A kind of preparation method of epoxy cyclohexane
Technical field
The invention belongs to the fine chemical product preparing technical field, be specifically related to that a kind of reaction conditions is gentle, Preparation of Catalyst is simple and be prone to separate with reaction solution, product convenient post-treatment, heterogeneous catalytic reaction low in the pollution of the environment prepare the method for epoxy cyclohexane.
Background technology
1, there is active epoxy group(ing) on the molecular structure of 2-epoxy cyclohexane, under acid or alkaline catalysts effect, the very easily open loop of ternary ether ring generates a kind of compound of high added value with multiple substance reactions such as ammonia, amine, alcohol, phenol, carboxylic acid, water.Therefore, epoxy cyclohexane is a kind of important organic intermediate, and the application in the industry has synthetic epoxy resin reactive thinner, novel agrochemical propargite etc.
The main method that early stage industriallization generates epoxy cyclohexane is the homogeneous phase method mostly, like chlorohydrination and inorganic acid method.Chlorohydrination is owing to produce a large amount of chlorine-contained wastewaters in process of production, and environmental pollution and equipment corrosion are serious.Adopt sulfuric acid to exist equally because of equipment corrosion and seriously bring environmental issue as the tetrahydrobenzene water of homogeneous catalyst and technology.The application of phase-transfer catalyst has solved the problem that exists in the above-mentioned homogeneous reaction accordingly; For example Chinese Academy of Sciences Dalian materialization institute (publication number CN1401640) produces epoxy cyclohexane with reaction control phase transfer catalyst: such catalyzer is insoluble to reaction medium; But under the effect of hydrogen peroxide, form and dissolve in the active specy in the reaction medium; Be consumed and work as hydrogen peroxide, catalyzer promptly returns to initial structure and from reaction system, separates out.But find in the production run that this catalyzer is difficult to keep stable, and production cost is high, is unfavorable for suitability for industrialized production.
Because the homogeneous catalysis process exists distinct disadvantage in processes such as separation, recovery and recycling, therefore, people attempt to overcome through the heterogenize of homogeneous catalyst the exemplary shortcomings of above-mentioned homogeneous catalytic reaction.For example template is done with organic amine by Sinopec Group's (authorizing publication number CN101348472A); In inert atmosphere, handle the catalyzer that makes epoxidation reaction through silylanization again to silicon dioxide skeleton with grafting inorganic titanium; Tetrahydrobenzene and organo-peroxide are as substrate, and epoxidation makes the product epoxy cyclohexane.Problems such as this method has well solved environmental pollution, and equipment corrosion is serious.But the Preparation of catalysts method is complicated; Organo-peroxide costs an arm and a leg as oxygenant, is not easy to large-scale industrial production.
For example Baling Petrochemical Co., Ltd., SINOPEC (publication number CN1542007A) with molecular oxygen as oxygen source, valeraldehyde etc. as intermediary; With one of oxide compound of Mn, Mn, Mn, Ni; One of oxide compound of W or Mo; Be re-dubbed catalyzer with one of oxygen acid such as N, P, the raw material cyclohexene oxide is become epoxy cyclohexane.This preparation technology as oxygenant, can obtain the epoxidation product of highly selective with the molecular oxygen of green non-pollution.But because molecular oxygen is difficult to be activated, reaction system is complicated, makes that the per pass conversion of tetrahydrobenzene is extremely low.
Use and to meet ydrogen peroxide 50 that Green Chemistry requires equally and solved the problems referred to above well as the oxygen source of epoxidation reaction.For example Sinopec Group (publication number CN101691363A) as catalyzer, uses alkaline assistant with the synthetic HTS, generates epoxide with hydrogen peroxide and tetrahydrobenzene reaction.Ydrogen peroxide 50-HTS the reaction system that alkene epoxidation is had highly selective is used in this reaction.But because traditional HTS such as TS-1 are the micro-pore zeolites with MFI structure; Its aperture has only 0.55 nanometer; The oxidizing reaction of can not catalysis macromole alkene (like cyclooctene and dodecylene etc.) participating in, and cause industrial application to receive great restriction because of its granularity causes difficult separation and recycling for a short time.
For example Institute of Chemistry, Academia Sinica (publication number CN101225076A) has used various organic or inorganic cationic phosphoramidate tungstate mixtures as catalyzer; In glyoxaline ion liquid, form peroxide heteropolyacid active specy, so highly selective olefin oxidation is become epoxy compounds.Ionic liquid in this patent and the preparation of multiple organophosphorus molybdate are complicated, make cost higher relatively.Zhengzhou University (publication number CN101020669A) discloses under a kind of condition of no solvent, with the mixture of complicated organic resin compound and salt as catalyzer, ydrogen peroxide 50 system epoxy cyclohexane.Catalytic activity is high, reaction preference is high, catalyzer is convenient to recycle.But all there are shortcomings such as preparation process complicacy, cost height in catalyst system therefor, is unfavorable for the heavy industrialization application.
Summary of the invention
To the problems referred to above that exist in the prior art, the object of the present invention is to provide that a kind of reaction conditions is gentle, Preparation of Catalyst is simple and be prone to separate with reaction solution, product convenient post-treatment, heterogeneous catalytic reaction low in the pollution of the environment prepare the method for epoxy cyclohexane.
The preparation method of described a kind of epoxy cyclohexane is characterized in that with the tetrahydrobenzene being substrate, and acetonitrile is a reaction solvent; The 30wt% ydrogen peroxide 50 is an oxygenant; Under the effect of multiphase load type composite oxide catalysts, carry out epoxidation reaction of olefines, 40 ~ 80 ℃, the reaction times is 4 ~ 10h; After reaction finishes with the reaction solution rectification process; Get 130 ~ 135 ℃ cut, obtain epoxy cyclohexane, described multiphase load type composite oxide catalysts is by the molecular sieve carried phosphorus molybdenum of Ti-MCM-41 manganese heteropolyacid sodium salt Na
3+nPMo
12-nMn
nO
40Obtain.
The preparation method of described a kind of epoxy cyclohexane, it is characterized in that the preparation method of described multiphase load type composite oxide catalysts is: with the Ti-MCM-41 mesopore molecular sieve is carrier, phosphorus molybdenum manganese heteropolyacid sodium salt Na
3+nPMo
12-nMn
nO
40Be the active ingredient presoma, after 400 ~ 600 ℃ of high-temperature roasting activation, make.
The preparation method of described a kind of epoxy cyclohexane is characterized in that described phosphorus molybdenum manganese heteropolyacid sodium salt Na
3+nPMo
12-nMn
nO
40Load quality be 10 ~ 50% of carrier Ti-MCM-41 quality.
The preparation method of described a kind of epoxy cyclohexane is characterized in that the titanium silicon mol ratio is 0.04 ~ 0.3:1 in the carrier Ti-MCM-41 mesopore molecular sieve.
The preparation method of described a kind of epoxy cyclohexane is characterized in that phosphorus molybdenum manganese heteropolyacid sodium salt Na
3+nPMo
12-nMn
nO
40Middle Mn element and P element mol ratio are 0.5 ~ 3:1.
The preparation method of described a kind of epoxy cyclohexane is characterized in that the mass ratio that feeds intake of tetrahydrobenzene and acetonitrile is 1:1 ~ 4.
The preparation method of described a kind of epoxy cyclohexane is characterized in that tetrahydrobenzene and catalyst quality ratio are 3.28 ~ 8.2:1.
The preparation method of described a kind of epoxy cyclohexane, the molar ratio that it is characterized in that tetrahydrobenzene and ydrogen peroxide 50 is 1:1 ~ 3.
Multiphase load type composite oxide catalysts of the present invention exchanges Ti by total silicon MCM-41 molecular sieve carrier through skeleton, one-step synthesis Ti-MCM-41 mesopore molecular sieve, load keggin structure heteropolyacid salt Na
3+nPMo
12-nMn
nO
40(brief note is PMo
12-nMn
n), through the phosphorus molybdenum manganese composite oxide that roasting makes, concrete preparation method is following:
1) preparation of carrier Ti-MCM-41:
Mass concentration is that 5% the cetyl trimethylammonium bromide aqueous solution stirs down in brute force and is heated to 40 ℃, be added dropwise to tetraethoxysilance, and the pH value of using sodium hydroxide to control solution is 11; Dropwising afterreaction liquid continues to stir 1 hour; Be added dropwise to tetrabutyl titanate again, dropwise the back and continuing stirring 1 hour; In 110 ℃ of crystallization 24 hours, use deionized water and absolute ethanol washing until neutrality more respectively then, 100 ℃ of dry 12h obtain Ti-MCM-41 mesopore molecular sieve work in-process; With the Ti-MCM-41 work in-process that obtain 550 ℃ of roastings 6 hours in air atmosphere, obtain one-step synthesis Ti-MCM-41 mesopore molecular sieve; The feed intake ratio of amount of substance of described cetyl trimethylammonium bromide and tetraethoxysilance is 1:2; The titanium silicon ratio of said molecular sieve is 0.04 ~ 0.3:1;
2) preparation method of phosphorus molybdenum manganese heteropolyacid sodium salt is following:
6.43 ~ 8.41mmol, four water ammonium paramolybdates are joined in the 50 mL zero(ppm) water stir, be heated to 100 ℃, add 1.5mL acetate, regulate PH to 4.5 ~ 5.0; Stirring the SODIUM PHOSPHATE, MONOBASIC, 2.5 ~ 15mmol Mn nitrate and the 10mL concentration that successively add 5mmol down is the sulfuric acid of 0.5M, continues stirring reaction liquid, steams to the small amount of liquid cooling and separates out solid, after the filtration drying, promptly obtains catalyst activity component PMo
12-nMn
n, 0.5≤n≤3 wherein.
3) load of active ingredient presoma and activation
The present invention with excessive pickling process with Ti-MCM-41 and catalyst precursor PMo
12-nMn
nAqueous solution; 60 ℃ are stirred evaporate to dryness down; 110 ℃ down dry 12 hours after 400 ~ 600 ℃ of air atmosphere roastings 4 hours; Obtain loading type phosphorus molybdenum Mn complex oxide catalyst finished product, through control feed ratio, i.e. charge capacity (the phosphorus molybdenum cobalt heteropolyacid sodium salt Na of the final carried oxide of may command
3+nPMo
12-nCo
nO
40With carrier Ti-MCM-41 mass ratio), charge capacity selects 10% ~ 50%.
Through adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is following:
1) activity of such catalysts component phosphorus molybdenum manganese composite oxide according to the invention has the oxygen storage capacity higher than pure manganese oxide, makes catalytic oxidation performance higher than simple Mn oxide.Heteropolyacid salt itself has good catalysis epoxidation effect, has synergistic effect with manganese element, further improves catalytic performance;
2) the present invention is a carrier with the Ti-MCM-41 mesopore molecular sieve.Ti-MCM-41 molecular sieve pore passage after titanium is modified is shorter than MCM-41, has shortened product residence time in catalyzer, reduces the generation of hydrolysising by-product, thereby increases reaction preference; Aperture ratio TS-1 is big, helps carrying out bulky molecular catalysis reaction (the for example selected substrate tetrahydrobenzene of the present invention), thereby increases catalyst performance, has improved reaction efficiency;
3) multiphase load type composite oxide catalysts of the present invention is easily separated in reaction solution, can be repeatedly used after the separation, and is easy to operate, cost is low, environmental friendliness, economic benefit high;
4) the present invention is oxygen source with the ydrogen peroxide 50, and its by product is a water, meets the Green Chemistry requirement; Acetonitrile is a solvent, and the solvent effect is obvious, and easily separated between reactant and the water byproduct; This is reflected under the normal pressure and carries out, and reaction conditions is gentle, good reaction selectivity, energy consumption of reaction be low, to conversion unit require low, easy to operate; The product epoxy-cyclohexane that obtains is easily separated, and the epoxy cyclohexane yield is high.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1: the preparation of multiphase load type composite oxide catalysts
9.70g (7.85mmol) four water ammonium paramolybdates are joined in the 50mL deionized water, be heated to 100 ℃ under stirring, add 1.5mL acetate and regulate PH to 4.5, successively add 5mmol NaH
2PO
4, 5mmol Mn (NO
3)
2, 0.5M H
2SO
410mL.Heating continues to stir down, and until the residue less water, cooling back title product solid is separated out, and after filtering drying, obtains product P Mo
11Mn
19.00g;
Utilize excessive pickling process: in three mouthfuls of round-bottomed flasks of 100mL, add titanium silicon according to the preparation of foregoing invention content and method than being the Ti of 0.12:1
0.12-MCM-41 molecular sieve 3.0g is with the heteropolyacid salt PMo of above-mentioned preparation
11Mn
10.60g be dissolved in the 40mL deionized water, and be poured in the round-bottomed flask and Ti
0.12-MCM-41 mixes; Constantly be stirred to the moisture evaporate to dryness in 60 ℃ of oil baths; Through 100 ℃ of baking oven inner dryings 24 hours, roasting 4 hours under 400,500 and 600 ℃ of air atmospheres in the retort furnace respectively at last obtained charge capacity and is 20% composite oxide catalysts: 20%PMo
11Mn
1/ Ti
0.12-MCM-41-400 ℃/500 ℃/600 ℃.
Embodiment 2 ~ 4: the composite oxide catalytic that different maturing temperatures make prepares epoxy cyclohexane
In three mouthfuls of round-bottomed flasks of three 50mL, the charge capacity that adds above-mentioned preparation is 20% PMo respectively
11Mn
1/ Ti
0.12-MCM-41-400 ℃/500 ℃/600 ℃ catalyzer 0.2g, tetrahydrobenzene 1.64g (20mmol), acetonitrile 4.9g (0.12mol); Flask isothermal reaction in 60 ℃ of oil baths, backflow 10 hours; Constantly stir simultaneously; The micro-sampling pump at the uniform velocity adds 30% ydrogen peroxide 50 2.05mL (20mmol), and the dropping time is half the (5h) in reaction times.After reaction finishes, filter to isolate catalyzer, filtrating is with the gas chromatographic analysis wherein content and the epoxy cyclohexane selectivity of tetrahydrobenzene, epoxy cyclohexane.130 ~ 135 ℃ cut is collected in filtrating rectifying, promptly gets the product epoxy cyclohexane.Product carries out qualitative analysis through GC-MS (CP-3800/Saturn2000 gas/matter combined instrument, kapillary look post: CP-SIL8,30m*0.25mm*0.25 μ m), confirms as epoxy cyclohexane.See table 1 with gc evaluate catalysts epoxidation results of property.
The reaction result of table 1 embodiment 2 ~ 4
Case study on implementation 5 ~ 8: the poly phase composite oxide catalyst that the phosphorus molybdenum manganese heteropolyacid salt of different Mn, P mol ratio makes prepares epoxy cyclohexane
Select 20% PMo for use
12-nMn
n/ Ti
0.2-MCM-41-600 ℃ as catalyzer, and other preparation conditions are with case 1 ~ 3.That different is heteropolyacid salt PMo
12-nMn
nThe mol ratio (being n) of middle Mn and P, the n=0.5 of case 5, the n=1 of case 6, the n=2 of case 7, the n=3 of case 8.Use the catalytic performance of investigating these three catalyzer with case 2 ~ 4 identical reaction conditionss again, the result sees table 2.
Comparative Examples 1: use 20% PMo
12/ Ti
0. 2Make catalyzer contrast Mn for-MCM-41-600 ℃ and replace several influences catalyst catalytic performance.Other conditions are with example 2 ~ 4.
The catalytic performance of the composite oxides of the different Mn of table 2, P mol ratio
Case study on implementation 9 ~ 11: different titanium silicon prepare epoxy cyclohexane than the poly phase composite oxide catalysis epoxidation that Ti-MCM-41 load makes
Select PMo for use
10.5Mn
1.5As catalyst activity component presoma, charge capacity is 30%, is loaded to Ti respectively
0.04-MCM-41, Ti
0.1-MCM-41, Ti
0.3In four kinds of carriers of-MCM-41, while 600 ℃ of calcination activations 4 hours, respectively as the catalyzer in the case 9 ~ 11, other conditions are with case 2 ~ 4.
Comparative Examples 2: the total silicon MCM-41 mesopore molecular sieve that will not exchange Ti makes catalyzer 30% PMo as carrier
10.5Mn
1.5/ MCM-41-600 ℃, other conditions are with case 9 ~ 11, and reaction result and comparing result are seen table 3.
The different titanium silicon of table 3 are the catalytic performance that carrier makes composite oxide catalysts than Ti-MCM-41
Case study on implementation 12 ~ 14: the poly phase composite oxide catalyst of different loads amount prepares epoxy cyclohexane
Select PMo for use
11Mn
1As catalyst precursor, Ti
0.12-MCM-41 is as support of the catalyst, and 600 ℃ of calcination activations are 4 hours after the load, produces charge capacity and is respectively 10%, 30% and 50% PMo
11Mn
1/ Ti
0.12-MCM-41-600 ℃, respectively as the catalyzer in the case 12 ~ 14, investigate the cyclohexene ring oxidation effectiveness, other conditions are with case 2 ~ 4, and reaction result is seen table 4.
Table 4 different loads amount is to the influence of catalytic performance
Case study on implementation 15 ~ 17: the poly phase composite oxide catalytic preparation epoxy cyclohexane of different catalysts consumption
Select 30% PMo for use
10.5Mn
1.5/ Ti
0.12-MCM-41-400 ℃ is catalyzer, takes by weighing 0.2g, 0.4g and 0.5g (mass ratio of substrate tetrahydrobenzene and catalyzer is respectively 8.20:1,5.47:1,3.28:1) respectively and puts into 4 50mL there-necked flasks, and other operational conditions are with embodiment 2 ~ 4.Wherein the catalyst levels among the embodiment 15 is 0.2g, and embodiment 16 catalyst levelss are 0.4g, and embodiment 17 catalyst levelss are 0.5g, and reaction result is seen table 5.
Table 5 different catalysts consumption is to the influence of epoxidation reaction
Case study on implementation 18 ~ 20: the epoxidation reaction of differential responses temperature prepares the result of epoxy cyclohexane
Select 50% PMo for use
10Mn
2/ Ti
0.12-MCM-41-500 ℃ as catalysts, under 40 ℃, 60 ℃, 80 ℃ temperature, reacts respectively, respectively as the temperature of reaction in case 18,19 and 20, investigates the epoxidation reaction effect, and other conditions are with case 2 ~ 4.The result sees table 6.
Table 6 differential responses temperature is to the influence of epoxidation reaction
Case study on implementation 21 ~ 23: the epoxidation reaction of differential responses time prepares the result of epoxy cyclohexane
Select 20% PMo for use
10Mn
2/ Ti
0.12-MCM-41-500 ℃ is catalyzer, and other are operated with embodiment 2 ~ 4, and different is adopts different reaction times and ydrogen peroxide 50 dropping time: the reaction times, embodiment 21 was 4 hours, and embodiment 22 is 6 hours, and embodiment 23 is 10 hours; And case 21 ~ 23 is at the uniform velocity added 30% ydrogen peroxide 50 2.25mL (22mmol) with 2h, 3h and 5h time with the micro-sampling pump respectively.The result sees table 7.
The table 7 differential responses time is to the influence of epoxidation reaction
Case study on implementation 24 ~ 26: the epoxidation reaction of different ydrogen peroxide 50/tetrahydrobenzene mol ratio prepares the result of epoxy cyclohexane
Select 30% PMo for use
10Mn
2/ Ti
0.3-MCM-41-600 ℃ is catalyzer, substrate tetrahydrobenzene 20mmol, and adopting ydrogen peroxide 50/tetrahydrobenzene mol ratio respectively is 1,1.5 and 30% ydrogen peroxide 50 of 3:1, and respectively as the reaction conditions in the case 24 ~ 26, other reaction conditionss are with embodiment 2 ~ 4, and the result sees table 8
The influence of the different ydrogen peroxide 50 of table 8/tetrahydrobenzene comparison epoxidation reaction
Case study on implementation 27 ~ 30: the epoxidation reaction of different solvents quality prepares the result of epoxy cyclohexane
Select 20% PMo for use
10Mn
2/ Ti
0.3-MCM-41-600 ℃ is catalyzer, substrate tetrahydrobenzene 20mmol (1.64g), adopt respectively tetrahydrobenzene/acetonitrile mass ratio be 1:1,2,3 and 4 acetonitrile as solvent, as the reaction conditions of case 27 ~ 30, other conditions are with embodiment 2 ~ 4 respectively, the result sees table 9
Table 9 different solvents quality is to the influence of epoxidation reaction