CN102941120A - Catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and use method of catalytic system - Google Patents
Catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and use method of catalytic system Download PDFInfo
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Abstract
The invention discloses a catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and a use method of the catalytic system. The catalytic system comprises a catalyst and an accelerant, wherein the catalyst is 80-99 percent metal porphyrin compound selected from one of three structures, namely a general formula (I), a general formula (II) or a general formula (III); the accelerant is cyclohexanol; and the mass ratio of the metal porphyrin compound to the cyclohexanol is 1:(10-30,000). The catalytic system is used for preparing the cyclohexanol and the cyclohexanone by liquid-phase catalytic oxidation of the cyclohexane; the conversion rate of the cyclohexane is as high as 10.8 percent; oxidation products have favorable selectivity which is as high as 97.2 percent; and metal porphyrin is low in consumption and no other impurities are introduced in the oxidizing reaction process, and thus the production efficiency can be increased and the production cost is reduced.
Description
Technical field
The present invention relates to catalyst system and catalyzing and the using method thereof of liquid phase catalytic oxidation, particularly a kind of catalyst system and catalyzing and using method thereof for preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane.
Background technology
Cyclohexane liquid phase air oxidation preparing cyclohexanone and cyclohexanol (being commonly called as KA oil) reaction is one of important oxidation reaction of petrochemical industry.The main production method of at present industry is liquid phase non-catalytic oxidation method, be specially the reaction temperature at 160 ~ 170 ℃, directly with air cyclohexane oxidation is produced peroxide under the reaction time of the reaction pressure of 9 ~ 12atm and 40 ~ 60 minutes, peroxide decomposes under alkali condition and produces KA oil.Because this oxidation technology need to be carried out under high-temperature and high-pressure conditions, the further oxidation of cyclohexane oxidation product cyclohexanone, side reaction is many, poor selectivity.All techniques by cyclohexane production cyclohexanone all are controlled at the conversion ratio 3.5 ~ 4.4% of cyclohexane at present, selectively reach 77 ~ 81% to guarantee KA oil.
Both at home and abroad relevant scientist done extensive work with solve non-catalyst oxidation and produce the productive rate that cyclohexanone technique exists and production efficiency is low, more than the oxidized byproduct and the problem such as production environment is unfriendly.Scientists is found, can reach the purpose that improves cyclohexane conversion and product cyclohexanone yield with the metalloporphyrin cyclohexane by bionic catalytic oxidation, what be considered to realize the cyclohexane clean catalytic oxidization has one of method of application prospect most, and has applied for accordingly many patents.The method of using many halos transition metal porphyrin catalytic air oxidation cyclohexane is disclosed such as US5077394, US5767320 discloses the method for using perhalogeno band cobalt porphyrin catalytic air oxidation cyclohexane, US280115, US5120882, US532326, US4895680, US4900871, EP471561 and EP274909 disclose at benzene, use the method for many halos catalysis of metalloporphyrin molecular oxygen oxidation cyclohexane and other alkane in acetic acid and the ethyl acetate solvent system, US4917784 discloses ferriporphyrin and manganoporphyrin descends catalytic molecular oxygen to the oxidation of alkane with photosensitive reagents tin porphyrin or the coexistence of antimony porphyrin.These methods all are to utilize metalloporphyrin as homogeneous catalyst, and catalytic air is to the oxidation of alkane.Because the synthetic price of employed many halos or perhalogeno metalloporphyrin is all extremely expensive in the disclosed method of these patents, and the consumption of metalloporphyrin is large in these patents, and does not also solve the repeat performance problem of metalloporphyrin on the technique.
Chinese patent CN1530358A and CN1435401A disclose at 0.5 ~ 6mg/L and (have amounted to approximately under 0.7 ~ 8.4ppm) the catalysis of metalloporphyrin agent concentration, control certain temperature and pressure, adopt the reactor of different structure and the technique that combination obtains KA oil thereof.But this method uses single metalloporphyrin to be catalyst, although conversion ratio can improve nearly one times than conventional method, KA oil is selectively the highest can only to arrive 88%, still leaves some room for improvement.CN1269343A and CN1405131A disclose take metalloporphyrin as major catalyst, and slaine or metal oxide are co-catalyst, the method for catalytic air oxidation cyclohexane.This method need use the slaine of 3 ~ 5 times of metalloporphyrin amounts or oxidation to use thing to be co-catalyst, can be caused the polymerization of cyclohexanone and by-product aldehydes by a large amount of metal ions of co-catalyst introducing, and easily blocking pipe affects normally carrying out of technique.
Liang Xuebo (Hunan University's master thesis, 2006) when carrying out the Study of optimization of atmospheric catalytic oxidation of cyclohexane by metalloporphyrin coproduction KA oil and adipic acid, investigated the impact of cyclohexanol on cyclohexane oxidation process, the conclusion that obtains is that cyclohexanol is the inhibitor of this oxidation reaction, is the poisonous substance of reaction.(J.Org.Chem., 1976,41 (1): 1-10) also reported in solvent-free system, can play effective inhibitor effect after cyclohexanol is added the cyclohexane oxidation system, be the poisonous substance of reaction to Hendry.
To sum up, catalysis of metalloporphyrin oxidizing ethyle alkyl KA oil processed is the KA oil production technology with wide market prospects, but still exist target product KA oil selective lower, high to the purity requirement of metalloporphyrin, maybe need use the problem such as slaine co-catalyst, therefore, develop a kind of the utilization without the metalloporphyrin of purifying and be catalyst, the cyclohexane liquid-phase oxidation technology of the high-selectivity oxidation KA oil processed that metal salt-free participates in is of great significance and value.
Summary of the invention
The present invention has overcome the defective of prior art, and catalyst system and catalyzing and the using method thereof that liquid-phase catalytic oxidization of cyclohexane prepares cyclohexanol and cyclohexanone that be used for that a kind of yield is high, product selectivity good, the purity requirement of metalloporphyrin is lower and use amount is few is provided.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of catalyst system and catalyzing for preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, comprise catalyst and promoter, the mass percentage concentration that described catalyst is selected from general formula (I) or one of general formula (II) or three kinds of structures of general formula (III) is 80 ~ 99% metal porphyrinses, and described promoter is cyclohexanol; The mass ratio of described metal porphyrins and cyclohexanol is 1:10 ~ 30000,
General formula (I):
General formula (II):
General formula (III):
Wherein, the metallic atom M in the general formula (I) is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe; Metallic atom M in the general formula (II) is selected from Fe, Mn, Cr, Co; Metallic atom M in the general formula (III)
1, M
2Be selected from respectively Fe, Mn, Cr; Dentate X in the general formula (II) is acetic acid, acetylacetone,2,4-pentanedione, halogen, acid radical anion; Substituent R in general formula (I), general formula (II) and the general formula (III)
1, R
2And R
3Be respectively a kind of in hydrogen, alkyl, alkoxyl, hydroxyl, halogen, amido, amino, the nitro.
The present invention also provides a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, oxygen-containing gas is passed in the mixture that is comprised of catalyst system and catalyzing and cyclohexane continuously, at reaction temperature 130 ~ 1600C, stirring reaction is 0.5 ~ 10 hour under reaction pressure 5 ~ 15atm, obtain cyclohexanol and cyclohexanone, the consumption of catalysis of metalloporphyrin agent is 1 ~ 30ppm of cyclohexane gross weight in the described catalyst system and catalyzing.
Further:
The quality percentage composition of oxygen is 15% ~ 100% in the described oxygen-containing gas
Described oxygen-containing gas is selected from a kind of in air, oxygen-enriched air, the pure oxygen.
Described reaction temperature is 140 ~ 155 ℃.
Described reaction pressure is 7 ~ 10atm.
The stirring reaction time is 0.7 ~ 8 hour.
The present invention can allow to contain more corresponding porphines impurity for the used catalyst metals porphyrin of catalyst system and catalyzing that liquid-phase catalytic oxidization of cyclohexane prepares cyclohexanol and cyclohexanone, in the metalloporphyrin building-up process, can after simple purification, directly use synthetic low price.This catalyst system and catalyzing also comprises a certain amount of cyclohexane oxidation product cyclohexanol, and the adding of promoter cyclohexanol can increase substantially the selective of product KA oil.
The metalloporphyrin as catalyst that the present invention proposes can allow to contain more corresponding porphines impurity, and does not need expensive and complicated refining purification process, is based on 2 reasons.First is exactly that metalloporphyrin is generally obtained by porphines and the reacting metal salt of correspondence, and reaction equation is:
This reaction is generally a reversible reaction, can remove the slaine of the overwhelming majority after the crude metal porphyrin that obtains washes with water, but be difficult to remove the not porphines of complete reaction.In existing bibliographical information, the flow process of removing the impurity porphines in the crude metal porphyrin is complicated and expensive.The inventor finds, can be with the crude metal porphyrin that is mixed with a small amount of impurity directly as the catalyst of cyclohexane reaction, and need not make with extra care purification.This is for the consideration that reduces the catalyst cost.
Another reason that the metalloporphyrin as catalyst that the present invention proposes can allow to contain more corresponding porphines impurity is because the inventor finds in experiment, the corresponding porphines that contains certain impurity in the metalloporphyrin is not but still can play corresponding catalytic action, and more better than the catalytic effect of the metalloporphyrin of purifying, be embodied in the selectively better of target product cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide (crossing hereinafter to be referred as alcohol ketone) under the same conversion.It is considered herein that reason wherein may can lose catalytic activity by decomposed for metalloporphyrin in course of reaction, also namely undertaken by the back reaction shown in the formula (1).The a small amount of corresponding porphines that is mixed with in the crude metal porphyrin can effectively delay this back reaction process, thus the catalytic activity of extending catalyst, and it is selective that the conversion ratio of raising reaction and target product alcohol ketone are crossed.
Behind the adding promoter cyclohexanol that the present invention proposes, that can improve significantly that cyclohexane oxidation alcohol ketone processed crosses selectively is based on a large amount of experiment of inventor.As background technology was described, persons skilled in the art were thought: cyclohexanol can play effective inhibitor effect after adding cycloalkanes oxidation reaction system, is the poisonous substance of reaction.But the present inventor finds, although can effectively suppress the conversion of cyclohexane behind the adding cyclohexanol, prolongs the induction period of reaction, can significantly improve the selective of cyclohexane oxidation alcohol ketone processed.In industrial continued operation, decomposition induction time only just occurs when device is driven, and does not have the problem of induction period after the device stable operation.Therefore, it is considered herein that cyclohexanol not only is not the poisonous substance of cyclohexane oxidation, and the adding cyclohexanol is optionally one of the effective ways that improve cyclohexane oxidation alcohol ketone processed in reaction system.
When catalyst system and catalyzing of the present invention is prepared cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, when the purity of metalloporphyrin is down to 80% from 99%, the overall selectivity of target product cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide also has no obvious decline, also sees on the contrary the rising that has slightly.The conversion ratio of reaction is substantially constant, and only when the purity of crude metal porphyrin dropped to 80%, total conversion ratio just had 0.2% decline.Therefore, among the present invention, the purity of catalysis of metalloporphyrin agent is 80 ~ 99%.Use such crude metal porphyrin to be catalyst, can greatly reduce the refining purification problem in the metalloporphyrin building-up process, reduce the industrial production cost.
In the present invention, the consumption of catalysis of metalloporphyrin agent is 1 ~ 30ppm of cyclohexane gross weight, because the consumption of metalloporphyrin is minimum among the present invention, and the part metals porphyrin resolves into low-molecular-weight compound in the course of reaction, along with oxidation residua is discharged outside the oxidative system together, need not carry out the catalyst recovery of extra costliness.Simultaneously, the promoter cyclohexanol that uses among the present invention is exactly one of target product of system, therefore also need not to separate after the reaction again, does not affect the quality of product.
The present inventor's discovery, larger as the initial addition of the cyclohexanol of promoter, the overall selectivity of reaction is higher, and except prolonging induction period, the conversion ratio of reaction is substantially constant under the same reaction conditions.But the increase along with the initial cyclohexanol amount that adds in the system, the mass percent of cyclohexanol significantly increases in the oxidation reaction product, the mass percent of cyclohexanone and cyclohexyl hydroperoxide significantly reduces in the oxidation reaction product, and the mass percent of accessory substance significantly reduces in the oxidation reaction product.This explanation is a certain amount of cyclohexanol of initial adding in reaction system, can effectively suppress the generation of accessory substance, improves the selective of principal product.But be higher than 30000 times of metalloporphyrin concentration when the initial cyclohexanol concentration that adds after, significantly increase the induction period of reaction.Be higher than 50000 times of metalloporphyrin concentration of adding when the cyclohexanol concentration of initial adding after, cause all having no obvious reaction in 7 hours and occur.Therefore, the mass ratio of metalloporphyrin and promoter cyclohexanol is 1:10 ~ 30000 among the present invention.
The prolongation reaction time can obviously be improved the conversion ratio of reaction, but the selectively also obviously decline of the target product of reaction.This is that cyclohexane conversion is higher because the reaction time is longer, and the cyclohexanol in the system and cyclohexanone concentration are also higher.And cyclohexanone is easy to by deep oxidation, and the deep oxidation of cyclohexanone is easier than the oxidation of cyclohexane, therefore the advancing the speed of by-product concentration that causes reacting when high cyclohexanone concentration is greater than gathering way of cyclohexanone concentration, causes the selective decline of target product.Therefore, the reaction time is controlled at 0.5 ~ 10 hour among the present invention, is preferably 0.7 ~ 8 hour.
According to the present invention, the liquid-phase catalytic oxidization of cyclohexane reaction can be single still intermittent reaction, and this moment, there was an induction period in reaction, and the logical oxygen time is decomposition induction time and liquid phase oxidation time sum continuously.Kind according to the catalysis of metalloporphyrin agent is different with the amount of the catalyst that adds and promoter, and decomposition induction time is 0.1 ~ 9 hour, and the liquid phase oxidation time is 0.5 ~ 3 hour.
According to the present invention, the liquid-phase catalytic oxidization of cyclohexane reaction also can be the continuous feeding and discharging flow-type reaction of single still or many stills.Reaction can the continuous feed reaction after only needing to cause when the reaction beginning.Kind according to the catalysis of metalloporphyrin agent is different with the amount of the catalyst that adds and promoter, and decomposition induction time is 0.1 ~ 8 hour.After the continuous feed, the mean residence time of cyclohexane in still is preferably between 0.7 ~ 1.2 hour generally at 0.5 ~ 1.5 hour.
According to the present invention, the liquid-phase catalytic oxidization of cyclohexane reaction temperature is generally carried out between 130 ~ 160 ℃, more preferably carries out between 140 ~ 155 ℃.The reaction minimum pressure generally between 5 ~ 15atm, is preferably between 7 ~ 10atm for keeping reaction for liquid system saturated vapor pressure under the respective reaction temperature.
According to the present invention, the oxidant of liquid-phase catalytic oxidization of cyclohexane reaction is oxygen-containing gas, and the quality percentage composition of oxygen is 15% ~ 100% in the described oxygen-containing gas, is preferably a kind of in air, oxygen-enriched air, the pure oxygen.
The present invention uses above-mentioned catalyst system and catalyzing to carry out the method for liquid-phase catalytic oxidization of cyclohexane reaction, to be that catalyst and cyclohexanol are the catalyst system and catalyzing that promoter forms by adding by the crude metal porphyrin, under the condition of not introducing other impurity, increase cyclohexane oxidation and generate the overall selectivity that alcohol ketone is crossed.According to the present invention, the liquid-phase catalytic oxidization of cyclohexane reaction can be expressed with following chemical expression:
According to the present invention, the primary product of oxidation reaction is cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide, and accessory substance mainly comprises adipic acid, glutaric acid, succinic acid and some other ester classes etc.In industrial reality, cyclohexyl hydroperoxide can become cyclohexanol or cyclohexanone after alkali decomposes.The ester that reaction generates is mainly the ester of cyclohexanol, and ester can become cyclohexanol after alkali decomposes.Calculating finally when selective, the present invention is calculated as the selective of target product to the overall selectivity of cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide, and wherein accessory substance is in adipic acid hexamethylene diester.
According to the present invention, cyclohexanol and cyclohexanone content are analyzed with gas-chromatography internal standard method (take chlorobenzene as internal standard compound) in the product; Cyclohexyl hydroperoxide consumption iodimetric analysis; The amount of organic acid and ester deter-mation is all analyzed with acid-base titration in the product.The concentration of water byproduct detects by moisture determination instrument.The selective percentage that accounts for the product gross mass for this component gross mass of each component in the product.
Advantage of the present invention is:
When 1, catalyst system and catalyzing of the present invention prepared cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, the conversion ratio of cyclohexane obviously improved, and reaches as high as 10.8%.
2, after the promoter cyclohexanol coupling of crude metal porphyrin and adding, liquid-phase catalytic oxidization of cyclohexane prepares the selective obviously raising that alcohol ketone is crossed, and reaches as high as 97.2%.
3, catalyst system and catalyzing of the present invention is that the quality percentage composition is the mixture of 80 ~ 99% crude metal porphyrins and promoter cyclohexanol.The crude metal porphyrin has the advantage that the large-scale industry of being easy to is combined to, and the production cost of the metalloporphyrin high than purity reduces greatly.
4, the consumption of metalloporphyrin is minimum among the present invention, 1 ~ 30ppm for the cyclohexane gross weight, metalloporphyrin natural degradation in the catalytic process, can not introduce other impurity in the oxidation reaction process, and the promoter cyclohexanol that uses in the catalyst system and catalyzing is one of target product, therefore also need not to separate again after the reaction, further improved production efficiency, reduced production cost.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, but the present invention is not limited to described embodiment.
The metal porphyrins that the present invention uses is selected from following general formula (I) or one of general formula (II) or three kinds of structures of general formula (III):
General formula (I):
General formula (II):
General formula (III):
Embodiment 1
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 99% 18mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Ru) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 2
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 18mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Ru) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 3
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 80% 18mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Ru) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 4
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 18mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Ru) and the 21g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 300 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 5
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=F, M=Cu) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 110 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 6
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 85% 0.9mg has general formula (I) structure with the quality percentage composition
1=R
3=Cl, R
2=H, M=Co) and the 18g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 145 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 1.5 hours, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 7
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=CH
3, M=Ni) add in the 600g cyclohexane with the 12g cyclohexanol, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 100 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 8
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 18mg has general formula (I) structure with the quality percentage composition
1=H, R
2=F, R
3=CH
3CH
2, M=Mn) add in the 600g cyclohexane with the 0.18g cyclohexanol, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 6 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.5 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 9
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 0.6mg has general formula (I) structure with the quality percentage composition
1=R
3=H, R
2=CH
3O, M=Fe) and the 6g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 115 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 1.2 hours, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 10
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 6mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=OH, M=Zn) and the 3g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 40 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 11
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 90% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Mn, X=CH
3COO) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 12
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Fe, X=Cl) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 150 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 13
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Cr, X=Cl) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 200 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 14
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 0.6mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Co, X=is acetylacetone based) and the 18g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 155 ℃ of lower reaction stirred.Approximately 520 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 1.2 hours, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 15
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 82% 12mg has general formula (III) structure with the quality percentage composition
1=R
2=H, R
3=NH
2, M
1=M
2=Fe) add in the 600g cyclohexane with the 12g cyclohexanol, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 480 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 2.0 hours, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
Embodiment 16
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (III) structure with the quality percentage composition
1=R
2=H, R
3=NO
2, M
1=M
2=Mn) add in the 600g cyclohexane with the 12g cyclohexanol, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 400 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 2.0 hours, with sample analysis after the quick cooling of reactant.The conversion ratio of the selective and ring hexane of the cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance, reaction result is shown in Table 1.
The liquid-phase catalytic oxidization of cyclohexane batch (-type) list still reaction result that table 1: embodiment 1 ~ 16 obtains
Embodiment 17
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 96% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=NH
2, M=Fe, X=Cl) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 10atm, 150 ℃ of lower reaction stirred.Approximately 145 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.7 hour, with sample analysis after the quick cooling of reactant.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 95.6%, and the conversion ratio of cyclohexane is 6.8%.
Embodiment 18
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=NH
4, M=Fe, X=CH
3COO) and the 12g cyclohexanol add in the 600g cyclohexane, the oxygen quality percentage composition that passes into 10atm is 15% oxygen denuded air, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and end induction period continues the logical oxygen denuded air that contains oxygen 15% and stops reaction after 1 hour, sample analysis after reactant is cooled off fast.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 87.6%, and the conversion ratio of cyclohexane is 8.1%.
Embodiment 19
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=H, R
3=NO
2, M=Co, X=is acetylacetone based) and the 12g cyclohexanol add in the 600g cyclohexane, the oxygen quality percentage composition that passes into 10atm is 35% oxygen-enriched air, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and end induction period continues the logical oxygen-enriched air that contains oxygen 35% and stops reaction after 1.4 hours, sample analysis after reactant is cooled off fast.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 85.2%, and the conversion ratio of cyclohexane is 10.8%.
Embodiment 20
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 80% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=R
3=CH
3, M=Mn, X=Cl) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 8atm, 140 ℃ of lower reaction stirred.Approximately 180 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 1.2 hours, with sample analysis after the quick cooling of reactant.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 89.2%, and the conversion ratio of cyclohexane is 6.1%.
Embodiment 21
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 3mg has general formula (I) structure with the quality percentage composition
1=NO
2, R
2=R
3=H, M=Ru) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the air of 15atm, 160 ℃ of lower reaction stirred.Approximately 60 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue blowing air and stop reaction after 0.5 hour, with sample analysis after the quick cooling of reactant.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 85.2%, and the conversion ratio of cyclohexane is 9.1%.
Embodiment 22
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 99% 18mg has general formula (I) structure with the quality percentage composition
1=R
3=Cl, R
2=H, M=Fe) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the oxygen-enriched air that contains oxygen 50% of 7atm, 130 ℃ of lower reaction stirred.Approximately 420 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue logical oxygen quality percentage composition and are 50% oxygen-enriched air and stop reaction after 3.0 hours, with the quick sample analysis after the cooling of reactant.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 93.2%, and the conversion ratio of cyclohexane is 7.5%.
Embodiment 23
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=R
3=H, M=Mn, X=F) and the 12g cyclohexanol add in the 600g cyclohexane, pass into the pure oxygen of 10atm, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and end induction period continues logical pure oxygen and stops reaction after 1 hour, sample analysis after reactant is cooled off fast.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 83.6%, and the conversion ratio of cyclohexane is 10.2%.Need pay special attention in the present embodiment, the gas-phase space of reactor need pass into a certain amount of N continuously
2, with the concentration that guarantees oxygen in the tail gas not in the gas phase explosive range.
Embodiment 24
In the batch oxidation reactor of a 1.2L, be the metalloporphyrin (R that 92% 12mg has general formula (II) structure with the quality percentage composition
1=R
2=R
3=H, M=Mn, X=Cl) and the 12g cyclohexanol add in the 600g cyclohexane, the oxygen concentration that passes into 10atm is 75% oxygen-enriched air, 150 ℃ of lower reaction stirred.Approximately 90 minutes afterreactions cause, and tail oxygen begins obvious decline, and finish induction period, continue logical oxygen quality percentage composition and are 75% oxygen-enriched air and stop reaction after 1 hour, with the quick sample analysis after the cooling of reactant.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 87.6%, and the conversion ratio of cyclohexane is 8.4%.Need pay special attention in the present embodiment, the gas-phase space of reactor need pass into a certain amount of N continuously
2, with the concentration that guarantees oxygen in the tail gas not in the gas phase explosive range.
Embodiment 25
At single still continuous feeding and discharging movable reactor of a 2L, be the metalloporphyrin (R that 92% 120mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Fe) and the 180g cyclohexanol add to mix in the 12000g cyclohexane and be placed in the head tank, with a former material conveying pump reaction mass that mixes in the head tank is delivered in single still reactor, export at single still and connect a reactant liquor collecting tank.Keep certain liquid level by overflow between the reactor and between reactor and the reactant liquor collecting tank.Use N
2Begin increasing temperature and pressure behind the air in the displacement reaction system, be raised to 150 ℃ of beginnings to temperature and in reactor, pass into continuously air, keep mansion internal pressure 9atm.Reaction process detects by online tail oxygen concentration instrument.Logical oxygen approximately after 100 minutes induction period finish, the oxygen concentration in the tail gas reduces gradually, begin to pump into reaction mass to oxidation reactor from head tank continuously this moment, the simultaneous oxidation reactor also begins continuous to pass through the overflow discharge to the reactant liquor collecting tank.The feed rate of reactant was determined by the time of staying of reactor.In the present embodiment, the mean residence time of cyclohexane in still is controlled at 1 hour.In course of reaction, the liquid level in the Real Time Monitoring reactant liquor collecting tank when the liquid in the reactant liquor collecting tank is full of collecting tank soon, is just carried out blowing by baiting valve.After the successive reaction 8 hours, from the reactant liquor collecting tank, emit reactant liquor and carry out sample analysis.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 94.2%, and the conversion ratio of cyclohexane is 8.1%.
Embodiment 26
At single still continuous feeding and discharging movable reactor of a 2L, be the metalloporphyrin (R that 92% 120mg has general formula (I) structure with the quality percentage composition
1=R
2=H, R
3=Cl, M=Co) and the 180g cyclohexanol add to mix in the 12000g cyclohexane and be placed in the head tank, with a former material conveying pump reaction mass that mixes in the head tank is delivered in single still reactor, export at single still and connect a reactant liquor collecting tank.Keep certain liquid level by overflow between the reactor and between reactor and the reactant liquor collecting tank.Use N
2Begin increasing temperature and pressure behind the air in the displacement reaction system, be raised to 150 ℃ of beginnings to temperature and in reactor, pass into continuously air, keep mansion internal pressure 9atm.Reaction process detects by online tail oxygen concentration instrument.Logical oxygen approximately after 100 minutes induction period finish, the oxygen concentration in the tail gas reduces gradually, begin to pump into reaction mass to oxidation reactor from head tank continuously this moment, the simultaneous oxidation reactor also begins continuous to pass through the overflow discharge to the reactant liquor collecting tank.The feed rate of reactant was determined by the time of staying of reactor.In the present embodiment, the mean residence time of cyclohexane in still is controlled at 0.6 hour.In course of reaction, the liquid level in the Real Time Monitoring reactant liquor collecting tank when the liquid in the reactant liquor collecting tank is full of collecting tank soon, is just carried out blowing by baiting valve.After the successive reaction 8 hours, from the reactant liquor collecting tank, emit reactant liquor and carry out sample analysis.The cyclohexanol that generates in the analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity are 96.2%, and the conversion ratio of cyclohexane is 7.2%.
Claims (7)
1. one kind is used for the catalyst system and catalyzing that liquid-phase catalytic oxidization of cyclohexane prepares cyclohexanol and cyclohexanone, comprise catalyst and promoter, it is characterized in that, the mass percentage concentration that described catalyst is selected from general formula (I) or one of general formula (II) or three kinds of structures of general formula (III) is 80 ~ 99% metal porphyrinses, and described promoter is cyclohexanol; The mass ratio of described metal porphyrins and cyclohexanol is 1:10 ~ 30000, general formula (I):
General formula (II):
General formula (III):
Wherein, the metallic atom M in the general formula (I) is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe; Metallic atom M in the general formula (II) is selected from Fe, Mn, Cr, Co; Metallic atom M in the general formula (III)
1, M
2Be selected from respectively Fe, Mn, Cr; Dentate X in the general formula (II) is acetic acid, acetylacetone,2,4-pentanedione, halogen, acid radical anion; Substituent R in general formula (I), general formula (II) and the general formula (III)
1, R
2And R
3Be respectively a kind of in hydrogen, alkyl, alkoxyl, hydroxyl, halogen, amido, amino, the nitro.
2. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 1, it is characterized in that, oxygen-containing gas is passed in the mixture that is comprised of catalyst system and catalyzing and cyclohexane continuously, at reaction temperature 130 ~ 1600C, stirring reaction is 0.5 ~ 10 hour under reaction pressure 5 ~ 15atm, obtain cyclohexanol and cyclohexanone, the consumption of catalysis of metalloporphyrin agent is 1 ~ 30ppm of cyclohexane gross weight in the described catalyst system and catalyzing.
3. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 2 is characterized in that, the oxygen quality percentage composition is 15% ~ 100% in the described oxygen-containing gas.
4. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 3 is characterized in that, described oxygen-containing gas is selected from a kind of in air, oxygen-enriched air, the pure oxygen.
5. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 2 is characterized in that, described reaction temperature is 140 ~ 155 ℃.
6. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 2 is characterized in that, described reaction pressure is 7 ~ 10atm.
7. a kind of using method for preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 2 is characterized in that, stirring reaction 0.7 ~ 8 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193654A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst |
| CN105237355A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Preparation method for cyclopentanol and cyclopentanone by oxidation of cyclopentane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062718A (en) * | 1992-01-29 | 1992-07-15 | 刘尚长 | The method of a kind of synthesizing cyclohexanol, pimelinketone, hexanodioic acid |
| CN1226255C (en) * | 2002-01-28 | 2005-11-09 | 中国石油化工股份有限公司 | Process for preparing cyclohexanol and cyclohexanone |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062718A (en) * | 1992-01-29 | 1992-07-15 | 刘尚长 | The method of a kind of synthesizing cyclohexanol, pimelinketone, hexanodioic acid |
| CN1226255C (en) * | 2002-01-28 | 2005-11-09 | 中国石油化工股份有限公司 | Process for preparing cyclohexanol and cyclohexanone |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193654A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst |
| CN105237355A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Preparation method for cyclopentanol and cyclopentanone by oxidation of cyclopentane |
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