WO2012146145A1 - Procédé d'oxydation de cyclohexane - Google Patents

Procédé d'oxydation de cyclohexane Download PDF

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Publication number
WO2012146145A1
WO2012146145A1 PCT/CN2012/074285 CN2012074285W WO2012146145A1 WO 2012146145 A1 WO2012146145 A1 WO 2012146145A1 CN 2012074285 W CN2012074285 W CN 2012074285W WO 2012146145 A1 WO2012146145 A1 WO 2012146145A1
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Prior art keywords
cyclohexane
hydrogen peroxide
cyclohexanone
weight
reaction
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PCT/CN2012/074285
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English (en)
Chinese (zh)
Inventor
何嘉勇
蒋卫和
林民
屈铠甲
杨浴
舒兴田
汪燮卿
Original Assignee
岳阳昌德化工实业有限公司
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Priority claimed from CN201110111332.3A external-priority patent/CN102757306B/zh
Priority claimed from CN2011101158540A external-priority patent/CN102766031A/zh
Application filed by 岳阳昌德化工实业有限公司 filed Critical 岳阳昌德化工实业有限公司
Publication of WO2012146145A1 publication Critical patent/WO2012146145A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups

Definitions

  • This invention relates to a process for the oxidation of cyclohexane. Background technique
  • cyclohexanone and cyclohexanol are widely used in various fields such as fiber, synthetic rubber, industrial coatings, medicines, pesticides, and organic solvents.
  • cyclohexanone and cyclohexanol which are intermediates for the preparation of nylon 6 and nylon 66, currently have a total annual demand of more than 2 million tons.
  • the first step is the oxidation of cyclohexane to cyclohexanol
  • the second step is the further oxidation of cyclohexanol to the ring.
  • the process of ketone therefore, increasing the conversion of cyclohexanol is the key to increasing the yield of cyclohexanone.
  • the above 3 ⁇ 40 2 is usually commercially available at a concentration of 27.5 wt%, 50 wt%, 70 wt% hydrogen peroxide, and the effective conversion rate of hydrogen peroxide is low, so that consumption is required in the process of producing cyclohexanone.
  • a large amount of hydrogen peroxide, and 3 ⁇ 40 2 is chemically active, it is an explosive and strong oxidant.
  • the object of the present invention is to overcome the defects of the prior art titanium silicon molecular sieve/H 2 2 2 system for catalyzing the oxidation of cyclohexane, and the defect of the commercially available raw material oxidant H 2 0 2 is provided.
  • the present invention provides a method of oxidizing cyclohexane, the method comprising the steps of:
  • the invention obtains the complete or complete conversion of cyclohexanol to cyclohexanone by catalytic dehydrogenation of the obtained oxidation product cyclohexanol, and the obtained final product is almost all cyclohexanone, which greatly improves the selectivity of cyclohexanone. And yield.
  • the hydrogen produced is synthesized into H 2 O 2 by ruthenium oxidation, so that the method of the present invention at least partially self-suppresses the oxidant H 2 O 2 , and the entire oxidation process mainly consumes oxygen and cyclohexane, thereby improving
  • the system has economic benefits, and the process is green and environmentally friendly.
  • the conversion of cyclohexane can be further increased, thereby increasing the yield of cyclohexanone, and the oxidation reaction conditions are more mild.
  • 1 is a process flow diagram of a cyclohexane oxidation process in accordance with an embodiment of the present invention.
  • 2 is a process flow diagram of a cyclohexane oxidation process in accordance with another embodiment of the present invention. Description of the reference numerals
  • the method of oxidizing cyclohexane of the present invention comprises:
  • the specific form of the titanium-silicon molecular sieve catalyst of the present invention is not particularly limited and should be selected according to a specific reaction form, and may be a titanium-silicon molecular sieve. In order to facilitate separation from the product, it may also be a shaped titanium-silicon molecular sieve catalyst.
  • the shaped titanium-silicon molecular sieve catalyst generally comprises a titanium-silicon molecular sieve and a carrier, wherein the content of the carrier may be 40-90% by weight, preferably 50-80% by weight based on the total amount of the formed titanium-silicon molecular sieve catalyst;
  • the content of the silicon molecular sieve may be from 10 to 60% by weight, preferably from 20 to 50% by weight.
  • the present invention has no special requirement for the carrier containing the titanium silica molecular sieve catalyst, and may be a carrier of various commonly used shaped catalysts, for example, may be a porous heat-resistant inorganic oxide and/or silicate, and specifically, for example, may be oxidized.
  • a carrier of various commonly used shaped catalysts for example, may be a porous heat-resistant inorganic oxide and/or silicate, and specifically, for example, may be oxidized.
  • the carrier is one or more of alumina, silica, magnesia and zirconia.
  • the titanium silicon molecular sieve is commercially available or can be prepared.
  • the method for preparing the titanium silicon molecular sieve is known to those skilled in the art. For example, reference can be made to [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS). -l) Prepared by the method described in Hydrogen Peroxide Journal of Natural Gas Chemistry 2001, 10(4): 295-307, and can also be obtained by the method of preparing a catalyst disclosed in CN101279959A.
  • the type of the titanium-silicon molecular sieve in the titanium-silicon molecular sieve catalyst of the present invention is not particularly limited, and may be a titanium-silicon molecular sieve of various structures.
  • the titanium silicon molecular sieve is a titanium silicon molecular sieve having an MFI structure
  • the crystal grains of the titanium silicon molecular sieve are hollow structures, and a cavity portion of the hollow structure has a radial length of 5 to 300 nm
  • the The adsorption capacity of benzene on the titanium silicalite at 25 ° C, P / P Q 0.10
  • adsorption time of 1 hour is not less than 70 mg / gram
  • the adsorption isotherm of the low temperature nitrogen adsorption of the titanium silicalite There is a hysteresis loop between the desorption isotherms.
  • Titanium silicon molecular sieves having the above structure and properties are generally referred to as hollow titanium silicon molecular sieves, which are commercially known as HTS.
  • the relevant parameters and preparation methods thereof can be referred to CN1301599A.
  • the particle size of the titanium-silicon molecular sieve catalyst of the present invention is not particularly limited, but the particle diameter of the formed titanium-silicon molecular sieve catalyst is preferably from 20 to 60 mesh from the viewpoints of easy separation of the catalyst and ensuring high catalytic activity.
  • the present invention has no special requirement for the concentration of the aqueous hydrogen peroxide solution (ie, hydrogen peroxide), and may be hydrogen peroxide at a concentration of 20-80% by weight, for example, commercially available 27.5 wt%, 50 wt%, 70 wt% hydrogen peroxide. .
  • the conditions of the oxidation reaction in the step (1) generally include cyclohexane, hydrogen peroxide, water, and the ratio of the titanium silica molecular sieve catalyst to the organic solvent is 1:0.003-5:0.15-3:0.1-15.
  • the temperature of the contact is 30-170 ° C, preferably 50-170 ° C; the contact pressure is 0.01-2 MPa, preferably 0.1-0.5 MPa; and further, for the batch reaction, the general contact time is 0.1-10 h, preferably l-5 h.
  • the pressure refers to the gauge pressure in the reaction system.
  • the organic solvent in the step (1) is not particularly limited and may be various organic solvents conventionally used in the art.
  • the inventors of the present invention have found that when the organic solvent is a nitrile and/or a halogenated hydrocarbon, the conversion of cyclohexane and the yield of cyclohexanol can be increased, and the nitrile and the halogenated hydrocarbon can be further mixed.
  • the conversion of cyclohexane can be greatly improved, that is, particularly preferably, the organic solvent is a mixture of a nitrile and a halogenated hydrocarbon, and preferably the mass ratio of the nitrile to the halogenated hydrocarbon is from 0.1 to 10.
  • the nitrile is a C1-C10 mononitrile and/or a dibasic nitrile, preferably a C2-C8 mononitrile and/or a dibasic nitrile, and more preferably, the nitrile is acetonitrile, propionitrile or valeronitrile.
  • adiponitrile; the halogenated The hydrocarbon is a C1-C10 alkane substituted by one and/or a plurality of the same or different halogen atoms and/or a C6-C10 cycloalkane substituted by one and/or a plurality of the same or different halogen atoms, further preferably C1.
  • dichloroalkane and / or trichloroalkane more preferably dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1- Trichloroethane, 1,1,2-trichloroethane, 1,2-dichloropropane, 2,2-dichloropropane, 1,3-dichloropropane, 1,2,3-trichloropropane, 1,2-dichlorobutane, 2,3-dichlorobutane, 1,4-dichlorobutane, 1,2-dichloropentane, 2,2-dichloropentane, 1,3-two Chloropentane, 2,3-dichloropentane, 3,3-dichloropentane, 1,4-dichloropentane, 2,4-dichloropentane, 1,2,5-trichloropentane
  • 1,1,5-trichloropentane 1,1,5-t
  • the temperature of the contact is preferably 60-12 CTC; or when the organic solvent is halogenated In the case of a hydrocarbon, the temperature of the contact should preferably be 50-9 CTC; or when the organic solvent is a nitrile and a halogenated hydrocarbon, the temperature of the contact is 50-120 ° C, preferably 60-110 ° C.
  • the cyclohexanol-containing mixture obtained in the step (1) generally contains an oxidation product of cyclohexanol and cyclohexanone, an unreacted raw material cyclohexane and hydrogen peroxide, and an organic solvent, and the present invention
  • the cyclohexanol-containing mixture obtained in the step (1) may be subjected to the second contact described in the step (2) without isolating or separating the alcohol or the mixture of the alcohol and the ketone therein.
  • the present invention preferably comprises the cyclohexanol-containing mixture obtained in the step (1). Separating, and separating the separated organic solvent and unreacted cyclohexane and hydrogen peroxide or aqueous hydrogen peroxide into the feed of step (1), separating cyclohexanol or cyclohexanol from cyclohexyl The mixture of ketones is subjected to the second contact reaction of step (2).
  • the invention has no specific requirement for the reaction form of the step (1), and may be a batch reaction or a continuous reaction, and in order to make the whole process of the invention more suitable for industrial application, the step (1) is preferably a continuous reaction.
  • the continuous reaction can be carried out, for example, in a reactor such as a fixed bed.
  • step (1) can be carried out in a fixed bed reactor T4, and then the product after the first contact reaction is separated, and the separated organic solvent And unreacted cyclohexane and hydrogen peroxide or aqueous hydrogen peroxide are returned to the feed of step (1), and the separated cyclohexanol or a mixture of cyclohexanol and cyclohexanone is subjected to the step (2).
  • the second contact reaction can be carried out, for example, in the distillation column T5.
  • the reaction process and conditions of the step (1) according to the present embodiment are common knowledge in the art and will not be described herein.
  • the gas-liquid or liquid-liquid separation in the distillation column is also a well-known means in the art, and the present invention will not be described herein.
  • the cyclohexane oxidation reaction in the titanium silicalite/H 2 O 2 system is an indispensable part of the solvent.
  • the addition of a suitable solvent can effectively carry out the reaction while improving the selectivity of the target product.
  • the solvent usually accounts for 30-90% by weight based on the total weight of the reaction liquid, so although it is effective because of the addition of the solvent. The reaction is efficiently carried out, but the large addition of the solvent also adds trouble and cost to the subsequent separation, thereby reducing its industrial application prospects.
  • reaction is a violent exothermic reaction, and the cooling energy is required for the reaction, and the energy consumption for heating is required to separate the target product. Therefore, how to save the required energy consumption or effectively utilize the heat generated by the system is also worth studying. The problem.
  • the inventors of the present invention have attempted to contemplate whether a process can not only enable the reaction to proceed continuously, but also achieve more efficient separation, and can also utilize the heat of reaction in the system to save energy. Another embodiment of the present invention has been made based on this assumption.
  • the first contact reaction is carried out in a catalytic distillation manner, and the organic solvent obtained by catalytic distillation and unreacted cyclohexane and hydrogen peroxide or hydrogen peroxide aqueous solution are carried out.
  • the cyclohexanol obtained by catalytic distillation or a mixture of cyclohexanol and cyclohexanone is subjected to the second contact reaction of the step (2).
  • the oxidation product refers to a product obtained by the oxidation reaction of cyclohexane, and generally includes cyclohexanol and cyclohexanone.
  • the method for oxidizing cyclohexane of the present invention is oxidized in a rectification column (i.e., under rectification conditions), and the latent heat of reaction is fully utilized, thereby achieving energy saving;
  • a rectification column i.e., under rectification conditions
  • the latent heat of reaction is fully utilized, thereby achieving energy saving;
  • the present invention has no particular requirement for the method of feeding cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from a feed port into a rectification column, but in order to make the reactants in the rectification column The contact is more complete and the reaction is more complete.
  • the method for feeding cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from the feed port to the rectification column comprises: treating the aqueous hydrogen peroxide solution from the first feed The mouth is sent to the rectification column, and the cyclohexane is sent from the second feed port to the rectification column; wherein the number of plates or the number of theoretical plates between the first feed port and the bottom of the column accounts for the fine 50 to 100%, more preferably 80 to 100%, of the total number of trays or the number of theoretical plates in the distillation column; the number of plates or the number of theoretical plates between the second feed port and the bottom of the column Said that the total number of plates in the distillation column or the number of theoretical plates is 10-80%, More preferably, it is 30-70%.
  • the invention has no special requirement for the feeding mode of the organic solvent, and specifically, the solvent feed inlet is selected as the first feed port and/or the second feed according to the operating parameters in the rectification column and the properties of the organic solvent.
  • the basic principle of the material inlet is: The composition of the feed and the choice of the feed port are less suitable for the reaction distillation column, which is beneficial to stabilize and strengthen the ratio of the reaction materials.
  • the organic solvent when the boiling point of the organic solvent is higher than the temperature of the distillation column, the organic solvent may be fed from the first feed port; when the boiling point of the organic solvent is lower than that of the distillation column At the temperature, the organic solvent can be fed from the second feed port, so that a stable rectification state can be formed, which will be known to those skilled in the art, and will not be further described herein, in the specific embodiment of the present invention. It is no longer specifically emphasized in China.
  • the present invention has no special requirements for the titanium silicon molecular sieve catalyst in the catalytic rectification, and can be various shaped titanium silicon molecular sieve catalysts which can be applied to the rectification column, and the shaped titanium silicon molecular sieve catalyst has been described in detail above. The description will not be repeated. Similarly, the titanium silicalite in the titanium silicalite catalyst has been described in detail above and will not be described herein.
  • the amount of the titanium silicalite catalyst in the filler can be selected in a wide range, but if the amount of the catalyst is too large, the reaction is too fast, the subsequent separation is not easy, and the amount of the catalyst is too small, the reaction is Too slow, which is disadvantageous for industrial applications, it is preferred that the filler contains 30 to 100% by weight, more preferably 30 to 70% by weight, of the titanium silicalite catalyst.
  • the filler of the titanium-silicon molecular sieve catalyst in the present invention is preferably a mixed filler obtained by mixing a conventional filler with a titanium-silicon molecular sieve catalyst.
  • the conventional filler may be various conventional fillers conventionally used in a rectification column, and may be, for example, one of a Raschig ring, a Pall ring, a step ring, an arc saddle, a saddle, and a metal ring saddle filler.
  • One or more kinds, and specific examples thereof may be an anthracene ring, a ⁇ -ring filler, or the like.
  • the organic solvent of the present invention has been described in detail. However, for the specific reaction form of catalytic distillation, it is further preferred that when the first contact reaction of the step (1) of the present invention is carried out by catalytic distillation, the organic solvent is The boiling point is from 50 to 140 ° C, preferably from 60 to 130 ° C.
  • the preferred organic solvent of the present invention is a nitrile and/or a halogenated hydrocarbon. Therefore, according to a particularly preferred embodiment of the present invention, it is preferred that the first contact reaction in the step (1) is in accordance with catalytic distillation. When the reaction is carried out in a manner, the organic solvent is a nitrile having a boiling point of 60 to 13 CTC and/or a halogenated hydrocarbon having 60 to 13 CTC.
  • the oxidation reaction conditions include a distillation column bottom temperature of 55-170 ° C, preferably It is 60-150 ° C.
  • the present invention has no special requirement for the reflux ratio in the rectification column, and may or may not be reflowed, may be selected according to specific needs, and the reflux ratio does not have much influence on the results of the present invention, and therefore, in the embodiment of the present invention, Again
  • the body illustrates the reflux ratio.
  • the total number of plates or the number of theoretical plates in the rectification column is 20- 45, more preferably 30-40.
  • the amount of hydrogen peroxide in the aqueous phase in the controlled discharge is from 0.01 to 1% by weight, preferably from 0.05 to 0.4% by weight.
  • the above method for controlling the amount of hydrogen peroxide in the aqueous phase in the discharge can be varied, for example, by controlling the amount of hydrogen peroxide fed in the rectification column, preferably, hydrogen peroxide per hour.
  • the feed amount is from 5 to 500 g, preferably from 10 to 150 g.
  • the reaction in the manner of the first contact reaction in the step (1) of the present invention, is carried out in a catalytic distillation manner, preferably in the course of the reaction (ie, in the first contact reaction), cyclohexane, hydrogen peroxide, water.
  • the mass ratio to the organic solvent is 1:0.03-3:0.1-3:0.5-30, preferably 1:0.3-1.5:0.1-2:3-15.
  • the molar ratio of cyclohexane to hydrogen peroxide is 1:1-2.
  • the rectification column in the actual reaction process, according to the specific situation, in order to prevent the collapse of the packed bed of the titanium silicon molecular sieve catalyst in the rectification column, the rectification column can be divided into a plurality of sections, and each section can be directly used conventionally.
  • the fillers are separated, wherein the thickness of the conventional filler between each section can be selected according to the height of each of the separated distillation columns. If the height of each fractionator is 3-6 m, the conventional packing between each section The thickness is generally 5-20 cm, preferably 8-15 cm.
  • the present invention has no special requirements on the discharge port position of the rectification column, and can be carried out by referring to the prior art, for example, it can be produced sideways or discharged from the bottom of the column. Since the target products cyclohexanol and cyclohexanone in the present invention are mostly at the bottom of the column, it is preferred that at least one discharge port of the present invention is disposed at the bottom of the column. Particularly when the rectification column is totally refluxed, it is preferred that the discharge port of the present invention is one, and is disposed at the bottom of the column, and the column material is discharged from the discharge port.
  • a condensing device may be disposed at the discharge port to collect the liquid bottom discharge material, or directly drain the bottom of the column. The material is sent to the next process to separate the product, which will be known to those skilled in the art, and will not be described herein.
  • the distillation column column material may contain, in addition to all or most of the oxidation products, a solvent, a small amount of cyclohexane and water, etc., depending on the temperature at the bottom of the column. These remaining materials may be known in the art.
  • the subsequent separation step is carried out to separate and remove, and the present invention will not be described herein.
  • the temperature at the bottom of the column is high or the solubility of water in the organic solvent is large, the water in the aqueous hydrogen peroxide solution and the water formed during the reaction may be partially or completely returned to the distillation column as part of the overhead stream.
  • the water is discharged from the top of the column for example, can be separated from the overhead of the column by a water separator to increase the concentration of hydrogen peroxide in the distillation column, and the remaining overhead of the column can be partially Or all of the circulation back to the rectification column inlet into the rectification column (the distillation column can be selected from the first feed port or the second feed port depending on the type of solvent, and those skilled in the art can
  • the present invention preferably returns all of the overhead effluent as a feed to the rectification column, thereby making full use of the reaction raw materials and being effective. Save on production costs.
  • the top discharge material, the top discharge, and the top discharge indicate the same meaning, the bottom discharge material, the bottom discharge, the bottom discharge, the tower discharge material, the tower discharge, the tower The kettle discharge also means the same meaning.
  • the amount of hydrogen peroxide in the aqueous phase in the above discharge in the present invention means the amount of hydrogen peroxide in the aqueous phase after removal of the organic matter, whether water is present in the overhead stream or in the column stream.
  • the second contact reaction of the step (2) of the present invention can be carried out in a fixed bed reactor, and there is no special requirement for the conditions of the second contact reaction, as long as the present invention can be realized.
  • the conditions of the second contact reaction include a temperature of 150-28 CTC, a pressure of 0.3-3.2 MPa, and a weight hourly space velocity of 0.35-0.55 h - the present invention is in the step (2)
  • the dehydrogenation catalyst is not particularly limited as long as the object of the present invention can be achieved.
  • the dehydrogenation catalyst contains the following components: a) copper or copper oxide 20-74% by weight; b) palladium And/or 0.001-2.0% by weight of platinum or palladium and/or platinum oxide; c) 24 to 78% by weight of other metals than copper, palladium and platinum, the other metals being It is at least one selected from the group consisting of zinc, magnesium, calcium, strontium, barium, silicon, aluminum, chromium, manganese, nickel, zirconium, and titanium.
  • the above dehydrogenation catalyst is prepared by the method described in CN1156425C.
  • the method of the present invention in order to obtain a reasonable application of the hydrogen obtained by the method according to the present invention, and in order to further save the input cost of the oxidant raw material of the present invention, it is preferred that the method of the present invention further comprises the step (3): the step (2) The resulting hydrogen is hydrolyzed by a hydrazine process, and the hydrogen peroxide is used in the first contact reaction of the step (1).
  • the method described in the step (3) of the present invention is a method well known to those skilled in the art and is the main method for producing hydrogen peroxide.
  • the general procedure of the hydrazine method comprises formulating an alkyl hydrazine and an organic solvent into a hydrazine working solution, and hydrogenating the hydrogen gas under the conditions of a pressure of 0.1-lMPa, a temperature of 55-65 ° C and a catalyst, and then 40-44 ° C
  • the product is subjected to countercurrent oxidation with air (or oxygen), and is subjected to extraction, regeneration, purification and concentration to obtain an aqueous hydrogen peroxide solution.
  • the catalyst may be, for example, a Pd/Al 2 O 3 catalyst, and the weight ratio of the alkyl hydrazine to the organic solvent may be 1:4-10.
  • the organic solvent may, for example, be a C9-C11 aromatic hydrocarbon, the liquid velocity of the hydrazine working fluid is 5-10 h - the hydrogen space velocity is 9-18 h - the oxygen space velocity is 150-340 h - the alkyl hydrazine may for example Is 2-ethyl hydrazine (EAQ), 2-tert-butyl hydrazine, 2-pentyl hydrazine and their tetrahydro derivatives such as 2-(4-methyl-3-pentenyl) hydrazine or One or more of 2-(4-methyl-methylpentyl)indole.
  • EAQ 2-ethyl hydrazine
  • 2-tert-butyl hydrazine 2-pentyl hydrazine
  • the solvent is usually one or more of a high boiling point heavy aromatic hydrocarbon (C9-C11 aromatic hydrocarbon), a higher aliphatic alcohol, an organic acid or an inorganic acid ester, wherein trioctyl phosphate (TOP), methyl acetate acetate Hexyl ester (MCA), tetrabutyl urea (TBU), diisobutylmethanol (DIBC) and the like are more commonly used.
  • a high boiling point heavy aromatic hydrocarbon C9-C11 aromatic hydrocarbon
  • MCA methyl acetate acetate Hexyl ester
  • TBU tetrabutyl urea
  • DIBC diisobutylmethanol
  • the process of the present invention is as shown in FIG. 1.
  • a mixture 1 of cyclohexane, hydrogen peroxide and an organic solvent is fed into a fixed bed reactor T4 loaded with a titanium silicalite catalyst, after oxidation.
  • the liquid product, that is, the mixture 7 containing cyclohexanol is separated into the distillation column T5 for separation, and the separated organic solvent, unreacted mixture of cyclohexane and hydrogen peroxide 2 is returned as a feed to the fixed bed reactor T4.
  • the first contact reaction, the oxidation product cyclohexanol or a mixture 3 of cyclohexanol and cyclohexanone enters the dehydrogenation reactor T2 (preferably a fixed bed reactor) for a second contact reaction to produce hydrogen gas.
  • the dehydrogenation reactor T2 preferably a fixed bed reactor
  • 4 together with the hydrazine working solution (not shown) enters the hydrazine oxidation reactor T3, and is subjected to hydrazine oxidation to prepare a hydrogen peroxide solution 6 by introducing air or oxygen (not shown), the peroxidation
  • the hydrogen solution 6 is returned to the fixed bed reactor T4 loaded with the titanium silicon molecular sieve catalyst as a feed for the first contact reaction.
  • the process flow of the present invention is as shown in FIG.
  • the process flow of Fig. 2 is similar to that of Fig. 1, except that the rectification column T1 is used in Fig. 2 instead of the fixed bed reactor T4 and the distillation column T5 in Fig. 1.
  • the specific procedure is to feed a mixture of cyclohexane, hydrogen peroxide and an organic solvent into a rectification column T1 loaded with a titanium silicon molecular sieve catalyst, and the oxidized liquid product, that is, a mixture 7 containing cyclohexanol, is separated in the rectification column T1.
  • the organic solvent, the mixture 2 of unreacted cyclohexane and hydrogen peroxide is returned to the rectification column T1 as a feed to carry out the first contact reaction described in the step (1), and the oxidation product cyclohexanol or cyclohexanol and the ring
  • the mixture 3 of ketone enters the dehydrogenation reactor ⁇ 2 (preferably a fixed bed reactor) for a second contact reaction, and the generated hydrogen 4 enters the ruthenium oxidation reactor together with the hydrazine working solution (not shown).
  • the hydrogen peroxide solution 6 is prepared by enthalpy oxidation by introducing air or oxygen (not shown), and the hydrogen peroxide solution 6 is returned to the fixed bed reactor ⁇ 4 loaded with the titanium silicalite catalyst as The first contact reaction feed.
  • the reagents used in the examples and comparative examples were all commercially available chemically pure reagents.
  • the hollow titanium silicon molecular sieve (HTS) catalyst of the embodiment based on the total weight of the catalyst, the hollow titanium silicon
  • the content of the sub-screen (HTS) is 50%
  • the content of silica is 50%.
  • the conventional titanium silicalite (TS-1) content was 50% and the silica content was 50% based on the total weight of the catalyst.
  • the hollow titanium silicon molecular sieve (HTS) used in the examples is an industrial product of titanium silicon molecular sieve described in CN1301599A (manufactured by Hunan Jianchang Co., Ltd., which is an MFI structure of titanium silicon molecular sieve by X-ray diffraction analysis, and the molecular sieve has low temperature nitrogen adsorption.
  • the benzene adsorption amount measured under conditions of 1 hour was 78 mg/g, and the content of titanium oxide was 2.5% by weight.
  • the conventional titanium silicalite (TS-1) used in the examples and comparative examples is according to the literature [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) With Hydrogen Peroxide Journal of Natural Gas Chemistry 2001, 10(4): 295-307
  • the (TS-1) molecular sieve sample prepared by the method described in lines 9-24 on page 296 has a titanium oxide content of 2.5% by weight.
  • the hydrogen peroxide used in the examples and the comparative examples was a commercially available hydrogen peroxide having a concentration of 27.5% by weight.
  • the titanium silicalite (TS-1 or HTS) catalysts in the examples and comparative examples were 40 mesh.
  • the analysis of each organic substance in the system by gas chromatography and quantification by the correction normalization method can be carried out by referring to the prior art, on the basis of which the conversion rate of the reactant, the yield and selectivity of the product, etc. are calculated. Evaluation indicators.
  • ⁇ cyclohexanone ⁇ cyclohexanone x ⁇ cyclohexane
  • X is the conversion rate
  • s is the selectivity (s » s means the total selectivity of the ketol, or ketol selectivity for short);
  • Oxidation of cyclohexane was carried out using the process flow shown in FIG. According to the ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and solvent 1,2-dichloropropane (boiling point 96.8 °C), the ratio of the ratio of 1:1.72:15 from the feed port of the rectification column T1 Feeding, and the amount of hydrogen peroxide per hour per kg of hollow titanium silicon molecular sieve (HTS) is 0.05 kg, wherein cyclohexane is fed from the second feed port, hydrogen peroxide and solvent 1,2-dichloropropane
  • the first feed port feeds wherein the bottom temperature of the control column is 115 ° C, and the top of the distillation column is discharged into the second feed port and recycled, and the number of theoretical plates of the distillation column is 35, The number of theoretical plates between a feed port and the bottom of the column is 30, the number of theoretical plates between the second feed port and the bottom of the
  • the column material is discharged from the outlet of the bottom of the distillation column (sampling analysis from the outlet of the bottom of the column after 18 hours of stable operation, the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • the column charge is fed from the top of the fixed bed reactor to a dehydrogenation catalyst (containing 40% by weight of copper, 40% by weight of zinc oxide, 12% by weight of magnesium oxide, 0.8% by weight of calcium oxide, 0.3% by weight).
  • the space-time velocity is 0.49h - the fixed bed T2 operating temperature is 220 ° C, the pressure is 1.0 MPa, and the obtained hydrogen directly enters the ruthenium catalytic fixed bed T3 from the upper part of the fixed bed reactor T2, and the remaining products are from the fixed bed reactor ⁇ 2
  • the lower part of the output was separated to obtain cyclohexanone.
  • the yield of cyclohexanone is shown in Table 1.
  • the ruthenium-catalyzed fixed bed 3 is filled with 30 ml of Pd/Al 2 0 3 catalyst, the reactor operating temperature is 60 ° C, the pressure is 0.3 MPa, and the hydrazine working solution is: hydrazine trihydrate 75 vol%, tetrabutyl 18% by volume of urea, 7% by volume of trioctyl phosphate, a working carrier of 149g/L of 2-ethyl hydrazine and 17g/L of 2-ethyltetrahydroanthracene, 2-ethyl hydrazine in the working carrier
  • the total content of cerium and 2-ethyltetrahydroanthracene was 166 g/L, that is, the effective cerium concentration was 166 g/L.
  • the weight hourly space velocity of the working fluid is 8h - the gas hourly space velocity of hydrogen is 16h - the gas hourly space velocity of oxygen is 240h - the H 2 0 2 obtained after the reaction is directly sent to the distillation column T1.
  • the oxidation of cyclohexane was carried out using the process flow shown in FIG. According to the ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and solvent 1,4-dichloropentane in the reaction process, the ratio of the ratio of 1:1.72:5 is fed from the feed port of the fixed bed reactor T4, The space velocity is 3h - the reaction pressure is lMPa, the reaction temperature is 120 ° C, and the product after the reaction enters the distillation column T5 for separation.
  • the pressure of the distillation column T5 is 0.2 MPa, the temperature is 160 ° C, and the conversion rate of cyclohexane is The total selectivity of keto alcohol and the yield of cyclohexanol are shown in Table 1.
  • the solvent, water and excess cyclohexane distilled from the top of the column were directly returned to the fixed bed reactor T4 (sampling analysis after 18 hours of stable operation, cyclohexane)
  • the conversion rate, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1), and the column charge was sent to a dehydrogenation catalyst (containing 10% by weight of copper, 59% by weight of copper oxide, and 25% by weight of oxidation).
  • Zinc 5% by weight of cerium oxide, 0.1% by weight of platinum, 0.8% by weight of nickel, 0.1% by weight of chromium, and is prepared by the method for preparing a catalyst disclosed in CN1156425C), fixed bed reactor T2, heavy time and space
  • the speed is 0.49h- fixed bed T2 operating temperature is 220 ° C
  • the pressure is l.OMPa
  • the obtained hydrogen directly enters the ruthenium catalytic fixed bed T3 from the upper part of the fixed bed reactor T2, and the rest of the product is discharged from the lower part of the fixed bed reactor ⁇ 2, and after separation, cyclohexanone is obtained.
  • the yield of cyclohexanone is shown in Table 1. .
  • the ruthenium catalytic fixed bed 3 is filled with 30 ml of Pd/Al 2 0 3 catalyst, the reactor operating temperature is 60 ° C, the pressure is 0.3 MPa, and the hydrazine working solution is: 70% by volume of trimethylbenzene, tetrabutyl 20% by volume of urea, 10% by volume of trioctyl phosphate, a mixture of 2-tert-butyl fluorene with a working carrier of 160 g/L and a 2-tert-butyltetrahydroindene mixture of 29 g/L, 2-tertyl in a working carrier
  • the total content of hydrazine and 2-tert-butyltetrahydroanthracene was 189 g/L, that is, the effective hydrazine concentration was 189 g/L.
  • the weight hourly space velocity of the working fluid is 5h - the gas hourly space velocity of hydrogen is 9h - the gas hourly space velocity of oxygen is 150h - the H 2 0 2 obtained after the reaction is directly sent to the rectification column T1.
  • Oxidation of cyclohexane was carried out using the process flow shown in FIG. According to the ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and solvent propionitrile in the reaction process, the ratio of the ratio of 1:1.72:10 is fed from the feed port of the rectification column T1, and relative to each kilogram of hollow titanium silicon.
  • Molecular sieve (HTS) The feed per hour of hydrogen peroxide is 0.1 kg, wherein cyclohexane is fed from the second feed port, and hydrogen peroxide and solvent propionitrile are fed from the first feed port, wherein the bottom temperature of the control column is 110°. C. The top of the distillation column is discharged into the second feed port and recycled.
  • the number of theoretical plates of the distillation column is 35, and the number of theoretical plates between the first feed port and the bottom of the column is 30.
  • the number of theoretical plates between the second feed port and the bottom of the column is 10, and the filler contains 30% by weight of a hollow titanium silicon molecular sieve (HTS) catalyst, 70% by weight of 9 rings.
  • HTS hollow titanium silicon molecular sieve
  • the material of the column was discharged from the outlet of the bottom of the distillation column (sampling analysis from the bottom outlet of the column after 18 hours of stable operation, the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1) , the bottom of the reactor is fed from the top of the fixed bed reactor to the dehydrogenation catalyst (containing 40% by weight of copper, 48.45% by weight of zinc, 8% by weight of magnesium oxide, 1.8% by weight of calcium oxide, 0.05% by weight of palladium, 0.2% by weight of titanium, 0.8% by weight of silicon, 0.1% by weight sodium, potassium 0.6% by weight, and is based on the method disclosed in CN1156425C preparing the catalyst obtained) fixed bed reactor T2, a weight hourly space velocity of 0.4911- 1, ⁇ 2 bed operating temperature is 220 ° C, a pressure of l .OMPa, the obtained hydrogen directly enters the ruthenium catalytic fixed bed T3 from the upper part of the fixed
  • the ruthenium catalyst fixed bed 3 is filled with 30 ml of Pd/Al 2 O 3 catalyst, the reactor operating temperature is 60 ° C, the pressure is 0.3 MPa, and the hydrazine working solution is: hydrazine trihydrate 75 vol%, tetrabutyl 20% by volume of urea, 5% by volume of trioctyl phosphate, a working carrier of 129 g/L of 2-ethylanthracene and 71 g/L of 2-ethyltetrahydroindole mixture, 2-ethylindole in the working carrier
  • the total content of 2-ethyltetrahydroanthracene was 200 g/L, that is, the effective hydrazine concentration was 200 g/L.
  • the weight hourly space velocity of the working fluid is 10 h - the gas hourly space velocity of hydrogen is 18 h - the gas hourly space velocity of oxygen is 340 h - the H 2 0 2 obtained after the reaction is directly sent to the rectification column T1.
  • the oxidation of cyclohexane was carried out using the process flow shown in FIG. According to the ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and solvent acetonitrile in the reaction process, the ratio of 1:2.26:10 is fed from the feed port of the fixed bed reactor T4, and the weight hourly space velocity is 3 h - the reaction pressure.
  • the reaction temperature is 120 ° C
  • the product after the reaction enters the distillation column T5 for separation.
  • the pressure in the distillation column T5 is 0.2 MPa
  • the temperature is 130 ° C
  • the conversion of cyclohexane the total selectivity of ketol
  • the yield of cyclohexanol is shown in Table 1.
  • the solvent, water and excess cyclohexane distilled from the top of the column are directly returned to the fixed bed reactor T4 (sampling analysis after 18 hours of stable operation, conversion of cyclohexane, keto alcohol)
  • the total selectivity and cyclohexanol yield are shown in Table 1), and the column reactor is fed with a dehydrogenation catalyst (containing 70% by weight of copper, 26.18% by weight of zinc oxide, 1.8% by weight of magnesium oxide, 1.5% by weight).
  • the ruthenium catalyst fixed bed 3 is filled with 30 ml of Pd/Al 2 O 3 catalyst, the reactor operating temperature is 60 ° C, the pressure is 0.3 MPa, and the hydrazine working solution is: hydrazine trihydrate 75 vol%, tetrabutyl 18% by volume of urea, 7% by volume of trioctyl phosphate, a working carrier of 149g/L of 2-ethylanthracene and 17g/L of 2-ethyltetrahydroindene mixture, 2-ethylindole in working carrier
  • the total content with 2-ethyltetrahydroanthracene was 166 g/L, that is, the effective hydrazine concentration was 166 g/L.
  • the weight hourly space velocity of the working fluid is 6h - the gas hourly space velocity of hydrogen is 151 - 1 , and the gas hourly space velocity of oxygen is 200h - the H 2 0 2 obtained after the reaction is directly sent to the distillation column T1.
  • Example 6 The same procedure as in Example 1 except that the organic solvent in the first contact reaction was chloroform.
  • Example 7 The same procedure as in Example 1 except that the organic solvent in the first contact reaction was 1,2,3-trichloropropane.
  • Example 8 The same as the method of Example 2, except that the organic solvent 1,4-dichloropentane in the first contact reaction is replaced by a mixed solvent of 1,4-dichloropentane and propionitrile, and the mass ratio of the two is 1:1, that is, the mass ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and solvent 1,4-dichloropentane, solvent propionitrile is 1:1.72:7.5:7.5, conversion of cyclohexane
  • Table 1 The total selectivity of keto alcohol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 8 The total selectivity of keto alcohol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 9 The same procedure as in Example 3 except that the organic solvent propionitrile in the first contact reaction was replaced by a mixed solvent of 1,2-dichloropropane and propionitrile, and the mass of 1,2-dichloropropane and propionitrile was obtained.
  • the ratio is 1:9, that is, the mass ratio of cyclohexane to hydrogen peroxide (concentration: 27.5% by weight) and the solvent 1,2-dichloropropane and solvent propionitrile is 1:1.72:1:9, the conversion of cyclohexane
  • the total selectivity of keto alcohol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 9 The total selectivity of keto alcohol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 10 The same procedure as in Example 4 except that the organic solvent acetonitrile in the first contact reaction was replaced by acetonitrile and 1,4-dichloropentane, and the mass ratio of acetonitrile to 1,4-dichloropentane was 1: 9, the mass ratio of cyclohexane to hydrogen peroxide (concentration: 27.5 wt%) and solvent acetonitrile and solvent 1,4-dichloropentane is 1:2.26:1:9, conversion of cyclohexane, total ketol
  • the selectivity, cyclohexanol yield and cyclohexanone yield are shown in Table 1.
  • Example 10 The selectivity, cyclohexanol yield and cyclohexanone yield are shown in Table 1.
  • Example 11 The same procedure as in Example 1, except that the organic solvent 1,2-dichloropropane was replaced by 1-chloropropane in the first contact reaction, the conversion of cyclohexane, the total selectivity of keto alcohol, and the cyclohexanol. The rate and cyclohexanone yield are shown in Table 1.
  • Example 11 The same procedure as in Example 1, except that the organic solvent 1,2-dichloropropane was replaced by 1-chloropropane in the first contact reaction, the conversion of cyclohexane, the total selectivity of keto alcohol, and the cyclohexanol. The rate and cyclohexanone yield are shown in Table 1.
  • Example 11 The same procedure as in Example 1, except that the organic solvent 1,2-dichloropropane was replaced by 1-chloropropane in the first contact reaction, the conversion of cyclohexane, the total selectivity of keto alcohol, and the cyclohexanol. The rate and cyclohexanone yield
  • Example 12 The same as the method of Example 2, except that the organic solvent 1,4-dichloropentane in the first contact reaction is 1-chloro
  • the conversion of pentane, the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 12 The conversion of pentane, the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 12 The conversion of pentane, the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1.
  • Example 12 The conversion of pentane, the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol and the yield of
  • Example 13 The procedure was the same as in Example 3 except that the organic solvent in the first contact reaction was acetone, and the conversion ratio of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 13 The procedure was the same as in Example 3 except that the organic solvent in the first contact reaction was acetone, and the conversion ratio of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 13 The procedure was the same as in Example 3 except that the organic solvent in the first contact reaction was acetone, and the conversion ratio of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 13 The procedure was the same as in Example 3 except that the organic solvent in the first contact reaction was
  • Example 14 The procedure of Example 3 was the same except that the organic solvent in the first contact reaction was acetic acid, and the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 14 The procedure of Example 3 was the same except that the organic solvent in the first contact reaction was acetic acid, and the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 14 The procedure of Example 3 was the same except that the organic solvent in the first contact reaction was acetic acid, and the conversion of cyclohexane, the total selectivity of ketol, the yield of cyclohexanol, and the yield of cyclohexanone are shown in Table 1.
  • Example 14 The procedure of Example 3 was the same except that the organic solvent in the first contact reaction was acetic acid,
  • Example 11 The procedure of Example 11 is the same, except that the catalyst in the first contact reaction is a catalyst containing a conventional titanium silicalite (TS-1), the conversion of cyclohexane, the total selectivity of ketol, and the yield of cyclohexanol. And the yield of cyclohexanone is shown in Table 1.
  • TS-1 titanium silicalite
  • the process of the present invention comprises a dehydrogenation reaction step under the action of a dehydrogenation catalyst, the process of the present invention has a much higher yield than cyclohexanone obtained by merely oxidizing cyclohexane; Examples 1-6 and Examples It can be seen from the comparison of 7-9 that when a mixture of nitrile and halogenated hydrocarbon is used as the organic solvent, the nitrile or the halogenated hydrocarbon alone is used as the organic solvent.
  • the method of the invention at least partially self-suppresses the oxidant H 2 O 2 by cyclic reaction, and the whole oxidation process mainly consumes oxygen and cyclohexane, which reduces the commercial or production cost of hydrogen peroxide, and greatly improves the economic efficiency of the system, and The process is green and environmentally friendly, and no waste is produced.
  • the process of dehydrogenating the intermediate product cyclohexanol to cyclohexanone is additionally increased, and the yield of cyclohexanone is obviously improved.
  • the conversion of cyclohexane can be further increased, thereby increasing the yield of cyclohexanone, and the oxidation reaction conditions are more mild.
  • the present invention employs a nitrile and/or a halogenated hydrocarbon as an organic solvent, which simplifies the subsequent product separation step and is advantageous for industrial applications.
  • a mixed solution of 100 g of cyclohexane, 172 g of an aqueous hydrogen peroxide solution (concentration of 27.5 wt%) and 1500 g of 1,3-dichloropropane was placed in a reactor containing 300 g of a hollow titanium silicon molecular sieve (HTS) catalyst.
  • the reaction temperature was controlled to 90 ° C and the pressure was controlled to 0.5 MPa.
  • the material was allowed to stand in the reactor for 1 hour and then subjected to solid-liquid separation.
  • the solid was directly returned to the reactor, and the liquid component was sent to a dehydrogenation catalyst (containing 70% by weight of copper, 26.18% by weight of zinc oxide, 1.8% by weight).
  • Example 16 In another reactor of magnesium oxide, 1.5% by weight of palladium, 0.5% by weight of nickel, 0.02% by weight of ruthenium according to the method disclosed in Example 1 of CN1156425C, the reaction temperature was controlled at 180 ° C, pressure control It is 0.3 MPa, and the weight hourly space velocity is 0.45 h. After the completion of the reaction, solid-liquid separation is carried out to obtain a liquid component containing cyclohexanone. The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 16 The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 16 Example 16
  • cyclohexane 100 g of cyclohexane, 172 g of an aqueous hydrogen peroxide solution (concentration of 27.5 wt%) and 500 g of 1,2-dichloropropane were mixed to form a reactor charged with 50 g of a hollow titanium silicon molecular sieve (HTS) catalyst.
  • HTS hollow titanium silicon molecular sieve
  • the reaction temperature was controlled to 50 ° C and the pressure was controlled to 0.3 MPa.
  • the material was allowed to stand in the reactor for 3 hours and then subjected to solid-liquid separation.
  • the solid was directly returned to the reactor, and the liquid component was sent to a dehydrogenation catalyst (containing 40% by weight of copper, 40% by weight of zinc oxide, and 12% by weight).
  • Example 17 Magnesium oxide, 0.8% by weight of calcium oxide, 0.3% by weight of palladium, 3.0% by weight of chromium, 3.0% by weight of silicon, 0.1% by weight of sodium, 0.8% by weight of potassium, according to the method disclosed in Example 4 of CN1156425C
  • the reaction temperature is controlled to 150 ° C
  • the pressure is controlled to 1.8 MPa
  • the weight hourly space velocity is 0.45 h -
  • solid-liquid separation was carried out to obtain a liquid component containing cyclohexanone.
  • the conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 17 The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • cyclohexane 100 g of cyclohexane, 172 g of an aqueous hydrogen peroxide solution (concentration of 27.5 wt%) and 1500 g of adiponitrile were mixed and added to a reactor equipped with 250 g of a hollow titanium silicon molecular sieve (HTS) catalyst.
  • the reaction temperature was controlled to 120 ° C and the pressure was controlled to 0.5 MPa.
  • the material was allowed to stand in the reactor for 2 hours and then subjected to solid-liquid separation.
  • the solid was directly returned to the reactor, and the liquid component was sent to a dehydrogenation catalyst (containing 10% by weight of copper, 59% by weight of copper oxide, and 25% by weight).
  • a mixed solution of 100 g of cyclohexane, 172 g of an aqueous hydrogen peroxide solution (concentration: 27.5 wt%), and 1000 g of acetonitrile was placed in a reactor containing 250 g of a hollow titanium silicon molecular sieve (HTS) catalyst.
  • HTS hollow titanium silicon molecular sieve
  • lMPa The reaction temperature is controlled to 90 ° C, the pressure control is 0. lMPa.
  • the material was allowed to stand in the reactor for 2 hours and then subjected to solid-liquid separation. The solid was directly returned to the reactor, and the liquid component was sent to a dehydrogenation catalyst (containing 50% by weight of copper, 34% by weight of zinc oxide, and 9.998% by weight).
  • Example 19 In another reactor of calcium oxide, 0.002% by weight of palladium, 5.9% by weight of aluminum, 0.05% by weight of manganese, 0.05% by weight of potassium, prepared according to the method disclosed in Example 2 of CN1156425C, the reaction temperature was controlled to At 180 ° C, the pressure is controlled to 0.3 MPa, and the weight hourly space velocity is 0.35 h. After the completion of the reaction, solid-liquid separation is carried out to obtain a liquid component containing cyclohexanone. The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 19 The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 19 The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity
  • Example 21 The procedure was the same as in Example 17, except that 1500 g of the organic solvent adiponitrile in the first contact reaction was replaced by adiponitrile (1,350 g) + 1,3-dichloropropane (150 g). The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of keto alcohol, and the selectivity of cyclohexanone are shown in Table 2. The procedure was the same as in Example 16 except that the mass of the hollow titanium silicon molecular sieve (HTS) catalyst in the first contact reaction was 9 g. The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 21 The conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 22 The same procedure as in Example 15 except that the oxidation reaction temperature in the first contact reaction was 40 °C.
  • the conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of keto alcohol, and the selectivity of cyclohexanone are shown in Table 2.
  • Example 23 The procedure was the same as in Example 16 except that 500 g of 1,2-dichloropropane was replaced by 500 g of acetone in the first contact reaction.
  • the conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol and the selectivity of cyclohexanone are shown in Table 2.
  • Example 22 The same procedure as in Example 22 except that the hollow titanium silicon molecular sieve (HTS) catalyst in the first contact reaction was replaced by a conventional titanium silicon molecular sieve (TS-1) catalyst, the conversion of cyclohexane, and the yield of cyclohexanone.
  • TS-1 titanium silicon molecular sieve
  • the rate, the total selectivity of ketol and the selectivity of cyclohexanone are shown in Table 2. Comparative example 1
  • the cyclohexanone was prepared by oxidation of cyclohexane according to the procedure of Example 23, except that the catalytic dehydrogenation step was eliminated, namely:
  • a mixed solution of 100 g of cyclohexane, 172 g of an aqueous hydrogen peroxide solution (concentration: 27.5 wt%) and 500 g of acetone was placed in a reactor containing 50 g of a conventional titanium silicon molecular sieve (TS-1) catalyst.
  • the reaction temperature is controlled to 50. C, the pressure control is 0.3MPa.
  • TS-1 titanium silicon molecular sieve
  • the conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketol and the selectivity of cyclohexanone are shown in Table 2.
  • Example 1 As can be seen from the results of Table 2, since the inventive examples 15-23 employ catalytic dehydrogenation of a cyclohexanol-containing solution obtained under oxidizing conditions, cyclohexanone The yield is significantly improved. Similarly, it can be seen from the comparison between Example 22 and Example 23 that the conversion of cyclohexane and the yield of cyclohexanone are obvious when using a hollow titanium silicon molecular sieve catalyst compared to the conventional titanium silicalite catalyst. improve.
  • Example 17 As can be seen from the comparison of Example 17 and Example 19, the use of a mixture of a nitrile and a halogenated hydrocarbon as an organic solvent is more effective than the use of a nitrile alone as an organic solvent.
  • the preferred oxidation conditions of the present invention the conversion of cyclohexane, the yield of cyclohexanone, the total selectivity of ketols, and the cyclohexanone The selectivity is higher.

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Abstract

L'invention concerne un procédé d'oxydation du cyclohexane, qui comprend les étapes suivantes : (1) réalisation d'une première réaction de mise en contact de cyclohexane et de peroxyde d'hydrogène ou d'une solution aqueuse de peroxyde d'hydrogène avec un catalyseur de type tamis moléculaire de silicate de titane dans un solvant organique dans des conditions de réaction d'oxydation de manière à obtenir un mélange contenant du cyclohexanol ; et (2) réalisation d'une deuxième réaction de mise en contact du cyclohexanol préparé dans l'étape (1) avec un catalyseur de déshydrogénation dans des conditions de déshydrogénation catalytique, de manière à convertir le cyclohexanol en cyclohexanone par déshydrogénation, en obtenant de la cyclohexanone et de l'hydrogène. Selon la présente invention, le produit oxydé obtenu, c'est-à-dire le cyclohexanol, est complètement ou substantiellement complètement converti en cyclohexanone par déshydrogénation catalytique, et la cyclohexanone représente virtuellement la totalité des produits finaux obtenus ; ce procédé augmente fortement la sélectivité et le rendement en cyclohexanone. De plus, dans des modes de réalisation préférés de la présente invention, l'hydrogène produit par l'oxydation d'anthraquinone est synthétisé en H2O2, de manière telle que le procédé selon l'invention est au moins partiellement autonome en ce qui concerne l'agent d'oxydation H2O2, et l'oxydation complète consomme principalement de l'oxygène et du cyclohexane ; ce procédé améliore les bénéfices économiques du système et le procédé est vert et écologique sans production des "trois déchets".
PCT/CN2012/074285 2011-04-29 2012-04-18 Procédé d'oxydation de cyclohexane WO2012146145A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (zh) * 1999-12-24 2001-07-04 中国石油化工集团公司 一种钛硅分子筛及其制备方法
CN1381434A (zh) * 2001-04-18 2002-11-27 中国石油化工股份有限公司 环己醇脱氢制环己酮的方法
CN101137608A (zh) * 2004-12-07 2008-03-05 罗狄亚化学公司 环己酮的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (zh) * 1999-12-24 2001-07-04 中国石油化工集团公司 一种钛硅分子筛及其制备方法
CN1381434A (zh) * 2001-04-18 2002-11-27 中国石油化工股份有限公司 环己醇脱氢制环己酮的方法
CN101137608A (zh) * 2004-12-07 2008-03-05 罗狄亚化学公司 环己酮的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAO JIALIN ET AL.: "Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) with Hydrogen Peroxide.", JOURNAL OF NATURAL GAS CHEMISTRY., vol. 10, no. 4, July 2001 (2001-07-01), pages 295 - 307 *

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