CN110452392B - Preparation method of cobalt-based metal organic framework material and application of cobalt-based metal organic framework material in p-xylene oxidation reaction - Google Patents
Preparation method of cobalt-based metal organic framework material and application of cobalt-based metal organic framework material in p-xylene oxidation reaction Download PDFInfo
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Abstract
The invention discloses a preparation method of a cobalt-based metal organic framework material and application of the cobalt-based metal organic framework material in p-xylene oxidation reaction. The cobalt-based metal organic framework material is prepared by using cheap trimesic acid as a ligand and cobalt salt as a cobalt source and using a hydrothermal synthesis method. The catalyst and the N-hydroxy-phthalic acid imine and the derivative thereof are jointly used for catalyzing the p-xylene oxidation reaction, compared with the existing p-xylene oxidation process, the reaction temperature is reduced, corrosive bromine and acetic acid are not used as media, the terephthalic acid is obtained in high selectivity, and the cobalt-based metal framework material can be recycled.
Description
Technical Field
The invention relates to a preparation method of a metal organic framework material, in particular to a preparation method of a cobalt-based metal organic framework material and application of the cobalt-based metal organic framework material in preparation of terephthalic acid by oxidizing paraxylene.
Background
Purified Terephthalic Acid (PTA) is an important polyester feedstock, and 90% of the PTA is used worldwide to produce polyethylene terephthalate (PET). PET is mainly applied to food and medicine grade packaging, and the demand of PET is continuously increased year by year. The autoxidation of paraxylene to terephthalic acid is typical of hydrocarbon free radical oxidation, which has two limiting factors relative to the general hydrocarbon oxidation: firstly, the stability of p-methylbenzyl radical is higher than that of methyl peroxy benzyl radical, so that oxygen is difficult to combine with the p-methylbenzyl radical to form peroxy radical; secondly, carboxyl in the intermediate p-methyl benzoic acid is an electron-withdrawing group, so that the p-carboxyl benzyl is unstable and has resistance to oxidation, and is difficult to oxidize into second carboxyl. The two difficulties need to be broken through by a corresponding catalytic system, and the process conditions for preparing terephthalic acid by oxidizing paraxylene in industrial production are also harsh.
Currently, the BP-Amoco process is commonly used in commercial p-xylene oxidation to produce terephthalic acid. The process takes acetic acid as a solvent, cobalt acetate and manganese acetate as catalysts, bromide as an accelerant, and p-xylene is oxidized by air at 180-200 ℃ and 14-16 MPa. The conversion rate of p-xylene and the content of terephthalic acid in the product both reach more than 95 percent. However, the method uses acetic acid as a solvent, the content of the acetic acid is 80 percent, the content of paraxylene is less than 20 percent, the production efficiency is low, and the energy consumption is high. In addition, a large amount of acetic acid solvent and bromide are used, equipment is corroded seriously and environmental pollution is serious, expensive titanium materials are adopted in the reactor, and the purchase and maintenance cost of the reaction equipment is high. According to the invention, CN1865214A in China effectively reduces the use of bromine, reduces the emission of tail gas containing bromine and reduces the corrosion degree of equipment by adding nitrogen oxide in a reaction system.
In order to allow the reaction to be carried out under mild conditions and without the use of corrosive bromine, adv. synth. cat. 343, vol.2 reports a new process for the oxidation of p-xylene. The method uses NHPI to replace strong corrosive bromine, uses p-xylene as a raw material, uses 0.5 mol% of cobalt acetate and manganese acetate as catalysts, uses acetic acid as a solvent, and reacts for 14 hours at 100 ℃ and 1atm, wherein the conversion rate of the p-xylene reaches 99%, but the selectivity of terephthalic acid is only 84%.
In order not to use corrosive acetic acid as a solvent, Green Chemistry volume 7, No. 6 reports a new process using supercritical water as a solvent. The process takes water as a solvent, takes manganese bromide as a catalyst and hydrogen peroxide as an oxidant at 380 ℃, and the yield of the terephthalic acid reaches 95%. However, the reaction temperature of the process is extremely high, the pressure is extremely high, and hydrogen peroxide which is extremely easily decomposed is used as an oxidizing agent, so that the process is extremely dangerous.
In a cobalt-manganese-bromine catalytic system, cobalt salt and manganese salt are dissolved in a reaction system, and after the reaction is finished, the cobalt salt and the manganese salt need to be recovered through a series of post-treatment processes, and the recovery rate is about 70%. Chinese invention CN101952039A discloses a method for recovering catalyst by using ion exchange resin, which can completely recover bromine, cobalt and manganese in reaction solution with recovery rate of about 80%. Chinese invention CN102626646A discloses another method for recovering metal cobalt and manganese, which is implemented by Na2CO3The pH value of the solution is adjusted to selectively precipitate cobalt and manganese, and a related process flow is designed. The process improves the recovery rate of cobalt and manganese from 70 percent to more than 85 percent.
Disclosure of Invention
The invention provides a preparation method of a cobalt-based metal organic framework material and application of the cobalt-based metal organic framework material in an oxidation reaction of paraxylene, aiming at solving the problems that the existing cobalt-manganese-bromine catalytic system is high in temperature, corrosive bromine and acetic acid are used, and the catalyst recovery process is complex. The method adopts a hydrothermal synthesis method to prepare the cobalt-based metal organic framework material, has simple steps and low preparation cost, and the prepared catalyst shows high activity and good reusability in the oxidation reaction of p-xylene.
The purpose of the invention is realized by the following steps:
a preparation method of a cobalt-based metal organic framework material comprises the following two steps:
(1) dissolving cobalt source, i.e. cobalt salt, in H completely2O, reacting an organic ligand, trimesic acid or H3BTC is completely dissolved in CH3CH2OH；
(2) And (2) mixing the two solutions obtained in the step (1), uniformly stirring, reacting at constant temperature, cooling to room temperature after the reaction is finished, taking out the obtained solid reaction product, washing, and drying in vacuum to obtain the cobalt-based metal organic framework material Co-BTC.
Further, in the step (1), the cobalt salt is one or more than two of cobalt acetate, cobalt nitrate, cobalt chloride and cobalt sulfate; cobalt salt, H2O、H3BTC and CH3CH2The ratio of the amount of OH species is 1: (16-160): (0.3-0.9): (105-210).
Further, in the step (2), the stirring temperature is 0-60 ℃ and the stirring time is 0-4 h, and the endpoint 0 is included (the endpoint 0 is only for the stirring time); the ultrasonic oscillation temperature is 0-60 ℃, the time is 0-4 h, and the endpoint 0 is not included (the endpoint 0 only aims at the oscillation time); the reaction temperature is 100-250 ℃, and the reaction time is 4-96 h; the vacuum drying temperature is 40-400 ℃.
The application of the cobalt-based metal organic framework material obtained by the preparation method in the oxidation reaction of paraxylene comprises the following steps:
the method comprises the steps of using p-xylene as a raw material, acetonitrile as a solvent, using a cobalt-based metal organic framework material, namely Co-BTC as a catalyst, and catalyzing oxidation reaction of the p-xylene by cooperating with a nitroxide free radical catalyst to obtain a product terephthalic acid.
Further, the nitroxide free radical catalyst is N-hydroxyphthalimide (NHPI), N-dihydroxypyromellitic dianhydride (NDHPI), 4-CH3OCO-NHPI、3-F-NHPI、4-CH3-NHPI、4-CH3O-NHPI、3-CH3O-NHPI、3,6-(CH3O)2-NHPI.
Further, the temperature of the oxidation reaction is 100-160 ℃, the time is 0.5-24 hours, the reaction pressure is 1-5 Mpa, and the mass fraction of Co-BTC in the reaction liquid is 0.05-5%; the mass fraction of the nitroxide free radical catalyst in the reaction liquid is 0.1-5%; the mass of the paraxylene accounts for 0-10% of the mass of the solvent, and the endpoint 0 is not included.
The invention has the beneficial effects that:
(1) the conversion rate of p-xylene in the invention reaches 100%, and the selectivity of terephthalic acid under the optimized condition reaches 97%.
(2) Compared with the reaction conditions for industrial production of terephthalic acid, the method provided by the invention has the advantages that the reaction temperature is obviously reduced, strong corrosive bromine is not used as a catalyst, and corrosive acetic acid is not used as a solvent.
(3) The catalyst Co-BTC obtained by the invention has better activity than cobalt acetate, is convenient to recover and has good reusability.
Drawings
FIG. 1 is an XRD diffractogram of Co-BTC obtained in example 1.
FIG. 2 is an SEM photograph of Co-BTC obtained in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which should be noted that the following examples are only illustrative and the present invention is not limited thereto.
Example 1
Weighing 4.8g of cobalt nitrate hexahydrate and dissolving in 20mL of ultrapure water, weighing 2g of trimesic acid and dissolving in 130mL of ethanol, mixing the two substances after the two substances are completely dissolved, stirring for 5min, pouring into a polytetrafluoroethylene lining of a pressure kettle, and ultrasonically oscillating for 20 min. The liner was then transferred to a self-autoclave and the reaction was carried out in an incubator. The reaction temperature was controlled as follows: the temperature of the constant temperature box is raised to 140 ℃ within 22min, and the reaction lasts 24 h; then linearly reducing the temperature of the constant temperature box to 120 ℃ within 200min, and reacting for 5 h; then linearly reducing the temperature of the constant temperature box to 100 ℃ within 200min, reacting for 5h, and naturally cooling the constant temperature box to room temperature after finishing reaction. Taking out the cobalt-based metal organic framework material Co-BTC from the pressure kettle, taking out the solid obtained by the reaction, washing the solid with ethanol for three times, and carrying out vacuum drying for 24 hours at the temperature of 100 ℃ to obtain the cobalt-based metal organic framework material Co-BTC. The XRD diffractogram of Co-BTC is shown in FIG. 1, and the SEM is shown in FIG. 2.
Example 2
The Co-BTC catalyst prepared in the above example 1 was used in combination with a nitroxide radical catalyst to catalyze the oxidation reaction of p-xylene. Firstly, before reaction, the catalyst is dried in vacuum at 100 ℃ for 6h to remove water adsorbed by the catalyst, dried Co-BTC (0.05g) and nitroxide radical catalyst NDHPI (0.372g) are weighed and placed into a quartz lining of a high-pressure reaction kettle, then 0.56gPX and 25g of acetonitrile are weighed and respectively poured into the quartz lining, then the quartz lining is placed into the reaction kettle, the high-pressure reaction kettle is sealed, oxygen is introduced and blown for purging twice, oxygen is introduced once, the pressure is kept at 3MPa, the magnetic stirring rotating speed is set to be 1000r/min, and the reaction is carried out for 12h at the set reaction temperature of 150 ℃. After the reaction is finished, the reaction kettle is quenched to room temperature. After slowly releasing the pressure, opening the reaction kettle, dissolving a product in the reaction liquid by using a solvent dimethyl sulfoxide, collecting the reaction liquid, and analyzing the raw material and the product by using a multi-wavelength high performance liquid chromatography.
Example 3
Other reaction conditions were the same as in example (2), and the reaction temperature was adjusted to 140 ℃.
Example 4
The other reaction conditions were the same as in example (2), and the amount of Co-BTC was adjusted to 0.04 g.
Example 5
The other reaction conditions were the same as in example (2), and the amount of Co-BTC was adjusted to 0.02 g.
Example 6
The other reaction conditions were the same as in example (2), and the reaction time was adjusted to 10 hours.
Example 7
The other reaction conditions were the same as in example (2), and the reaction time was adjusted to 8 hours.
Example 8
Other reaction conditions were the same as in example (2), and the amount of acetonitrile used was adjusted to 30 g.
Example 9
The other reaction conditions were the same as in example (2), and the amount of Co-BTC was adjusted to 0.1g, the amount of acetonitrile was 50g, the amount of NDHPI was 0.744g, the amount of p-xylene was 1.08g, the oxygen pressure was adjusted to 4.0MPa when the reaction temperature was raised to 150 ℃ and oxygen was continuously supplied.
Example 10
The reaction conditions were the same as in example (2), except that the amount of Co-BTC was adjusted to 0.075g, the amount of acetonitrile was adjusted to 37.5g, the amount of NDHPI was adjusted to 0.558g, the amount of p-xylene was adjusted to 0.81g, the oxygen pressure was adjusted to 4.0MPa as the reaction temperature rose to 150 ℃ and oxygen was continuously supplied. Among them, the Co-BTC used in this example was recovered from example 9.
Example 11
The other reaction conditions were the same as in example (2), and the amount of Co-BTC was adjusted to 0.54g, the amount of acetonitrile was adjusted to 27g, the amount of NDHPI was adjusted to 0.4g, the amount of p-xylene was adjusted to 0.58g, the oxygen pressure was adjusted to 4.0MPa when the reaction temperature was raised to 150 ℃ and oxygen was continuously supplied. Among them, the Co-BTC used in this example was recovered from example 10.
The conversion of p-xylene PX obtained in examples (2) to (11) under the reaction conditions used, and the selectivity results for p-TA toluic acid, p-carboxybenzaldehyde 4-CBA, and PTA terephthalic acid are shown in table 1.
TABLE 1
It can be seen from the above examples that under the optimized reaction conditions, NDHPI has a good effect in cooperation with Co-BTC in catalyzing the oxidation reaction of p-xylene, the conversion rate of p-xylene is 100%, and the selectivity of terephthalic acid is higher than 90% and can reach 98% at most. As can be seen from the data of examples 9 to 11, the recycling effect of Co-BTC is not changed much, which shows that the catalyst Co-BTC obtained by the invention has good recycling performance. Compared with industrial production, the method has the obvious advantages of reducing the reaction temperature, not using corrosive bromine and acetic acid, and the like.
Claims (4)
1. The application of the cobalt-based metal organic framework material in the p-xylene oxidation reaction is characterized in that p-xylene is used as a raw material, acetonitrile is used as a solvent, the cobalt-based metal organic framework material, namely Co-BTC, is used as a catalyst, and the cobalt-based metal organic framework material, namely Co-BTC, is cooperated with a nitroxide free radical catalyst to catalyze the p-xylene oxidation reaction to obtain a product terephthalic acid;
the nitroxide free radical catalyst is N-hydroxyphthalimide (NHPI, N)’-Dihydroxy pyromellitic dianhydride or NDHPI, 4-CH3OCO-NHPI、3-F-NHPI、4-CH3-NHPI、4-CH3O-NHPI、3-CH3O-NHPI、3,6-(CH3O)2-one or more than two of NHPIs;
the preparation method of the cobalt-based metal organic framework material comprises the following two steps:
(1) dissolving cobalt source, i.e. cobalt salt, in H completely2O, reacting an organic ligand, trimesic acid or H3BTC is completely dissolved in CH3CH2OH；
(2) And (2) mixing the two solutions obtained in the step (1), uniformly stirring, reacting at constant temperature, cooling to room temperature after the reaction is finished, separating a solid reaction product, washing, and drying in vacuum to obtain the cobalt-based metal organic framework material Co-BTC.
2. The application of claim 1, wherein the temperature of the oxidation reaction is 100-160 ℃, the time is 0.5-24 h, the reaction pressure is 1-5 Mpa, and the mass fraction of Co-BTC in the reaction solution is 0.05-5%; the mass fraction of the nitroxide free radical catalyst in the reaction liquid is 0.1-5%; the mass of the paraxylene accounts for 0-10% of the mass of the solvent, and the endpoint 0 is not included.
3. The use according to claim 1, wherein in step (1), the cobalt salt is one or more of cobalt acetate, cobalt nitrate, cobalt chloride and cobalt sulfate; cobalt salt, H2O、H3BTC and CH3CH2The ratio of the amount of OH species is 1: (16-160): (0.3-0.9): (105-210).
4. The use according to claim 1, wherein in the step (2), the stirring temperature is 0-60 ℃ and the stirring time is 0-4 h; the reaction temperature is 100-250 ℃, and the reaction time is 4-96 h; the vacuum drying temperature is 40-200 ℃.
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| CN113976181B (en) * | 2021-09-29 | 2023-05-30 | 江苏大学 | Preparation of cobalt-based metal organic framework immobilized organic catalyst and application thereof in fuel desulfurization field |
| CN115215739A (en) * | 2022-02-25 | 2022-10-21 | 上海应用技术大学 | Method for preparing p-toluic acid by oxidizing p-xylene through synergistic catalytic system |
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