CN111068790A - 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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- CN111068790A CN111068790A CN201811214409.8A CN201811214409A CN111068790A CN 111068790 A CN111068790 A CN 111068790A CN 201811214409 A CN201811214409 A CN 201811214409A CN 111068790 A CN111068790 A CN 111068790A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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Abstract
The invention relates to a catalyst for synthesizing 2, 6-naphthalenedicarboxylic acid, which mainly solves the problem that the activity and the selectivity of a 2, 6-naphthalenedicarboxylic acid catalyst in the prior art are lower, and the catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst comprises Co, Mn and at least one selected from a substance group consisting of IIA metal elements and IVA metal elements; the technical proposal that the cocatalyst is bromide better solves the technical problem and can be used in the industrial production of the poly (ethylene 2, 6-naphthalate).
Description
Technical Field
The present invention relates to a catalyst for synthesizing 2, 6-naphthalenedicarboxylic acid and a method for synthesizing 2, 6-naphthalenedicarboxylic acid.
Background
2,6-naphthalene dicarboxylic acid (2,6-NDA), a novel functional material known as 21 st century, is an important monomer for synthesizing high-performance plastics and liquid crystal polyester resins. In recent years, the use of polyethylene 2, 6-naphthalate (PEN) in place of polyethylene terephthalate (PET) has become a trend due to its excellent properties. The synthesis of 2,6-NDA becomes the bottleneck and key of PEN production, and how to research and develop an industrially feasible 2,6-NDA synthesis process route is favored by domestic and foreign research institutions.
The Henke method is similar to the method for preparing terephthalic acid by utilizing the synthesis of 2,6-NDA, and mainly comprises a disproportionation method and an isomerization method, wherein the disproportionation method is used for directly oxidizing naphthalene carboxylation or β -methylnaphthalene to obtain naphthoic acid, then reacting the naphthoic acid with potassium hydroxide to obtain potassium salt, and then carrying out disproportionation by the Henkel method to prepare the 2,6-NDA, the isomerization method is used for preparing disubstituted naphthalene obtained by extracting coal tar fractions or alkylating naphthalene (methylnaphthalene) alkyl, oxidizing the disubstituted naphthalene into naphthalenedicarboxylic acid, and then isomerizing the naphthalenedicarboxylic acid potassium by the Henkel method to generate the 2, 6-NDA.
The carbonyl transfer method mainly adopts di-iodo naphthalene as a raw material to carry out carbonylation reaction in an acetic acid environment to obtain the 2, 6-NDA. U.S. Pat. No. 4,4845273 (titled: Carbonylation process for production of aromatic) discloses a process for separating 2,6-NDA from naphthalenedicarboxylic acid isomers by crystallization from a mixture of 2, 6-diiodonaphthalene and 2, 7-diiodonaphthalene as starting materials by Carbonylation using an Rh-containing substance as a catalyst in the presence of acetic acid as a solvent.
The oxidation method is mainly 2, 6-dialkylnaphthalene oxidation method 2,6-NDA, which adopts Co-Mn-Br catalyst system, uses acetic acid as solvent, reaction temperature is about 200 ℃, reaction pressure is about 3 MPa.2, 6-dialkylnaphthalene oxidation method including 2, 6-dimethylnaphthalene oxidation method, 2, 6-isopropylnaphthalene oxidation method, 2, 6-alkylacylnaphthalene oxidation method and 2, 6-diethylnaphthalene oxidation method, among the above mentioned different 2, 6-dialkylnaphthalene Liquid phase oxidation methods, because physical and chemical properties of 2, 6-dimethylnaphthalene and 2, 7-dimethylnaphthalene are similar (such as melting point and boiling point difference are small), separation is difficult and operation cost is high, 2,6-diisopropylnaphthalene (2,6-DIPN) is easy to separate and purify raw material (isomer mixture), operation cost is low, 2,6-diisopropylnaphthalene (2,6-DIPN) is a very likely to be prepared by a single phase oxidation method, 2, 6-DIPIC) is a catalyst system which is developed under the conditions of 2, 6-dimethylnaphthalene oxidation, 2-Mn-solvent system, reaction temperature is about 200 ℃, reaction pressure is about 50-Mn-2-Mn-2-C, and the reaction pressure is found in the research under the conditions of a theory, the reaction pressure of 2, 2-6-dimethylnaphthalene Liquid phase oxidation method, 2-dimethylnaphthalene Liquid phase oxidation method, 2-dimethylnaphthalene Liquid phase oxidation method, 2-6-dimethylnaphthalene, 2-6-dimethylnaphthalene, 2-dimethylnaphthalene.
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 problems of low yield and low selectivity of the 2, 6-naphthalenedicarboxylic acid, and the invention provides a catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid, which has the characteristic of high yield of the 2, 6-naphthalenedicarboxylic acid and high selectivity of the 2, 6-naphthalenedicarboxylic acid.
The second technical problem to be solved by the present invention is a method for synthesizing 2, 6-naphthalenedicarboxylic acid using the catalyst described in the first technical problem.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows:
the catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid comprises a main catalyst and an auxiliary catalyst, 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 is bromide.
IIA metal element or IVA metal element can improve the selectivity and yield of 2,6-naphthalene dicarboxylic acid.
In the above technical solution, the main catalyst preferably includes IIA metal element and IV metal element at the same time. At the moment, the IIA metal element and the IVA metal element have synergistic effect on the aspect of improving the selectivity and the yield of the 2,6-naphthalene dicarboxylic acid. The ratio between the metal elements of IIA and IVA 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, the weight ratio of the IIA metal element to the IVA metal element is 0.10 to 10.00, and more specific non-limiting examples 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, and the like.
In the above-mentioned embodiment, the IVA metal is preferably at least one selected from the group consisting of Ge, Sn, and Pb. It is further preferable to include both Sn and Pb. Sn and Pb have a synergistic effect in increasing 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, and comparable synergistic effects can be achieved, for example, but not limited to, a weight ratio of Sn to Pb of 0.10 to 10.00, and more specific non-limiting examples of weight ratios within this range can 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, and the like.
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. Further preferably both Mg and Sr. Mg and Sr have a synergistic effect in increasing 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, and both can achieve comparable synergistic effects as long as both are present in the catalyst. For example, but not limited to, a weight ratio of Mg to Sr of 0.10 to 10.00, and more specific non-limiting examples 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, and the like.
In the above technical solution, the cocatalyst is preferably at least one selected from the group consisting of alkali metal bromide, HBr and organic bromide, and more preferably potassium bromide.
In the above technical solution, as the most preferable technical solution, the main catalyst simultaneously comprises a Co element, a Mn element, a IIA metal element and an IVA metal element, and the components have a combined effect in improving the yield of 2, 6-naphthalenedicarboxylic acid and the selectivity of 2, 6-naphthalenedicarboxylic acid; for example, the main catalyst consists of Co, Mn, Sn and Pb, or the main catalyst consists of Co, Mn, Sr and Mg, or consists 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 the Co element in the catalyst is calculated as 100 parts, and the weight part of the Mn element 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, and the like, and more preferably 85 to 100 parts.
In the above technical solution, the weight part of the Co element in the catalyst is 100 parts, and the weight part of the IIA metal element 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, and the like, and more preferably 8 to 18 parts.
In the above technical solution, the weight part of the Co element in the catalyst is calculated as 100 parts, and the weight part of the IVA metal element 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, and the like, and more preferably 8 to 18 parts.
In the above technical solution, the weight part of the Co element in the catalyst is 100 parts, and the weight part of the bromide is preferably 50 to 250 parts, such as 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, and the like, and more preferably 170 to 210 parts, based on the bromine.
To solve the second technical problem, the technical solution of the present invention is as follows:
a method for synthesizing 2, 6-naphthalenedicarboxylic acid comprising: 2,6-diisopropyl naphthalene and air are taken as raw materials, acetic acid is taken as a solvent, and the reaction is carried out in the presence of the catalyst in one technical scheme of the technical problems to generate the 2,6-naphthalene dicarboxylic acid.
The key of the invention is the selection of the catalyst, and the skilled person knows how to determine the appropriate reaction temperature, reaction time, reaction pressure and material ratio according to the actual needs. However:
in the technical scheme, the reaction temperature is preferably 120-200 ℃;
the reaction pressure in the technical scheme is preferably 1.5-3.0 MPa;
the reaction time in the technical scheme is preferably 2.0-5.0 h.
In the technical scheme, the molar ratio of acetic acid to 2,6-diisopropyl naphthalene is 1 (0.02-0.10).
In a specific embodiment, the number of moles of the catalyst refers to 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 and then dried, and is analyzed by high performance liquid chromatography after being dissolved by ammonia water, and the conversion rate of 2,6-diisopropyl naphthalene and the yield and the selectivity of 2,6-naphthalene dicarboxylic acid are calculated according to the following formulas:
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, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield and selectivity of the 2,6-naphthalene dicarboxylic acid.
Experimental results show that the yield of the 2, 6-naphthalenedicarboxylic acid prepared by the invention can reach 80.45%, the selectivity can reach 94.53%, and a good technical effect is achieved, particularly when the catalyst simultaneously 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 prominent technical effect is achieved, and the catalyst can be used in the industrial production of poly (ethylene 2, 6-naphthalenedicarboxylate). The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 90 portions, the weight portion of Sr element is 12 portions, and the weight portion of bromide is 200 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.45% and the selectivity was calculated to be 94.53%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 2 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Pb(OAc)2·3H2O, KBr, wherein the weight portion of Co element is 100, the weight portion of Mn element is 90, the weight portion of Pb element is 12, the weight portion of bromide is 200.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.63% and the selectivity was calculated to be 94.48%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O, KBr. Wherein the weight portion of Co element is 100 portions, the weight portion of Mn element is 90 portions, and the weight portion of bromide is 200 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.04mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 67.85%, and the selectivity was calculated to be 85.73%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
Compared with the examples 1-2, the catalyst adopted by the invention has better performance than that of the catalyst only containing Co, Mn and Sr, and simultaneously containing Co, Mn and Pb, and has high selectivity and yield of the 2,6-naphthalene dicarboxylic acid.
[ example 3 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Be(OAc)2·H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 85 portions, the weight portion of Be element is 8 portions, and the weight portion of bromide is 170 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.03% and the selectivity was calculated to be 94.14%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 4 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Ba(OAc)2·H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn elementThe number is 100 parts, the weight part of Ba element is 18 parts, and the weight part of bromide is 210 parts counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
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, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 5 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Mg(OAc)2·4H2O, KBr. Wherein the weight portion of Co element is 100 portions, the weight portion of Mn element is 100 portions, the weight portion of Mg element is 12 portions, and the weight portion of bromide is 200 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.47% and the selectivity was calculated to be 94.51%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 6 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Ca(OAc)2·H2O, KBr. Wherein the weight portion of Co element is 100 portions, the weight portion of Mn element is 100 portions, the weight portion of Ca element is 12 portions, and the weight portion of bromide is 200 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.34% and the selectivity was calculated to be 94.44%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 7 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sn(OAc)2·2H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 100 portions, the weight portion of Sn element is 100 portionsIs 12 parts, and the weight part of bromide is 200 parts calculated by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.64% and the selectivity was calculated to be 94.41%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 8 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 90 portions, the weight portion of Sr element is 12 portions, and the weight portion of bromide is 170 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.05mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 1.5MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 120 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 2.0 hours.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 80.11% and the selectivity was calculated to be 93.87%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 9 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 90 portions, the weight portion of Sr element is 12 portions, and the weight portion of bromide is 210 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.25mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure is 3.0MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 200 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 5.0 hours.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 79.56% and the selectivity was calculated to be 92.68%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
[ example 10 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O、Mg(OAc)2·4H2O, KBr. Wherein, the weight portion of Co element is 100 portions, the weight portion of Mn element is 90 portions, and the weight of Sr element isThe weight portion is 7 portions, the weight portion of Mg element is 5 portions, and the weight portion of bromide is 200 portions counted by bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 81.94% and the selectivity was calculated to be 95.05%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison between example 10 and examples 1 and 5, the catalyst used in the present invention has a synergistic effect between alkaline earth metals Sr and Mg in increasing the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. The good synergistic effect among the four metal elements of Co, Mn, Sr and Mg is demonstrated.
[ example 11 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Pb(OAc)2·3H2O、、Sn(OAc)2·2H2O, KBr. Wherein the weight portion of Co element is 100, the weight portion of Mn element is 90, the weight portion of Pb element is 7, the weight portion of Sn element is 5, and the weight portion of bromide is 200 in terms of bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
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, feed amount of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from example 11 in comparison with examples 2 and 7, the catalyst used in the present invention has a synergistic effect between the IVA metals Pb and Sn in improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. The good synergistic effect among the four metal elements of Co, Mn, Pb and Sn is demonstrated.
[ example 12 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O、Pb(OAc)2·3H2O、Sn(OAc)2·2H2O, KBr. Wherein, the weight portion of Co element is 100, the weight portion of Mn element is 90, the weight portion of Sr element is 7, the weight portion of Pb element is 2, the weight portion of Sn element is 3, and the weight portion of bromide is 200 in terms of bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 81.94% and the selectivity was calculated to be 95.95%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison of example 12 with examples 1 and 10, in the catalyst used in the present invention, alkaline earth metal Sr has a synergistic effect with IVA metals Pb and Sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. The good synergistic effect among five metal elements of Co, Mn, Sr, Sn and Pb is demonstrated.
[ example 13 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Mg(OAc)2·4H2O、Pb(OAc)2·3H2O、Sn(OAc)2·2H2O, KBr. Wherein the weight portion of Co element is 100, the weight portion of Mn element is 90, the weight portion of Mg element is 7, the weight portion of Pb element is 2, the weight portion of Sn element is 3, and the weight portion of bromide is 200 in terms of bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 81.97% and the selectivity was calculated to be 95.98%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison of example 13 with examples 5 and 11, the catalyst used in the present invention has a synergistic effect between the alkaline earth metal Mg and the IVA metals Pb and Sn in improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. The good synergistic effect among five metal elements of Co, Mn, Mg, Sn and Pb is proved.
[ example 14 ]
Composition of the catalyst: according to the composition of the catalyst, Co (OAc)2·4H2O、Mn(OAc)2·4H2O、Sr(OAc)2·0.5H2O、Mg(OAc)2·4H2O、Pb(OAc)2·3H2O、Sn(OAc)2·2H2O, KBr. Wherein, the weight portion of Co element is 100, the weight portion of Mn element is 90, the weight portion of Sr element is 4, the weight portion of Mg element is 3, the weight portion of Pb element is 2, the weight portion of Sn element is 3, and the weight portion of bromide is 200 according to the weight portion of bromine.
Synthesis of 2, 6-naphthalenedicarboxylic acid: 2.5mol of acetic acid, 0.15mol of catalyst and 0.08mol of 2,6-diisopropyl naphthalene are added into a 1L titanium material reaction kettle. Discharging air in the kettle by using argon, pressurizing to 1.0MPa, keeping the pressure of the reaction kettle, starting stirring and heating, introducing high-purity air until the pressure reaches 2.8MPa when the temperature reaches 80 ℃, increasing the stirring speed to 800rpm, heating to the reaction temperature, controlling the reaction temperature to be 175 ℃, controlling the air flow to be 9500ml/min, and stopping the reaction after continuously reacting for 4.0 h.
And (3) product analysis: cooling, decompressing and separating the reaction mixture obtained by the reaction, washing the product with hot distilled water after centrifugal separation, drying, dissolving the product with ammonia water, and analyzing the product by high performance liquid chromatography.
The yield of 2, 6-naphthalenedicarboxylic acid was calculated to be 82.77%, and the selectivity was calculated to be 96.30%, and the catalyst composition, reaction conditions, feed amounts of materials, yield of 2, 6-naphthalenedicarboxylic acid and selectivity are shown in Table 1 for convenience of explanation and comparison.
As can be seen from the comparison between example 14 and examples 12 and 13, the catalyst used in the present invention has a synergistic effect between alkaline earth metals Sr and Mg and IVA metals Pb and Sn in terms of improving the selectivity and yield of 2, 6-naphthalenedicarboxylic acid. The excellent synergistic effect among six metal elements of Co, Mn, Sr, Mg, Sn and Pb is proved.
TABLE 1
Claims (12)
1. The catalyst for synthesizing the 2, 6-naphthalenedicarboxylic acid comprises a main catalyst and an auxiliary catalyst, 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 is bromide.
2. The catalyst of claim 1, wherein the procatalyst comprises a IIA metal element and an IV metal element. The weight ratio of the IIA metal element to the IVA metal element is 0.10 to 10.00, and more specific non-limiting examples within this range may 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.
3. The catalyst according to claim 1, wherein said IVA metal element is at least one selected from the group consisting of Ge, Sn and Pb.
4. The catalyst as set forth in claim 1, characterized in that the IIA metal element is preferably at least one member selected from the group consisting of Be, Mg, Ca, Sr and Ba.
5. The catalyst of claim 1, wherein the promoter is at least one member selected from the group consisting of alkali metal bromide, HBr, and organic bromides.
6. The catalyst of claim 1, wherein the weight part of the Co element in the catalyst is 50 to 100 parts based on 100 parts, and the weight part of the Mn element in the catalyst is 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., and more preferably 85 to 100 parts.
7. The catalyst according to claim 1, wherein the weight part of the Co element in the catalyst is 1-20 parts based on 100 parts of the IVA metal element. 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.
8. The catalyst of claim 1, wherein the weight portion of Co element in the catalyst is 100, and the weight portion of bromide is 50-250 parts based on bromine. 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.
A method for synthesizing 2, 6-naphthalenedicarboxylic acid comprising: 2,6-diisopropyl naphthalene and air are taken as raw materials, acetic acid is taken as a solvent, and the 2,6-naphthalene dicarboxylic acid is synthesized in the presence of a catalyst. The catalyst comprises a main catalyst and an auxiliary catalyst, 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 is bromide.
10. The method according to claim 7, wherein the reaction temperature is 120 to 200 ℃.
11. The synthesis method according to claim 7, wherein the reaction pressure is preferably 1.5 to 3 MPa. The reaction time is preferably 2.0-5.0 h.
12. The method according to claim 7, wherein the molar ratio of 2,6-diisopropylnaphthalene to 1 (0.02-0.10).
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