8 parts by weight, and the bromide is 170 parts by weight calculated as bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 80.03% and the selectivity to 94.14%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity to 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 4 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Ba(OAc) 2 ·H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 100 parts, the weight part of Ba element is 18 parts, and the weight part of bromide is 210 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.75% and the selectivity was calculated to be 94.24%, and the catalyst composition, reaction conditions, material feed amounts, and the yield and selectivity of 2, 6-naphthalenedicarboxylic acid were shown in Table 1 for convenience of explanation and comparison.
[ example 5 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Mg(OAc) 2 ·4H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 100 parts, the weight part of Mg element is 12 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was 80.47% and the selectivity was 94.51%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 6 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Ca(OAc) 2 ·H 2 O, KBr it is weighed. Wherein the weight part of Co element is 100 parts, the weight part of Mn element is 100 parts, and CThe weight part of the a element is 12 parts, and the weight part of the bromide is 200 parts calculated as bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 80.34% and the selectivity to 94.44%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 7 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sn(OAc) 2 ·2H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 100 parts, the weight part of Sn element is 12 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 80.64% and the selectivity to 94.41%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 8 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 12 parts, and the weight part of bromide is 170 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.05mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure reaches 1.5MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 120 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 2.0 h.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 80.11% and the selectivity was 93.87%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 9 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O, KBr it is weighed. Wherein the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 12 parts,the weight portion of bromide was 210 parts calculated as bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.25mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure reaches 3.0MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to be 200 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 5.0h.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 79.56% and the selectivity to 92.68%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
[ example 10 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O、Mg(OAc) 2 ·4H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 7 parts, the weight part of Mg element is 5 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 81.94% and the selectivity to 95.05%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
As is apparent from the comparison of example 10 with examples 1 and 5, the catalyst used in the present invention has a synergistic effect between the alkaline earth metals Sr and Mg in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. It is shown that there is a good synergy between the four metallic elements Co, mn, sr and Mg.
[ example 11 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Pb(OAc) 2 ·3H 2 O、、Sn(OAc) 2 ·2H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Pb element is 7 parts, the weight part of Sn element is 5 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 81.87% and the selectivity was calculated to be 95.12%, and the catalyst composition, reaction conditions, material feed amounts, and the yield and selectivity of 2, 6-naphthalenedicarboxylic acid were shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison of example 11 with examples 2 and 7, the catalyst used in the present invention has a synergistic effect between IVA metals Pb and Sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. It is shown that there is a good synergy between the four metallic elements Co, mn, pb and Sn.
[ example 12 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O、Pb(OAc) 2 ·3H 2 O、Sn(OAc) 2 ·2H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 7 parts, the weight part of Pb element is 2 parts, the weight part of Sn element is 3 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 81.94% and the selectivity to 95.95%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison of example 12 with example 1 and example 10, the catalyst used in the present invention has a synergistic effect between the alkaline earth metals Sr and the IVA metals Pb, sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. It is shown that there is a good synergy between the five metallic elements Co, mn, sr, sn and Pb.
[ example 13 ]
Composition of the catalyst: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Mg(OAc) 2 ·4H 2 O、Pb(OAc) 2 ·3H 2 O、Sn(OAc) 2 ·2H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Mg element is 7 parts, the weight part of Pb element is 2 parts, the weight part of Sn element is 3 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was calculated to be 81.97% and the selectivity to 95.98%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
As is evident from the comparison of example 13 with example 5 and example 11, the catalyst used in the present invention has a synergistic effect between the alkaline earth metal Mg and the IVA metals Pb, sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. It is shown that there is a good synergy between the five metallic elements Co, mn, mg, sn and Pb.
[ example 14 ]
Of catalystsThe composition is as follows: co (OAc) is added according to the composition of the catalyst 2 ·4H 2 O、Mn(OAc) 2 ·4H 2 O、Sr(OAc) 2 ·0.5H 2 O、Mg(OAc) 2 ·4H 2 O、Pb(OAc) 2 ·3H 2 O、Sn(OAc) 2 ·2H 2 O, KBr it is weighed. Wherein, the weight part of Co element is 100 parts, the weight part of Mn element is 90 parts, the weight part of Sr element is 4 parts, the weight part of Mg element is 3 parts, the weight part of Pb element is 2 parts, the weight part of Sn element is 3 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2,6-naphthalene dicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropylnaphthalene are added into a 1L titanium reaction kettle. Firstly, argon is used for discharging air in a kettle, then the air is pressurized to 1.0MPa, the pressure of the reaction kettle is kept, stirring and heating are started, when the temperature reaches 80 ℃, high-purity air is introduced until the pressure is 2.8MPa, the stirring speed is increased to 800rpm, meanwhile, the heating is carried out until the reaction temperature is reached, the reaction temperature is controlled to 175 ℃, the air flow rate is 9500ml/min, and the reaction is stopped after the reaction is continued for 4.0 hours.
Product analysis: the reaction mixture obtained by the above reaction is cooled, decompressed and separated, and the product is washed with hot distilled water and dried after centrifugal separation, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water.
The yield of 2,6-naphthalene dicarboxylic acid was 82.77% and the selectivity was 96.30%, and the catalyst composition, reaction conditions, material feed amount, yield and selectivity of 2,6-naphthalene dicarboxylic acid are shown in Table 1 for convenience of explanation and comparison.
As is evident from the comparison of example 14 with example 12 and example 13, the catalyst used in the present invention has a synergistic effect between the alkaline earth metals Sr, mg and the IVA metals Pb, sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. It is shown that there is a good synergistic effect between Co, mn, sr, mg, sn and Pb six metal elements.
TABLE 1
Claims (6)
1. The catalyst for synthesizing 2,6-naphthalene dicarboxylic acid comprises a main catalyst and a cocatalyst, wherein the main catalyst consists of Co, mn, IIA metal elements Sr and Mg and IVA metal elements Pb and Sn, and the weight ratio of IIA metal elements to IVA metal elements is 0.10-10.00; the cocatalyst is bromide; in the catalyst, the weight parts of Co elements are calculated as 100 parts, the weight parts of Mn elements are 85-100 parts, the weight parts of IVA metal elements are 5-10 parts, the weight parts of IIA metal elements are 7-10 parts, and the weight parts of bromide are 170-210 parts calculated as bromine.
2. The catalyst of claim 1, wherein the promoter is selected from at least one of the group consisting of alkali metal bromide, HBr, and organic bromide.
3. A method for synthesizing 2,6-naphthalene dicarboxylic acid, comprising: 2,6-naphthalene dicarboxylic acid is synthesized by using 2,6-diisopropyl naphthalene and air as raw materials and acetic acid as a solvent in the presence of the catalyst as claimed in claim 1 or 2.
4. The synthesis method according to claim 3, wherein the reaction temperature is 120-200 ℃.
5. The method according to claim 3, wherein the reaction pressure is 1.5 to 3mpa and the reaction time is 2.0 to 5.0 hours.
6. The method according to claim 3, wherein the molar ratio of acetic acid is 2, 6-diisopropylnaphthalene=1 (0.02 to 0.10).
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