CN103787857A - Method for synthesizing cyclohexenone through catalytic oxidation of cyclohexene - Google Patents
Method for synthesizing cyclohexenone through catalytic oxidation of cyclohexene Download PDFInfo
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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Abstract
The invention discloses a method for synthesizing cyclohexenone through the catalytic oxidation of cyclohexene. The method comprises the following steps: adding reactants including cyclohexene, a solvent and a solid catalyst into a reactor to mix, and carrying out ultrasonic processing on the obtained mixture so as to form suspension liquid, wherein the solid catalyst is a carbon material, the carbon material is a carbon nanotube, a nitrogen-doped carbon nanotube, diamond, graphite or activated carbon, and the solvent is an organic solvent mutually soluble in cyclohexene and oxidation products thereof; heating the suspension liquid to 40-150 DEG C, feeding oxygen or air as an oxidant, and reacting 0.1-20 h at a pressure of 0.1-5 MPa; separating the obtained reaction mixture so as to obtain the solid catalyst and a liquid mixture containing a reaction product, unreacted reactants and the solvent; carrying out separation and purification to obtain a product cyclohexenone, mixing residual mother liquor with reaction raw materials and then returning the mixture to the reactor. According to the invention, the used nonmetal catalyst is non-corrosive, environment-friendly, cheap, reusable, high in reaction selectivity, and good in activity.
Description
Technical field
The present invention relates to a kind of synthetic method of cyclonene, particularly relate to a kind of method of tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes, belong to organic synthesis applied technical field.
Background technology
Thereby by double bond containing organism allylic be oxidized obtain α β ?beta-unsaturated carbonyl compounds or allyl alcohol compound be one of important chemical industry building-up process, the hydroxyl or the carbonyl product that generate can be extensively as the elementary cells in organic synthesis, are the important intermediates of producing medicine, spices, foodstuff additive, agrochemistry product etc.Catalytic performance research to allylic oxidation catalyzer used and the selection of reaction conditions are the keys of this class reaction.And the allylic oxidation Chan Wu of tetrahydrobenzene ?cyclonene, be a kind of important chemical intermediate, be widely used in medicine and pesticide producing field, such as nowadays widely used cyclohexenone analog weedicide.There is at present the synthesis method of multiple cyclonene and derivative thereof to be in the news, mainly concentrate on selective oxidation reaction from tetrahydrobenzene (J.Heterocycl.Chem.9,741 (1972) and J.Org.Chem.42.1349 (1977)).Early stage cyclonene synthetic method is to adopt chromic acid (acid anhydride) for catalyzer, and Glacial acetic acid is that solvent makes.But this method productive rate is low, separation difficulty and seriously polluted, is difficult to realize industrialization.The people such as recent Diao Guowang have developed take nano cupric oxide as catalyzer, and tertbutyl peroxide is the technique (Catal.Sci.Technol., 2012,2,82) that oxidizer catalytic cyclohexene oxide is prepared cyclonene.But the preparation of the catalyzer of this method is complicated, and adopting tertbutyl peroxide is that oxidant cost is higher, has reduced throughput.
Adopt molecular oxygen oxidation tetrahydrobenzene to prepare cyclonene and there is undoubtedly huge prospects for commercial application.In recent years, people conduct in-depth research and obtain good achievement to this this.Such as having developed,, people such as Guo Cancheng (Journal of Chemical Industry and Engineering, 2004,55,1537) utilize Metalloporphyrins to carry out catalyzed oxidation tetrahydrobenzene to prepare cyclonene.One or more in the people such as Yu Lei (Chinese invention patent application publication number is CN 102442895A) employing copper compound are complex as catalyst tetrahydrobenzene and prepare cyclonene.But these catalyzer are compounds of more complicated, cost is all higher, and homogeneous catalyst exists the shortcoming that is difficult to recovery.
In view of the deficiency that above-mentioned all kinds of catalyzer exist, the solid catalyst that develop a kind of low price, is easy to separate, has the reusable edible of better low temperature active is still the emphasis of cyclohexene oxide research.
In recent years, carbon material because preparation is simple, low price, environmental friendliness and there is catalytic activity, by extensive concern.As carbon material can well catalysis ethylbenzene, hexanaphthene etc. carries out free-radical oxidn reaction (ZL 200810026686.6; CN201210169970.5).But up to the present, also do not see take carbon nanotube as heterogeneous catalyst, oxygen or air are oxygenant, and the allylic oxidation of selective catalytic oxidation tetrahydrobenzene is prepared the open report of cyclonene technique.
Summary of the invention
The object of the invention is to overcome the existing deficiency of preparing cyclonene technique, provide that a kind of flow process is simple, the method for operational safety, eco-friendly tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes.
Object of the present invention is achieved through the following technical solutions:
A method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes, comprises the following steps:
(1) reactant tetrahydrobenzene, solvent and solid catalyst are joined in reactor and mixed, then supersound process forms suspension; Described solid catalyst is carbon material, and carbon material is carbon nanotube (CNT), nitrogen doped carbon nanotube (NCNT), diamond, graphite or gac; Described solvent is the organic solvent dissolving each other with tetrahydrobenzene and oxidation products thereof; Described catalyzer and the weight ratio of tetrahydrobenzene are 0.00125～0.01125:1;
(2) suspension of gained is heated to 40 ℃～150 ℃, passes into oxygen or air oxidant, pressure is (0.1～5) MPa, reaction (0.1～20) h;
(3) after the reaction of step (2) finishes, reaction mixture is separated, obtain solid catalyst and contain the liquid mixture of reaction product, unreacted reactant and solvent;
(4) by the liquid mixture separating-purifying in step (3), obtain product cyclonene, residue mother liquor mixes and turns back in reactor with reaction raw materials.
For further realizing the object of the invention, the described solid catalyst of step (3) is for step (1), as solid catalyst raw material.Described solid catalyst and tetrahydrobenzene weight ratio are 0.001～0.00617:1.The temperature of reaction of described step (2) is preferably 40～80 ℃.The reaction pressure of described step (2) is preferably 0.1～1MPa.The reaction times of described step (2) is preferably 0.1～4h.The described organic solvent dissolving each other with tetrahydrobenzene and oxidation products thereof is preferably acetonitrile, methyl alcohol or ethanol.Described solid catalyst is the carbon nanotube (NCNT) of nitrogen doping more preferably.More preferably acetonitrile of described solvent.
Method of the present invention is that tetrahydrobenzene, solvent and solid catalyst are formed to suspension, and suspension heating, passes into oxygen or air oxidant reacts, and then purifies.The present invention is take oxygen as oxygenant, the active ingredient using carbon material as heterogeneous catalyst, and catalysis tetrahydrobenzene peroxidation is prepared cyclonene.The present invention is applied to non-metal carbon material the liquid-phase oxidation fixture of tetrahydrobenzene first for the reaction of the alcohol ketone of high added value, and possesses very high activity and stability, changes the dependence to metal catalyst in the past, the Application Areas of expansion New Type of Carbon catalytic material.
The present invention compared with prior art, has the following advantages:
(1) the present invention is using nonmetal-carbon material as catalyzer, and catalyzer can direct filtration separate with product; Simultaneously carbon material has wide material sources, low price, and environmental friendliness, the advantage such as can be recycled.In the allyl reaction of tetrahydrobenzene, carbon material is mainly activation oxygen molecule, adsorbs and the superoxide of stable allyl group position simultaneously, improves the selectivity of allylic oxidation product.Wherein, different carbon material catalyzer presents different ketone selectivity (in table 4).When plain carbon material makees catalyzer, the transformation efficiency of tetrahydrobenzene is between 13～20%, the selectivity of ketone remains between 5～8%, and carbon nanotube after nitrogen doping can be contributed 59% cyclohexene conversion rate and 41.1% ketone selectivity in this reaction system, thus the allyl reaction efficiency of the tetrahydrobenzene greatly improving.
(2) temperature of reaction of the present invention is lower, has not only reduced the energy consumption in reaction process, has also improved the safety coefficient of reaction.
(3) the present invention adopts direct oxidation tetrahydrobenzene one step to prepare cyclonene.
(4) the present invention's carbon material used is higher to cyclohexene oxide catalytic reaction activity, and selectivity is better.
Accompanying drawing explanation
Fig. 1 is the gas chromatogram of the reacted reaction solution of embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but protection scope of the present invention is not limited to the scope of embodiment statement.
Below in embodiment about the measuring method (marker method) of cyclohexene conversion rate (%) and cyclonene selectivity (%) is as follows: reaction arrive specify time after, from reactor, take out liquid-solid phase mixture, it is filtered, obtained liquid phase mixture analysis is determined to transformation efficiency and the selectivity of reaction.The analysis of product is carried out in the Agilent6820 gas-chromatography that capillary column is housed, thereby be wherein (the J Mol Catal A:Chem that the amount by adding triphenylphosphine to change cyclohexenol calculates for the detection of tetrahydrobenzene hydrogen peroxide, 2002,189 (1): 39 ?66).The condition of gas chromatographic detection is: 280 ℃ of samplers, and 280 ℃ of detectors, pillar adopts temperature programming: initial 90 ℃ keep 4min, are then raised to 180 ℃ with 10 ℃/min, then keep 4min.Accompanying drawing 1 is the gas chromatogram of the reacted reaction solution of embodiment 1, is also the typical gas chromatogram of product simultaneously.
Embodiment 1
8.1g tetrahydrobenzene and acetonitrile, solid catalyst nitrogen-doped carbon nanometer pipe, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe (nitrogen content is 3.96%, atom content) of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1.0MPa in reaction.React after 4 hours, from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture, it is filtered, and the liquid phase mixture that obtains solid catalyst and contain unreacted reactant and reaction product, analyzes this liquid phase mixture, the retention time (accompanying drawing 1) of each material in gas-chromatography is respectively: tetrahydrobenzene 4.5min, epoxy cyclohexane 6.2min, cyclohexenol 6.9min, cyclonene 8.1min, orthodichlorobenzene ring 8.9min, cyclohexanediol 9.8min.Wherein, the amount of tetrahydrobenzene hydrogen peroxide is according to adding the triphenylphosphine change calculations gained of the amount of cyclohexenol afterwards.Calculating gained hexene transformation efficiency is 59.0%, and cyclonene selectivity is 41.1%, and the selectivity of other primary products is respectively epoxy cyclohexane 5.9%, cyclohexenol 11.2%, cyclohexanediol 4.5%, tetrahydrobenzene hydrogen peroxide 27.3%.
8.1g tetrahydrobenzene and acetonitrile, solid catalyst nitrogen-doped carbon nanometer, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to respectively the temperature shown in table 1, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1.0MPa in reaction.After reaction 4h, liquid mixture is analyzed, measure the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 1, can find out, temperature raises and is conducive to the oxidation of tetrahydrobenzene, exceedes 80 ℃ but work as temperature, and cyclonene decomposes acceleration, when transformation efficiency significantly improves, cyclonene elective reduction.
The impact of table 1 temperature of reaction on cyclohexene oxide reaction
| |
2 | 1 | 3 | 4 | 5 |
| Temperature of reaction (℃) | 40 | 80 | 100 | 120 | 150 |
| Cyclohexene conversion rate (%) | 8.5 | 59.0 | 70.5 | 80.4 | 95.7 |
| Cyclonene selectivity (%) | 36.5 | 41.1 | 23.5 | 18.4 | 16.7 |
Embodiment 6～9
8.1g tetrahydrobenzene and acetonitrile, solid catalyst nitrogen-doped carbon nanometer pipe, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to respectively 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1.0MPa in reaction, react to the time shown in table 2, measure the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 2.In analytical table, data are known, and along with the increase in reaction times, cyclonene selectivity is on a declining curve, therefore in the time range of studying at table 2,4h left and right is preferably.
The impact of table 2 reaction times on cyclohexene oxide reaction
| Embodiment | 6 | 1 | 7 | 8 | 9 |
| Reaction times (h) | 0.1 | 4 | 8 | 15 | 20 |
| Cyclohexene conversion rate (%) | 7.9 | 59 | 72.7 | 80.1 | 88.2 |
| Cyclonene selectivity (%) | 39.5 | 41.1 | 29.9 | 25.6 | 18.4 |
8.1g tetrahydrobenzene and acetonitrile, solid catalyst nitrogen-doped carbon nanometer pipe, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to respectively 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure in reaction, reaction pressure is as shown in table 3.After reaction 4h, the liquid mixture that gained mixed solution can obtain after filtration solid catalyst and contain cyclonene.Liquid mixture is analyzed, measured the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 3.As shown in Table 3, along with the increase of reaction pressure, cyclonene selectivity is the rear downtrending of first rising, and in the time range of studying at table 3,1MPa left and right is preferably.
The impact of table 3 reaction pressure on cyclohexene oxide
| |
10 | 1 | 11 | 12 | 13 |
| Reaction pressure (Mpa) | 0.1 | 1 | 2 | 3 | 5 |
| Cyclohexene conversion rate (%) | 32.3 | 59 | 64.2 | 72.0 | 79.3 |
| Cyclonene selectivity (%) | 33.3 | 41.1 | 26.4 | 23.6 | 21.6 |
Embodiment 14～17
8.1g tetrahydrobenzene and acetonitrile, solid catalyst, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, and the different catalyzer adding is as shown in table 4, and the weight ratio of catalyzer and tetrahydrobenzene is 0.00617:1.This mixed suspension is under agitation heated to 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1.0MPa in reaction.After reaction 4h, the liquid mixture that gained mixed solution can obtain after filtration solid catalyst and contain cyclonene.Liquid mixture is analyzed, measured the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 4.In analytical table, data are known, and the carbon nanotube of nitrogen doping presents best cyclohexene conversion rate and cyclonene selectivity.
The impact of the different carbon materials of table 4 on cyclohexene oxide
| Embodiment | 14 | 1 | 15 | 16 | 17 |
| The catalyzer using | CNT | NCNT | Gac | Diamond | Graphite |
| Cyclohexene conversion rate (%) | 20.9 | 59.0 | 17.0 | 13.2 | 14.5 |
| Cyclonene selectivity (%) | 5.3 | 41.1 | 7.5 | 8.0 | 7.6 |
Embodiment 18～22
8.1g tetrahydrobenzene and acetonitrile, solid catalyst, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0～0.011:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene, as shown in table 5.This mixed suspension is under agitation heated to respectively 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore to carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure in reaction be 1MPa.After reaction 4h, the liquid mixture that gained mixed solution can obtain after filtration solid catalyst and contain cyclonene.Liquid mixture is analyzed, measured the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 5.Result demonstration, when catalytic amount is 50mg, the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene are best.
The impact of the amount of table 5 catalyzer on cyclohexene oxide
| Embodiment | 18 | 19 | 20 | 1 | 21 | 22 |
| The amount (mg) of catalyzer | 0 | 10 | 30 | 50 | 70 | 90 |
| Cyclohexene conversion rate (%) | 13.5 | 22.4 | 38.1 | 59.0 | 60.9 | 65.1 |
| Cyclonene selectivity (%) | 9.9 | 39.2 | 38.4 | 41.1 | 31.3 | 29.3 |
Embodiment 23～50
8.1g tetrahydrobenzene and different solvents, solid catalyst nitrogen-doped carbon nanometer pipe, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mixed, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the volume ratio of solvent and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1MPa in reaction.Different solvents is as shown in table 6, after reaction 4h, and the liquid mixture that gained mixed solution can obtain after filtration solid catalyst and contain cyclonene.Liquid mixture is analyzed, measured the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene the results are shown in Table 6.Result demonstration, when acetonitrile is made solvent, the transformation efficiency of tetrahydrobenzene and the selectivity of cyclonene are best.
The impact of table 6 different solvents on cyclohexene oxide
| Embodiment | Solvent | Cyclohexene conversion rate (%) | Cyclonene selectivity (%) |
| 1 | Acetonitrile | 59.0 | 41.1 |
| 23 | Methyl alcohol | 34.4 | 44.2 |
| 24 | Toluene | 38.2 | 26.4 |
| 25 | P-Xylol | 37.0 | 37.8 |
| 26 | Trimethylbenzene | 37.0 | 27.2 |
| 27 | Normal hexane | 26.5 | 34.1 |
| 28 | Hexanaphthene | 25.2 | 33.0 |
| 29 | Acetone | 31.9 | 31.4 |
| 30 | Butanone | 37.2 | 33.5 |
| 31 | Mibk | 38.5 | 26.5 |
| 32 | N, N ?dimethyl formamide | 5.7 | 46.6 |
| 33 | Virahol | 16.4 | 32.7 |
| 34 | Dioxan | 30.9 | 40.5 |
| 35 | Chloroform | 46.6 | 27.7 |
| 36 | Ethyl acetate | 29.3 | 25.8 |
| 37 | Ethanol | 23.2 | 34.9 |
| 38 | Diethylamine | 2.8 | 47.6 |
| 39 | Triethylamine | 3.7 | 31.2 |
| 40 | The trimethyl carbinol | 27.1 | 21.6 |
| 41 | Hexalin | 20.2 | 11.2 |
| 42 | Pimelinketone | 37.6 | 20.7 |
| 43 | Tetracol phenixin | 23.5 | 29.0 |
| 44 | Benzylamine | 2.9 | 39.6 |
| 45 | Isopropyl benzene | 25.1 | 23.7 |
| 46 | Methyl phenyl ketone | 32.3 | 20.0 |
| 47 | 1,2 ethylene dichloride | 40.7 | 22.5 |
| 48 | Ethylbenzene | 31.2 | 25.8 |
| 49 | Methyl-formiate | 2.9 | 36.2 |
| 50 | Dimethyl sulfoxide (DMSO) | 26.2 | 20.4 |
Stability embodiment
(1) 8.1g tetrahydrobenzene and acetonitrile, solid catalyst, orthodichlorobenzene (internal standard substance) are joined in an airtight reactor and mix, form mixed suspension, then supersound process forms suspension (frequency is that 40KHz, power 200W and time are 15min).Wherein, the weight ratio of acetonitrile and tetrahydrobenzene is 2:1, is 0.00617:1 as the nitrogen-doped carbon nanometer pipe of catalyzer and the weight ratio of tetrahydrobenzene.This mixed suspension is under agitation heated to 80 ℃, passes into oxygen.Because reaction process constantly consumes oxygen with stoichiometric ratio, therefore carry out in process stable-pressure device and the continuous supplemental oxygen of under meter by being connected with source of oxygen and keep constant pressure at 1.0MPa in reaction.React after 4 hours, from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture, it is filtered, the liquid phase mixture that obtains solid catalyst and contain unreacted reactant and reaction product, can analyze this liquid phase mixture subsequently.
(2) using the carbon nanotube after step (1) cleaning-drying as catalyzer, under the condition identical with step (1), react, with identical method mensuration productive rate.So this catalyst recirculation is used four times, measuredly the results are shown in Table 7.Reuse four times, the selectivity of cyclonene changes little, illustrates that the carbon nanotube of nitrogen doping can recycle, thereby can reduce the cost of catalyzer.
Table 7 catalyst stability experimental result
| The catalyzer using | 1 | 2 | 3 | 4 | 5 |
| Transformation efficiency | 59% | 59.6% | 60.2% | 60.7% | 60.5% |
| Selectivity | 41.1% | 39.2% | 41.8% | 42.2% | 42.7% |
Claims (7)
1. a method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes, is characterized in that comprising the following steps:
(1) reactant tetrahydrobenzene, solvent and solid catalyst are joined in reactor and mixed, then supersound process forms suspension; Described solid catalyst is carbon material, and carbon material is carbon nanotube, nitrogen doped carbon nanotube, diamond, graphite or gac; Described solvent is the organic solvent dissolving each other with tetrahydrobenzene and oxidation products thereof; Described catalyzer and the weight ratio of tetrahydrobenzene are 0.00125～0.01125:1;
(2) suspension of gained is heated to 40 ℃～150 ℃, passes into oxygen or air oxidant, pressure is (0.1～5) MPa, reaction (0.1～20) h;
(3) after the reaction of step (2) finishes, reaction mixture is separated, obtain solid catalyst and contain the liquid mixture of reaction product, unreacted reactant and solvent;
(4) by the liquid mixture separating-purifying in step (3), obtain product cyclonene, residue mother liquor mixes and turns back in reactor with reaction raw materials.
2. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: the described solid catalyst of step (3) is for step (1), as solid catalyst raw material.
3. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: described solid catalyst and tetrahydrobenzene weight ratio are 0.001～0.00617:1.
4. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: the temperature of reaction of described step (2) is 40～80 ℃.
5. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: the reaction pressure of described step (2) is 0.1～1MPa.
6. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: the reaction times of described step (2) is 0.1～4h.
7. the method for tetrahydrobenzene catalyzed oxidation synthesizing cyclohexane 1 ketenes according to claim 1, is characterized in that: the described organic solvent dissolving each other with tetrahydrobenzene and oxidation products thereof is acetonitrile, methyl alcohol or ethanol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000159693A (en) * | 1998-12-01 | 2000-06-13 | Noguchi Inst | Oxidation of organic unsaturated compound |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| CN102442895A (en) * | 2011-12-22 | 2012-05-09 | 江苏扬农化工集团有限公司 | Method for synthesizing cyclohexenone from cyclohexene |
| CN102675072A (en) * | 2012-05-28 | 2012-09-19 | 华南理工大学 | Method for producing acetophenone through catalytic oxidation of ethylbenzene |
-
2014
- 2014-01-20 CN CN201410026031.4A patent/CN103787857B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000159693A (en) * | 1998-12-01 | 2000-06-13 | Noguchi Inst | Oxidation of organic unsaturated compound |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| CN102442895A (en) * | 2011-12-22 | 2012-05-09 | 江苏扬农化工集团有限公司 | Method for synthesizing cyclohexenone from cyclohexene |
| CN102675072A (en) * | 2012-05-28 | 2012-09-19 | 华南理工大学 | Method for producing acetophenone through catalytic oxidation of ethylbenzene |
Non-Patent Citations (2)
| Title |
|---|
| 王娟娟: "催化空气氧化环己烯制环己烯酮", 《陕西师范大学学报（自然科学版）》, vol. 36, 30 June 2008 (2008-06-30), pages 73 - 74 * |
| 谈俊等: "掺氮碳纳米管的结构、制备及催化应用", 《工业催化》, vol. 19, no. 2, 28 February 2011 (2011-02-28), pages 15 - 21 * |
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| CN109694312A (en) * | 2018-12-26 | 2019-04-30 | 青岛市资源化学与新材料研究中心 | A kind of method of photocatalysis cyclohexene selection synthesis cyclohexenone |
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