阅读说明：本技术 一种环己基过氧化氢的分解方法 (A kind of decomposition method of cyclohexyl hydroperoxide ) 是由 徐杰 孙志强 苗虹 于维强 马红 于 2018-05-23 设计创作，主要内容包括：本申请公开了一种环己基过氧化氢的分解方法,至少包括：将含有环己基过氧化氢的溶液和含有催化剂的溶液在反应器内反应,得到含有环己醇和环己酮的混合物；其中,所述反应器为柱塞流反应器。所述方法在连续进出料的塔式或管式柱塞流反应器中,将环己烷氧化液中的环己基过氧化氢高选择性地转化为高酮醇比的分解液；具有分解反应不需要碱,产物酮醇比高,设备简单等特点。(This application discloses a kind of decomposition methods of cyclohexyl hydroperoxide, include at least: the solution containing cyclohexyl hydroperoxide and the solution containing catalyst being reacted in reactor, obtain the mixture containing cyclohexanol and cyclohexanone；Wherein, the reactor is plunger flow reactor.The method converts the cyclohexyl hydroperoxide in cyclohexane oxide solution to the decomposed solution of high keto-alcohol ratio in the tower or tubular type plunger flow reactor of continuous feeding and discharging with high selectivity；Alkali is not needed with decomposition reaction, product keto-alcohol is than high, the features such as equipment is simple.)

1. a kind of decomposition method of cyclohexyl hydroperoxide, which is characterized in that include at least: will be containing cyclohexyl hydroperoxide Solution and solution containing catalyst react in reactor, obtain the mixture containing cyclohexanol and cyclohexanone；

Wherein, the reactor is plunger flow reactor.

2. the method according to claim 1, wherein the reactor is selected from the tower plug flow of continuous feeding and discharging The tubular type plunger flow reactor of reactor or continuous feeding and discharging.

3. according to the method described in claim 2, it is characterized in that, the tower plunger flow reactor is selected from packed tower or board-like Tower；

Preferably, the filler of the packed tower includes at least one of ripple packing, gauze packing, Ball-type packing；

The ratio of the tower diameter of the diameter and packed tower of filler unit is 1:5~1:20 in the packed tower；

The tower diameter of the packed tower and the ratio of tower height are 1:5~1:10；

Preferably, the ratio of the tower diameter of the diameter and packed tower of filler unit is 1:5~1:10 in the packed tower；

Preferably, the ratio of the pipe range of the tubular type plunger flow reactor and caliber is greater than 10:1；

It include baffle plate in the tubular type plunger flow reactor.

4. the method according to claim 1, wherein the residence time of reaction solution is 10~60 in the reactor Minute.

5. the method according to claim 1, wherein the solution containing cyclohexyl hydroperoxide and containing urging The volume ratio of the solution of agent is 2:1~20:1；

Preferably, the solution containing cyclohexyl hydroperoxide and the solution containing catalyst are fed in the form of cocurrent.

6. the method according to claim 1, wherein the solution containing cyclohexyl hydroperoxide and containing urging The solution of agent is mixed before entering reactor by static mixer.

7. the method according to claim 1, wherein cyclohexyl in the solution containing cyclohexyl hydroperoxide Hydrogen peroxide weight percent is 0.1%~15.0%；

The solution containing cyclohexyl hydroperoxide is the cyclohexane solution containing cyclohexyl hydroperoxide.

8. the method according to claim 1, wherein the catalyst is selected from water-soluble transition metal organic complex At least one of object；

The dosage of the catalyst is 1~5000ppm.

9. the method according to claim 1, wherein the temperature of the reaction is 50 DEG C~120 DEG C；

Preferably, the volume space velocity of the reaction is 2~3h^-1；

Preferably, the pressure of the reaction is 0.1Mpa~1Mpa；Reaction atmosphere is air or non-active gas.

10. the method according to claim 1, wherein the mixture middle ring containing cyclohexanol and cyclohexanone The molar ratio of hexanone and cyclohexanol is 1.8~2.3:1.

Technical field

This application involves a kind of decomposition methods of cyclohexyl hydroperoxide, belong to chemical field.

Background technique

Cyclohexyl hydroperoxide decomposition reaction is that cyclohexane oxidation prepares important link during cyclohexanol and cyclohexanone One of.

Its decomposition reaction can be expressed as follows with chemical equation:

Existing commercial run is to decompose cyclohexyl hydroperoxide using the sodium hydroxide lye largely containing cobalt ions. This method generates a large amount of alkaline waste waters and pollutes environment there are at high cost, corrodes equipment and the disadvantages such as yield is low.Use non-alkali Catalytic decomposition decomposing cyclohexylhdroperoxide is one of the target that scientific and technological circle and business circles are laid siege in recent years.Another party Face, in process of cyclohexanone production, the cyclohexanol that oxygenolysis generates will can just be converted into cyclohexanone by high-temperature catalytic dehydrogenation. In order to reduce cyclohexanol dehydrogenation load and energy consumption, it is desirable to which the keto-alcohol molar ratio of cleavage reaction product is as high as possible.

Plunger flow reactor, such as tower reactor and tubular type continuous feeding and discharging decomposition reactor, with tank reactor of connecting It compares, with the advantages that dynamic equipment without mixing, material back mixing is few, and equipment is simple, receives industry favor.

Patent CN201010103789.5 is reported using alkali and Co ion as catalyst, decomposes hexamethylene using tower reactor The method of alkoxide liquid, this method do not illustrate the keto-alcohol molar ratio of decomposition product.

Patent CN201310195936.x is reported using alkali and Co ion as catalyst, decomposes hexamethylene using tubular reactor The method of alkoxide liquid.The invention compared to other techniques, improves the keto-alcohol molar ratio of decomposition product, decomposes in embodiment The keto-alcohol ratio of product has been up to 1.08:1.

Summary of the invention

According to the one aspect of the application, a kind of decomposition method of cyclohexyl hydroperoxide is provided, this method is continuous In the tower or tubular reactor of input and output material, by the cyclohexyl hydroperoxide in cyclohexane oxide solution be converted into high selectivity with Cyclohexanone is the mixture of primary product.

The patent of cyclohexane oxide solution method is decomposed in earlier application using complexing decomposition catalyst aqueous solution CN200710159027.5, the application is intended to using the catalyst system, using tubular type or tower reactor, in continuous feeding and discharging Under the conditions of, realize that cyclohexane oxide solution decomposes, and obtain the decomposition product of high keto-alcohol molar ratio.

The purpose of the application is to develop a kind of plug flow without base decomposing technology, gives birth to cyclohexane oxide solution decomposition selectively At high keto-alcohol molar ratio decomposition product.

This application involves the process of air oxidation of cyclohexane production cyclohexanol and cyclohexanone, specifically a kind of plug flows The method of complex catalytic decomposition of cyclohexyl hydrogen peroxide is catalyst using water-soluble transition metal organic complex, continuous In the tower or tubular reactor of input and output material, by the cyclohexyl hydroperoxide in cyclohexane oxide solution be converted into high selectivity with Cyclohexanone is the mixture of primary product.

The decomposition method of the cyclohexyl hydroperoxide, which is characterized in that include at least: cyclohexyl hydroperoxide will be contained Solution and solution containing catalyst reacted in reactor, obtain the mixture containing cyclohexanol and cyclohexanone；

Wherein, the reactor is plunger flow reactor.

As a kind of specific embodiment, the decomposition method of the cyclohexyl hydroperoxide, comprising: use water-soluble mistake Crossing metallo-organic complex is catalyst, in the tower or tubular type plunger flow reactor of continuous feeding and discharging, by cyclohexane oxidation Cyclohexyl hydroperoxide in liquid is converted into the decomposed solution of high keto-alcohol ratio with high selectivity.

Optionally, the decomposition product keto-alcohol molar ratio is between 1.8~2.3:1.

Optionally, the reactor is selected from the tower plunger flow reactor of continuous feeding and discharging or the tubular type column of continuous feeding and discharging Plug flow reactor.

Optionally, the tower plunger flow reactor is selected from packed tower or plate column.

Optionally, the filler of the packed tower includes at least one of ripple packing, gauze packing, Ball-type packing；

The ratio of the tower diameter of the diameter and packed tower of filler unit is 1:5~1:20 in the packed tower；

The tower diameter of the packed tower and the ratio of tower height are 1:5~1:10.

Optionally, the ratio of the tower diameter of the diameter and packed tower of filler unit is 1:5~1:10 in the packed tower.

Optionally, in the packed tower tower diameter of the diameter and packed tower of filler unit the ratio upper limit be selected from 1:6,1:7, 1:8,1:9,1:10,1:11,1:15 or 1:20；Lower limit is selected from 1:5,1:6,1:7,1:8,1:9,1:10,1:11 or 1:15.

Optionally, the ratio upper limit of the tower diameter of the packed tower and tower height is selected from 1:6,1:7,1:8,1:9 or 1:10；Lower limit Selected from 1:5,1:6,1:7,1:8 or 1:9.

Optionally, the ratio of the pipe range of the tubular type plunger flow reactor and caliber is greater than 10:1；

It include baffle plate in the tubular type plunger flow reactor.

Optionally, the ratio upper limit of the pipe range of the tubular type plunger flow reactor and caliber be selected from 11:1,15:1,20:1, 25:1,30:1,35:1,40:1,45:1 or 50:1；Lower limit is selected from 10:1,11:1,15:1,20:1,25:1,30:1,35:1,40: 1,45:1 or 50:1.

Optionally, the ratio of the pipe range of the tubular type plunger flow reactor and caliber be 11:1,15:1,20:1,25:1, 30:1,35:1,40:1,45:1 or 50:1.

Optionally, the baffle plate is helical form.

Optionally, the reactor is packed tower or the tube type apparatus with hydraulic barrier.

Optionally, the residence time of reaction solution is 10~60 minutes in the reactor.

Tower reactor used in this application can be packed tower or plate column, and for example packed tower, filler can be used Any filler for being conducive to two phase liquid mixing, mass transfer.Such as ripple packing, gauze packing or spherical shape.Filler material can be selected The material of any resistance to aqueous solutions of organic acids corrosion, such as 304 or 316L stainless steel, organic plastics, ceramics or sintered alumina.For Even fluid distribution, filler unit diameter and tower diameter ratio should be between 1:5~1:10, and tower diameter height ratio should be between 1:5~1:10.

Tubular reactor pipe range and caliber bank note used in this application should be greater than 10:1, to promote catalytic liquid and oxidation solution It mixes, baffle plate etc. can be set in reaction tube and promotes two-phase mixtures baffle.

Reactor net volume used in this application should ensure that so that reaction solution is flowed through the residence time in it decomposes instead enough Required time, the residence time completely it should increase and shorten with reaction temperature, increase with catalyst effective component and reduce.Generally Control is between 10~60 minutes.

For the application organic phase compared with the volume of catalytic liquid between 2:1~10:1, cocurrent form is can be used in two kinds of fluids Charging.

To be uniformly mixed organic phase and catalytic liquid water phase, two bursts of liquid streams into can first pass through before reactor static mixer into Row mixing.

Optionally, the alternate volume ratio of the hexamethylene-water two-phase two is 20~2:1；Hexamethylene phase cyclohexane The weight concentration 0.1%~15.0% of hydrogen peroxide.

Optionally, the volume ratio of the solution containing cyclohexyl hydroperoxide and the solution containing catalyst be 2:1~ 20:1。

Optionally, the solution containing cyclohexyl hydroperoxide and the solution containing catalyst are added in the form of cocurrent Material.

Optionally, the solution containing cyclohexyl hydroperoxide and the solution containing catalyst pass through before entering reactor Static mixer is mixed.

Optionally, reaction substrate is the cyclohexane solution containing cyclohexyl hydroperoxide in the method, is by air Oxidizing ethyle alkyl produces the intermediate product during cyclohexanol and cyclohexanone, weight containing cyclohexyl hydroperoxide hundred in this solution Divide ratio between 0.1%~15.0%.

The reaction substrate is the cyclohexane solution containing cyclohexyl hydroperoxide, is produced by air oxidation of cyclohexane Intermediate product during cyclohexanol and cyclohexanone；Used cyclohexyl hydroperoxide cyclohexane solution can be through further net Change processing or without any processing and directly as cartalytic decomposition effect liquid；Weight containing cyclohexyl hydroperoxide hundred in this solution Divide ratio generally between 0.1%~15.0%；But usually between 0.5%~8.0%), meanwhile, wherein also containing a certain amount of Other ingredients such as cyclohexanol, cyclohexanone and organic acid；The cyclohexyl hydroperoxide catalytic decomposition product of the application is mainly hexamethylene Pure and mild cyclohexanone.

Weight percent containing cyclohexyl hydroperoxide generally exists between 0.1%~10%, but usually in this solution Between 0.5%~5.0%.

Optionally, cyclohexyl hydroperoxide weight percent is 0.1% in the solution containing cyclohexyl hydroperoxide ~15.0%；

The solution containing cyclohexyl hydroperoxide is the cyclohexane solution containing cyclohexyl hydroperoxide.

Optionally, cyclohexyl hydroperoxide weight percent is 0.5% in the solution containing cyclohexyl hydroperoxide ~8.0%.

Optionally, cyclohexyl hydroperoxide weight percent is 0.1% in the solution containing cyclohexyl hydroperoxide ~10%.

Optionally, cyclohexyl hydroperoxide weight percent is 0.5% in the solution containing cyclohexyl hydroperoxide ~5.0%.

Optionally, the catalytic liquid is catalyst solution described in patent CN200710159027.5.

Optionally, the solvent of the solution containing catalyst is water.

Optionally, the catalyst is selected from least one of water-soluble transition metal organic complex；

The dosage of the catalyst is 1~5000ppm.

The catalyst solution is patent CN200710159027.5 catalyst used.Wherein transition metal is manganese, molybdenum Or vanadium, organic ligand are the organic matter that stable water soluble complex can be formed with these three metal ions, such as amino acid or Polypeptide, the unitary organic acid or multicomponent organic acid (citric acid, tartaric acid, oxalic acid, maleficent acid, lactic acid) of hydroxyl, sugared (Portugal Grape sugar, fructose, sucrose), soluble starch, water-soluble aromatic race organic heterocyclic molecule (pyridine -2- formic acid, 2,6- diformazans Sour pyridine, indole-2-carboxylic acid, thiophene -2-carboxylic acid, 2,6- thiophenedicarboxylic acids) etc..

Optionally, the temperature of the reaction is 50 DEG C~120 DEG C.

Optionally, the volume space velocity of the reaction is 2~3h^-1。

Optionally, the upper limit of the volume space velocity of the reaction is selected from 2.3h^-1、2.4h^-1、2.5h^-1Or 3.0h^-1；Lower limit is selected from 2.0h^-1、2.3h^-1、2.4h^-1Or 2.5h^-1。

Optionally, the pressure of the reaction is 0.1Mpa~1Mpa；Reaction atmosphere is air or non-active gas.

Optionally, the non-active gas is selected from least one of nitrogen, inert gas.

The application cartalytic decomposition effect temperature is between 50 DEG C~120 DEG C；Preferably between 80 DEG C~100 DEG C.Reaction Pressure is corresponding with reaction temperature, between 0.1Mpa~1Mpa, preferably with normal pressure decomposition reaction.Reaction can be in nitrogen or sky It is carried out under gas atmosphere.

Optionally, in the mixture containing cyclohexanol and cyclohexanone the molar ratio of cyclohexanone and cyclohexanol be 1.8~ 2.3:1。

The cyclohexylhydroperoxconversion conversion rate that method described herein obtains is the hexamethylene alcohol ketone overall selectivity greater than 97% Greater than 97%.

The beneficial effect that the application can generate includes:

The cyclohexyl hydroperoxide in cyclohexane oxide solution is converted height with high selectivity by method provided herein The decomposed solution of keto-alcohol ratio；It does not need to subtract with decomposition reaction, product keto-alcohol is than high, the features such as equipment is simple.

Specific embodiment

The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.

Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources, wherein catalyst passes through CN200710159027.5 is prepared.

Analysis method is as follows in embodiments herein:

In the application, cyclohexyl hydroperoxide content iodimetric analysis；Cyclohexanol and cyclohexanone gas-chromatography internal standard Standard measure.

Conversion ratio, selectivity calculate as follows in embodiments herein:

In embodiments herein, cyclohexylhydroperoxconversion conversion rate and hexamethylene alcohol ketone selectivity are all based in oxidation solution Contained cyclohexyl hydroperoxide molal quantity is calculated:

Cyclohexylhydroperoxconversion conversion rate=(A-B)/C × 100%,

Wherein: cyclohexyl hydroperoxide molal quantity contained in A=oxidation solution；Remaining cyclohexyl mistake in B=decomposed solution Hydrogen oxide molal quantity；Cyclohexyl hydroperoxide molal quantity contained in C=oxidation solution.

Hexamethylene alcohol ketone overall selectivity=(D+E)/(A-B) × 100%,

Wherein: the cyclohexanol molal quantity that D=decomposition reaction generates；The cyclohexanone molal quantity that E=decomposition reaction generates.

Keto-alcohol molar ratio=E/D.