CN105315128B - Method for preparing KA oil through cyclohexane oxidation - Google Patents
Method for preparing KA oil through cyclohexane oxidation Download PDFInfo
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
Abstract
The invention discloses a method for preparing KA oil through cyclohexane oxidation. The method comprises the steps of synthesizing cyclohexane oxidation reaction liquid, decomposing cyclohexyl hydroperoxide, and carrying out rectification to obtain the AK oil, and is characterized in that before the cyclohexyl hydroperoxide decomposition step, the cyclohexane oxidation reaction liquid is treated through the following steps: (1) hydrolysis reaction: continuously introducing water and cyclohexane oxidation reaction liquid into a hydrolysis reactor for reaction, so as to obtain the reaction liquid; (2) liquid-liquid layering: layering the reaction liquid into an upper layer as an oil phase and a lower layer as a water phase, and collecting the upper oil phase, so as to obtain the treated cyclohexane oxidation reaction liquid rich in cyclohexane, cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone. According to the method, the follow-up saponification alkali liquor dosage and waste alkali liquor discharge amount can be greatly decreased, the concentrations of cyclohexyl hydroperoxide in the oxidation reaction liquid and various intermediate products are remarkably decreased, the yield of AK oil is increased, mixed dibasic acid with a high added value is produced, and the method has the advantages of being simple in process, high in yield, good in economic benefits and capable of greatly reducing waste water and waste residue emission.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of method that cyclohexane oxidation prepares KA oil.
Background technology
The preparation of industrial KA oil (mixture of Hexalin and Ketohexamethylene), including synthesizing cyclohexane 1 alkoxide reactant liquor, ring
Hexyl hydrogen peroxide decomposes, rectification obtains that KA is oily, and key industry flow process is as shown in Figure 2.
It is reported that, there is more than 200 kinds of chemical substance in cyclohexane oxidation liquid, composition is extremely complex, but mainly contains jointly
There is following material：Hexamethylene, KA are oily, and CHHP, the organic acid with adipic acid, 1,3-propanedicarboxylic acid and succinic acid as main component (are referred to as mixed
Binary acid is closed, is represented with DBA), the organic ester (ME) based on the ester that Hexalin is esterified with binary acid, caprolactone, with aldehyde
Mixing formylsalicylic acid (MAA) based on base propanoic acid, aldehyde radical butanoic acid, aldehyde radical valeric acid etc., with hydroxybutyric acid, hydroxypentanoic acid and hydroxycaproic acid
Based on mixing hydroxy acid (MOA) etc., wherein in the technical process with KA oil as key targets, ME, DBA, caprolactone,
The amount of MAA and MOA accounts for the 15～20% of cyclohexane conversion, and it is 90% left that KA, CHHP and DBA three accounts for cyclohexane conversion altogether
It is right.
The decomposition of industrial CHHP is carried out in the basic conditions, can bring following problem：
The KA oil yields of 1.CHHP catabolic processes are undesirable, significantly reduce hexamethylene to the yield of KA oil；
2. the excess base for adding increased the cost of material of cyclohexane oxidation process.
3. industrial CHHP catabolic processes need to be carried out in the basic conditions, cyclohexane oxidation KA oil and CHHP under the conditions of being somebody's turn to do
The hexamethylene alcohol ester (E) of the 15～20% of byproduct in process, mixed dibasic acid (DBA) and mixing hydroxy acid (MOA) will be neutralized
It is into salt, mixing formylsalicylic acid MAA and caprolactone also generation side reaction loss in the basic conditions, final all to become waste liquid or waste residue
The final yield of cyclohexane oxidation KA oil outside discharge system, is not only significantly reduced, and generates substantial amounts of " three wastes ", ring
Border is unfriendly.
For this purpose, technical staff's three big problems to more than, have carried out many improvement, improvement direction first is by adjusting
The decomposition catalyst composition of whole CHHP, the decomposition technique condition of optimization CHHP, improve the KA in CHHP catabolic processes as far as possible
The yield of oil.
Such as Chinese patent CN1105970A：From the technique that hexamethylene prepares Hexalin, Ketohexamethylene.The method is characterized in that
Two steps of technique point for decomposing the oxidation mixture containing CHHP are carried out, and the first step is to use heterogeneous catalysis technique in the range of 5～8 in PH
Decompose or use homogeneous catalysis production breakdown CHHP in acid condition.Second step is in PH>Under 13 strong alkaline condition, with heterogeneous
Catalytic decomposition process further decomposes, and second step decomposition reaction is to carry out immediately carrying out after first step decomposition reaction
Separating treatment.Using the method, CHHP is decomposed into the molecule yield of KA oil and brings up to 90～94% by 88%.
Such as Chinese patent CN1397538A：From the method that hexamethylene prepares Hexalin, Ketohexamethylene.The method is characterized in that
The technique point two-stage nitration for decomposing the oxidation mixture containing CHHP is carried out, first paragraph containing sodium carbonate or containing sodium carbonate and various carboxylic acids
The alkaline aqueous solution of sodium salt carries out heterogeneous catalysis and decomposes CHHP.Second segment is with containing sodium hydroxide or containing sodium hydroxide and various carboxylics
The alkaline aqueous solution of the sodium salt of acid further decomposes.The molecule yield that KA oil is decomposed into using method CHHP can be carried by 85～86%
It is high to 88～95%.
And for example Chinese patent CN101172931A：A kind of improved method for preparing Hexalin and Ketohexamethylene.The spy of the method
Levy is that the decomposition of CHHP is carried out in two steps.When first step decomposition reaction is carried out, the flow of circulation alkali is made to be equal to or more than ring
The flow of hexane oxidation liquid, so that aqueous alkali is referred to as continuous phase in the material of first step decomposition reaction, hexamethylene is mutually referred to as
Dispersion phase, then decomposition reaction mixture crude separation is carried out by cyclone hydraulic separators, cyclone hydraulic separators lower part outlet is isolated greatly
Amount alkali liquor, carries out recirculation.Cyclone hydraulic separators upper outlet material hexamethylene mutually becomes continuous phase, and a small amount of alkali liquor of entrainment is to divide
Dephasing, Jing gravity settling separation grooves are isolated spent lye, then carry out second step decomposition reaction, make decomposition reaction complete.Using this
Method CHHP is decomposed into the molecule yield of KA oil and can improve 5%.
Although decomposition technique condition of the above method by adjusting and optimizing CHHP, significantly improves in CHHP catabolic processes
The yield of KA oil, but still in the basic conditions by cyclohexane oxidation KA oil and the 15～20% of CHHP byproduct in process hexamethylene
Alcohol ester (E), mixed dibasic acid (DBA) and mixing hydroxy acid (MOA) neutralize into salt, and mixed aldehyde MA and caprolactone are also in alkalescence condition
Lower generation side reaction loss, it is final all to become outside waste liquid or waste residue discharge system, not only significantly reduce cyclohexane oxidation system
The final overall yield of KA oil, and generate substantial amounts of " three wastes ", environment is unfriendly.In order to reduce the use of alkali liquor as far as possible
Amount, reclaim by-product high added value 15～20% hexamethylene alcohol ester (E) and mixed dibasic acid (DBA) etc., technical staff is carried out
Further improvement, main improvement direction be first with the mixed dibasic acid in solvent extraction oxidation liquid, it is remaining organic
The operation of identical caustic digestion CHHP is carried out again mutually.
Such as Chinese patent CN101085715A：A kind of oxidizing cyclohexane using oxygen enriched method for preparing Ketohexamethylene, Hexalin.The method
Including three steps：(1) in oxidation reactor with the oxygen-enriched air that oxygen content is 24%～30% by cyclohexane oxidation generate CHHP,
The oxidation mixture of KA oil and adipic acid；(2) acidic materials are separated from oxidation mixture in extraction tower；(3) divide
Separating out material Jing decomposition, saponification, washing and rectification after acidic materials, to finally give KA oily.
Chinese patent CN1530358A：Catalyst oxdie cyclohexane process.The technique is referred to cyclohexane oxidation product Jing
After crossing heat exchange, the organic acid in oxidation product is extracted with 2%～20% fresh water (FW), water was communicated after concentrating at 0～30 DEG C
Crystallization, centrifugation, filter cake are the adipic acid for reclaiming.The total recovery of the patent adipic acid and Ketohexamethylene is 93%, adipic acid：Ring
Hexanone is 1:3.5.
Although above method by carrying out pretreatment to cyclohexane oxidation liquid, recyclable by-product adipic acid,
During conventional cyclohexane oxidation KA is oily, the major impurity in cyclohexane oxidation liquid also contains in addition to the acid such as adipic acid
The by-product binary acid reactions such as various Hexalin and adipic acid, 1,3-propanedicarboxylic acid, succinic acid into ester.The method of above water extraction can not have
Effect reclaims these hexamethylene alcohol esters, causes final these methods reclaim about 50% by-product, and substantial amounts of ester byproducts are still
Can not reclaim, salt finally all becomes waste liquid or waste residue discharges system to cause Hexalin ester (E) in alkali separation process be neutralized into
System is outer, not only significantly reduces the final yield of cyclohexane oxidation KA oil, and content respectively (is accounted for 0.1% or so in system
2～3% of cyclohexane conversion or so) mixing formylsalicylic acid MAA, mixing hydroxy acid MOA, caprolactone etc. also in the basic conditions
Generation side reaction is lost, and generates substantial amounts of " three wastes ", and environment is unfriendly.
The content of the invention
It is an object of the invention to overcome the defect of prior art, there is provided a kind of process is simple, environmental protection, economic benefit
It is good, intermediate product can be converted into into the by-product of high added value effectively and improve the cyclohexane oxidation preparation KA of target product yield
The method of oil.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of cyclohexane oxidation system
The method of standby KA oil, including that synthesizing cyclohexane 1 alkoxide reactant liquor, cyclohexyl hydroperoxide decompose, rectification obtains KA is oily, in hexamethylene
Before base hydroperoxide decomposition step, cyclohexane oxidation liquid is processed, process step is as follows：
(1) hydrolysis：Water is continuously passed through in hydrolysis reactor with cyclohexane oxidation liquid and is reacted, it is described to add
It is 0.05～1 to enter the water yield with reactant liquor volume ratio:1, reaction temperature be 80～155 DEG C, reaction pressure be 0.1～2.0MPa, water
In solution reactor, the liquid phase time of staying is 0.4～6 hour, obtains reactant liquor；
(2) liquid liquid layering：In 35～145 DEG C of temperature, pressure is 0.1～1.1MPa bars to the reactant liquor that step (1) is obtained
Part lower leaf, upper strata are oil phase, and lower floor is water phase, collects upper oil phase and obtains rich in hexamethylene, cyclohexyl hydroperoxide, ring
Cyclohexane oxidation liquid after the process of hexanol and Ketohexamethylene.
Further：
As the preferred embodiment of the present invention, the water that step (2) obtain can mutually be cooled down, crystallizes, be filtered, obtain filter cake
And filtrate, filtrate cycle is returned and continue in hydrolysis reactor reaction.
As the preferred embodiment of the present invention, when being continuously added to water in hydrolysis reactor and being reacted, can be simultaneously
Oxygen weight/mass percentage composition oxygen-containing gas more than or equal to 5% is passed through in hydrolysis reactor continuously, and by controlling oxygen-containing gas
Intake control tail oxygen concentration be less than 3%.
Water is continuously passed through in hydrolysis reactor with cyclohexane oxidation liquid and is reacted, following effect can be reached：
A () simply and easily can be extracted into by-product DBA in water phase from hexamethylene phase, realize and principal product KA oil
Separate.DBA is soluble in water, is slightly soluble in hexamethylene.Under conditions of water is present, the DBA for accounting for by-product nearly 40% will be from organic faciess
In be extracted in water phase, and KA oil is slightly soluble in water, is soluble in hexamethylene, thus is primarily present in the oil phase based on hexamethylene
In.So, separating in organic faciess for DBA and KA oil is simply realized, while also certain acidity is mutually provided for water
Condition.
B () accounts for the ME of amount of by-products nearly 40% and hydrolysis will occur in acid condition, generate Hexalin and mixing two
First acid.Mixed dibasic acid is soluble in the water under the conditions of hydrolysis, rests in water phase, and the mutual solubility of the Hexalin and water of generation
It is low, it is primarily present in oil phase, reduce further the alkali number consumed due to decomposing ester in subsequent treatment and the waste liquid of generation
Amount.
The Hexalin of decomposing into of high selectivity in acid condition is further dropped by c CHHP that () is dissolved in the water
CHHP concentration in low system so that follow-up CHHP catabolic process operating costs are greatly reduced, while after being significantly reduced
The yield of KA oil is lost in the further processing procedure of continuous oxidation liquid as CHHP decomposes, follow-up processing procedure can be caused
The yield of middle KA oil is significantly improved.
D () by-product caprolactone will occur hydrolysis in acid condition, generate hydroxycaproic acid.
Amount of water number and reaction temperature height can be according to demand KA oil and the concentration ratio of adipic acid adjusted
Section.Amount of water is more, and reaction temperature is higher, and the amount of the mixed dibasic acid being extracted in water phase is also more, remains in hexamethylene oil
Mixed dibasic acid in phase is also fewer.But amount of water is too much or reaction temperature too Gao Junhui causes the increase of running cost, therefore,
The currently preferred addition water yield is 0.05～1 with reactant liquor volume ratio:1 preferred reaction temperature is 80～155 DEG C, corresponding
Reaction pressure is 0.1～2.0MP.
Depending on speed of the hydrolysis time according to reaction temperature and ME hydrolysis.Hydrolysis time is longer, and ME hydrolysis is got over
Thoroughly, the yield of target product KA oil is also higher.But long hydrolysis time will cause equipment volume increase, equipment investment
Increase.Preferred hydrolysis time is 0.4～6 hour.
As the preferred embodiment of the present invention, when being continuously added to water in hydrolysis reactor and being reacted, can be simultaneously
Oxygen weight/mass percentage composition oxygen-containing gas more than or equal to 5% is passed through in hydrolysis reactor continuously, and by controlling oxygen-containing gas
Intake control tail oxygen concentration be less than 3%, following effect can be reached：
A () accounts for the impurity being most difficult to away that the MAA and MOA of amount of by-products nearly 20% is association during generation DBA.MAA
Hot water is soluble in MOA, hexamethylene oil phase is slightly soluble in.To be extracted in water phase under hydrolysis state, be passed through oxygenous
After body, in acid condition, MOA and MAA can be converted into DBA, not only increase the yield of important by-products DBA, also removes
Important impurity MOA and MAA in DBA so that follow-up DBA separating-purifying processes are simple.
The Hexalin of decomposing into of high selectivity in acid condition is further dropped by b CHHP that () is dissolved in the water
CHHP concentration in low system so that follow-up CHHP catabolic process operating costs are greatly reduced.
After above-mentioned hydrolysis operation, outside eliminating water and hexamethylene, it is oily that the main component of cyclohexane oxidation liquid is changed into KA,
CHHP, DBA, three account for more than the 99% of the hexamethylene of conversion, can further carry out liquid liquid hierarchical operations.Hydrolysis liquid is entered
Enter liquid liquid quantizer, in 50～145 DEG C of temperature, pressure is stratification under the conditions of 0.1～1.1MPa.Upper strata is rich in hexamethylene
The oil phase of alkane, CHHP and KA oil, lower floor are the water phase rich in DBA and water saturation dissolving KA oil.To oil phase substance, can be by normal
The methods such as the saponification of rule, rectification are further processed and obtain hexamethylene and KA is oily.To aqueous phase substance, crystallization can be carried out and be separated by filtration,
Filter cake is the DBA for reclaiming, and filtrate is recycled directly back to continue reaction in hydrolysis reactor.
According to the present invention, material that can be quantitative in cyclohexane oxide solution is mainly hexamethylene, KA oil, CHHP, DBA and ME,
After the present invention, the prime cost in cyclohexane oxidation liquid is changed into KA oil, CHHP and DBA.The amount of hexamethylene and KA oil
Quantitative by gas chromatogram fixative, the amount of CHHP, DBA and ME adopts the method for chemistry titration quantitative.Calculating final choosing
During selecting property, the present invention is calculated as the overall selectivity of KA oil and CHHP the selectivity of target product.
Present invention beneficial effect compared with prior art is：
1st, by-product DBA ratios in the product greatly improved.By being passed through oxygen-containing gas oxidation, will be big in system
Cyclohexane oxidation intermediate product of the amount with MAA, MOA as representative is converted for important by-product DBA, by the hydrolysis that adds water, will
ME substantial amounts of in system is converted for important by-product DBA so that ratios of the DBA in cyclohexane oxidation product is significantly carried
Height is simultaneously recycled；
2nd, KA oil and CHHP toatl proportion in the product is improve, concentration of the CHHP in target product is reduced.Pass through
Add water hydrolysis, substantial amounts of CHHP in system has been resolved into KA oily so that what the overall selectivity that the alcohol ketone after conversion is crossed increased
In the case of, the concentration of CHHP is greatly reduced, and this is substantially reduced the KA oil losses in follow-up CHHP catabolic processes；
3rd, by extraction, the intermediate product overwhelming majority for accounting for cyclohexane conversion is changed in order to KA is oily, nearly 10%
Intermediate product convert for by-product DBA so that KA oil in cyclohexane oxidation product, the ratio of CHHP and DBA is by before processing
90% or so increase 99% or so, the remarkable in economical benefits of product is improved, while quantity of three wastes, particularly salkali waste amount is obvious
It is greatly reduced, it is possible to decrease construction investment and environmental protection；
4th, hydrolyze and be passed through oxygen-containing gas oxidation using adding water, then liquid liquid hierarchical operations, low energy consumption realize KA oil with
The separation of by-product DBA, has a clear superiority compared with adding alkali to carry out acid-base neutralization removing DBA in traditional handicraft, is not only greatly reduced
The usage amount of alkali liquor, reduce cost of material, while the by-product DBA products of high added value, also significantly reduce generation
" three wastes " are measured, environmental friendliness；
5th, the operation of oxygen-containing gas oxidation is hydrolyzed and is passed through using adding water, the content of CHHP is significantly reduced so that follow-up
Because the product volume of CHHP decomposition penalties is substantially reduced, the yield of final products KA oil is improve.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention, wherein, 1 is hydrolysis reactor, and 2 is liquid liquid quantizer, and 3 is water phase
Piece-rate system；
Fig. 2 is industrial flow schematic diagram prepared by KA oil.
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but the present invention is not limited to described reality
Apply example.
Hydrolysis reactor 1 in the embodiment of the present invention is integrated stirred tank titanium reactor of the product for 500mL, band inner disk
Pipe is cooled down and kettle wall jacket steam is heated.Liquid liquid quantizer 2 be an internal diameter 32mm, the 316L rustless steel cylinders of high 400mm.Water phase
Piece-rate system 3 includes that the volume of three series connection is the PP stirred tanks of 2L and being continuously separated by filtration for two interval filter-pressing device compositions
System.
Being embodied as flow process is：Using continuous operation.Water and cyclohexane oxidation liquid are continuously passed through into hydrolysis reactor 1
In be hydrolyzed reaction, obtain reactant liquor；As the preferred embodiment of the present invention, it is continuously added in hydrolysis reactor 1
When water is reacted, oxygen weight/mass percentage composition can be continuously passed through simultaneously in hydrolysis reactor 1 oxygenous more than or equal to 5%
Body, and tail oxygen concentration is controlled less than 3% by the intake for controlling oxygen-containing gas.The reactant liquor that hydrolysis reactor 1 is obtained
It is layered in liquid liquid quantizer 2, lower floor is rich in adipic acid, 1,3-propanedicarboxylic acid, succinic acid and water and saturation dissolving Hexalin and ring
Water phase Jing aqueous phase separation system 3 is crystallized, is filtered, obtaining filter cake and filtrate by the water phase of hexanone, and filter cake is mixed dibasic acid, will
Filter cake reclaims otherwise processed, filtrate cycle is returned and continue in hydrolysis reactor 1 reaction.Upper strata is rich in hexamethylene, cyclohexyl mistake
The oil phase of hydrogen oxide, Hexalin and Ketohexamethylene, collects upper oil phase and obtains final product the cyclohexane oxidation liquid after process.
The cyclohexane oxidation liquid that embodiment 1～6 is used takes to cyclohexane oxidation the industrial installation for preparing KA oil
On oxidation reactor outlet.The mass percent of its composition of Jing quantitative analyses and each material in reactant liquor is：Hexamethylene
94.95%th, Ketohexamethylene 0.44%, Hexalin 0.68%, DBA0.35%, ME0.37%, CHHP2.75%, unknown material 0.46%.
By industrial traditional translation method, DBA is converted to into adipic acid, ME and is converted to adipic acid dicyclohexano ester, unknown material conversion
Calculate into hydroxycaproic acid, the conversion per pass of hexamethylene is：4.18%, the molar selectivity of each product is：Ketohexamethylene
11.70%th, Hexalin 17.65%, DBA6.81%, ME2.23%, CHHP54.86%, unknown material 7.84%.ME is converted to
After Hexalin, the overall selectivity of KA oil and CHHP is 8.07% for the selectivity of 84.09%, DBA, and the selectivity of unknown material is
7.84%.
The synthetic method of the cyclohexane oxidation liquid that embodiment 7～13 is used is：By China Patent Publication No.
The method described in embodiment 19 in CN102941120A prepares cyclohexane oxidation liquid.Its composition of Jing quantitative analyses and
Mass percent of each material in reactant liquor be：Hexamethylene 86.37%, Ketohexamethylene 2.92%, Hexalin 3.59%,
DBA1.12%, ME1.41%, CHHP3.48%, unknown material 1.09%.By industrial traditional translation method, DBA is converted to
Adipic acid, ME are converted to adipic acid dicyclohexano ester, unknown material and are converted to hydroxycaproic acid calculating, the conversion per pass of hexamethylene
For：10.86%, the molar selectivity of each product is：Ketohexamethylene 23.79%, Hexalin 28.66%, DBA6.12%,
ME3.63%, CHHP23.95%, unknown material 6.59%.ME is converted to after Hexalin, the overall selectivity of KA oil and CHHP is
The selectivity of 83.65%, DBA is 9.76%, and the selectivity of unknown material is 6.59%.
Embodiment 1
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 125.0mL/h, adds hydrolysis
The fresh water of reactor is 0.40 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 142 DEG C, reaction pressure is 1.5MPa, and is reacted while being continuously passed through compressed air, now hydrolysis reactor
The interior liquid phase time of staying is 2.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 129
DEG C, pressure is 0.8MPa.Sampled analysis, the concentration row of each organic component of other after hydrolysis in reactant liquor in addition to water
In table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 57.09%, can reduce follow-up CHHP catabolic processes
Loss about 57%；The concentration of ME reduces 64.86%, can reduce the alkali consumption of decomposition ME of follow-up CHHP catabolic processes about
65%；The concentration of MAA reduces 95.65%, is transformed to the by-product mixed dibasic acid of high added value.Using the present invention's
After operation, the selectivity of DBA increases to 15.22% by 8.07%, and the selectivity that alcohol ketone is crossed increases to 84.51%, two by 84.09
Person's selectivity sum is increased as 99.73% by 92.16%, it is impossible to quantitative unknown material selectivity by 7.84% decline to a great extent to
0.27%.
Embodiment 2
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 29.2mL/h, adds hydrolysis
The fresh water of reactor is 1.00 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 80 DEG C, reaction pressure is 0.1MPa, and is carried out instead while being continuously passed through the oxygen denuded air that oxygen mass fraction is 5%
Should, now in hydrolysis reactor, the liquid phase time of staying is 6.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 50 DEG C, and pressure is 0.1MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water respectively have
The concentration of machine component is listed in table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 38.18%, can reduce follow-up
The loss of CHHP catabolic processes about 38%；The concentration of ME reduces 94.59%, can reduce the decomposition ME of follow-up CHHP catabolic processes
Alkali consumption 94%；The concentration of MAA reduces 52.17%, is transformed to the by-product mixed dibasic acid of high added value.Using
After the operation of the present invention, the selectivity of DBA increases to 10.81% by 8.07%, and the selectivity that alcohol ketone is crossed is increased to by 84.09%
85.78%, both selectivity sums are increased as 96.17% by 92.16%, it is impossible to which quantitative unknown material selectivity is big by 7.84%
Width drops to 3.83%.
Embodiment 3
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 179.5mL/h, adds hydrolysis
The fresh water of reactor is 0.30 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 140 DEG C, reaction pressure is 1.6MPa, and is carried out instead while being continuously passed through the oxygen-enriched air that oxygen mass fraction is 30%
Should, now in hydrolysis reactor, the liquid phase time of staying is 1.5h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 126 DEG C, and pressure is 0.8MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water are each
The concentration of organic component is listed in table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 64.73%, after can reducing
The loss about 65% of continuous CHHP catabolic processes；The concentration of ME reduces 56.76%, can reduce the decomposition of follow-up CHHP catabolic processes
The alkali consumption 57% of ME；The concentration of MAA reduces 89.13%, is transformed to the by-product mixed dibasic acid of high added value.Adopt
After operation with the present invention, the selectivity of DBA increases to 13.30% by 8.07%, and the selectivity that alcohol ketone is crossed is constant, and both select
Property sum increased as 99.08% by 92.16%, it is impossible to quantitative unknown material selectivity is declined to a great extent to 0.92% by 7.84%.
Embodiment 4
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 72.9mL/h, adds hydrolysis
The fresh water of reactor is 0.60 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 128 DEG C, reaction pressure is 1.3MPa, and is reacted while being continuously passed through compressed air, now hydrolysis reactor
The interior liquid phase time of staying is 3.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 111
DEG C, pressure is 0.7MPa.Sampled analysis, the concentration of each organic component of other after hydrolysis in reactant liquor in addition to water are listed in
Table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 50.91%, can reduce the damage of follow-up CHHP catabolic processes
Consumption about 51%；The concentration of ME reduces 75.68%, can reduce the alkali consumption 76% of the decomposition ME of follow-up CHHP catabolic processes；MAA
Concentration reduce 86.96%, be transformed to the by-product mixed dibasic acid of high added value.After operation using the present invention,
The selectivity of DBA increases to 13.24% by 8.07%, and the selectivity that alcohol ketone is crossed increases to 85.78%, Liang Zhexuan by 84.09%
Selecting property sum is increased as 99.02% by 92.16%, it is impossible to quantitative unknown material selectivity by 7.84% decline to a great extent to
0.98%.
Embodiment 5
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 48.6mL/h, adds hydrolysis
The fresh water of reactor is 0.80 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 120 DEG C, reaction pressure is 0.7MPa, and is carried out instead while being continuously passed through the oxygen denuded air that oxygen mass fraction is 15%
Should, now in hydrolysis reactor, the liquid phase time of staying is 4.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 101 DEG C, and pressure is 0.4MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water are each
The concentration of organic component is listed in table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 41.82%, after can reducing
The loss about 42% of continuous CHHP catabolic processes；The concentration of ME reduces 89.19%, can reduce the decomposition of follow-up CHHP catabolic processes
The alkali consumption 89% of ME；The concentration of MAA reduces 86.97%, is transformed to the by-product mixed dibasic acid of high added value.Adopt
After operation with the present invention, the selectivity of DBA increases to 14.04% by 8.07%, and the selectivity that alcohol ketone is crossed is increased by 84.09%
To 84.94%, both selectivity sums are increased as 98.98% by 92.16%, it is impossible to which quantitative unknown material selectivity is by 7.84%
Decline to a great extent to 1.02%.
Embodiment 6
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 36.8mL/h, adds hydrolysis
The fresh water of reactor is 0.90 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 108 DEG C, reaction pressure is 0.5MPa, and is reacted while being continuously passed through compressed air, now hydrolysis reactor
The interior liquid phase time of staying is 5.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 85
DEG C, pressure is 0.3MPa.Sampled analysis, the concentration of each organic component of other after hydrolysis in reactant liquor in addition to water are listed in
Table 1.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 35.64%, can reduce the damage of follow-up CHHP catabolic processes
Consumption about 35%；The concentration of ME reduces 94.59%, can reduce the alkali consumption 94% of the decomposition ME of follow-up CHHP catabolic processes；MAA
Concentration reduce 80.49%, be transformed to the by-product mixed dibasic acid of high added value.After operation using the present invention,
The selectivity of DBA increases to 12.90% by 8.07%, and the selectivity that alcohol ketone is crossed increases to 85.57%, Liang Zhexuan by 84.09%
Selecting property sum is increased as 98.47% by 92.16%, it is impossible to quantitative unknown material selectivity by 7.84% decline to a great extent to
1.53%.
Embodiment 7
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 80.0mL/h, adds hydrolysis
The fresh water of reactor is 0.75 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 146 DEG C, reaction pressure is 1.6MPa, now the liquid phase time of staying is 2.5h in hydrolysis reactor.Hydrolysis reactor
Outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 35 DEG C, and pressure is 0.1MPa.Sampled analysis, hydrolysis
The concentration of other each organic components after reaction in reactant liquor in addition to water is listed in table 1.It can be seen that, the remarkable result of acquirement is：CHHP
Concentration reduce 33.45%, the loss about 33% of follow-up CHHP catabolic processes can be reduced；The concentration of ME reduces 81.08%,
The alkali consumption 81% of the decomposition ME of follow-up CHHP catabolic processes can be reduced；The concentration of MAA reduces 43.48%, is transformed to
The by-product mixed dibasic acid of high added value.After operation using the present invention, the selectivity of DBA is increased to by 8.07%
10.19%, the selectivity that alcohol ketone is crossed increases to 85.36% by 84.09%, and both selectivity sums by 92.17% increase are
95.55%, it is impossible to which quantitative unknown material selectivity is declined to a great extent to 4.45% by 7.84%.
Embodiment 8
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 397.7mL/h, adds hydrolysis
The fresh water of reactor is 0.10 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 150 DEG C, reaction pressure is 1.9MPa, and is carried out instead while being continuously passed through the oxygen-enriched air that oxygen mass fraction is 75%
Should, now in hydrolysis reactor, the liquid phase time of staying is 0.8h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 139 DEG C, and pressure is 0.9MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water are each
The concentration of organic component is listed in table 2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 69.25%, after can reducing
The loss about 69% of continuous CHHP catabolic processes；The concentration of ME reduces 47.52%, can reduce the decomposition of follow-up CHHP catabolic processes
The alkali consumption 47% of ME；The concentration of MAA reduces 94.74%, is transformed to the by-product mixed dibasic acid of high added value.
After operation using the present invention, the selectivity of DBA increases to 15.16% by 9.76%, and the selectivity that alcohol ketone is crossed is increased by 83.65%
Add to 84.49%, both selectivity sums are increased as 99.65% by 93.41%, it is impossible to quantitative unknown material selectivity by
6.59% declines to a great extent to 0.35%.
Embodiment 9
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 32.6mL/h, adds hydrolysis
The fresh water of reactor is 0.95 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 100 DEG C, reaction pressure is 0.3MPa, and is carried out instead while being continuously passed through the oxygen denuded air that oxygen mass fraction is 10%
Should, now in hydrolysis reactor, the liquid phase time of staying is 5.5h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 75 DEG C, and pressure is 0.2MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water respectively have
The concentration of machine component is listed in table 2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 24.71%, can reduce follow-up
The loss of CHHP catabolic processes about 24%；The concentration of ME reduces 98.01%, can reduce the decomposition ME of follow-up CHHP catabolic processes
Alkali consumption 98%；The concentration of MAA reduces 74.39%, is transformed to the by-product mixed dibasic acid of high added value.Using
After the operation of the present invention, the selectivity of DBA increases to 13.74% by 9.76%, and the selectivity that alcohol ketone is crossed is increased to by 83.65%
84.57%, both selectivity sums are increased as 98.31% by 93.41%, it is impossible to which quantitative unknown material selectivity is by 6.59%
Decline to a great extent to 1.69%.
Embodiment 10
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 64.3mL/h, adds hydrolysis
The fresh water of reactor is 0.70 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 125 DEG C, reaction pressure is 0.9MPa, and is reacted while being continuously passed through compressed air, now hydrolysis reactor
The interior liquid phase time of staying is 3.2h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 107
DEG C, pressure is 0.5MPa.Sampled analysis, the concentration of each organic component of other after hydrolysis in reactant liquor in addition to water are listed in
Table 2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 43.68%, can reduce the damage of follow-up CHHP catabolic processes
Consumption about 44%；The concentration of ME reduces 80.15%, can reduce the alkali consumption 80% of the decomposition ME of follow-up CHHP catabolic processes；MAA
Concentration reduce 85.53%, be transformed to the by-product mixed dibasic acid of high added value.After operation using the present invention,
The selectivity of DBA increases to 14.73% by 9.76%, and the selectivity that alcohol ketone is crossed increases to 84.32% by 83.65%, Liang Zhexuan
Selecting property sum is increased as 99.05% by 93.41%, it is impossible to quantitative unknown material selectivity by 6.59% decline to a great extent to
0.95%.
Embodiment 11
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 93.3mL/h, adds hydrolysis
The fresh water of reactor is 0.50 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, in maintaining hydrolysis reactor
Reaction temperature is 132 DEG C, and reaction pressure is 1.1MPa, and is reacted while being continuously passed through compressed air, now hydrolysis
In device, the liquid phase time of staying is 2.5h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is
116 DEG C, pressure is 0.6MPa.Sampled analysis, the concentration of each organic component of other after hydrolysis in reactant liquor in addition to water
It is listed in table 2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 52.59%, can reduce follow-up CHHP catabolic processes
Loss about 52%；The concentration of ME reduces 69.55%, can reduce the alkali consumption of the decomposition ME of follow-up CHHP catabolic processes
70%；The concentration of MAA reduces 87.74%, is transformed to the by-product mixed dibasic acid of high added value.Using the present invention's
After operation, the selectivity of DBA increases to 15.46% by 9.76%, and the selectivity that alcohol ketone is crossed is increased to by 83.65%
84.73%, both selectivity sums are increased as 99.19% by 93.41%, it is impossible to which quantitative unknown material selectivity is by 6.59%
Decline to a great extent to 0.81%.
Embodiment 12
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 833.3mL/h, adds hydrolysis
The fresh water of reactor is 0.05 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 155 DEG C, reaction pressure is 2.0MPa, and is reacted while being continuously passed through pure oxygen, now liquid in hydrolysis reactor
The phase time of staying is 0.4h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, and liquid liquid quantizer temperature is 145 DEG C,
Pressure is 1.1MPa.Sampled analysis, the concentration of each organic component of other after hydrolysis in reactant liquor in addition to water are listed in table
2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 71.55%, can reduce the loss of follow-up CHHP catabolic processes
About 71%；The concentration of ME reduces 44.60%, can reduce the alkali consumption 45% of the decomposition ME of follow-up CHHP catabolic processes；MAA's
Concentration reduces 97.60%, is transformed to the by-product mixed dibasic acid of high added value.After operation using the present invention, DBA
Selectivity increase to 15.60% by 9.76%, the selectivity that alcohol ketone is crossed increases to 84.24% by 83.65%, both select
Property sum increased as 99.84% by 93.41%, it is impossible to quantitative unknown material selectivity is declined to a great extent to 0.16% by 6.59%.
Embodiment 13
During device steady-state operation, the flow of the oxidation liquid in addition hydrolysis reactor is 291.7mL/h, adds hydrolysis
The fresh water of reactor is 0.20 with the oxidation liquid volume ratio for entering hydrolysis reactor:1, it is anti-in maintenance hydrolysis reactor
Temperature is answered for 144 DEG C, reaction pressure is 1.7MPa, and is carried out instead while being continuously passed through the oxygen-enriched air that oxygen mass fraction is 60%
Should, now in hydrolysis reactor, the liquid phase time of staying is 1.0h.Hydrolysis reactor outlet liquid phase continuously enters liquid liquid quantizer, liquid
Liquid quantizer temperature is 131 DEG C, and pressure is 0.9MPa.Sampled analysis, other after hydrolysis in reactant liquor in addition to water are each
The concentration of organic component is listed in table 2.It can be seen that, the remarkable result of acquirement is：The concentration of CHHP reduces 69.25%, after can reducing
The loss about 69% of continuous CHHP catabolic processes；The concentration of ME reduces 50.46%, can reduce the decomposition of follow-up CHHP catabolic processes
The alkali consumption 50% of ME；The concentration of MAA reduces 88.51%, is transformed to the by-product mixed dibasic acid of high added value.Adopt
After operation with the present invention, the selectivity of DBA increases to 14.50% by 9.76%, and the selectivity that alcohol ketone is crossed is increased by 83.65%
To 84.74%, both selectivity sums are increased as 99.24% by 93.41%, it is impossible to quantitative unknown material selectivity by
6.59% declines to a great extent to 0.76%.
Table 1：1～7 implementation result of embodiment
Table 2：8～13 implementation result of embodiment
Claims (3)
1. a kind of method that cyclohexane oxidation prepares KA oil, including synthesizing cyclohexane 1 alkoxide reactant liquor, cyclohexyl hydroperoxide point
Solution, that rectification obtains KA is oily, it is characterised in that before cyclohexyl hydroperoxide decomposition step, at cyclohexane oxidation liquid
Reason, process step are as follows：
(1) hydrolysis：Water is continuously passed through in hydrolysis reactor with cyclohexane oxidation liquid and is reacted, the addition water
Amount is 0.05～1 with reactant liquor volume ratio:1, reaction temperature is 80～155 DEG C, and reaction pressure is 0.1～2.0MPa, and hydrolysis is instead
Answer the liquid phase time of staying in device to be 0.4～6 hour, obtain reactant liquor；
(2) liquid liquid layering：The reactant liquor that step (1) is obtained in 35～145 DEG C of temperature, under the conditions of pressure is 0.1～1.1MPa
Layering, upper strata are oil phase, and lower floor is water phase, collects upper oil phase and obtains rich in hexamethylene, cyclohexyl hydroperoxide, Hexalin
With the cyclohexane oxidation liquid after the process of Ketohexamethylene.
2. the method that cyclohexane oxidation according to claim 1 prepares KA oil, it is characterised in that the water that step (2) is obtained
Mutually crystallization, filtration, obtain filter cake and filtrate, and filtrate cycle is returned continuation reaction in hydrolysis reactor.
3. the method that cyclohexane oxidation according to claim 1 prepares KA oil, it is characterised in that connect in hydrolysis reactor
When continuous addition water is reacted, while it is oxygen-containing more than or equal to 5% that oxygen weight/mass percentage composition is continuously passed through in hydrolysis reactor
Gas, and tail oxygen concentration is controlled less than 3% by the intake for controlling oxygen-containing gas.
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