CN102941120B - A kind of catalyst system and catalyzing and using method thereof preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane - Google Patents
A kind of catalyst system and catalyzing and using method thereof preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane Download PDFInfo
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Abstract
The invention discloses a kind of catalyst system and catalyzing and the using method thereof of preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, this catalyst system and catalyzing comprises catalyst and promoter, the mass percentage concentration that catalyst is selected from general formula (I) or one of general formula (II) or general formula (III) three kinds of structures is 80 ~ 99% metal porphyrinses, and promoter is cyclohexanol; The mass ratio of metal porphyrins and cyclohexanol is 1: 10 ~ 30000, and this catalyst system and catalyzing is used for liquid-phase catalytic oxidization of cyclohexane and prepares cyclohexanol and cyclohexanone, and cyclohexane conversion is high, reaches as high as 10.8%; Oxidation product selective good, reaches as high as 97.2%; The consumption of metalloporphyrin is little, can not introduce other impurity in oxidation reaction process, can further improve production efficiency, reduces production cost.
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 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 are one of important oxidation reactions of petrochemical industry.Current industrial main production process is liquid phase non-catalytic oxidation method, be specially the reaction temperature at 160 ~ 170 DEG C, under the reaction time of the reaction pressure of 9 ~ 12atm and 40 ~ 60 minutes, cyclohexane oxidation is produced peroxide by direct air, and peroxide decomposes in the basic conditions and produces KA oil.Because this oxidation technology needs to carry out under high-temperature and high-pressure conditions, cyclohexane oxidation product cyclohexanone can be oxidized further, and side reaction is many, poor selectivity.All technique by cyclohexane production cyclohexanone all controls the conversion ratio 3.5 ~ 4.4% at cyclohexane at present, reaches 77 ~ 81% to ensure that KA oil is selective.
Domestic and international relevant scientific man has made extensive work with problems such as solving non-catalyst oxidation and produce productive rate that cyclohexanone technique exists and production efficiency is low, oxidized byproduct is many and production environment is unfriendly.Scientists finds, the object improving cyclohexane conversion and product cyclohexanone yield can be reached with metalloporphyrin cyclohexane by bionic catalytic oxidation, be considered to one of the method having application prospect most realizing cyclohexane clean catalytic oxidization, and apply for many patents accordingly.As US5077394 discloses the method using many halos transition metal porphyrin catalytic air oxidation cyclohexane, US5767320 discloses the method using perhalogeno band Cob altporphyrin catalytic air oxidation cyclohexane, US280115, US5120882, US532326, US4895680, US4900871, EP471561 and EP274909 discloses at benzene, the method of many halos catalysis of metalloporphyrin molecular oxygen oxidation cyclohexane and other alkane is used in acetic acid and ethyl acetate solvent system, US4917784 discloses ferriporphyrin and manganoporphyrin and photosensitive reagents tin porphyrin or antimony porphyrin and coexists lower catalytic molecular oxygen to the oxidation of alkane.These methods are all utilize metalloporphyrin as homogeneous catalyst, and catalytic air is to the oxidation of alkane.The many halos used in method disclosed in these patents or the synthesis price of perhalogeno metalloporphyrin are all extremely expensive, and in these patents, the consumption of metalloporphyrin is large, and technique also do not solve the repeat performance problem of metalloporphyrin.
Chinese patent CN1530358A and CN1435401A discloses under the catalysis of metalloporphyrin agent concentration of 0.5 ~ 6mg/L (amounting to about 0.7 ~ 8.4ppm), control certain temperature and pressure, adopt the reactor of different structure and combination thereof to obtain the technique of KA oil.But this method uses single metalloporphyrin for catalyst, although conversion ratio comparatively conventional method can improve nearly one times, KA oil is selective the highlyest to 88%, still can only leave some room for improvement.It is major catalyst that CN1269343A and CN1405131A discloses with metalloporphyrin, and slaine or metal oxide are the method for co-catalyst, 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, and a large amount of metal ions introduced by co-catalyst can cause the polymerization of cyclohexanone and by-product aldehydes, and easy 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, investigate the impact of cyclohexanol on cyclohexane oxidation process, the inhibitor of the conclusion obtained to be cyclohexanol be this oxidation reaction is the poisonous substance of reaction.Hendry (J.Org.Chem., 1976,41 (1): 1-10) also reports in solvent-free system, can play effective inhibitor effect after cyclohexanol being added cyclohexane oxidation system, is the poisonous substance of reaction.
To sum up, catalysis of metalloporphyrin oxidizing ethyle alkyl KA oil is the KA oil production technology with broad mass market prospect, but still exist target product KA oil selective lower, high to the purity requirement of metalloporphyrin, maybe need to use the problems such as slaine co-catalyst, therefore, developing a kind of utilization is catalyst without the metalloporphyrin of purifying, and the cyclohexane liquid-phase oxidation technology of the high-selectivity oxidation KA oil that metal salt-free participates in is of great significance and value.
Summary of the invention
Instant invention overcomes the defect of prior art, provide that a kind of yield is high, product selectivity good, the purity requirement of metalloporphyrin is lower and catalyst system and catalyzing and the using method thereof of preparing cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane that use amount is few.
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 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 general formula (III) three kinds of structures 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 general formula (I) is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe; Metallic atom M in general formula (II) is selected from Fe, Mn, Cr, Co; Metallic atom M in general formula (III)
1, M
2be selected from Fe, Mn, Cr respectively; Dentate X in general formula (II) is acetic acid, acetylacetone,2,4-pentanedione, halogen, acid radical anion; Substituent R in general formula (I), general formula (II) and general formula (III)
1, R
2and R
3be respectively the one in hydrogen, alkyl, alkoxyl, hydroxyl, halogen, amido, amino, nitro.
The present invention also provides a kind of using method preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, oxygen-containing gas is passed into continuously in the mixture be made up of catalyst system and catalyzing and cyclohexane, at reaction temperature 130 ~ 1600C, stirring reaction 0.5 ~ 10 hour under reaction pressure 5 ~ 15atm, obtain cyclohexanol and cyclohexanone, the consumption of catalysis of metalloporphyrin agent in described catalyst system and catalyzing is 1 ~ 30ppm of cyclohexane gross weight.
Further:
In described oxygen-containing gas, the mass percentage of oxygen is 15% ~ 100%
Described oxygen-containing gas is selected from the one in air, oxygen-enriched air, pure oxygen.
Described reaction temperature is 140 ~ 155 DEG C.
Described reaction pressure is 7 ~ 10atm.
The stirring reaction time is 0.7 ~ 8 hour.
The present invention is used for the catalyst metals porphyrin that liquid-phase catalytic oxidization of cyclohexane prepares the catalyst system and catalyzing of cyclohexanol and cyclohexanone used and can allows containing more corresponding porphines impurity, directly can use after simply purifying in metalloporphyrin building-up process, synthesis low price.This catalyst system and catalyzing also comprises a certain amount of cyclohexane oxidation product cyclohexanol, and adding of promoter cyclohexanol can increase substantially the selective of product KA oil.
The metalloporphyrin as catalyst that the present invention proposes can allow containing 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 the porphines of correspondence and reacting metal salt, and reaction equation is:
This reaction is generally a reversible reaction, can remove the slaine of the overwhelming majority, but be difficult to the porphines removing non-complete reaction after the crude metal porphyrin obtained washes with water.In existing bibliographical information, the flow process of the impurity porphines in removing crude metal porphyrin is complicated and expensive.Inventor finds, with being mixed with the crude metal porphyrin of a small amount of impurity directly as the catalyst of cyclohexane reaction, and can need not carry out refining purification.This is the consideration for reducing catalyst cost.
The metalloporphyrin as catalyst that the present invention proposes can allow another reason containing more corresponding porphines impurity to be because inventor finds in an experiment, corresponding porphines containing certain impurity in metalloporphyrin is not but still can play corresponding catalytic action, and more better than the catalytic effect of purified metalloporphyrin, be embodied in the selective better of target product cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide (crossing hereinafter referred to as alcohol ketone) under same conversion.It is considered herein that reason wherein may can decomposed and lose catalytic activity in course of reaction for metalloporphyrin, also namely undertaken by the back reaction shown in formula (1).The a small amount of corresponding porphines be mixed with in crude metal porphyrin effectively can delay this back reaction process, thus the catalytic activity of extending catalyst, it is selective that the conversion ratio of raising reaction and target product alcohol ketone are crossed.
After what the present invention proposed add promoter cyclohexanol, significantly can improve selective that cyclohexane oxidation alcohol ketone crosses is based on a large amount of experiment of inventor.Described by background technology, persons skilled in the art are thought: cyclohexanol can play effective inhibitor effect after adding cycloalkanes oxidation reaction system, are the poisonous substances of reaction.But the present inventor finds, although the conversion of cyclohexane effectively can be suppressed after adding cyclohexanol, extend the induction period of reaction, the selective of cyclohexane oxidation alcohol ketone can be significantly improved.In industrial continued operation, decomposition induction time only just occurs when device is driven, and there is not the problem of induction period after device stable operation.Therefore, it is considered herein that cyclohexanol is not not only the poisonous substance of cyclohexane oxidation, and to add in cyclohexanol to reaction system be optionally one of the effective ways improving cyclohexane oxidation alcohol ketone.
Catalyst system and catalyzing of the present invention is used for liquid-phase catalytic oxidization of cyclohexane when preparing cyclohexanol and cyclohexanone, 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 the rising had slightly on the contrary.The conversion ratio of reaction is substantially constant, and only when the purity of crude metal porphyrin drops to 80%, total conversion ratio just has the decline of 0.2%.Therefore, in the present invention, the purity of catalysis of metalloporphyrin agent is 80 ~ 99%.Use such crude metal porphyrin to be catalyst, greatly can reduce the refining purification problem in metalloporphyrin building-up process, reduce industrial production cost.
In the present invention, the consumption of catalysis of metalloporphyrin agent is 1 ~ 30ppm of cyclohexane gross weight, because in the present invention, the consumption of metalloporphyrin is minimum, and part metals porphyrin resolves into low-molecular-weight compound in course of reaction, along with oxidation residua is discharged outside oxidative system together, the catalyst recovery of extra costliness need not be carried out.Meanwhile, the promoter cyclohexanol used in the present invention is exactly one of target product of system, also without the need to being separated after therefore reacting, does not affect the quality of product again.
The present inventor finds, the cyclohexanol initial incremental amount as promoter is larger, and the overall selectivity of reaction is higher, and under same reaction conditions except extending induction period, the conversion ratio of reaction is substantially constant.But along with the increase of the cyclohexanol amount initially added in system, in oxidation reaction product, the mass percent of cyclohexanol significantly increases, the mass percent of oxidation reaction product cyclohexanone and cyclohexyl hydroperoxide significantly reduces, and in oxidation reaction product, the mass percent of accessory substance significantly reduces.This explanation initially adds a certain amount of cyclohexanol in reaction system, effectively can suppress the generation of accessory substance, improves the selective of principal product.But after the cyclohexanol concentration initially added is higher than 30000 times of metalloporphyrin concentration, the induction period of reaction significantly increases.After the cyclohexanol concentration initially added is higher than 50000 times of the metalloporphyrin concentration added, causes all to have no for 7 hours and significantly react generation.Therefore, in the present invention, the mass ratio of metalloporphyrin and promoter cyclohexanol is 1:10 ~ 30000.
Extend the conversion ratio that the reaction time can significantly improve reaction, but the selective of target product of reaction also obviously declines.This is because the reaction time is longer, cyclohexane conversion is higher, the cyclohexanol in system and cyclohexanone concentration also higher.And cyclohexanone is easy to by deep oxidation, and the deep oxidation of cyclohexanone is easier than the oxidation of cyclohexane, therefore cause the advancing the speed of by-product concentration of reacting when high cyclohexanone concentration to be greater than gathering way of cyclohexanone concentration, cause the selective decline of target product.Therefore, in the present invention, the reaction time controls at 0.5 ~ 10 hour, is preferably 0.7 ~ 8 hour.
According to the present invention, liquid-phase catalytic oxidization of cyclohexane reaction can be single still intermittent reaction, now reacts an induction period of existence, and leading to the oxygen time is continuously decomposition induction time and liquid phase oxidation time sum.Different with the amount of promoter with added catalyst according to the kind of catalysis of metalloporphyrin agent, decomposition induction time is 0.1 ~ 9 hour, and the liquid phase oxidation time is 0.5 ~ 3 hour.
According to the present invention, liquid-phase catalytic oxidization of cyclohexane reaction also can be the continuous feeding and discharging flow-type reaction of single still or many stills.Can continuous feed reaction after reaction only need cause when reacting and starting.Different with the amount of promoter with added catalyst according to the kind of catalysis of metalloporphyrin agent, decomposition induction time is 0.1 ~ 8 hour.After continuous feed, the mean residence time of cyclohexane in still generally at 0.5 ~ 1.5 hour, preferably between 0.7 ~ 1.2 hour.
According to the present invention, liquid-phase catalytic oxidization of cyclohexane reaction temperature is generally carried out between 130 ~ 160 DEG C, more preferably carries out between 140 ~ 155 DEG C.Reaction minimum pressure is at respective reaction temperature, maintain reaction for liquid system saturated vapor pressure, generally between 5 ~ 15atm, is preferably between 7 ~ 10atm.
According to the present invention, the oxidant of liquid-phase catalytic oxidization of cyclohexane reaction is oxygen-containing gas, and in described oxygen-containing gas, the mass percentage of oxygen is 15% ~ 100%, is preferably the one in air, oxygen-enriched air, 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, be the catalyst system and catalyzing that promoter forms by add by crude metal porphyrin be catalyst and cyclohexanol, under the condition not introducing other impurity, increase the overall selectivity that cyclohexane oxidation generation alcohol ketone is crossed.According to the present invention, 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 caustic digestion.The ester that reaction generates is mainly the ester of cyclohexanol, and ester can become cyclohexanol after caustic digestion.Calculate final selective time, the present invention is calculated as the selective of target product the overall selectivity of cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide, and wherein accessory substance is in adipic acid hexamethylene diester.
According to the present invention, in product, cyclohexanol and cyclohexanone content gas chromatogram fixative (taking chlorobenzene as internal standard compound) are analyzed; Cyclohexyl hydroperoxide consumption iodimetric analysis; In product, the amount of organic acid and ester deter-mation is all analyzed by acid-base titration.The concentration of water byproduct is detected by moisture determination instrument.The selective percentage being this component gross mass and accounting for product gross mass of each component in product.
Advantage of the present invention is:
1, when catalyst system and catalyzing of the present invention prepares cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane, the conversion ratio of cyclohexane significantly improves, and reaches as high as 10.8%.
2, after crude metal porphyrin and the promoter cyclohexanol coupling that adds, liquid-phase catalytic oxidization of cyclohexane is prepared selective that alcohol ketone crosses and is significantly improved, and reaches as high as 97.2%.
3, the mixture of catalyst system and catalyzing of the present invention to be mass percentage be 80 ~ 99% crude metal porphyrins and promoter cyclohexanol.Crude metal porphyrin has the advantage being easy to large-scale industry and being combined to, and the production cost of the metalloporphyrin high compared with purity reduces greatly.
4, in the present invention, the consumption of metalloporphyrin is minimum, for 1 ~ 30ppm of cyclohexane gross weight, metalloporphyrin natural degradation in catalytic process, other impurity can not be introduced in oxidation reaction process, and the promoter cyclohexanol used in catalyst system and catalyzing is one of target product, therefore also without the need to being separated again after reacting, further increasing production efficiency, reducing production cost.
Detailed description of the invention
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 general formula (III) three kinds of structures:
General formula (I):
General formula (II):
General formula (III):
Embodiment 1
In the batch oxidation reactor of a 1.2L, be that the 18mg of 99% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Ru) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 2
In the batch oxidation reactor of a 1.2L, be that the 18mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Ru) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 3
In the batch oxidation reactor of a 1.2L, be that the 18mg of 80% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Ru) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 4
In the batch oxidation reactor of a 1.2L, be that the 18mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Ru) and 21g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 300 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 5
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=F, M=Cu) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 110 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 6
In the batch oxidation reactor of a 1.2L, be that the 0.9mg of 85% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
3=Cl, R
2=H, M=Co) and 18g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 145 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 1.5 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 7
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=CH
3, M=Ni) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 100 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 8
In the batch oxidation reactor of a 1.2L, be that the 18mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=H, R
2=F, R
3=CH
3cH
2, M=Mn) and 0.18g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 6 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.5 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 9
In the batch oxidation reactor of a 1.2L, be that the 0.6mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
3=H, R
2=CH
3o, M=Fe) and 6g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 115 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 1.2 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 10
In the batch oxidation reactor of a 1.2L, be that the 6mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=OH, M=Zn) and 3g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 40 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 11
In the batch oxidation reactor of a 1.2L, be that the 12mg of 90% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=Cl, M=Mn, X=CH
3cOO) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 12
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=Cl, M=Fe, X=Cl) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 150 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 13
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=Cl, M=Cr, X=Cl) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 200 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 14
In the batch oxidation reactor of a 1.2L, be that the 0.6mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=Cl, M=Co, X=are acetylacetone based) and 18g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 155 DEG C.After about 520 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 1.2 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 15
In the batch oxidation reactor of a 1.2L, be that the 12mg of 82% has the metalloporphyrin (R of general formula (III) structure by mass percentage
1=R
2=H, R
3=NH
2, M
1=M
2=Fe) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 480 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 2.0 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Embodiment 16
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (III) structure by mass percentage
1=R
2=H, R
3=NO
2, M
1=M
2=Mn) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 400 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 2.0 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide and other accessory substance selective the conversion ratio of ring hexane, reaction result is shown in Table 1.
Table 1: the liquid-phase catalytic oxidization of cyclohexane batch (-type) list still reaction result that embodiment 1 ~ 16 obtains
Embodiment 17
In the batch oxidation reactor of a 1.2L, be that the 12mg of 96% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=NH
2, M=Fe, X=Cl) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 10atm, reaction stirred at 150 DEG C.After about 145 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.7 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 95.6%, and the conversion ratio of cyclohexane is 6.8%.
Embodiment 18
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=NH
4, M=Fe, X=CH
3cOO) and 12g cyclohexanol add in 600g cyclohexane, the oxygen quality percentage composition passing into 10atm is the oxygen denuded air of 15%, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues the logical oxygen denuded air containing oxygen 15% and stops reaction after 1 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 87.6%, and the conversion ratio of cyclohexane is 8.1%.
Embodiment 19
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=H, R
3=NO
2, M=Co, X=are acetylacetone based) and 12g cyclohexanol add in 600g cyclohexane, the oxygen quality percentage composition passing into 10atm is the oxygen-enriched air of 35%, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues the logical oxygen-enriched air containing oxygen 35% and stops reaction after 1.4 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 85.2%, and the conversion ratio of cyclohexane is 10.8%.
Embodiment 20
In the batch oxidation reactor of a 1.2L, be that the 12mg of 80% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=R
3=CH
3, M=Mn, X=Cl) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 8atm, reaction stirred at 140 DEG C.After about 180 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 1.2 hours, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 89.2%, and the conversion ratio of cyclohexane is 6.1%.
Embodiment 21
In the batch oxidation reactor of a 1.2L, be that the 3mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=NO
2, R
2=R
3=H, M=Ru) and 12g cyclohexanol add in 600g cyclohexane, pass into the air of 15atm, reaction stirred at 160 DEG C.After about 60 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues blowing air and stops reaction after 0.5 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 85.2%, and the conversion ratio of cyclohexane is 9.1%.
Embodiment 22
In the batch oxidation reactor of a 1.2L, be that the 18mg of 99% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
3=Cl, R
2=H, M=Fe) and 12g cyclohexanol add in 600g cyclohexane, pass into 7atm containing the oxygen-enriched air of oxygen 50%, reaction stirred at 130 DEG C.After about 420 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, continue logical oxygen quality percentage composition be 50% oxygen-enriched air stops after 3.0 hours reacting, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 93.2%, and the conversion ratio of cyclohexane is 7.5%.
Embodiment 23
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=R
3=H, M=Mn, X=F) and 12g cyclohexanol add in 600g cyclohexane, pass into the pure oxygen of 10atm, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, and continues logical pure oxygen and stops reaction after 1 hour, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 83.6%, and the conversion ratio of cyclohexane is 10.2%.Need in the present embodiment to pay special attention to, the gas-phase space of reactor need pass into a certain amount of N continuously
2, to ensure that the concentration of oxygen in tail gas is not in gas phase explosive range.
Embodiment 24
In the batch oxidation reactor of a 1.2L, be that the 12mg of 92% has the metalloporphyrin (R of general formula (II) structure by mass percentage
1=R
2=R
3=H, M=Mn, X=Cl) and 12g cyclohexanol add in 600g cyclohexane, the oxygen concentration passing into 10atm is the oxygen-enriched air of 75%, reaction stirred at 150 DEG C.After about 90 minutes, reaction causes, and tail oxygen starts obvious decline, and induction period terminates, continue logical oxygen quality percentage composition be 75% oxygen-enriched air stops after 1 hour reacting, reactant is cooled rear sample analysis fast.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 87.6%, and the conversion ratio of cyclohexane is 8.4%.Need in the present embodiment to pay special attention to, the gas-phase space of reactor need pass into a certain amount of N continuously
2, to ensure that the concentration of oxygen in tail gas is not in gas phase explosive range.
Embodiment 25
At single still continuous feeding and discharging movable reactor of a 2L, be that the 120mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Fe) and 180g cyclohexanol add in 12000g cyclohexane to mix and be placed in a head tank, with a feedstock transportation pump, the reaction mass mixed in head tank is delivered in single still reactor, connects a reactant liquor collecting tank in single still outlet.Certain liquid level is maintained by overflow between reactor and between reactor and reactant liquor collecting tank.Use N
2start increasing temperature and pressure after air in displacement reaction system, be raised to 150 DEG C of beginnings to temperature and pass into air continuously in reactor, keep pressure 9atm in mansion.Reaction process is detected by online tail oxygen concentration instrument.Logical oxygen after about 100 minutes induction period terminate, the oxygen concentration in tail gas reduces gradually, now starts to pump into reaction mass to oxidation reactor from head tank continuously, and simultaneous oxidation reactor also starts continuously through overflow discharge in 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 controlled at 1 hour.In course of reaction, the liquid level in real time in monitoring reactant liquor collecting tank, when the liquid in reactant liquor collecting tank is full of collecting tank soon, just carries out blowing by baiting valve.Successive reaction, after 8 hours, is released reactant liquor and is carried out sample analysis from reactant liquor collecting tank.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 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 that the 120mg of 92% has the metalloporphyrin (R of general formula (I) structure by mass percentage
1=R
2=H, R
3=Cl, M=Co) and 180g cyclohexanol add in 12000g cyclohexane to mix and be placed in a head tank, with a feedstock transportation pump, the reaction mass mixed in head tank is delivered in single still reactor, connects a reactant liquor collecting tank in single still outlet.Certain liquid level is maintained by overflow between reactor and between reactor and reactant liquor collecting tank.Use N
2start increasing temperature and pressure after air in displacement reaction system, be raised to 150 DEG C of beginnings to temperature and pass into air continuously in reactor, keep pressure 9atm in mansion.Reaction process is detected by online tail oxygen concentration instrument.Logical oxygen after about 100 minutes induction period terminate, the oxygen concentration in tail gas reduces gradually, now starts to pump into reaction mass to oxidation reactor from head tank continuously, and simultaneous oxidation reactor also starts continuously through overflow discharge in 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 controlled at 0.6 hour.In course of reaction, the liquid level in real time in monitoring reactant liquor collecting tank, when the liquid in reactant liquor collecting tank is full of collecting tank soon, just carries out blowing by baiting valve.Successive reaction, after 8 hours, is released reactant liquor and is carried out sample analysis from reactant liquor collecting tank.The cyclohexanol generated in analytical reactions cooling fluid, cyclohexanone, cyclohexyl hydroperoxide, its overall selectivity is 96.2%, and the conversion ratio of cyclohexane is 7.2%.
Claims (7)
1. prepare the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane for one kind, 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 general formula (III) three kinds of structures 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 general formula (I) is selected from Cu, Ni, Zn, Ru, Mn; Metallic atom M in general formula (II) is selected from Fe, Mn, Cr, Co; Metallic atom M in general formula (III)
1, M
2be selected from Fe, Mn, Cr respectively; Dentate X in general formula (II) is acetic acid, acetylacetone,2,4-pentanedione, halogen, acid radical anion; Substituent R in general formula (I), general formula (II) and general formula (III)
1, R
2and R
3be respectively the one in hydrogen, alkyl, alkoxyl, hydroxyl, halogen, amido, amino, nitro.
2. a kind of using method 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 into continuously in the mixture be made up of catalyst system and catalyzing and cyclohexane, reaction temperature 130 ~ 160 DEG C, stirring reaction 0.5 ~ 10 hour under reaction pressure 5 ~ 15atm, obtain cyclohexanol and cyclohexanone, the consumption of catalysis of metalloporphyrin agent in described catalyst system and catalyzing is 1 ~ 30ppm of cyclohexane gross weight.
3. a kind of using method 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, in described oxygen-containing gas, oxygen quality percentage composition is 15% ~ 100%.
4. a kind of using method preparing the catalyst system and catalyzing of cyclohexanol and cyclohexanone for liquid-phase catalytic oxidization of cyclohexane according to claim 3, it is characterized in that, described oxygen-containing gas is selected from the one in air, oxygen-enriched air, pure oxygen.
5. a kind of using method 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 DEG C.
6. a kind of using method 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 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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