CN107082892B - Preparation method of bimetallic organic framework material and application of bimetallic organic framework material in cyclohexyl hydrogen peroxide decomposition reaction - Google Patents
Preparation method of bimetallic organic framework material and application of bimetallic organic framework material in cyclohexyl hydrogen peroxide decomposition reaction Download PDFInfo
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Abstract
The invention discloses a preparation method of a bimetallic organic framework material and application of the bimetallic organic framework material in cyclohexyl hydroperoxide decomposition reaction. The invention adopts metal organic framework material MIL-101(Cr) as a carrier, obtains the bimetallic organic framework material by introducing second metal ions, and applies the material as a catalyst in a cyclohexyl hydrogen peroxide decomposition system under the alkali-free condition. The catalyst prepared by the method has the advantages of simple preparation process, stable property, difficult deterioration, high and stable catalytic performance, and basically unchanged catalytic activity after repeated recycling. The catalyst is used for catalyzing the decomposition reaction of cyclohexyl hydroperoxide, the conversion rate of the cyclohexyl hydroperoxide can reach more than 96 percent, the total selectivity of alcohol ketone can reach more than 100 percent, and simultaneously, the proportion of cyclohexanol to cyclohexanone in the product is obviously improved.
Description
Technical Field
The invention relates to a preparation method of a bimetallic organic framework material and application thereof in the reaction of generating cyclohexanol and cyclohexanone by catalytically decomposing cyclohexyl hydroperoxide under the alkali-free condition.
Background
Cyclohexanone is an important organic chemical raw material, is an important intermediate for manufacturing nylon, oxalic acid and caprolactam, is also an important industrial solvent in the industries of medicine, coating, plastic recovery and the like, has very wide application and continuously increases the demand.
Currently, the common process for the industrial production of cyclohexanone is the cyclohexane oxidation process, the most widely used of which is the uncatalyzed oxidation process developed by DSM, the netherlands. The process flow mainly comprises two steps: firstly, oxidizing cyclohexane to generate intermediate product cyclohexyl hydrogen peroxide (CHHP), wherein the oxidation conversion rate is controlled to be 3% -4%, the CHHP mass fraction is controlled to be 4% -5%, and the high yield is 95% -97%, and secondly, performing catalytic decomposition reaction on the oxidation solution obtained in the first step in an alkaline water solution of transition metal ions of 1 mu g/g at the reaction temperature of 70-115 ℃ to obtain cyclohexanol and cyclohexanone. The conversion rate of the decomposition reaction reaches 100%, but the selectivity of alcohol ketone is 87%, wherein the selectivity of cyclohexanol is 33%, the selectivity of cyclohexanone is 54%, the ratio of ketone to alcohol is 1:0.61, the yield of the decomposition reaction is 87%, the total alcohol ketone selectivity of the whole section is 84%, a large amount of alkali liquor is consumed in the reaction, the alkali liquor is difficult to separate from the oil phase, and the waste alkali liquor can only be incinerated, so that the serious environmental pollution is caused. The invention of China is CN1105970, CN1147499A, CN96118441 and CN 98112730. By changing the decomposition reaction into a two-step decomposition method, the first step adopts oil-soluble transition metal salt to carry out homogeneous catalysis in an alkali-free or low-alkali environment, and the second step adopts water-soluble transition metal salt to carry out heterogeneous catalysis in a high-alkali environment, so that the decomposition yield of the cyclohexyl hydrogen peroxide is improved to 95 percent. However, the process has the disadvantages that the used oil-soluble transition metal salt is easy to generate precipitate to form scale in a pipeline, the continuous production is seriously influenced, and the environment pollution problem of waste alkali still exists because alkali is used in the reaction. Therefore, there is a need to establish a production process for the catalytic decomposition of cyclohexyl hydroperoxide to cyclohexanol and cyclohexanone with high selectivity and high conversion rate under alkali-free conditions.
In addition, French Rodiya corporation invented a homogeneous catalytic decomposition process of cyclohexyl hydroperoxide using tert-butyl chromate and octyl phosphate as the scale inhibitor. The method generates chromium adipate sediment in the decomposition process, causes the scaling of production pipelines, needs to consume a large amount of octyl phosphate scale inhibitor, still cannot thoroughly solve the scaling problem, and has a continuous production period of four months. In addition, the decomposition conversion rate of the cyclohexyl hydroperoxide in the process is about 92 percent, and the total molar yield is 80 percent.
The invention CN01118441.8 and CN01118438.8 in China respectively disclose a chromium-phosphorus-aluminum molecular sieve with an AFI structure and a chromium-silicon molecular sieve with an MFI structure, the decomposition of cyclohexyl hydrogen peroxide by the chromium-containing molecular sieve has higher yield, but the loss of chromium metal is faster, so that a catalyst is deactivated quickly, the conversion rate is lower, the reaction retention time is long, and the industrial application is quite difficult.
The Metal-Organic Frameworks (Metal-Organic Frameworks) material is a material with a three-dimensional network structure formed by Metal ions and multi-site Organic ligands. The porous material has the characteristics of higher specific surface area, adjustable pore size, functional modification and the like, is another important novel porous material except zeolite and carbon nano tubes, and has wide application in the aspects of catalysis, gas storage, gas separation, drug transportation, luminescent materials and the like.
The chromium metal organic framework MIL-101 is designed and synthesized for the first time by French Ferey team in 2005 by combining computer simulation, and 1, 4-terephthalic acid is used as an organic ligand, Cr (NO)3)3·9H2O is metal salt, HF is mineralizer, the mixture is prepared by a hydrothermal synthesis method and reacts for 8 hours at 220 ℃, and pure MIL-101 is finally obtained by dissolving and activating N, N-dimethylformamide, hot ethanol and ammonium fluoride.
The invention adopts metal organic framework material MIL-101(Cr) as a carrier, obtains the bimetallic organic framework material by introducing second metal ions, obtains the catalyst with stable performance and difficult loss of the metal ions, applies the material as the catalyst to a cyclohexyl hydrogen peroxide decomposition system in an alkali-free environment, ensures high decomposition reaction conversion rate and alcohol-ketone selectivity, and simultaneously improves the catalyst stability and the alcohol-ketone ratio, thereby improving the industrial application value.
Disclosure of Invention
The invention aims to provide a preparation method of a bimetallic organic framework material which has good catalyst stability and can be recycled for multiple times, and provides application of the bimetallic organic framework material as a catalyst in cyclohexyl hydrogen peroxide decomposition reaction, so that the proportion of cyclohexanol to cyclohexanone in a product is improved while high decomposition reaction conversion rate and alcohol-ketone selectivity are ensured, and the formation of a by-product acid ester is obviously reduced.
The purpose of the invention is realized by the following steps:
a preparation method of a bimetallic organic framework material comprises the following steps:
(1) dissolving sodium acetate solid in deionized water to obtain a sodium acetate aqueous solution, and adding the sodium acetate aqueous solution into the deionized water successively according to the mass ratio of (0.1-10): 1, stirring the chromium nitrate and the terephthalic acid until the chromium nitrate and the terephthalic acid are completely dissolved;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal synthesis reaction to obtain a reaction product a, and carrying out centrifugal separation to obtain a solid b;
(3) washing, centrifugally separating and drying the solid b obtained in the step (2) to obtain a metal organic framework material MIL-101 (Cr);
(4) slowly adding the metal organic framework material MIL-101(Cr) obtained in the step (3) into an ethanol solution dissolved with transition metal salt, and stirring to react to obtain a reaction product c;
(5) and (4) carrying out centrifugal separation on the reaction product c obtained in the step (4) to obtain a solid d, washing, carrying out centrifugal separation, and drying to obtain the bimetallic organic framework material.
Further, in the step (1), the concentration of the sodium acetate aqueous solution is 0.01-0.1 mol/L; the ratio of the amounts of terephthalic acid and sodium acetate is (1-10): 1.
further, in the step (2), the hydrothermal synthesis reaction is carried out at the temperature of 150-300 ℃ for 8-20 h.
Further, in the step (3), the washing is carried out for 1 to 2 times by respectively washing with dimethylformamide and ethanol at the temperature of 50 to 90 ℃ for 0.5 to 2 hours; the drying is vacuum drying, the temperature is 100-200 ℃, and the time is 5-24 hours.
Further, in the step (4), the transition metal salt is one of ferric chloride, copper nitrate and cobalt acetate; the mass ratio of the metal ions of the transition metal salt to the metal organic framework material MIL-101(Cr) is (0.05-0.3): 1; the stirring reaction is carried out, the reaction temperature is room temperature, and the reaction time is 2-6 hours.
Further, in the step (5), the drying is vacuum drying, the temperature is 100-200 ℃, and the time is 5-24 hours; the washing mode is to wash for 2-3 times by adopting ethanol.
The application of the bimetallic organic framework material in the decomposition reaction of cyclohexyl hydroperoxide comprises the following steps:
cyclohexane oxidation liquid is used as reaction liquid, a bimetallic organic framework material is added as a catalyst, and the mixture is stirred and reacts under the alkali-free condition to obtain cyclohexanol and cyclohexanone.
Further, the mass fraction of the bimetallic organic framework material in the reaction liquid is 0.5-5.0%; the reaction is carried out at the temperature of 50-150 ℃ for 1-5 h.
Further, the cyclohexane oxidation liquid is oxidation liquid of cyclohexane without catalytic oxidation, wherein the mass fraction of cyclohexyl hydrogen peroxide is 3% -30%, the mass fraction of cyclohexanol is 0.5% -5%, the mass fraction of cyclohexanone is 1.0% -5.0%, and the mass fraction of cyclohexane is 65% -95%.
The invention has the beneficial effects that:
(1) the catalyst obtained by the invention has simple preparation process, stable property, difficult deterioration, high and stable catalytic performance, basically unchanged catalytic activity after repeated recycling, and can be reused after being simply washed and dried after being recycled, thereby avoiding the problem that the active metal is easy to lose in the reaction and recycling processes after the multi-metal is compounded in the prior art.
(2) In the decomposition reaction of the cyclohexyl hydroperoxide, the conversion rate of the cyclohexyl hydroperoxide can reach more than 96 percent, the total selectivity of alcohol ketone can reach more than 100 percent, meanwhile, the alcohol ketone ratio is obviously improved, the content of alcohol is greatly increased, more hydrogen can be generated in the subsequent cyclohexanol dehydrogenation section, and the generated hydrogen can be used in the section of preparing cyclohexane by hydrogenating benzene, so that the hydrogen consumption of producing cyclohexanone by taking benzene as a raw material is obviously reduced.
(3) The catalyst obtained by the invention can achieve a better effect of catalyzing the decomposition of the cyclohexyl hydroperoxide under the condition of no alkali, compared with the current industrial production mode, the catalyst avoids the use of a large amount of alkali liquor, obviously reduces the pollution to the environment, and has reaction conditions of temperature, pressure and the like which are obviously milder than the prior art, so the application process provided by the invention is a process which is more energy-saving and environment-friendly compared with the prior art.
Detailed Description
The invention will be further illustrated by the following examples, without restricting the scope of the invention thereto.
Example 1
0.41g of sodium acetate solid is weighed and dissolved in 100mL of deionized water, 3.32g of terephthalic acid and 8g of chromium nitrate nonahydrate are slowly added into the solution, and the solution is stirred at room temperature for 30min to completely dissolve the solid. Transferring the obtained solution into an autogenous pressure kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into an air-blowing drying oven heated to 200 ℃ for reaction for 12 hours. And after the reaction is finished, standing the reaction kettle until the reaction kettle is naturally cooled to room temperature, performing centrifugal separation on the obtained reaction product, sequentially washing the solid product with N, N-dimethylformamide and ethanol at 70 ℃ for 1h, and after the washing is finished, performing centrifugal separation to obtain a solid, and performing vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material MIL-101 (Cr). Slowly adding 1g of MIL-101(Cr) solid into 25mL of absolute ethanol solution dissolved with 0.46g of cobalt acetate, stirring and reacting for 4h at room temperature, centrifugally separating to obtain a solid after the reaction is finished, washing the solid with ethanol, and drying in vacuum at 150 ℃ for 12h to obtain a Cr and Co bimetallic organic framework material, which is marked as Co/MIL-101 (Cr).
The following examples illustrate the catalytic decomposition of cyclohexyl hydroperoxide in cyclohexane oxidation liquors as provided by the present invention.
In the following examples and comparative examples, the cyclohexyl hydroperoxide content before and after the reaction was analyzed by iodometry, the cyclohexanol and cyclohexanone content before and after the reaction was analyzed by gas chromatography internal standard method, and the acid ester content before and after the reaction was analyzed by chemical titration.
Example 2
0.1g of the catalyst prepared in example 1 and 10mL (about 8.32 g) of cyclohexane oxidation solution (composition: 8.16% of cyclohexyl hydroperoxide, 1.71% of cyclohexanone, 2.56% of cyclohexanol, 0.76% of acid, 1.98% of ester and 84.83% of cyclohexane) were charged into a 50mL three-necked flask, and the mixture was stirred at 80 ℃ for reaction for 90min, and after the reaction, the mixture was allowed to stand and cool to room temperature, and the reaction solution was taken out and analyzed. The analysis result shows that the conversion rate of the cyclohexyl hydroperoxide is 96.5 percent, the total selectivity of the alcohol ketone is 99 percent, and the ratio of the cyclohexanone: cyclohexanol =1:1.51 (molar ratio).
Example 3
The procedure of example 2 was followed, differing from example 2 in that the catalyst was a catalyst obtained by repeating example 2 three times. The conversion of cyclohexyl hydroperoxide was 95.1%, the overall selectivity to alcohol ketone was 95.2%, cyclohexanone: cyclohexanol =1:1.53 (molar ratio).
Example 4
The procedure of example 2 was followed, differing from example 2 in that the catalyst was a catalyst obtained by repeating example 2 six times. The conversion of cyclohexyl hydroperoxide was 96.6%, the overall selectivity to alcohol ketone was 95.7%, cyclohexanone: cyclohexanol =1:1.55 (molar ratio). The results of examples 3 and 4 show that the catalyst provided by the invention has good stability, and the activity of the catalyst is basically unchanged after being recycled for many times.
Comparative example 1
No catalyst was added and a blank reaction was run. Namely, 10mL (about 8.32 g) of cyclohexane oxide solution (composition: 8.16% of cyclohexylhydroperoxide, 1.71% of cyclohexanone, 2.56% of cyclohexanol, 0.76% of acid, 1.98% of ester, and 84.83% of cyclohexane) was charged in a 50mL three-necked flask. Stirring and reacting at 80 ℃ for 90min, standing and cooling to room temperature after the reaction is finished, and taking out reaction liquid for analysis. The conversion of cyclohexyl hydroperoxide was 4.5%, the overall selectivity to alcohol ketone was 52.8%, cyclohexanone: cyclohexanol =1:2.91 (molar ratio). Compared with the example 2, the cyclohexyl hydroperoxide conversion rate is extremely low, the alcohol ketone selectivity is also very low, and a plurality of byproducts are generated in the reaction.
Comparative example 2
Taking 10mL (about 8.32 g) cyclohexane oxidation solution (the composition is 8.16% of cyclohexyl hydrogen peroxide, 1.71% of cyclohexanone, 2.56% of cyclohexanol, 0.76% of acid, 1.98% of ester and 84.83% of cyclohexane), adding the solution into a 50mL three-neck flask, preparing sodium hydroxide aqueous solution with mass fraction of 4.43% as an inorganic phase, adding cobalt acetate as a catalyst into an aqueous phase, wherein the content of the cobalt acetate is 1 mu g.g.g.g-1The organic phase and the inorganic phase are stirred and reacted for 90min at 96 ℃ according to the volume ratio of 85: 15. After the reaction is finished, standing and cooling to room temperature, taking out the reaction solution for analysis. The conversion of cyclohexyl hydroperoxide was 66.10%, the selectivity for cyclohexanone and cyclohexanol was 83.91%, cyclohexanone: cyclohexanol =1:2.15 (molar ratio). Compared with example 2, the conversion of cyclohexyl hydroperoxide is lower and the selectivity of cyclohexanone to cyclohexanol is also lower.
Comparative example 3
The operation of comparative example 3 is different from that of comparative example 2 in that cobalt acetate is not added to the inorganic phase and the oxidizing solution is reacted only in an alkaline water environment. The conversion of cyclohexyl hydroperoxide was 48.42%, the selectivity for cyclohexanone and cyclohexanol was 102.76%, cyclohexanone: cyclohexanol =1:3.20 (molar ratio). The conversion of cyclohexyl hydroperoxide was lower compared to example 2.
Comparative example 4
0.1g of metal organic framework material MIL-101(Cr) catalyst and 10mL (about 8.22 g) of cyclohexane oxidation solution are added into a 50mL three-neck flask, and the mixture is heated to 70 ℃ while stirring and reacts for 100min at constant temperature. The reaction mixture was cooled to room temperature, and the reaction mixture was taken out for analysis. The conversion of cyclohexyl hydroperoxide was 98.2%, the selectivity of cyclohexanone and cyclohexanol was 100%, cyclohexanone: cyclohexanol =1:0.16 (molar ratio).
This comparative example uses a monometallic organic framework material, and the ratio of ketols in the reaction product is 1:0.16, i.e. the molar ratio of alcohols is 0.16/(0.16+1) =13.79%, while the ratio of ketols in example 2 is 1:1.51, i.e. the molar ratio of alcohols is 1.51/(1.51+1) =60.16%, so the ratio of alcohols is significantly increased, and it can be seen that the catalyst obtained by the present invention has a very significant effect on increasing the cyclohexanol content in the product.
Claims (10)
1. The preparation method of the bimetallic organic metal framework material is characterized by comprising the following steps of:
(1) dissolving sodium acetate solid in deionized water to obtain a sodium acetate aqueous solution, and adding the sodium acetate aqueous solution into the deionized water successively according to the mass ratio of (0.1-10): 1, stirring the chromium nitrate and the terephthalic acid until the chromium nitrate and the terephthalic acid are completely dissolved;
(2) transferring the solution obtained in the step (1) to a high-pressure reaction kettle, carrying out hydrothermal synthesis reaction to obtain a reaction product a after the reaction is finished, and carrying out centrifugal separation to obtain a solid b;
(3) washing, centrifugally separating and drying the solid b obtained in the step (2) to obtain a metal organic framework material MIL-101 (Cr);
(4) adding the metal organic framework material MIL-101(Cr) obtained in the step (3) into an ethanol solution dissolved with transition metal salt cobalt acetate, and stirring and reacting for 2-6 hours at room temperature to obtain a reaction product c;
(5) and (4) carrying out centrifugal separation on the reaction product c obtained in the step (4) to obtain a solid d, washing, carrying out centrifugal separation, and drying to obtain the bimetallic organic framework material.
2. The method for preparing the bimetallic organic metal framework material as claimed in claim 1, wherein in the step (1), the concentration of the sodium acetate aqueous solution is 0.01-0.1 mol/L; the ratio of the amounts of terephthalic acid and sodium acetate is (1-10): 1.
3. the method for preparing the bimetallic organometallic framework material as claimed in claim 1, wherein in the step (2), the hydrothermal synthesis reaction is carried out at a temperature of 150-300 ℃ for 4-20 h.
4. The method for preparing the bimetallic organic metal framework material as claimed in claim 1, wherein in the step (3), the washing is performed by respectively washing with dimethylformamide and ethanol for 1-2 times at 50-90 ℃ for 0.5-2 h; the drying is vacuum drying, the temperature is 100-200 ℃, and the time is 5-24 hours.
5. The method for preparing a bimetallic organometallic framework material as claimed in claim 1, wherein in the step (4), the mass ratio of the metal ions of the transition metal salt to the metal-organic framework material MIL-101(Cr) is (0.05-0.3): 1.
6. the method for preparing the bimetallic organic metal framework material as claimed in claim 1, wherein in the step (5), the drying is vacuum drying at 100-200 ℃ for 5-24 h; the washing mode is to wash for 2-3 times by adopting ethanol.
7. Use of the bimetallic organic framework material prepared by the preparation method of any one of claims 1 to 6 in cyclohexyl hydroperoxide decomposition reaction.
8. Use of a bimetallic organic framework material according to claim 7 in a cyclohexyl hydroperoxide decomposition reaction, characterised by the steps of: cyclohexane oxidation liquid is used as reaction liquid, a bimetallic organic framework material is added as a catalyst, and the mixture is stirred and reacted under the alkali-free condition to obtain cyclohexanol and cyclohexanone.
9. The use of the bimetallic organic framework material in the decomposition reaction of cyclohexyl hydroperoxide according to claim 8, characterized in that the mass fraction of the bimetallic organic framework material in the reaction solution is 0.5% -5.0%; the reaction temperature is 50-150 ℃, and the reaction time is 1-5 h.
10. The use of the bimetallic organic framework material as defined in claim 8, wherein the cyclohexane oxidation liquid is an oxidation liquid without catalytic oxidation of cyclohexane, and the mass fraction of the cyclohexyl hydroperoxide is 3-30%, the mass fraction of cyclohexanol is 0.5-5.0%, the mass fraction of cyclohexanone is 1.0-5.0%, and the mass fraction of cyclohexane is 65-95%.
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| CN114768880A (en) * | 2022-05-13 | 2022-07-22 | 湘潭大学 | Preparation method of bimetal node MOFs material and application of bimetal node MOFs material in catalysis of cyclohexyl hydroperoxide decomposition reaction |
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| CN105080490A (en) * | 2015-08-04 | 2015-11-25 | 华南理工大学 | Magnesite-chrome bimetallic MOFs adsorbent MIL-101 (Cr, Mg) and preparation method thereof |
| CN105712867A (en) * | 2016-01-27 | 2016-06-29 | 湘潭大学 | Preparation method of metal organic framework material and application of metal organic framework material in cyclohexyl hydroperoxide decomposition reaction |
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| CN105080490A (en) * | 2015-08-04 | 2015-11-25 | 华南理工大学 | Magnesite-chrome bimetallic MOFs adsorbent MIL-101 (Cr, Mg) and preparation method thereof |
| CN105712867A (en) * | 2016-01-27 | 2016-06-29 | 湘潭大学 | Preparation method of metal organic framework material and application of metal organic framework material in cyclohexyl hydroperoxide decomposition reaction |
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