CN107082892A - A kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction - Google Patents
A kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction.The present invention is used as carrier using metal-organic framework materials MIL 101 (Cr), bimetallic organic framework material is obtained by introducing the second metal ion species, and under the conditions of this material is applied into alkali-free as catalyst in cyclohexyl hydroperoxide decomposing solution.Gained catalyst preparation process of the invention is simple, and catalyst property is stable to be unlikely to deteriorate, and catalytic performance is high and stably, is basically unchanged by repeatedly recycling its catalytic activity.The catalyst of the present invention is used to be catalyzed cyclohexylhydroperoxdecomposition decomposition reaction, and the conversion ratio of cyclohexyl hydroperoxide can reach more than 96%, and the overall selectivity of alcohol ketone can reach more than 100%, while significantly improving ratio of the cyclohexanol with respect to cyclohexanone in product.
Description
Technical field
Cyclohexyl is catalytically decomposed the present invention relates to a kind of preparation of bimetallic organic framework material and its under the conditions of alkali-free
Hydrogen peroxide generates cyclohexanol and the application in hexamethylene reactive ketone.
Background technology
Cyclohexanone is important Organic Chemicals, is the important intermediate for manufacturing nylon, ethanedioic acid and caprolactam,
It is the important industrial solvent of the industries such as medicine, coating, plastics recovery, widely, its demand is constantly increasing purposes.
At present, the conventional method of industrial production cyclohexanone is cyclohexane oxidation process, wherein what is be most widely used is lotus
The non-catalyst oxidation method of blue DSM N. V.'s exploitation.The technological process is broadly divided into two steps：In the middle of the first step, cyclohexane oxidation generation
Product cyclohexyl hydroperoxide（CHHP）, conversion rate of oxidation control is that the control of 3%~4%, CHHP mass fractions is 4%~5%, is obtained
Higher yield is 95%~97%, second step, and the oxidation solution that the first step is obtained is in 70~115 DEG C of reaction temperature, in 1 μ g/g transition
Cartalytic decomposition effect is carried out in the aqueous alkali of metal ion, reaction obtains cyclohexanol and cyclohexanone.The conversion of the decomposition reaction
Rate reaches 100%, but the selectivity of alcohol ketone is 87%, and wherein cyclohexanol is selectively 33%, and cyclohexanone selectivity is 54%, keto-alcohol ratio
For 1:0.61, the yield of decomposition reaction is 87%, and total alcohol ketone selectivity of whole workshop section is 84%, a large amount of alkali lye of reaction consumption and difficulty
With with separation of oil, spent lye can only cause serious environmental pollution by burning disposal.Chinese invention CN1105970,
CN1147499A, CN96118441, CN98112730 are improved this technique.Decomposed by the way that decomposition reaction is changed into two steps
Method, the first step carries out homogeneous catalysis in alkali-free or low alkali environment using oil soluble transition metal salt, and second step is in high alkali environment
Middle use water-soluble transition metal salt carries out heterogeneous catalysis so that decomposition yield of cyclohexyl hydrogen peroxide brings up to 95%.But this
The deficiency of technique is that the oil soluble transition metal salt used, which is easily generated, to be precipitated and the fouling in pipeline, has a strong impact on life
Production is carried out continuously, and in reaction using having arrived alkali, however it remains the problem of environmental pollution of salkali waste.Accordingly, it would be desirable to set up one kind
The cyclohexyl hydroperoxide catalytic decomposition generation cyclohexanol and cyclohexanone of the high selectivity high conversion carried out under the conditions of alkali-free
Production method.
In addition, French Rhodia has been invented and decomposed using chromic acid tert-butyl homogeneous catalysis decomposing cyclohexylhdroperoxide
Technique, make antisludging agent using octyl phosphate.The method generates adipic acid chromium precipitation in decomposable process, causes to produce pipeline knot
Dirt is, it is necessary to consume substantial amounts of octyl phosphate antisludging agent, but still can not thoroughly solve scale problems, the continuous production cycle is four
Month.The other technique cyclohexyl hydroperoxide rates of decomposing and transforming is 92% or so, and total moles yield is 80%.
The chromium phosphorus aluminium molecule with AFI structure is individually disclosed in Chinese invention CN01118441.8, CN01118438.8
Sieve and the chrome-silicon molecular sieve with MFI structure, decomposition of the molecular sieve containing chromium to cyclohexyl hydroperoxide have higher yields, but chromium
Metal loss is very fast, and so that catalyst is inactivated quickly, conversion ratio is relatively low, and reaction time is long, and commercial Application has quite difficult
Degree.
Metal organic framework（Metal-Organic Frameworks）Material is by metal ion and many sites are organic matches somebody with somebody
Body constitutes the material of tridimensional network.It has higher specific surface area, regulatable hole size and can functional modification
The features such as, it is the important novel porous materials of another class outside zeolite and CNT, in catalysis, gas storage, gas point
From all there is extensive use in terms of, medicament transport and luminescent material.
Chromium metal organic framework MIL-101 2005 by French Ferey team combine computer simulation design and first
Synthesis, using Isosorbide-5-Nitrae-terephthalic acid (TPA) as organic ligand, Cr (NO3)3·9H2O is metal salt, and HF is that mineralizer is closed by hydro-thermal
Cheng Fa, reacts 8 hours at 220 DEG C and is made, and final by DMF, hot ethanol and ammonium fluoride dissolving activation
Obtain pure MIL-101.
The present invention uses metal-organic framework materials MIL-101 (Cr) as carrier, by introducing the second metal ion species
Bimetallic organic framework material is obtained, to obtain the catalyst that the stable metal ion of performance is not easy to be lost in, and by this material
It is applied to as catalyst in alkali free environment cyclohexyl hydroperoxide decomposing solution, is ensuring high decomposition reaction conversion ratio and alcohol
While ketone is selective, lifting catalyst stability and alcohol ketone ratio, so as to improve its industrial applications value.
The content of the invention
It is an object of the invention to provide a kind of catalyst stability is good and the organic bone of bimetallic that can repeatedly recycle
The preparation method of frame material, and there is provided its application as catalyst in cyclohexylhydroperoxdecomposition decomposition reaction, ensureing
While high de-agglomeration reaction conversion ratio and alcohol ketone selectivity, improve cyclohexanol in product and, with respect to the ratio of cyclohexanone, and substantially subtract
The formation of few accessory substance acid esters.
The purpose of the present invention is realized in the following way：
A kind of preparation method of bimetallic organic framework material, comprises the following steps：
（1）The ratio between sodium acetate solid is dissolved in deionized water and obtains sodium acetate aqueous solution, then amount to its priority addition material
For（0.1~10）：1 chromic nitrate and terephthalic acid (TPA) are simultaneously stirred to being completely dissolved；
（2）By step（1）Obtained solution is transferred to autoclave, carries out hydrothermal synthesis reaction, obtains reaction product a, centrifuges
Solid b is obtained after separation；
（3）By step（2）Obtained solid b is washed, and is centrifuged, and is dried, and metal-organic framework materials MIL-101 is made
（Cr）；
（4）By step（3）Obtained metal-organic framework materials MIL-101（Cr）It is slowly added to dissolved with transition metal salt
Simultaneously stirring reaction obtains reaction product c in ethanol solution；
（5）By step（4）Obtained reaction product c is centrifuged, and obtains solid d, is centrifuged after washing, dries, system
Obtain bimetallic organic framework material.
Further, step（1）In, the concentration of the sodium acetate aqueous solution is 0.01 ~ 0.1mol/L；Terephthalic acid (TPA) with
The ratio between amount of material of sodium acetate is（1~10）：1.
Further, step（2）In, described hydrothermal synthesis reaction, temperature is 150 ~ 300 DEG C, and the time is 8 ~ 20h.
Further, step（3）In, described washing, washing time mode is to be distinguished using dimethylformamide and ethanol
Washing 1 ~ 2 time, temperature is 50 ~ 90 DEG C, and the time is 0.5 ~ 2h；Described drying is vacuum drying, and temperature is 100 ~ 200 DEG C, when
Between be 5 ~ 24h.
Further, step（4）In, described transition metal salt is one kind in iron chloride, copper nitrate, cobalt acetate；Cross
Cross the metal ion and metal-organic framework materials MIL-101 of metal salt（Cr）Mass ratio be（0.05~0.3）：1；Described
Stirring reaction, reaction temperature is room temperature, and the reaction time is 2 ~ 6 hours.
Further, step（5）In, described drying is vacuum drying, and temperature is 100 ~ 200 DEG C, and the time is 5 ~ 24h；
Mode of washing is to be washed 2 ~ 3 times using ethanol.
Application of the above-mentioned bimetallic organic framework material in cyclohexylhydroperoxdecomposition decomposition reaction, including following step
Suddenly：
Using cyclohexane oxide solution as reaction solution, bimetallic organic framework material is added as catalyst, is stirred under the conditions of alkali-free
Reaction, obtains cyclohexanol and cyclohexanone.
Further, mass fraction of the bimetallic organic framework material in reaction solution is 0.5% ~ 5.0%；Described is anti-
Should, reaction temperature is 50 ~ 150 DEG C, and the reaction time is 1 ~ 5h.
Further, described cyclohexane oxide solution is the oxidation solution of hexamethylene non-catalyst oxidation, wherein cyclohexyl peroxide
The mass fraction for changing hydrogen is 3% ~ 30%, and the mass fraction of cyclohexanol is 0.5% ~ 5%, and the mass fraction of cyclohexanone is 1.0% ~ 5.0%,
The mass fraction of hexamethylene is 65% ~ 95%.
The beneficial effects of the present invention are：
（1）Gained catalyst preparation process of the invention is simple, and catalyst property is stable to be unlikely to deteriorate, and catalytic performance is high and stably,
It is basically unchanged, can be reused after simple washing is dried after recovery by repeatedly recycling its catalytic activity, it is to avoid
In the prior art after many metal composites, the problem of active metal is easy to run off in reaction and removal process.
（2）Gained catalyst of the invention is in cyclohexylhydroperoxdecomposition decomposition reaction, the conversion ratio of cyclohexyl hydroperoxide
More than 96% is can reach, the overall selectivity of alcohol ketone can reach more than 100%, at the same time, alcohol ketone ratio is significantly improved, alcohol contains
Amount is significantly increased, and makes that more hydrogen can be produced in follow-up cyclohexanol dehydrogenation workshop section, and the hydrogen of generation can be used for prepared from benzene and hydrogen standby
Hexamethylene workshop section, so as to substantially reduce the hydrogen consumption that cyclohexanone is produced by raw material of benzene.
（3）Gained catalyst of the invention can reach preferably catalysis cyclohexyl hydroperoxide point under conditions of complete alkali-free
Effect is solved, compared with current industrial mode of production, it is to avoid the uses of a large amount of alkali lye, significantly reduces the pollution to environment,
And the reaction condition such as temperature, pressure is clearly more gentle compared with prior art, therefore the technique for applying that the present invention is provided is a kind of phase
To the technique of prior art more energy-conserving and environment-protective.
Embodiment
With reference to example, the invention will be further described, and present invention is not limited only to this.
Embodiment 1
0.41g sodium acetates solid dissolving is weighed in 100mL deionized waters, 3.32g is slowly added into above-mentioned solution to benzene two
Formic acid and 8g Chromium nitrate (Cr(NO3)3),nonahydrates, 30min, which is stirred at room temperature, is completely dissolved solid.Obtained solution is transferred to band polytetrafluoroethyl-ne
In the self-generated pressure kettle of alkene liner, reactor is put into and has been heated to reacting 12h in 200 DEG C of air dry oven.Reaction terminates
Reactor is stood afterwards and treats that it naturally cools to room temperature, reaction product is obtained and is centrifuged, take solid product priority N,
Dinethylformamide and ethanol wash 1h at 70 DEG C, and washing is centrifugally separating to obtain solid vacuum at 150 DEG C and done after terminating
Dry 12h, obtains metal-organic framework materials MIL-101 (Cr).Take 1gMIL-101（Cr）Solid be slowly added into 25mL dissolved with
In the ethanol solution of 0.46g cobalt acetates, stirring reaction 4h, reacts and is centrifugally separating to obtain solid after terminating, use second at room temperature
Alcohol washs solid, is dried in vacuo 12h at 150 DEG C, obtains Cr, Co bimetallic organic framework material, be denoted as Co/MIL-101
(Cr)。
Following examples illustrate the catalytic decomposing method of cyclohexyl hydroperoxide in the cyclohexane oxide solution that the present invention is provided.
Cyclohexyl hydroperoxide content before and after iodometric titrationiodimetry titration analytical reactions is used in the following example and comparative example, is made
With the content of cyclohexanol and cyclohexanone before and after gas chromatogram fixative analytical reactions, with acid esters before and after chemical titration analytical reactions
Content.
Embodiment 2
The catalyst for taking 0.1g embodiments 1 to prepare, 10mL（About 8.32g）Cyclohexane oxide solution（Constitute as cyclohexyl hydroperoxide
8.16%, cyclohexanone 1.71%, cyclohexanol 2.56%, acid 0.76%, ester 1.98%, hexamethylene 84.83%）, it is added to tri- mouthfuls of burnings of 50mL
In bottle, the stirring reaction 90min at 80 DEG C, reaction stands after terminating and is cooled to room temperature, takes out reaction solution and is analyzed.Analysis knot
The conversion ratio that fruit obtains cyclohexyl hydroperoxide is 96.5%, and alcohol ketone overall selectivity is 99%, cyclohexanone：Cyclohexanol=1:1.51（Mole
Than）.
Embodiment 3
By the operating process of embodiment 2, it is in the difference of embodiment 2 in, catalyst to repeat the catalysis after embodiment 2 three times
Agent.The conversion ratio of cyclohexyl hydroperoxide is 95.1%, and alcohol ketone overall selectivity is 95.2%, cyclohexanone：Cyclohexanol=1:1.53（Rub
You compare）.
Embodiment 4
By the operating process of embodiment 2, it is in the difference of embodiment 2 in, catalyst to repeat the catalysis after embodiment 2 six times
Agent.The conversion ratio of cyclohexyl hydroperoxide is 96.6%, and alcohol ketone overall selectivity is 95.7%, cyclohexanone：Cyclohexanol=1:1.55（Rub
You compare）.The result of embodiment 3 and 4 shows that catalyst provided by the present invention has good stability, after repeatedly reclaiming
Catalyst activity is basically unchanged.
Comparative example 1
Catalyst is added without, enters line blank reaction.10mL is added into 50mL three-necked flasks（About 8.32g）Cyclohexane oxide solution
（Constitute as cyclohexyl hydroperoxide 8.16%, cyclohexanone 1.71%, cyclohexanol 2.56%, acid 0.76%, ester 1.98%, hexamethylene
84.83%）.The stirring reaction 90min at 80 DEG C, reaction stands after terminating and is cooled to room temperature, takes out reaction solution analysis.Cyclohexyl
The conversion ratio of hydrogen peroxide is 4.5%, and alcohol ketone overall selectivity is 52.8%, cyclohexanone：Cyclohexanol=1:2.91（Mol ratio）.With reality
Apply example 2 to compare, cyclohexylhydroperoxconversion conversion rate is extremely low, and alcohol ketone selectivity is also very low, reaction generation accessory substance is more.
Comparative example 2
Take 10mL（About 8.32g）Cyclohexane oxide solution（Constitute as cyclohexyl hydroperoxide 8.16%, cyclohexanone 1.71%, cyclohexanol
2.56%, acid 0.76%, ester 1.98%, hexamethylene 84.83%）, add in 50mL three-necked flasks, it is 4.43% to prepare mass fraction
Sodium hydrate aqueous solution adds cobalt acetate into aqueous phase as catalyst, the content of cobalt acetate is 1 μ gg as inorganic phase-1,
By organic phase and inorganic phase volume ratio 85:15 ratio, the stirring reaction 90min at 96 DEG C.Reaction stands after terminating and is cooled to
Room temperature, takes out reaction solution analysis.The conversion ratio of cyclohexyl hydroperoxide is 66.10%, and the selectivity of cyclohexanone and cyclohexanol is
83.91%, cyclohexanone：Cyclohexanol=1:2.15（Mol ratio）.Compared with Example 2, the conversion ratio of cyclohexyl hydroperoxide is relatively low,
The selectivity of cyclohexanone and cyclohexanol is also than relatively low.
Comparative example 3
By the operating process of comparative example 3, it is in the difference of comparative example 2 in being added without cobalt acetate in inorganic phase, oxidation solution only exists
Reacted under buck environment.The conversion ratio of cyclohexyl hydroperoxide is 48.42%, and the selectivity of cyclohexanone and cyclohexanol is
102.76%, cyclohexanone：Cyclohexanol=1:3.20（Mol ratio）.Compared with Example 2, the conversion ratio of cyclohexyl hydroperoxide compared with
It is low.
Comparative example 4
Take 0.1g metal-organic framework materials MIL-101 (Cr) catalyst, 10mL（About 8.22g）Cyclohexane oxide solution, is added
In 50mL three-necked flasks, 70 DEG C, isothermal reaction 100min are heated to while stirring.Room temperature is cooled to, reaction solution analysis is taken out.Ring
The conversion ratio of hexyl hydrogen peroxide is 98.2%, and the selectivity of cyclohexanone and cyclohexanol is 100%, cyclohexanone：Cyclohexanol=1:0.16
（Mol ratio）.
This comparative example uses keto-alcohol ratio in monometallic organic framework material, reaction product to be 1:0.16, i.e. alcohol mole are accounted for
It is 1 than the keto-alcohol ratio for 0.16/ (0.16+1)=13.79%, and in embodiment 2:Mole accounting of 1.51, i.e. alcohol is 1.51/
(1.51+1)=60.16%, therefore, the ratio of alcohol are substantially substantially improved, it is seen that present invention gained catalyst is to improving product middle ring
The effect highly significant of hexanol content.
Claims (10)
1. a kind of preparation method of bimetallic Organometallic framework material, it is characterised in that comprise the following steps：
（1）The ratio between sodium acetate solid is dissolved in deionized water and obtains sodium acetate aqueous solution, then amount to its priority addition material
For（0.1~10）：1 chromic nitrate and terephthalic acid (TPA) are simultaneously stirred to being completely dissolved；
（2）By step（1）Obtained solution goes to autoclave, carries out hydrothermal synthesis reaction, and reaction is reacted after terminating
Solid b is obtained after product a, centrifugation；
（3）By step（2）Obtained solid b is washed, and is centrifuged, and is dried, and metal-organic framework materials MIL-101 is made
（Cr）；
（4）By step（3）Obtained metal-organic framework materials MIL-101（Cr）Add ethanol dissolved with transition metal salt
Simultaneously stirring reaction obtains reaction product c in solution；
（5）By step（4）Obtained reaction product c is centrifuged, and obtains solid d, is centrifuged after washing, dries, system
Obtain bimetallic organic framework material.
2. the preparation method of bimetallic Organometallic framework material according to claim 1, it is characterised in that step（1）
In, the concentration of described sodium acetate aqueous solution is 0.01 ~ 0.1mol/L；The ratio between amount of material of terephthalic acid (TPA) and sodium acetate is
（1~10）：1.
3. the preparation method of bimetallic Organometallic framework material according to claim 1, it is characterised in that step（2）
In, described hydrothermal synthesis reaction, temperature is 150 ~ 300 DEG C, and the time is 4 ~ 20h.
4. the preparation method of bimetallic Organometallic framework material according to claim 1, it is characterised in that step（3）
In, described washing, mode of washing is to be washed respectively 1 ~ 2 time using dimethylformamide and ethanol, and temperature is 50 ~ 90 DEG C, when
Between be 0.5 ~ 2h；Described drying is vacuum drying, and temperature is 100 ~ 200 DEG C, and the time is 5 ~ 24h.
5. the preparation method of bimetallic Organometallic framework material according to claim 1, it is characterised in that step（4）
In, described transition metal salt is one kind in iron chloride, copper nitrate, cobalt acetate；The metal ion and metal of transition metal salt
Organic framework material MIL-101（Cr）Mass ratio be（0.05~0.3）：1；Described stirring reaction, reaction temperature is room temperature,
Reaction time is 2 ~ 6 hours.
6. the preparation method of bimetallic Organometallic framework material according to claim 1, it is characterised in that step（5）
In, described drying is vacuum drying, and temperature is 100 ~ 200 DEG C, and the time is 5 ~ 24h；Mode of washing is using ethanol washing 2 ~ 3
It is secondary.
7. bimetallic organic framework material prepared by the preparation method described in any one of claim 1 to 6 is in cyclohexyl peroxidating
Application in hydroperoxide decomposition reaction.
8. application of the bimetallic organic framework material according to claim 7 in cyclohexylhydroperoxdecomposition decomposition reaction,
It is characterised in that it includes following steps：Using cyclohexane oxide solution as reaction solution, add bimetallic organic framework material and be used as catalysis
Agent, stirs and reacts under the conditions of alkali-free, obtains cyclohexanol and cyclohexanone.
9. application of the bimetallic organic framework material according to claim 8 in cyclohexylhydroperoxdecomposition decomposition reaction,
Characterized in that, mass fraction of the bimetallic organic framework material in reaction solution is 0.5% ~ 5.0%；Reaction temperature is 50 ~ 150
DEG C, the reaction time is 1 ~ 5h.
10. application of the bimetallic organic framework material according to claim 8 in cyclohexylhydroperoxdecomposition decomposition reaction,
Characterized in that, oxidation solution of the described cyclohexane oxide solution for hexamethylene non-catalyst oxidation, wherein cyclohexyl hydroperoxide
Mass fraction is 3% ~ 30%, and the mass fraction of cyclohexanol is 0.5% ~ 5.0%, and the mass fraction of cyclohexanone is 1.0% ~ 5.0%, hexamethylene
The mass fraction of alkane is 65% ~ 95%.
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| CN112138673A (en) * | 2019-06-27 | 2020-12-29 | 湘潭大学 | Preparation method of bimetallic oxide material and application of bimetallic oxide material in cyclohexyl hydroperoxide decomposition reaction |
| 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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| CN107754859A (en) * | 2017-09-27 | 2018-03-06 | 中国建筑材料科学研究总院 | Catalyst and its preparation method and application |
| CN107754859B (en) * | 2017-09-27 | 2019-09-10 | 中国建筑材料科学研究总院 | Catalyst and its preparation method and application |
| CN107930698A (en) * | 2017-11-28 | 2018-04-20 | 万华化学集团股份有限公司 | The preparation method and N of catalyst1The preparation method of (2 aminoethyl) 1,2 ethylenediamines |
| CN112138673A (en) * | 2019-06-27 | 2020-12-29 | 湘潭大学 | Preparation method of bimetallic oxide material and application of bimetallic oxide material in cyclohexyl hydroperoxide decomposition reaction |
| 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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