WO2012146145A1 - Process for oxidizing cyclohexane - Google Patents

Process for oxidizing 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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WIPO (PCT)
Prior art keywords
cyclohexane
hydrogen peroxide
cyclohexanone
weight
reaction
Prior art date
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PCT/CN2012/074285
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French (fr)
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/en
Priority claimed from CN2011101158540A external-priority patent/CN102766031A/en
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/en

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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

Disclosed is a process for oxidizing cyclohexane, which comprises the following steps: (1) performing a first contact reaction of cyclohexane and hydrogen peroxide or an aqueous hydrogen peroxide solution with a titanium silicate molecular sieve catalyst in an organic solvent under conditions for oxidization reaction, so as to obtain a mixture containing cyclohexanol; and (2) performing a second contact reaction of the cyclohexanol produced in step (1) with a dehydrogenation catalyst under conditions for catalytic dehydrogenation, so as to convert cyclohexanol to cyclohexanone by dehydrogenation, and obtaining cyclohexanone and hydrogen. In the present invention, the oxidized product obtained, i.e. cyclohexanol, is completely or substantially completely converted into cyclohexanone by catalytic dehydrogenation, and cyclohexanone accounts for virtually all of the final products obtained; this greatly increases the selectivity and yield of the cyclohexanone. In addition, in preferred embodiments of the present invention, the hydrogen produced by the oxidization of anthraquinone is synthesized to H2O2, such that the process of the present invention is at least partly self-supported in respect of oxidizing agent H2O2, and the whole oxidization process mainly consumes oxygen and cyclohexane; this improves the economic benefits of the system, and the process is green and environmentally friendly without the production of the "three wastes".

Description

一种环己浣氧化的方法 技术领域  Method for oxidizing cyclohexanthene
本发明涉及一种环己烷氧化的方法。 背景技术  This invention relates to a process for the oxidation of cyclohexane. Background technique
环己酮、 环己醇作为重要的化工原料， 广泛应用于纤维、 合成橡胶、 工业涂料、 医 药、 农药、 有机溶剂等各个领域。 随着聚酰胺行业的迅速发展， 作为制备尼龙 6和尼龙 66中间体的环己酮、 环己醇， 目前全世界每年的总需求量在 200万吨以上。  As an important chemical raw material, cyclohexanone and cyclohexanol are widely used in various fields such as fiber, synthetic rubber, industrial coatings, medicines, pesticides, and organic solvents. With the rapid development of the polyamide industry, 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.
针对上述需求， 各国研究者一直致力于开发高效、无污染的环己酮（醇）生产工艺， 研究者认为以过氧化氢为氧化剂，以钛硅分子筛为催化剂将环己烷氧化制备环己酮（醇) 的工艺符合绿色化学和原子经济发展理念的要求，是一种极具发展前景的绿色环己烷氧 化工艺。  In response to the above needs, researchers in various countries have been working to develop a highly efficient and pollution-free process for the production of cyclohexanone (alcohol). The researchers believe that cyclohexanone is oxidized to produce cyclohexanone by using hydrogen peroxide as an oxidant and titanium silicalite as a catalyst. The process of (alcohol) meets the requirements of green chemistry and atomic economic development, and is a promising green cyclohexane oxidation process.
文献调研可知， 研究者为了提高环己烷氧化过程中环己酮的选择性， 主要致力于开 发更加高效的钛硅分子筛催化剂， 现有技术中以钛硅分子筛 /H202体系催化氧化环己烷 制备环己酮的研究花费了大量的人力物力去提高该过程中环己酮的选择性。 事实上， 在 钛硅分子筛 /H202体系内， 环己烷氧化分为两步， 第一步是环己烷氧化生成环己醇的过 程， 第二步是环己醇进一步氧化生成环己酮的过程， 因此， 提高环己醇的转化率是提高 环己酮的收率的关键。 另夕卜， 上述 ¾02通常为商购的浓度为 27.5重量％、 50重量％、 70重量％的双氧水， 而且过氧化氢的有效转化率较低， 因此， 生产环己酮的过程中需要 消耗大量的双氧水， 而 ¾02化学性质活泼， 是一种***性强氧化剂， 因此 ¾02的储存 和运输均存在较大的安全隐患， 而且上述工艺也产生大量的废水， 运输成本和废水处理 成本较高，故除提高环己酮的收率以外，如果反应过程中能至少部分自给原料过氧化氢， 也是降低成本、 提高***经济效益的有效手段， 而现有技术对此鲜有研究报道。 因此迫 切需要研发一种***高效的以钛硅分子筛 /H202体系催化氧化环己烷制备环己酮的方 法。 According to the literature research, in order to improve the selectivity of cyclohexanone in the oxidation of cyclohexane, the researchers are mainly devoted to the development of a more efficient titanium-silicon molecular sieve catalyst. In the prior art, the titanium-silicon molecular sieve/H 2 0 2 system is used to catalyze the oxidation of the cyclohexane. The study of the preparation of cyclohexanone from alkane requires a lot of manpower and resources to improve the selectivity of cyclohexanone in the process. In fact, in the titanium silicalite/H 2 O 2 system, cyclohexane oxidation is divided into two steps. The first step is the oxidation of cyclohexane to cyclohexanol, and 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. In addition, 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. Therefore, there are major safety hazards in the storage and transportation of 3⁄40 2 , and the above process also produces a large amount of wastewater, and the transportation cost and wastewater treatment cost are high. Therefore, in addition to increasing the yield of cyclohexanone, if the hydrogen peroxide can be at least partially self-supplied during the reaction, it is also an effective means to reduce the cost and improve the economic efficiency of the system, and the prior art has rarely reported this. Therefore, there is an urgent need to develop a system-efficient method for the catalytic oxidation of cyclohexane to cyclohexanone by a titanium silicalite/H 2 O 2 system.
另外， 提高环己烷在该过程中的转化率也是提高后续环己酮的收率的关键， 而影响 环己烷转化率的因素很多， 如钛硅分子筛本身的性质， 溶剂的选择等。 有文献表明， 采 用常规的钛硅分子筛 （TS-1 ) /H202体系催化氧化环己烷的过程中， 环己烷的转化率通 常小于 20%。例如， Sooknoi等在文献 [Sooknoi T, et al. Activity Enhancement by Acetic Acid in Cyclohexane Oxidation Using Ti-Containing Zeolite Catalyst[J].Appl Catal A, 2002, 233(1-2): 227-237]中指出用醋酸作溶剂， 以含钛的分子筛为催化剂， 80°C条件下反应， 环己烷的转化率可达 12%以上。 文献 [TaoJialin, et al. CYCLOHEXANE OXIDATION CATALYZED BY TITANIUM SILICALITE(TS-l) WITH HYDROGEN PEROXIDE. [J]. Journal of Natural Gas Chemistry, 2001， 10(4)， 295-349]等在考察不同溶剂 种类对环己烷氧化反应的影响时发现丙酮是 TS-1/H202催化环己烷氧化反应的最佳溶 剂。 由此可见， 现有技术中环己烷的转化率仍有待进一步提高。 发明内容 In addition, increasing the conversion of cyclohexane in the process is also the key to increasing the yield of subsequent cyclohexanone, and there are many factors affecting the conversion of cyclohexane, such as the nature of the titanium silica molecular sieve itself, the choice of solvent, and the like. It has been shown in the literature that the conversion of cyclohexane is catalyzed by a conventional titanium silicalite (TS-1) / H 2 O 2 system for the catalytic oxidation of cyclohexane. Often less than 20%. For example, Sooknoi et al., in the literature [Sooknoi T, et al. Activity Enhancement by Acetic Acid in Cyclohexane Oxidation Using Ti-Containing Zeolite Catalyst [J]. Appl Catal A, 2002, 233(1-2): 227-237] Using acetic acid as a solvent and a titanium-containing molecular sieve as a catalyst, the conversion of cyclohexane can reach more than 12% under the condition of 80 °C. [TaoJialin, et al. CYCLOHEXANE OXIDATION CATALYZED BY TITANIUM SILICALITE (TS-l) WITH HYDROGEN PEROXIDE. [J]. Journal of Natural Gas Chemistry, 2001, 10(4), 295-349], etc. The effect of cyclohexane oxidation reaction was found to be the best solvent for the oxidation of cyclohexane by TS-1/H 2 O 2 . It can be seen that the conversion rate of cyclohexane in the prior art still needs to be further improved. Summary of the invention
本发明的目的在于为克服现有技术的钛硅分子筛 /H202体系催化氧化环己烷过程中 环己酮的收率不高， 且大量耗费商购原料氧化剂 H202的缺陷， 提供一种更加高效且系 统经济的以钛硅分子筛 /H202体系催化氧化环己烷制备环己酮的方法。 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. A more efficient and systematic method for the preparation of cyclohexanone by catalytic oxidation of cyclohexane with a titanium silicalite/H 2 O 2 system.
本发明提供了一种环己烷氧化的方法， 该方法包括以下步骤：  The present invention provides a method of oxidizing cyclohexane, the method comprising the steps of:
( 1 ) 在氧化反应条件下， 将环己烷和过氧化氢或过氧化氢水溶液与钛硅分子筛催 化剂在有机溶剂中进行第一接触反应， 得到含有环己醇的混合物；  (1) subjecting a cyclohexane and hydrogen peroxide or an aqueous hydrogen peroxide solution to a first contact reaction with a titanium silicon molecular sieve catalyst in an organic solvent under an oxidation reaction condition to obtain a mixture containing cyclohexanol;
(2)将步骤（1 ) 中生成的环己醇在催化脱氢的条件下与一种脱氢催化剂进行第二 接触反应， 使环己醇脱氢转化为环己酮， 得到环己酮和氢气。  (2) subjecting the cyclohexanol formed in the step (1) to a second contact reaction with a dehydrogenation catalyst under catalytic dehydrogenation to dehydrogenate cyclohexanol to cyclohexanone to obtain cyclohexanone and hydrogen.
本发明通过对所得的氧化产物环己醇进行催化脱氢，使得环己醇完全或基本完全转 化成环己酮， 得到的最终产物几乎全部为环己酮， 大大提高了环己酮的选择性和收率。 另外在本发明的优选实施方式中， 通过蒽醌氧化将产生的氢气合成 H202， 使得本发明 的方法至少部分自给氧化剂 H202， 整个氧化过程主要消耗氧气和环己烷， 提高了*** 经济效益， 且工艺绿色环保， 无三废产生。 另外， 当根据本发明的一种实施方式采用特 定选择的钛硅分子筛催化剂时，可进一步提高环己烷的转化率，从而提高环己酮的收率， 并且氧化反应条件更加温和。 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. Further in a preferred embodiment of the present invention, 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. Further, when a specifically selected titanium silicon molecular sieve catalyst is employed in accordance with an embodiment of the present invention, the conversion of cyclohexane can be further increased, thereby increasing the yield of cyclohexanone, and the oxidation reaction conditions are more mild.
由此可见， 本发明的方法非常适合于工业化应用。  It can thus be seen that the method of the invention is very suitable for industrial applications.
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。 附图说明  Other features and advantages of the invention will be described in detail in the detailed description which follows. DRAWINGS
图 1是根据本发明的一种实施方式的环己烷氧化方法的工艺流程图。 图 2是根据本发明的另一种实施方式的环己烷氧化方法的工艺流程图。 附图标记说明 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
1 环己烷、 过氧化氢或双氧水与有机溶剂的混合物； 2 部分有机溶剂、 部分未反应 的环己烷和过氧化氢或双氧水； 3 含氧化产物的反应液； 4氢气； 5 环己酮； 6 双氧水； 7 第一接触反应后的产物； T1 精馏塔； T2催化脱氢固定床反应器； T3 蒽醌催化固定 床反应器； T4环己烷氧化固定床反应器； T5 蒸馏塔。 具体实施方式  1 cyclohexane, hydrogen peroxide or a mixture of hydrogen peroxide and an organic solvent; 2 part of an organic solvent, partially unreacted cyclohexane and hydrogen peroxide or hydrogen peroxide; 3 reaction solution containing an oxidation product; 4 hydrogen; 5 cyclohexanone 6 Hydrogen peroxide; 7 Product after first contact reaction; T1 rectification column; T2 catalytic dehydrogenation fixed bed reactor; T3 ruthenium catalytic fixed bed reactor; T4 cyclohexane oxidation fixed bed reactor; T5 distillation column. detailed description
以下对本发明的具体实施方式进行详细说明。 应当理解的是， 此处所描述的具体实 施方式仅用于说明和解释本发明， 并不用于限制本发明。  Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are intended to be illustrative and not restrictive.
本发明的环己烷氧化的方法包括：  The method of oxidizing cyclohexane of the present invention comprises:
( 1 ) 在氧化反应条件下， 将环己烷和过氧化氢或过氧化氢水溶液与钛硅分子筛催 化剂在有机溶剂中进行第一接触反应， 得到含有环己醇的混合物；  (1) subjecting a cyclohexane and hydrogen peroxide or an aqueous hydrogen peroxide solution to a first contact reaction with a titanium silicon molecular sieve catalyst in an organic solvent under an oxidation reaction condition to obtain a mixture containing cyclohexanol;
(2)将步骤（1 ) 中生成的环己醇在催化脱氢的条件下与一种脱氢催化剂进行第二 接触反应， 使环己醇脱氢转化为环己酮， 得到环己酮和氢气。  (2) subjecting the cyclohexanol formed in the step (1) to a second contact reaction with a dehydrogenation catalyst under catalytic dehydrogenation to dehydrogenate cyclohexanol to cyclohexanone to obtain cyclohexanone and hydrogen.
本发明对所述钛硅分子筛催化剂的具体形态没有特别的限制，应根据具体的反应形 式进行选择， 可以是钛硅分子筛， 为了便于将其与产物分离， 也可以是成型的钛硅分子 筛催化剂。 所述成型的钛硅分子筛催化剂一般含有钛硅分子筛和载体， 其中， 以成型的 钛硅分子筛催化剂的总量为基准， 载体的含量可以为 40-90重量％， 优选为 50-80重量 ； 钛硅分子筛的含量可以为 10-60重量％， 优选为 20-50重量％。  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.
本发明对所述含有钛硅分子筛催化剂的载体无特殊要求，可以为常用的各种成型催 化剂的载体，例如可以为多孔的耐热无机氧化物和 /或硅酸盐，具体的例如可以为氧化铝、 氧化硅、 氧化钛、 氧化镁、 氧化锆、 氧化钍、 氧化铍和粘土中的一种或多种。 优选情况 下， 所述载体为氧化铝、 氧化硅、 氧化镁和氧化锆中的一种或多种。  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. One or more of aluminum, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, cerium oxide, cerium oxide, and clay. Preferably, the carrier is one or more of alumina, silica, magnesia and zirconia.
在本发明中， 所述钛硅分子筛可以商购得到， 也可以通过制备得到， 制备所述钛硅 分子筛的方法为本领域技术人员所公知， 例如， 可以参照 [Cyclohexane Oxidation Catalyzed by Titanium Silicalite(TS-l) With Hydrogen Peroxide Journal of Natural Gas Chemistry 2001, 10(4): 295-307]中所描述的方法制备，也可以参照 CN101279959A中公 开的制备催化剂的方法制得。 本发明对所述钛硅分子筛催化剂中的钛硅分子筛的种类没有特别限制，可以是各种 结构的钛硅分子筛。优选情况下， 所述钛硅分子筛为具有 MFI结构的钛硅分子筛， 且该 钛硅分子筛的晶粒为空心结构， 该空心结构的空腔部分的径向长度为 5-300纳米， 且所 述钛硅分子筛在 25°C、 P/PQ=0.10、 吸附时间为 1 小时的条件下测得的苯吸附量不少于 70 毫克 /克， 该钛硅分子筛的低温氮吸附的吸附等温线和脱附等温线之间存在滞后环， 具有上述结构和性质的钛硅分子筛一般称为空心钛硅分子筛， 商业上称为 HTS, 其相关 参数及其制备方法可以参见 CN1301599A。 In the present invention, 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. Preferably, the titanium silicon molecular sieve is a titanium silicon molecular sieve having an MFI structure, and 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, and 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.
本发明对钛硅分子筛催化剂的颗粒大小没有特殊的限制，但从催化剂易于分离和保 证获得较高的催化活性方面考虑， 所述成型的钛硅分子筛催化剂的颗粒直径优选为 20-60目。  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.
本发明对所述过氧化氢水溶液（即双氧水）的浓度无特殊要求，可以为浓度为 20-80 重量％的双氧水， 例如可以为市售的 27.5重量％、 50重量％、 70重量％的双氧水。  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. .
根据本发明， 步骤 （1 ) 所述氧化反应的条件一般包括环己烷、 过氧化氢、 水、 钛 硅分子筛催化剂与有机溶剂的质量比为 1:0.003-5:0.15-3:0.1-15:0.5-30; 接触的温度为 30-170°C , 优选为 50-170°C ; 接触的压力为 0.01-2MPa， 优选为 0.1-0.5MPa; 且进一步， 对于间歇反应， 一般接触的时间为 0.1-10h， 优选为 l-5h。  According to the present invention, 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.
本发明中， 所述压力指的是反应体系内的表压。  In the present invention, the pressure refers to the gauge pressure in the reaction system.
本发明中， 对步骤 （1 ) 中所述有机溶剂无特别地限制， 可以是本领域常规使用的 各种有机溶剂。但是本发明的发明人发现， 当所述有机溶剂为腈和 /或卤代烃时， 能够提 高环己烷的转化率和环己醇的收率， 进一步将所述腈和卤代烃混用作为有机溶剂时， 能 够使得环己烷的转化率获得很大的提高， 即特别优选情况下， 所述有机溶剂为腈和卤代 烃的混合物， 优选腈和卤代烃的质量比为 0.1-10:1。 尽管采用两种溶剂时， 环己烷的转 化率、 目标产物的收率有进一步的提高， 然而两种溶剂的反应体系， 无疑会给后续的分 离工作带来麻烦， 因此， 一般而言， 可以根据具体工业生产中的具体目标进行选择是否 需采用两种溶剂进行反应，如在生产中主要追求环己烷的转化率以及目标产物的收率的 话， 可以选择在前述两种溶剂的反应体系下进行反应， 反之， 若整体工艺对分离过程要 求较为严格的话， 则可以选择在优选的一种溶剂体系下进行反应， 本领域技术人员对此 均能知悉， 在此不再一一赘述。  In the present invention, the organic solvent in the step (1) is not particularly limited and may be various organic solvents conventionally used in the art. However, 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. In the case of an organic solvent, 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. :1. Although the conversion of cyclohexane and the yield of the target product are further improved by using two solvents, the reaction system of the two solvents will undoubtedly bring trouble to the subsequent separation work, and therefore, generally, According to the specific objectives in specific industrial production, it is necessary to use two solvents for the reaction. For example, in the production, the conversion rate of cyclohexane and the yield of the target product are mainly pursued, and the reaction system of the above two solvents can be selected. The reaction is carried out. Conversely, if the overall process requires stricter separation processes, the reaction can be carried out under a preferred solvent system, which will be known to those skilled in the art and will not be further described herein.
优选情况下， 所述腈为 C1-C10的一元腈和 /或二元腈， 优选为 C2-C8的一元腈和 /或 二元腈， 进一步优选， 所述腈为乙腈、 丙腈、 戊腈、 己二腈中的一种或多种； 所述卤代 烃为被一个和 /或多个相同或不同的卤素原子取代的 C1-C10 的烷烃和 /或被一个和 /或多 个相同或不同的卤素原子取代 C6-C10的环烷烃， 进一步优选为 C1-C6的二氯代烷烃和 / 或三氯代烷烃， 更优选为二氯甲烷、 三氯甲烷、 1,1-二氯乙烷、 1,2-二氯乙烷、 1,1,1-三 氯乙烷、 1,1,2-三氯乙烷、 1,2-二氯丙烷、 2,2-二氯丙烷、 1,3-二氯丙烷、 1,2,3-三氯丙烷、 1,2-二氯丁烷、 2,3-二氯丁烷、 1,4-二氯丁烷、 1,2-二氯戊烷、 2,2-二氯戊烷、 1,3-二氯戊 烷、 2,3-二氯戊烷、 3,3-二氯戊烷、 1,4-二氯戊烷、 2,4-二氯戊烷、 1,2,5-三氯戊烷、 1,1,5- 三氯戊烷和 1,2-二氯环己烷中的一种或多种。 Preferably, 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. One or more of 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. -C6 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 One or more of 1,1,5-trichloropentane and 1,2-dichlorocyclohexane.
本发明的发明人研究发现， 对于间歇反应， 为了提高环己烷的转化率， 当所述有机 溶剂为腈时， 所述接触的温度优选为 60-12CTC ; 或者当所述有机溶剂为卤代烃时， 所述 接触的温度应优选为 50-9CTC ; 或者当所述有机溶剂为腈和卤代烃时， 所述接触的温度 为 50-120 °C， 优选为 60-110°C。  The inventors of the present invention have found that, for the batch reaction, in order to increase the conversion of cyclohexane, when the organic solvent is a nitrile, 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.
本发明所述方法， 所述步骤 （1 ) 中得到的含有环己醇的混合物一般含有氧化产物 环己醇和环己酮、 未反应的原料环己烷和过氧化氢、 以及有机溶剂， 本发明可以将所述 步骤 （1 ) 中得到的含有环己醇的混合物不经分离或分离出其中的醇或醇和酮的混合物 进行步骤 （2) 所述的第二接触。 但为了减小后续反应器的负荷以及有效利用所述步骤 ( 1 ) 中得到的含有环己醇的混合物的可用物料， 本发明优选将所述步骤（1 ) 中得到的 含有环己醇的混合物进行分离， 并将分离出的有机溶剂和未反应的环己烷以及过氧化氢 或过氧化氢水溶液返回到步骤 （1 ) 的进料中， 分离出的环己醇或者环己醇与环己酮的 混合物进行步骤 （2)所述第二接触反应。 本发明对所述步骤 （1 ) 的反应形式无具体要 求， 可以为间歇反应， 也可以为连续反应， 而为了使得本发明的整个工艺能够更加适合 于工业应用， 优选步骤 （1 ) 为连续反应， 连续反应例如可以在固定床等反应器中进行。  In the method of the present invention, 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. However, in order to reduce the load of the subsequent reactor and to effectively utilize the available material of the cyclohexanol-containing mixture obtained in the step (1), 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.
因此， 根据本发明的一种实施方式， 如图 1所示， 步骤 （1 ) 可在固定床反应器 T4 中进行， 然后将所述第一接触反应后的产物进行分离， 分离出的有机溶剂和未反应的环 己烷以及过氧化氢或过氧化氢水溶液返回到步骤 （1 ) 的进料中， 分离出的环己醇或者 环己醇与环己酮的混合物进行步骤 （2) 所述第二接触反应。 所述分离例如可以在蒸馏 塔 T5中进行。 根据本实施方式的步骤（1 ) 的反应工艺和条件为本领域公知常识， 在此 不再赘述。在蒸馏塔中进行气液或液液分离也是本领域公知的手段， 本发明在此不再赘 述。  Therefore, according to an embodiment of the present invention, as shown in Fig. 1, 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. The separation 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.
目前， 钛硅分子筛 /H202体系内的环己烷氧化反应， 溶剂是不可或缺的一部分， 合 适的溶剂的加入可以使反应有效的进行， 同时可以提高目标产物的选择性， 然而就目前 的研究看来， 在钛硅分子筛 /H202体系内的环己烷氧化反应中， 以反应液总重量为基准， 溶剂通常占到 30-90重量％， 因此虽然因为溶剂的加入有效的实现了反应高效的进行， 然而溶剂的大量加入也给后续的分离增加了麻烦与成本， 从而降低了其工业应用前景。 并且该反应为剧烈的放热反应， 反应时需要冷却能耗， 而分离目标产物又需要加热的能 耗， 因此如何能够节约所需的能耗或者是有效利用该体系产生的热也是非常值得研究的 问题。 At present, 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. Currently It seems that in the cyclohexane oxidation reaction in the titanium silicalite/H 2 O 2 system, 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. Moreover, the 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.
本发明的发明人试图设想能否有一种工艺不仅能够使该反应连续的进行， 同时能够 实现更有效的分离， 而且还能利用体系中的反应热从而节约能耗呢。 基于这种设想制造 了本发明的另一种实施方式。  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.
根据本发明的另一种实施方式， 步骤 （1 ) 所述第一接触反应按照催化精馏的方式 进行，催化精馏所得有机溶剂和未反应的环己烷以及过氧化氢或过氧化氢水溶液返回到 步骤 （1 ) 的进料中， 催化精馏所得环己醇或者环己醇与环己酮的混合物进行步骤 （2) 所述第二接触反应。  According to another embodiment of the present invention, 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. Returning to the feed of step (1), the cyclohexanol obtained by catalytic distillation or a mixture of cyclohexanol and cyclohexanone is subjected to the second contact reaction of the step (2).
如图 2所示， 在氧化反应条件下， 将环己烷、 过氧化氢水溶液以及有机溶剂从进料 口送入精馏塔中进行接触， 并从精馏塔的塔底得到全部或大部分的氧化产物， 其中， 所 述精馏塔内的部分或全部填料为钛硅分子筛催化剂。 其中， 优选氧化产物的 95-100 重 量％从精馏塔的塔底得到， 所述氧化产物的 95-100 重量％从精馏塔的塔底得到是指 95-100重量％的氧化产物从精馏塔的塔底得到。 本发明中， 所述氧化产物是指环己烷发 生氧化反应得到的产物， 一般包括环己醇和环己酮。  As shown in FIG. 2, under the oxidation reaction conditions, cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent are fed from the feed port to the rectification column for contact, and all or most of the bottom of the rectification column is obtained. The oxidation product, wherein part or all of the filler in the rectification column is a titanium silicalite catalyst. Wherein, preferably 95-100% by weight of the oxidation product is obtained from the bottom of the rectification column, and 95-100% by weight of the oxidation product is obtained from the bottom of the rectification column, meaning that 95-100% by weight of the oxidation product is refined. The bottom of the distillation column is obtained. In the present invention, the oxidation product refers to a product obtained by the oxidation reaction of cyclohexane, and generally includes cyclohexanol and cyclohexanone.
根据本发明的优选实施方式， 本发明的环己烷氧化的方法通过在精馏塔中 （即精馏 条件下）进行氧化， 一是充分的利用了反应潜热， 从而实现节能； 二是本发明通过在精 馏塔中进行环己烷的氧化反应， 使得氧化产物可以与原料环己烷边反应边分离， 从而可 以节约后续的分离成本。  According to a preferred embodiment of the present invention, 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; By carrying out the oxidation reaction of cyclohexane in the rectification column, the oxidation product can be separated while reacting with the raw material cyclohexane, so that the subsequent separation cost can be saved.
根据本发明， 本发明对所述将环己烷、 过氧化氢水溶液以及有机溶剂从进料口送入 精馏塔中进行接触的方法无特殊要求，但为了使得在精馏塔内的反应物接触更加充分从 而反应更加完全， 优选情况下， 所述将环己烷、 过氧化氢水溶液以及有机溶剂从进料口 送入精馏塔中的方法包括： 将过氧化氢水溶液从第一进料口送入精馏塔， 将环己烷从第 二进料口送入精馏塔； 其中， 所述第一进料口到塔底之间的塔板数或理论塔板数占所述 精馏塔中总的塔板数或理论塔板数的 50-100%， 更优选为 80-100% ; 所述第二进料口到 塔底之间的塔板数或理论塔板数占所述精馏塔中总的塔板数或理论塔板数的 10-80%， 更优选为 30-70%。 According to the present invention, 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. Preferably, 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%.
本发明对所述有机溶剂的进料方式无特殊要求，具体可以根据精馏塔内的操作参数 以及有机溶剂的性质进行选择溶剂进料口为所述第一进料口和 /或第二进料口，基本原则 是： 进料组成与进料口的选择对反应精馏塔影响较小为宜， 以有益于稳定、 强化反应物 料配比为宜。 一般而言， 当所述有机溶剂的沸点高于精馏塔塔釜的温度时， 可以将有机 溶剂从第一进料口进料； 当所述有机溶剂的沸点低于精馏塔塔釜的温度时， 可以将有机 溶剂从第二进料口进料， 如此形成稳定的精馏状态即可， 对此， 本领域技术人员均能知 悉， 在此不再赘述， 在本发明的具体实施例中也不再具体强调。  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. In general, 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.
本发明对催化精馏中所述钛硅分子筛催化剂无特殊要求，可以为各种能够适用于精 馏塔内的成型钛硅分子筛催化剂， 所述成型钛硅分子筛催化剂在前述已经详细描述， 在 此不再重复赘述， 同样， 所述钛硅分子筛催化剂中的钛硅分子筛在前述也已详细描述， 在此不再赘述。  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.
根据本发明， 所述填料中钛硅分子筛催化剂的量的可选范围较宽， 但是如果催化剂 的量过大， 则容易造成反应过快， 不容易实现后续的分离， 催化剂量过少， 则反应过慢， 不利于工业化应用，因此优选情况下，所述填料中含有 30-100重量％，更优选含有 30-70 重量％的所述钛硅分子筛催化剂。  According to the present invention, 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.
本发明中所述钛硅分子筛催化剂的填料优选为是将常规填料与钛硅分子筛催化剂 混合均匀后的混合填料。本发明中， 所述常规填料可以为精馏塔内常规使用的各种常规 填料， 例如可以为拉西环、 鲍尔环、 阶梯环、 弧鞍、 矩鞍、 金属环矩鞍填料中的一 种或多种， 具体的例如可以为 Θ环、 β环填料等。  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. In the present invention, 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 β-ring filler, or the like.
前述对本发明所述有机溶剂已有详细描述， 然而针对催化精馏的特殊反应形式， 进 一步优选当采用催化精馏进行本发明步骤 （1 ) 所述第一接触反应时， 所述有机溶剂为 的沸点为 50-140°C， 优选为 60-130 °C。  The foregoing 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.
如前所述， 本发明优选有机溶剂为腈和 /或卤代烃， 因此， 根据本发明的一种特别优 选的实施方式， 优选步骤 （1 ) 中所述第一接触反应按照催化精馏的方式进行反应时， 所述有机溶剂为沸点为 60-13CTC的腈和 /或 60-13CTC的卤代烃。  As described above, 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.
本发明中， 针对本发明步骤 （1 ) 中所述第一接触反应按照催化精馏的方式进行反 应的方式， 优选所述氧化反应条件包括精馏塔塔底温度为 55-170°C， 优选为 60-150°C。  In the present invention, in the manner in which the first contact reaction in the step (1) of the present invention is carried out in a catalytic distillation manner, it is preferred that the oxidation reaction conditions include a distillation column bottom temperature of 55-170 ° C, preferably It is 60-150 ° C.
本发明对精馏塔内的回流比无特殊要求， 可以选择回流或不回流， 可以根据具体需 要进行选择， 且回流比对本发明的结果无太大影响， 因此， 在本发明的实施例中不再具 体说明回流比。 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.
本发明中， 针对本发明步骤 （1 ) 中所述第一接触反应按照催化精馏的方式进行反 应的方式， 优选所述精馏塔内的总的塔板数或理论塔板数为 20-45， 更优选为 30-40。  In the present invention, in the manner in which the first contact reaction in the step (1) of the present invention is carried out in a catalytic distillation manner, it is preferred that the total number of plates or the number of theoretical plates in the rectification column is 20- 45, more preferably 30-40.
本发明中， 针对本发明步骤 （1 ) 中所述第一接触反应按照催化精馏的方式进行反 应的方式， 为了使环己烷转化的更加完全或者双氧水的有效利用率更高， 优选情况下， 控制出料中水相中的过氧化氢含量为 0.01-1重量％， 优选为 0.05-0.4重量％。 上述控制 出料中水相中的过氧化氢的量的方法可以有很多种，例如可以通过控制精馏塔内的过氧 化氢的进料量来控制，优选情况下，每小时的过氧化氢进料量为 5-500克，优选为 10-150 克。  In the present invention, in order to carry out the reaction of the first contact reaction in the step (1) of the present invention in the manner of catalytic distillation, in order to make the conversion of cyclohexane more complete or the effective utilization rate of hydrogen peroxide is higher, preferably 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.
本发明中， 针对本发明步骤 （1 ) 中所述第一接触反应按照催化精馏的方式进行反 应的方式， 优选反应过程中 （即第一接触反应中）环己烷、 过氧化氢、 水与有机溶剂的 质量比为 1:0.03-3:0.1-3:0.5-30，优选为 1:0.3-1.5:0.1-2:3-15。而为了简化后续的分离步骤， 一般而言， 优选在精馏反应过程中， 采取原料尽量在精馏塔内反应完全， 从而不用再继 续将反应原料环己烷分离出来， 因此， 特别优选情况下， 环己烷与过氧化氢的摩尔比为 1:1-2。  In the present invention, in the manner of the first contact reaction in the step (1) of the present invention, the reaction 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. In order to simplify the subsequent separation step, in general, it is preferred to carry out the reaction in the rectification column as much as possible in the rectification reaction process, so that the reaction raw material cyclohexane is not further separated, so that it is particularly preferable. The molar ratio of cyclohexane to hydrogen peroxide is 1:1-2.
根据本发明， 在实际的反应过程中， 可以依据具体情况， 为了防止精馏塔内钛硅分 子筛催化剂的填料床层的坍塌， 可以将精馏塔分成多段， 每段之间可以直接采用常规的 填料进行隔开，其中每段之间常规填料的厚度可以根据隔开的每段精馏塔的高度进行选 择， 如果每段精馏塔的高度为 3-6m， 则每段之间常规填料的厚度一般为 5-20cm， 优选 为 8-15cm。  According to the present invention, 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.
本发明对精馏塔的出料口位置无特殊要求， 可以参照现有技术进行， 例如可以侧线 采出，也可以从塔底排出。由于本发明中目标产物环己醇和环己酮大部分在塔底， 因此， 优选本发明的至少一个出料口设置在塔底。特别是当精馏塔内为全回流时， 优选本发明 的出料口为一个， 并且设置在塔底， 塔釜物料从该出料口排出。 当所述精馏塔的塔底温 度高于目标产物环己醇和环己酮的沸点温度时，可在出料口设置冷凝装置从而收集得到 液态的塔底排出物料， 也可直接将塔底排出物料送入下一工序分离产品， 本领域技术人 员对此均能知悉， 在此不再赘述。  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. When the bottom temperature of the rectification column is higher than the boiling temperature of the target products cyclohexanol and cyclohexanone, 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.
本发明中， 精馏塔塔釜物料除了含有全部或大部分的氧化产物以外， 视塔底温度不 同一般还可能含有溶剂、 少量环己烷及水等其余物质， 这些其余物质可以通过本领域公 知的后续的分离工序进行分离除去， 本发明在此不再赘述。 当塔底温度较高或者水在有机溶剂中的溶解性较大时，过氧化氢水溶液中的水以及 反应过程中生成的水可以作为塔顶物流的一部分而部分或全部回流到精馏塔内，但优选 情况下， 将水从塔顶排出， 例如可以通过分水器从塔顶排出物中分出， 以提高精馏塔内 过氧化氢的浓度，而剩余的塔顶排出物则可以部分或全部循环返回精馏塔的进料口进入 到精馏塔内 （可以根据溶剂的种类不同选择从第一进料口或第二进料口进入精馏塔， 对 此本领域技术人员均能熟知， 在此不再一一赘述）， 为了充分利用反应过程中的原料， 本发明优选将塔顶排出物分水后全部返回作为精馏塔的进料， 由此可以充分利用反应原 料， 有效节约了生产成本。 本发明中塔顶排出物料、 塔顶排出物、 塔顶出料表示的是同 一个意思， 塔底排出物料、 塔底排出物、 塔底出料、 塔釜排出物料、 塔釜排出物、 塔釜 出料亦表示相同的意思。 In the present invention, 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. When 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. , but preferably, 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 As is well known in the art, in order to make full use of the raw materials in the reaction process, 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. In the present invention, 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.
当塔底温度较低时， 水进入塔釜物料随氧化产物从塔底排出。 无论水存在于塔顶物 流中还是塔釜物流中，本发明中上述出料中水相中的过氧化氢的量均表示除去有机物后 的水相中的过氧化氢的量。  When the temperature at the bottom of the column is low, the water enters the column and the material is discharged from the bottom of the column along with the oxidation product. 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.
根据本发明， 为了适于工业应用， 本发明的步骤 （2) 的所述第二接触反应可在固 定床反应器中进行， 对所述第二接触反应的条件无特殊要求， 只要能实现本发明的目的 即可，优选情况下，所述第二接触反应的条件包括温度为 150-28CTC，压力为 0.3-3.2MPa， 重时空速为 0.35-0.55h- 本发明对步骤 （2) 中所述的脱氢催化剂无特殊要求， 只要能实现本发明的目的即 可， 优选情况下， 所述脱氢催化剂含有以下组份： a)铜或铜的氧化物 20-74 重量％; b) 钯和 /或铂或钯和 /或铂的氧化物 0.001-2.0重量％; c)除铜、 钯和铂之外的其他金属或该 其他金属的氧化物 24-78重量％， 所述其他金属为选自锌、 镁、 钙、 锶、 钡、 硅、 铝、 铬、 锰、 镍、 锆和钛中的至少一种。 上述脱氢催化剂参照 CN1156425C中所述的方法制 备。  According to the present invention, in order to be suitable for industrial applications, 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. For the purpose of the invention, preferably, 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. Preferably, 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.
根据本发明的方法， 为了使得按照本发明的方法得到的氢气得到合理的应用同时为 了进一步节约本发明的氧化剂原料的投入成本， 优选本发明的方法还包括步骤（3): 将 步骤 （2)所得氢气通过蒽醌法合成过氧化氢， 并将该过氧化氢用于步骤 （1 ) 的所述第 一接触反应中。  According to 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).
本发明步骤 （3) 所述的蒽醌法为本领域技术人员所熟知的方法， 是生产过氧化氢 的主要方法。 蒽醌法的一般步骤包括将烷基蒽醌与有机溶剂配制成蒽醌工作溶液， 在压 力为 0.1-lMPa、 温度 55-65°C和催化剂存在的条件下， 通入氢气进行氢化， 再在 40-44°C 下与空气 （或氧气）进行逆流氧化， 经萃取、 再生、 精制与浓縮制得过氧化氢水溶液产 品。 所述催化剂例如可以为 Pd/Al203催化剂， 烷基蒽醌与有机溶剂的重量比可以为 1:4-10。 所述有机溶剂例如可以为 C9-C11的芳烃， 蒽醌工作液的液空速为 5-10h- 氢气 空速为 9-18h— 氧气空速为 150-340h— 所述烷基蒽醌例如可以是 2-乙基蒽醌 (EAQ)、 2- 特丁基蒽醌、 2-戊基蒽醌以及它们的四氢衍生物如 2-(4-甲基 -3-戊烯基)蒽醌或 2-(4-甲基- 甲基戊基)蒽醌中的一种或多种。溶剂多采用高沸点的重芳烃 (C9-C11的芳烃)、高级脂肪 醇类、 有机酸或无机酸的酯类中的一种或多种， 其中磷酸三辛酯 (TOP)、 醋酸甲基环己 酯 (MCA)、 四丁基脲 (TBU)、 二异丁基甲醇 (DIBC)等较为常用。 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. 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.
根据本发明的一种实施方式， 本发明的工艺流程如图 1所示， 将环己烷、 双氧水与 有机溶剂的混合物 1送入装载有钛硅分子筛催化剂的固定床反应器 T4中， 氧化后的液 体产物即含有环己醇的混合物 7进入蒸馏塔 T5进行分离， 分离出的有机溶剂、 未反应 的的环己烷和双氧水的混合物 2则作为进料返回固定床反应器 T4中进行步骤（1 )所述 的第一接触反应， 氧化产物环己醇或环己醇与环己酮的混合物 3则进入脱氢反应器 T2 (优选为固定床反应器）进行第二接触反应，产生的氢气 4与蒽醌工作液（图中未示出） 一起进入蒽醌氧化反应器 T3中， 并通入空气或氧气 （图中未示出） 进行蒽醌氧化制备 过氧化氢溶液 6，该过氧化氢溶液 6则回到装载有钛硅分子筛催化剂的固定床反应器 T4 中， 作为第一接触反应的进料。  According to an embodiment of the present invention, 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. 1) 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. 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.
根据本发明的另一种实施方式， 本发明的工艺流程如图 2所示。 图 2的工艺流程与 图 1类似， 不同的是， 图 2中采用精馏塔 T1代替图 1中的固定床反应器 T4和蒸馏塔 T5。具体流程为将环己烷、双氧水与有机溶剂的混合物送入装载有钛硅分子筛催化剂的 精馏塔 T1中，氧化后的液体产物即含有环己醇的混合物 7在精馏塔 T1中分离出的有机 溶剂、未反应的的环己烷和双氧水的混合物 2则作为进料返回精馏塔 T1中进行步骤（1 ) 所述的第一接触反应，氧化产物环己醇或环己醇与环己酮的混合物 3则进入脱氢反应器 Τ2 (优选为固定床反应器）进行第二接触反应， 产生的氢气 4与蒽醌工作液（图中未示 出） 一起进入蒽醌氧化反应器 Τ3中， 并通入空气或氧气 （图中未示出） 进行蒽醌氧化 制备过氧化氢溶液 6， 该过氧化氢溶液 6则回到装载有钛硅分子筛催化剂的固定床反应 器 Τ4中， 作为第一接触反应的进料。  According to another embodiment of the present invention, 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 Τ2 (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 Τ4 loaded with the titanium silicalite catalyst as The first contact reaction feed.
以下的实施例将对本发明作进一步的说明， 但并不因此限制本发明。  The invention is further illustrated by the following examples, which are not intended to limit the invention.
实施例和对比例中所用到的试剂均为市售的化学纯试剂。  The reagents used in the examples and comparative examples were all commercially available chemically pure reagents.
实施例中空心钛硅分子筛 （HTS) 催化剂中， 以催化剂总重量为基准， 空心钛硅分 子筛 （HTS ) 的含量为 50%， 二氧化硅的含量为 50%。 In 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%, and the content of silica is 50%.
实施例和对比例中传统钛硅分子筛 （TS-1 )催化剂中， 以催化剂总重量为基准， 传 统钛硅分子筛 （TS-1 ) 的含量为 50%， 二氧化硅的含量为 50%。  In the conventional titanium silicon molecular sieve (TS-1) catalysts of the examples and the comparative examples, the conventional titanium silicalite (TS-1) content was 50% and the silica content was 50% based on the total weight of the catalyst.
实施例中所用的空心钛硅分子筛（HTS)系 CN1301599A所述钛硅分子筛的工业产 品 （湖南建长公司制造， 经 X-射线衍射分析为 MFI结构的钛硅分子筛， 该分子筛的低 温氮吸附的吸附等温线和脱附等温线之间存在滞后环， 晶粒为空心晶粒且空腔部分的径 向长度为 15-180纳米； 该分子筛样品在 25°C， P/Po=0.10, 吸附时间 1小时的条件下测 得的苯吸附量为 78毫克 /克）， 氧化钛的含量为 2.5重量％。  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. There is a hysteresis loop between the adsorption isotherm and the desorption isotherm, the crystal grains are hollow crystal grains and the radial length of the cavity portion is 15-180 nm; the molecular sieve sample is at 25 ° C, P/Po=0.10, adsorption time 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.
实施例和对比例中所用的传统钛硅分子筛 （TS-1 ) 是按文献 [Cyclohexane Oxidation Catalyzed by Titanium Silicalite(TS-l) With Hydrogen Peroxide Journal of Natural Gas Chemistry 2001, 10(4): 295-307]中第 296页 9-24行所描述的方法制备出的 （TS-1 ) 分子 筛样品， 氧化钛的含量为 2.5重量％。  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.
实施例和对比例中采用的双氧水均为市售的浓度为 27.5重量％的双氧水。  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.
除非特别说明， 实施例和对比例中的常规填料 Θ环均购自天津凯美特化工科技有限 公司。  Unless otherwise specified, the conventional packing anthracene rings in the examples and comparative examples were purchased from Tianjin Kaimet Chemical Technology Co., Ltd.
实施例和对比例中钛硅分子筛 （TS-1或 HTS ) 催化剂均为 40目。  The titanium silicalite (TS-1 or HTS) catalysts in the examples and comparative examples were 40 mesh.
本发明中， 采用气相色谱进行体系中各有机物的分析， 通过校正归一法进行定量， 均可参照现有技术进行， 在此基础上计算反应物的转化率、 产物的收率和选择性等评价 指标。  In the present invention, 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.
本发明中， 环己烷的转化率计算公式如下：  In the present invention, the conversion formula of cyclohexane is calculated as follows:
。环己烷 _m环己烷  . Cyclohexane _m cyclohexane
X环己烷 ■χ100%  X cyclohexane ■χ100%
m环己烷  m cyclohexane
组分选择性的计算公式如下  The formula for calculating the component selectivity is as follows
n环己醇 + w环己酮 N-cyclohexanol + w cyclohexanone
S酮醇总 χ 100  S-keto alcohol total χ 100
wQ环己烧 — i环己烷 w Q ring hexane - i cyclohexane
S环己醇 0 ¾己醇—— χ 100% S cyclohexanol 0 3⁄4 hexanol - χ 100%
η 环己烷 — η环己烷 η cyclohexane - η cyclohexane
^环己酮 ― o x丄 U(J lo ^cyclohexanone ― o x丄 U(J lo
n 环己焼 — n环己烷 组分收率的计算公式如下： n cyclohexanyl — n cyclohexane The formula for calculating the component yield is as follows:
^环己醇 = S环己醇 x ^环己垸 ^cyclohexanol = S cyclohexanol x ^cyclohexane
^环己酮 = ^环己酮 x ^环己垸 ^cyclohexanone = ^cyclohexanone x ^cyclohexane
其中， X为转化率； s为选择性 （s »,s即表示酮醇总选择性， 或简称酮醇选择性）；Wherein X is the conversion rate; s is the selectivity (s », s means the total selectivity of the ketol, or ketol selectivity for short);
Y为收率； m为出料口组分的质量； w为出料口组分的物质的量； 其中 mQ和 nQ分别表 示进料口的质量和摩尔量。 实施例 1 Y is the yield; m is the mass of the discharge port component; w is the amount of the material of the discharge port component; wherein m Q and n Q represent the mass and molar amount of the feed port, respectively. Example 1
采用图 2所示的工艺流程进行环己烷的氧化。 按照反应过程中环己烷与双氧水（浓 度为 27.5重量％)及溶剂 1,2-二氯丙烷（沸点 96.8 °C ) 的质量比为 1:1.72:15的比例从精 馏塔 T1的进料口进料， 且相对于每千克空心钛硅分子筛（HTS )每小时双氧水的进料量 为 0.05千克， 其中环己烷从第二进料口进料， 双氧水及溶剂 1,2-二氯丙烷从第一进料口 进料，其中控制塔底温度为 115°C，精馏塔塔顶出料分水后进入第二进料口而循环使用， 精馏塔的理论塔板数为 35， 第一进料口到塔底之间的理论塔板数为 30， 第二进料口到 塔底之间的理论塔板数为 10， 填料中含有 60重量％的空心钛硅分子筛 （HTS)催化剂， 40重量％的9环。 塔釜物料从精馏塔塔底的出料口排出 （稳定运行 18h后从塔底的出料 口取样分析， 环己烷的转化率、酮醇总选择性及环己醇收率见表 1 )， 塔釜出料从固定床 反应器的顶部送入含脱氢催化剂 （含有 40重量％的铜、 40重量％的氧化锌、 12重量％ 的氧化镁、 0.8重量％的氧化钙、 0.3重量％的钯、 3.0重量％的锆、 3.0重量％的硅、 0.1 重量％的钠、 0.8重量％的钾， 并且是按 CN1156425C中公开的制备催化剂的方法制得） 的固定床反应器 T2， 重时空速为 0.49h- 固定床 T2操作温度为 220°C， 压力为 l.OMPa, 得到的氢气从固定床反应器 T2 的上部直接进入蒽醌催化固定床 T3， 其余产物从固定床 反应器 Τ2的下部出料， 经分离后得到环己酮， 环己酮的收率见表 1。 其中， 蒽醌催化固 定床 Τ3内装填 30ml的 Pd/Al203催化剂， 反应器操作温度为 60°C， 压力为 0.3MPa， 蒽醌 工作液为： 连三甲苯 75体积％， 四丁基脲 18体积％， 磷酸三辛酯 7体积％， 工作载体 为 149g/L的 2-乙基蒽醌和 17g/L的 2-乙基四氢蒽醌的混合物，工作载体中 2-乙基蒽醌与 2-乙基四氢蒽醌的总含量为 166g/L， 即有效蒽醌浓度为 166g/L。蒽醌工作液的重时空速 为 8h- 氢气的气时空速为 16h- 氧气的气时空速为 240h- 反应后得到的 H202直接送 入精馏塔 T1中。 实施例 2 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 column is 10, and the filler contains 60% by weight of hollow titanium silicon molecular sieve (HTS) catalyst. 40% by weight of 9 rings. 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). % palladium, 3.0% by weight of zirconium, 3.0% by weight of silicon, 0.1% by weight of sodium, 0.8% by weight of potassium, and is a fixed bed reactor T2 prepared by the method for preparing a catalyst disclosed in CN1156425C, heavy 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 Τ 2 The lower part of the output was separated to obtain cyclohexanone. The yield of cyclohexanone is shown in Table 1. Among them, 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. Example 2
采用图 1所示的工艺流程进行环己烷的氧化。 按照反应过程中环己烷与双氧水（浓 度为 27.5重量％) 及溶剂 1,4-二氯戊烷的质量比为 1:1.72:5的比例从固定床反应器 T4 的进料口进料， 重时空速为 3h- 反应压力为 lMPa， 反应温度为 120°C， 反应后的产物 进入蒸馏塔 T5中进行分离， 蒸馏塔 T5的压力为 0.2MPa， 温度为 160°C， 环己烷的转 化率、 酮醇总选择性及环己醇收率见表 1， 从塔顶蒸馏出的溶剂、 水和过量的环己烷直 接返回固定床反应器 T4中 （稳定运行 18h后取样分析， 环己烷的转化率、 酮醇总选择 性及环己醇收率见表 1 )， 塔釜出料送入含脱氢催化剂 （含有 10重量％的铜、 59重量％ 的氧化铜、 25重量％的氧化锌、 5重量％的氧化钡、 0.1重量％的铂、 0.8重量％的镍、 0.1重量％的铬， 并且是按 CN1156425C中公开的制备催化剂的方法制得） 的固定床反 应器 T2， 重时空速为 0.49h- 固定床 T2操作温度为 220°C， 压力为 l.OMPa, 得到的氢 气从固定床反应器 T2 的上部直接进入蒽醌催化固定床 T3， 其余产物从固定床反应器 Τ2 的下部出料， 经分离后得到环己酮， 环己酮的收率见表 1。 其中， 蒽醌催化固定床 Τ3内装填 30ml的 Pd/Al203催化剂， 反应器操作温度为 60°C， 压力为 0.3MPa， 蒽醌工 作液为： 连三甲苯 70体积％， 四丁基脲 20体积％， 磷酸三辛酯 10体积％， 工作载体为 160g/L的 2-特丁基蒽醌和 29g/L的 2-特丁基四氢蒽醌混合物，工作载体中 2-特丁基蒽醌 与 2-特丁基四氢蒽醌的总含量为 189g/L， 即有效蒽醌浓度为 189g/L。 蒽醌工作液的重 时空速为 5h- 氢气的气时空速为 9h- 氧气的气时空速为 150h- 反应后得到的 H202 直接送入精馏塔 T1中。 实施例 3 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 Τ2, and after separation, cyclohexanone is obtained. The yield of cyclohexanone is shown in Table 1. . Among them, 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. Example 3
采用图 2所示的工艺流程进行环己烷的氧化。 按照反应过程中环己烷与双氧水（浓 度为 27.5重量％) 及溶剂丙腈的质量比为 1:1.72:10的比例从精馏塔 T1的进料口进料， 且相对于每千克空心钛硅分子筛 （HTS ) 每小时双氧水的进料量为 0.1千克， 其中环己 烷从第二进料口进料， 双氧水及溶剂丙腈从第一进料口进料， 其中控制塔底温度为 110°C，精馏塔塔顶出料分水后进入第二进料口而循环使用，精馏塔的理论塔板数为 35， 第一进料口到塔底之间的理论塔板数为 30，第二进料口到塔底之间的理论塔板数为 10， 填料中含有 30重量％的空心钛硅分子筛 （HTS ) 催化剂， 70重量％的9环。 塔釜物料 从精馏塔塔底的出料口排出（稳定运行 18h后从塔底出料口取样分析，环己烷的转化率、 酮醇总选择性及环己醇收率见表 1 )，塔釜出料从固定床反应器的顶部送入含脱氢催化剂 (含有 40重量％的铜、 48.45重量％的锌、 8重量％的氧化镁、 1.8重量％的氧化钙、 0.05 重量％的钯、 0.2重量％的钛、 0.8重量％的硅、 0.1重量％的钠、 0.6重量％的钾， 并且是 按 CN1156425C 中公开的制备催化剂的方法制得） 的固定床反应器 T2， 重时空速为 0.4911-1 , 固定床 Τ2操作温度为 220°C， 压力为 l.OMPa, 得到的氢气从固定床反应器 T2 的上部直接进入蒽醌催化固定床 T3， 其余产物从固定床反应器 Τ2的下部出料， 经分离 后得到环己酮，环己酮的收率见表 1。其中，蒽醌催化固定床 Τ3内装填 30ml的 Pd/Al203 催化剂， 反应器操作温度为 60°C， 压力为 0.3MPa， 蒽醌工作液为： 连三甲苯 75体积％， 四丁基脲 20体积％， 磷酸三辛酯 5体积％， 工作载体为 129g/L的 2-乙基蒽醌和 71g/L 的 2-乙基四氢蒽醌混合物， 工作载体中 2-乙基蒽醌和 2-乙基四氢蒽醌的总含量为 200g/L, 即有效蒽醌浓度为 200g/L。 蒽醌工作液的重时空速为 10h- 氢气的气时空速 为 18h- 氧气的气时空速为 340h- 反应后得到的 H202直接送入精馏塔 T1中。 实施例 4 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. 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, Τ2 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 bed reactor T2, and the rest of the product is discharged from the lower part of the fixed bed reactor Τ2, and after separation, cyclohexanone is obtained, and the yield of cyclohexanone is obtained. See Table 1. Among them, 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. Example 4
采用图 1所示的工艺流程进行环己烷的氧化。 按照反应过程中环己烷与双氧水（浓 度为 27.5重量％)及溶剂乙腈的质量比为 1:2.26:10的比例从固定床反应器 T4的进料口 进料， 重时空速为 3h- 反应压力为 lMPa， 反应温度为 120°C， 反应后的产物进入蒸馏 塔 T5中进行分离， 蒸馏塔 T5中的压力为 0.2MPa， 温度为 130°C， 环己烷的转化率、 酮醇总选择性及环己醇收率见表 1， 从塔顶蒸馏出的溶剂、 水和过量的环己烷直接返回 固定床反应器 T4中 （稳定运行 18h后取样分析， 环己烷的转化率、 酮醇总选择性及环 己醇收率见表 1 )， 塔釜出料送入含脱氢催化剂 （含有 70重量％的铜、 26.18重量％的氧 化锌、 1.8重量％的氧化镁、 1.5重量％的钯、 0.5重量％的镍、 0.02重量％的铯， 并且是 按 CN1156425C 中公开的制备催化剂的方法制得） 的固定床反应器 T2， 重时空速为 0.4911-1 , 固定床 Τ2操作温度为 220°C， 压力为 l.OMPa, 得到的氢气从固定床反应器 T2 的上部直接进入蒽醌催化固定床 T3， 其余产物从固定床反应器 Τ2的下部出料， 经分离 后得到环己酮，环己酮的收率见表 1。其中，蒽醌催化固定床 Τ3内装填 30ml的 Pd/Al203 催化剂， 反应器操作温度为 60°C， 压力为 0.3MPa， 蒽醌工作液为： 连三甲苯 75体积％， 四丁基脲 18体积％， 磷酸三辛酯 7体积％， 工作载体为 149g/L的 2-乙基蒽醌和 17g/L 的 2-乙基四氢蒽醌混合物， 工作载体中 2-乙基蒽醌与 2-乙基四氢蒽醌的总含量为 166g/L, 即有效蒽醌浓度为 166g/L。 蒽醌工作液的重时空速为 6h- 氢气的气时空速为 151 -1, 氧气的气时空速为 200h- 反应后得到的 H202直接送入精馏塔 T1中。 实施例 5 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, and 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). palladium, 0.5 wt% nickel, 0.02 wt.% of cesium, 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, Τ2 bed operating temperature of 220 °C, the pressure is l.OMPa, the obtained hydrogen is solid T2 bed reactor directly into the upper portion of the catalytic fixed bed anthraquinone T3, discharge from the bottom product remaining fixed bed reactor Τ2, dried cyclohexanone obtained after separation, the yield of cyclohexanone in Table 1. Among them, 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 5
与实施例 1的方法相同， 不同的是， 第一接触反应中有机溶剂为三氯甲烷。 实施例 6  The same procedure as in Example 1 except that the organic solvent in the first contact reaction was chloroform. Example 6
与实施例 1的方法相同， 不同的是， 第一接触反应中有机溶剂为 1,2,3-三氯丙烷。 实施例 7  The same procedure as in Example 1 except that the organic solvent in the first contact reaction was 1,2,3-trichloropropane. Example 7
与实施例 2的方法相同， 不同的是， 第一接触反应中有机溶剂 1,4-二氯戊烷由 1,4- 二氯戊烷和丙腈的混合溶剂代替， 且二者的质量比为 1:1， 即环己烷与双氧水 （浓度为 27.5重量％) 及溶剂 1,4-二氯戊烷、 溶剂丙腈的质量比为 1:1.72:7.5:7.5， 环己烷的转化 率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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 The total selectivity of keto alcohol, the yield of cyclohexanol and the yield of cyclohexanone are shown in Table 1. Example 8
与实施例 3的方法相同，不同的是，第一接触反应中有机溶剂丙腈由 1,2-二氯丙烷和 丙腈的混合溶剂代替， 且 1,2-二氯丙烷与丙腈的质量比为 1:9， 即环己烷与双氧水（浓度 为 27.5重量％)及溶剂 1,2-二氯丙烷、溶剂丙腈的质量比为 1:1.72:1:9，环己烷的转化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 4的方法相同， 不同的是， 第一接触反应中有机溶剂乙腈由乙腈和 1,4-二 氯戊烷代替， 且乙腈与 1,4-二氯戊烷的质量比为 1:9， 即环己烷与双氧水 （浓度为 27.5 重量％)及溶剂乙腈、 溶剂 1,4-二氯戊烷的质量比为 1:2.26:1:9， 环己烷的转化率、 酮醇 总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 1的方法相同， 不同的是， 第一接触反应中有机溶剂 1,2-二氯丙烷由 1-氯 丙烷代替， 环己烷的转化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 2的方法相同， 不同的是， 第一接触反应中有机溶剂 1,4-二氯戊烷由 1-氯 戊烷代替， 环己烷的转化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 3的方法相同， 不同的是， 第一接触反应中有机溶剂为丙酮， 环己烷的转 化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 3的方法相同， 不同的是， 第一接触反应中有机溶剂为乙酸， 环己烷的转 化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。 实施例 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
与实施例 11 的方法相同， 不同的是， 第一接触反应中催化剂为含有常规钛硅分子 筛 （TS-1 ) 的催化剂， 环己烷的转化率、 酮醇总选择性、 环己醇收率及环己酮收率见表 1。  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.
表 1  Table 1
Figure imgf000018_0001
因本发明的方法包括在脱氢催化剂作用下的脱氢反应步骤， 因此， 本发明方法比仅 进行环己烷氧化获得的环己酮收率要高很多； 将实施例 1-6与实施例 7-9进行对比可以 看出，采用腈和卤代烃的混合物作为有机溶剂时较单独采用腈或单独采用卤代烃作为有 机溶剂时效果更好； 由实施例 1-11与实施例 12和 13进行对比可以看出， 采用腈和 /或 卤代烃作为有机溶剂相比于采用丙酮或乙酸作为有机溶剂的反应， 环己烷的转化率更 高， 环己酮的收率也更高； 由实施例 1-13与实施例 14进行对比可以看出， HTS的活性 较常规的 TS-1的活性更高。
Figure imgf000018_0001
Since 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 effect of the solvent is better; from the comparison of Examples 1-11 with Examples 12 and 13, it can be seen that the reaction of using a nitrile and/or a halogenated hydrocarbon as an organic solvent compared to the use of acetone or acetic acid as an organic solvent, The conversion of hexane was higher and the yield of cyclohexanone was also higher; as can be seen from the comparison of Examples 1-13 with Example 14, the activity of HTS was higher than that of conventional TS-1.
本发明方法通过循环反应至少部分自给氧化剂 H202， 整个氧化过程主要消耗氧气 和环己烷， 降低了过氧化氢的商购或生产成本， 在很大程度上提高了***经济效益， 且 工艺绿色环保，无三废产生；由于另外增加了将中间产物环己醇脱氢制备环己酮的过程， 明显提高了环己酮的收率。 另外， 当根据本发明的一种实施方式采用特定选择的钛硅分 子筛催化剂时， 可进一步提高环己烷的转化率， 从而提高环己酮的收率， 并且氧化反应 条件更加温和。并且本发明采用腈和 /或卤代烃作为有机溶剂，可以简化后续的产物分离 步骤， 有利于工业应用。 实施例 15 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. Further, when a specifically selected titanium silicalite catalyst is employed in accordance with an embodiment of the present invention, the conversion of cyclohexane can be further increased, thereby increasing the yield of cyclohexanone, and the oxidation reaction conditions are more mild. Moreover, 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. Example 15
将 100g环己烷、 172g过氧化氢水溶液 （浓度为 27.5重量％)和 1500g 1,3-二氯丙烷 配成混合溶液， 加入到装有 300g空心钛硅分子筛（HTS )催化剂的反应器中。 反应温度 控制为 90°C， 压力控制为 0.5MPa。 物料在反应器中停留 1小时后进行固液分离， 固体 直接返回反应器中， 液体组分送入装有脱氢催化剂 （含有 70重量％的铜、 26.18重量％ 的氧化锌、 1.8重量％的氧化镁、 1.5重量％的钯、 0.5重量％的镍、 0.02重量％的铯， 根 据 CN1156425C中实施例 1公开的方法制得） 的另一反应器中， 控制反应温度为 180°C， 压力控制为 0.3MPa， 重时空速为 0.45h- 反应完毕后进行固液分离， 得到含环己酮的 液体组分。环己烷的转化率、环己酮的收率、酮醇总选择性以及环己酮的选择性见表 2。 实施例 16  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). 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
将 100g环己烷、 172g过氧化氢水溶液（浓度为 27.5重量％)和 500g 1,2-二氯丙烷配 成混合溶液， 加入到装有 50g空心钛硅分子筛 （HTS ) 催化剂的反应器中。 反应温度控 制为 50°C， 压力控制为 0.3MPa。 物料在反应器中停留 3小时后进行固液分离， 固体直 接返回反应器中， 液体组分送入装有脱氢催化剂 （含有 40重量％的铜、 40重量％的氧 化锌、 12重量％的氧化镁、 0.8重量％的氧化钙、 0.3重量％的钯、 3.0重量％的铬、 3.0 重量％的硅、 0.1重量％的钠、 0.8重量％的钾， 根据 CN1156425C中实施例 4公开的方法 制得）的另一反应器中，控制反应温度为 150°C，压力控制为 1.8MPa，重时空速为 0.45h- 反应完毕后进行固液分离，得到含环己酮的液体组分。环己烷的转化率、环己酮的收率、 酮醇总选择性以及环己酮的选择性见表 2。 实施例 17 100 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. 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). 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 In another reactor, the reaction temperature is controlled to 150 ° C, the pressure is controlled to 1.8 MPa, and the weight hourly space velocity is 0.45 h - After the completion of the reaction, 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
将 100g环己烷、 172g过氧化氢水溶液 （浓度为 27.5重量％) 和 1500g己二腈配成 混合溶液， 加入到装有 250g 空心钛硅分子筛 （HTS ) 催化剂的反应器中。 反应温度控 制为 120°C， 压力控制为 0.5MPa。物料在反应器中停留 2小时后进行固液分离， 固体直 接返回反应器中， 液体组分送入装有脱氢催化剂 （含有 10重量％的铜、 59重量％的氧 化铜、 25重量％的氧化锌、 5重量％的氧化钡、 0.1重量％的铂、 0.8重量％的镍、 0.1重 量％的铬， 根据 CN1156425C中实施例 3公开的方法制得） 的另一反应器中， 控制反应 温度为 220Ό， 压力控制为 3.2MPa， 重时空速为 0.55h- 反应完毕后进行固液分离， 得 到含环己酮的液体组分。 环己烷的转化率、 环己酮的收率、 酮醇总选择性以及环己酮的 选择性见表 2。 实施例 18  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). Controlling the reaction temperature in another reactor of zinc oxide, 5% by weight of cerium oxide, 0.1% by weight of platinum, 0.8% by weight of nickel, 0.1% by weight of chromium, prepared according to the method disclosed in Example 3 of CN1156425C) It is 220 Torr, the pressure is controlled to 3.2 MPa, and the weight hourly space velocity is 0.55 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 18
将 100g环己烷、 172g过氧化氢水溶液（浓度为 27.5重量％)、 1000g乙腈配成混合 溶液， 加入到装有 250g 空心钛硅分子筛 （HTS ) 催化剂的反应器中。 反应温度控制为 90°C， 压力控制为 0. lMPa。 物料在反应器中停留 2小时后进行固液分离， 固体直接返 回反应器中， 液体组分送入装有脱氢催化剂 （含有 50重量％的铜、 34重量％的氧化锌、 9.998重量％的氧化钙、 0.002重量％的钯、 5.9重量％的铝、 0.05重量％的锰、 0.05重量 %的钾， 根据 CN1156425C中实施例 2公开的方法制得） 的另一反应器中， 控制反应温 度为 180°C， 压力控制为 0.3MPa， 重时空速为 0.35h- 反应完毕后进行固液分离， 得到 含环己酮的液体组分。 环己烷的转化率、 环己酮的收率、 酮醇总选择性以及环己酮的选 择性见表 2。 实施例 19  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. 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). 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
与实施例 17的方法相同， 不同的是， 第一接触反应中有机溶剂己二腈 1500g由己 二腈 （1350g ) +1,3-二氯丙烷 （150g ) 代替。 环己烷的转化率、 环己酮的收率、 酮醇总 选择性以及环己酮的选择性见表 2。 与实施例 16 的方法相同， 不同的是， 第一接触反应中空心钛硅分子筛 （HTS) 催 化剂的质量为 9g。环己烷的转化率、环己酮的收率、酮醇总选择性以及环己酮的选择性 见表 2。 实施例 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
与实施例 15的方法相同， 不同的是， 第一接触反应中氧化反应温度为 40°C。 环己 烷的转化率、 环己酮的收率、 酮醇总选择性以及环己酮的选择性见表 2。 实施例 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 22
与实施例 16的方法相同， 不同的是， 第一接触反应中 500g 1,2-二氯丙烷由 500g丙 酮代替。 环己烷的转化率、 环己酮的收率、 酮醇总选择性以及环己酮的选择性见表 2。 实施例 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 23
与实施例 22 的方法相同， 不同的是， 第一接触反应中空心钛硅分子筛 （HTS) 催 化剂由传统钛硅分子筛 （TS-1 )催化剂代替， 环己烷的转化率、 环己酮的收率、 酮醇总 选择性以及环己酮的选择性见表 2。 对比例 1  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. The rate, the total selectivity of ketol and the selectivity of cyclohexanone are shown in Table 2. Comparative example 1
按照实施例 23的方法由环己烷氧化制备环己酮， 不同的是， 少了催化脱氢的步骤， 即：  The cyclohexanone was prepared by oxidation of cyclohexane according to the procedure of Example 23, except that the catalytic dehydrogenation step was eliminated, namely:
将 100g环己烷、 172g过氧化氢水溶液 （浓度为 27.5重量％) 和 500g丙酮配成混合 溶液， 加入到装有 50g传统钛硅分子筛 （TS-1 )催化剂的反应器中。 反应温度控制为 50 。C , 压力控制为 0.3MPa。 物料在反应器中停留 3小时后进行固液分离， 固体直接返回 反应器中， 得到含环己酮的液体组分。 环己烷的转化率、 环己酮的收率、 酮醇总选择性 以及环己酮的选择性见表 2。  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. After the material was allowed to stand in the reactor for 3 hours, solid-liquid separation was carried out, and the solid was directly returned to the reactor 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.
表 2 Table 2
实施 环己烷 酮醇总 环己酮的 环己酮 例编号 转化率 /% 选择性 /% 选择性 /% 收率 /%Cyclohexanone with cyclohexanol total cyclohexanone Example number conversion rate /% selectivity /% selectivity /% yield /%
15 72% 97% 96% 69.1%15 72% 97% 96% 69.1%
16 65% 95% 93% 60.4%16 65% 95% 93% 60.4%
17 71% 95% 94% 66.7%17 71% 95% 94% 66.7%
18 74% 99% 97% 71.8%18 74% 99% 97% 71.8%
19 79% 100% 99% 78.2%19 79% 100% 99% 78.2%
20 46% 94% 93% 42.7%20 46% 94% 93% 42.7%
21 54% 91% 90% 48.6%21 54% 91% 90% 48.6%
22 45% 91% 89% 40.1%22 45% 91% 89% 40.1%
23 22% 90% 89% 19.6% 对比 23 22% 90% 89% 19.6% Comparison
22% 90% 53% 11.7% 例 1 从表 2的结果可以看出， 由于本发明实施例 15-23采用对氧化条件下所得的含有环 己醇的溶液进行催化脱氢， 因此环己酮的收率明显提高。 同样， 通过实施例 22和实施 例 23 的对比可以看出， 相对传统钛硅分子筛催化剂而言， 采用空心钛硅分子筛催化剂 时， 环己烷的转化率和环己酮的收率都有明显的提高。 通过实施例 17和实施例 19的对 比同样可以看出，采用腈和卤代烃的混合物作为有机溶剂时较单独采用腈作为有机溶剂 时效果更好。 从实施例 15-19和实施例 20-23的对比可以看出， 采用本发明优选的氧化 条件， 环己烷的转化率、 环己酮的收率、 酮醇总选择性以及环己酮的选择性均更高。  22% 90% 53% 11.7% 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. 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. As can be seen from the comparison of Examples 15-19 and Examples 20-23, 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.
综合表 1和表 2的结果可以知道， 本发明的方法无论采用何种反应方式进行， 均相 比于现有技术的方法具有更高的环己酮收率， 并且由表 1和表 2的结果可以知道， 采用 催化精馏方式进行本发明的所述第一接触反应能够获得更高的环己酮收率。  From the results of Tables 1 and 2, it can be understood that the method of the present invention has a higher cyclohexanone yield than the prior art method, regardless of the reaction mode employed, and is determined by Tables 1 and 2. As a result, it is known that the first contact reaction of the present invention by catalytic distillation can obtain a higher yield of cyclohexanone.
以上详细描述了本发明的优选实施方式， 但是， 本发明并不限于上述实施方式中的 具体细节， 在本发明的技术构思范围内， 可以对本发明的技术方案进行多种简单变型， 这些简单变型均属于本发明的保护范围。  The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是， 在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾 的情况下， 可以通过任何合适的方式进行组合。  It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction.
此外， 本发明的各种不同的实施方式之间也可以进行任意组合， 只要其不违背本发 明的思想， 其同样应当视为本发明所公开的内容。  In addition, any combination of various embodiments of the invention may be made, as long as it does not deviate from the idea of the invention, and should also be regarded as the disclosure of the invention.

Claims

权利要求 Rights request
1、 一种环己烷氧化的方法， 该方法包括以下步骤： A method for oxidizing cyclohexane, the method comprising the steps of:
( 1 ) 在氧化反应条件下， 将环己烷和过氧化氢或过氧化氢水溶液与钛硅分子筛催 化剂在有机溶剂中进行第一接触反应， 得到含有环己醇的混合物；  (1) subjecting a cyclohexane and hydrogen peroxide or an aqueous hydrogen peroxide solution to a first contact reaction with a titanium silicon molecular sieve catalyst in an organic solvent under an oxidation reaction condition to obtain a mixture containing cyclohexanol;
(2)将步骤（1 ) 中生成的环己醇在催化脱氢的条件下与一种脱氢催化剂进行第二 接触反应， 使环己醇脱氢转化为环己酮， 得到环己酮和氢气。  (2) subjecting the cyclohexanol formed in the step (1) to a second contact reaction with a dehydrogenation catalyst under catalytic dehydrogenation to dehydrogenate cyclohexanol to cyclohexanone to obtain cyclohexanone and hydrogen.
2、 根据权利要求 1所述的方法， 其中， 步骤 （1 )所述钛硅分子筛催化剂中的钛硅 分子筛为具有 MFI结构的钛硅分子筛，且该钛硅分子筛的晶粒为空心结构，该空心结构 的空腔部分的径向长度为 5-300纳米， 且所述钛硅分子筛在 25 °C、 P/Po=0.10 吸附时间 为 1小时的条件下测得的苯吸附量不少于 70毫克 /克， 该钛硅分子筛的低温氮吸附的吸 附等温线和脱附等温线之间存在滞后环。 2. The method according to claim 1, wherein the titanium silicon molecular sieve in the titanium silicon molecular sieve catalyst in step (1) is a titanium silicon molecular sieve having an MFI structure, and the crystal grains of the titanium silicon molecular sieve are hollow structures, The radial portion of the hollow structure has a radial length of 5 to 300 nm, and the titanium silicate molecular sieve has a benzene adsorption amount of not less than 70 measured at 25 ° C and a P/Po = 0.10 adsorption time of 1 hour. Mg/g, a hysteresis loop exists between the adsorption isotherm of the low temperature nitrogen adsorption of the titanium silicalite and the desorption isotherm.
3、 根据权利要求 1所述的方法， 其中， 步骤 （1 ) 所述氧化反应条件包括环己烷、 过氧化氢、水、钛硅分子筛催化剂与有机溶剂的质量比为 1:0.003-5:0.15-3:0.1-15:0.5-30， 接触的温度为 30-170°C、 压力为 0.01-2MPa。 3. The method according to claim 1, wherein the oxidation reaction condition comprises the cyclohexane, hydrogen peroxide, water, titanium silica molecular sieve catalyst and the organic solvent mass ratio of 1:0.003-5: 0.15-3: 0.1-15: 0.5-30, the contact temperature is 30-170 ° C, and the pressure is 0.01-2 MPa.
4、 根据权利要求 1所述的方法， 其中， 步骤 （1 ) 所述有机溶剂为腈和 /或卤代烃; 优选所述有机溶剂为腈和卤代烃， 且腈和卤代烃的质量比为 0.1-10:1。 4. The method according to claim 1, wherein the organic solvent in the step (1) is a nitrile and/or a halogenated hydrocarbon; preferably the organic solvent is a nitrile and a halogenated hydrocarbon, and the quality of the nitrile and the halogenated hydrocarbon The ratio is 0.1-10:1.
5、 根据权利要求 4所述的方法， 其中， 所述腈为 C1-C10的一元腈和 /或二元腈， 优 选为 C2-C8的一元腈和 /或二元腈，更优选为乙腈、丙腈、戊腈和己二腈中的一种或多种； 所述卤代烃为被一个和 /或多个相同或不同的卤素原子取代的 C1-C10 的烷烃和 /或 C6-C10的环烷烃， 优选为 C1-C6的二氯代烷烃和 /或三氯代烷烃， 更优选为二氯甲烷、 三氯甲烷、 1,1-二氯乙烷、 1,2-二氯乙烷、 1,1,1-三氯乙烷、 1,1,2-三氯乙烷、 1,2-二氯丙 烷、 2,2-二氯丙烷、 1,3-二氯丙烷、 1,2,3-三氯丙烷、 1,2-二氯丁烷、 2,3-二氯丁烷、 1,4- 二氯丁烷、 1,2-二氯戊烷、 2,2-二氯戊烷、 1,3-二氯戊烷、 2,3-二氯戊烷、 3,3-二氯戊烷、 1,4-二氯戊烷、 2,4-二氯戊烷、 1,2,5-三氯戊烷、 1,1,5-三氯戊烷和 1,2-二氯环己烷中的一 种或多种。 5. The method according to claim 4, wherein the nitrile is a C1-C10 mononitrile and/or a dibasic nitrile, preferably a C2-C8 mononitrile and/or a dibasic nitrile, more preferably acetonitrile, One or more of propionitrile, valeronitrile, and adiponitrile; the halogenated hydrocarbon is a C1-C10 alkane and/or a C6-C10 ring substituted with one and/or a plurality of the same or different halogen atoms The alkane, preferably a C1-C6 dichloroalkane and/or a 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-Dichloropentane, 2,3-dichloropentane, 3,3-dichloropentane, 1,4-dichloropentane, 2,4-dichloropentane, 1,2,5 One or more of trichloropentane, 1,1,5-trichloropentane and 1,2-dichlorocyclohexane.
6、 根据权利要求 1所述的方法， 其中， 步骤 （1 )所述第一接触反应在固定床反应 器中进行。 6. The method according to claim 1, wherein the step (1) of the first contact reaction is carried out in a fixed bed reactor.
7、 根据权利要求 6所述的方法， 其中， 该方法还包括将所述第一接触反应后的产 物进行分离，分离出的有机溶剂和未反应的环己烷以及过氧化氢或过氧化氢水溶液返回 到步骤 （1 ) 的进料中， 分离出的环己醇或者环己醇与环己酮的混合物进行步骤 （2)所 述第二接触反应。 7. The method according to claim 6, wherein the method further comprises separating the product after the first contact reaction, separating the organic solvent and unreacted cyclohexane, and hydrogen peroxide or hydrogen peroxide. The aqueous solution is returned to the feed of step (1), and the separated cyclohexanol or a mixture of cyclohexanol and cyclohexanone is subjected to the second contact reaction of the step (2).
8、 根据权利要求 1所述的方法， 其中， 步骤 （1 )所述第一接触反应按照催化精馏 的方式进行，催化精馏所得有机溶剂和未反应的环己烷以及过氧化氢或过氧化氢水溶液 返回到步骤 （1 ) 的进料中， 催化精馏所得环己醇或者环己醇与环己酮的混合物进行步 骤 （2) 所述第二接触反应。 8. The method according to claim 1, wherein the step (1) of the first contact reaction is carried out by catalytic distillation, the organic solvent obtained by catalytic distillation and unreacted cyclohexane and hydrogen peroxide or The aqueous hydrogen peroxide solution is returned to the feed of step (1), and the resulting cyclohexanol or a mixture of cyclohexanol and cyclohexanone is subjected to the second contact reaction of the step (2).
9、 根据权利要求 8所述的方法， 其中， 步骤 （1 ) 中， 将环己烷、 过氧化氢水溶液 以及有机溶剂从进料口送入精馏塔中进行接触， 并从精馏塔的塔底得到全部或大部分的 氧化产物， 优选氧化产物的 95-100重量％从精馏塔的塔底得到； 其中， 所述精馏塔内的 部分或全部填料为钛硅分子筛催化剂。 9. The method according to claim 8, wherein in the step (1), cyclohexane, an aqueous hydrogen peroxide solution, and an organic solvent are fed from the feed port to the rectification column for contacting, and from the rectification column. The bottom of the column gives all or most of the oxidation product, preferably 95-100% by weight of the oxidation product is obtained from the bottom of the rectification column; wherein some or all of the filler in the rectification column is a titanium silicalite catalyst.
10、 根据权利要求 9所述的方法， 其中， 将过氧化氢水溶液从第一进料口送入精馏 塔， 将环己烷从第二进料口送入精馏塔； 其中， 所述第一进料口到塔底之间的塔板数或 理论塔板数占所述精馏塔中总的塔板数或理论塔板数的 50-100%， 优选为 80-100%; 所 述第二进料口到塔底之间的塔板数或理论塔板数占所述精馏塔中总的塔板数或理论塔 板数的 10-80%， 优选为 30-70%。 10. The method according to claim 9, wherein the aqueous hydrogen peroxide solution is sent from the first feed port to the rectification column, and the cyclohexane is sent from the second feed port to the rectification column; The number of trays or the number of theoretical plates between the first feed port and the bottom of the column accounts for 50-100%, preferably 80-100%, of the total number of plates or the number of theoretical plates in the rectification column; The number of trays or the number of theoretical plates between the second feed port and the bottom of the column accounts for 10-80%, preferably 30-70%, of the total number of plates or the number of theoretical plates in the rectification column.
11、 根据权利要求 9或 10所述的方法， 其中， 所述填料中含有 20-100重量％， 优 选含有 30-70重量％的所述钛硅分子筛催化剂； 优选所述钛硅分子筛催化剂包括载体和 钛硅分子筛， 其中， 以催化剂总重量为基准， 载体的含量为 10-90重量％， 钛硅分子筛 的含量为 10-90重量％。 The method according to claim 9 or 10, wherein the filler contains 20 to 100% by weight, preferably 30 to 70% by weight of the titanium silicalite catalyst; preferably the titanium silicalite catalyst comprises a carrier And a titanium silicon molecular sieve, wherein the content of the carrier is 10 to 90% by weight based on the total weight of the catalyst, and the content of the titanium silicon molecular sieve is 10 to 90% by weight.
12、根据权利要求 1-5和 8-10中任意一项所述的方法， 其中， 所述有机溶剂的沸点 为 50-140 °C， 优选为 60-130 °C , The method according to any one of claims 1 to 5, wherein the boiling point of the organic solvent 50-140 ° C, preferably 60-130 ° C,
13、 根据权利要求 12所述的方法， 其中， 所述氧化反应条件包括精馏塔的塔底温 度为 55-170°C， 优选为 60-150 °C。 The method according to claim 12, wherein the oxidation reaction condition comprises a column bottom temperature of the rectification column of 55 to 170 ° C, preferably 60 to 150 ° C.
14、 根据权利要求 13所述的方法， 其中， 所述精馏塔的总的塔板数或理论塔板数 为 20-45， 优选为 30-40。 14. Process according to claim 13, wherein the total number of plates or theoretical plates of the rectification column is from 20 to 45, preferably from 30 to 40.
15、 根据权利要求 9或 10所述的方法， 其中， 第一接触反应中环己烷、 过氧化氢、 水与有机溶剂的质量比为 1:0.03-3:0.1-3:0.5-30, 优选为 1:0.3-1.5:0.1-2:3-15。 The method according to claim 9 or 10, wherein a mass ratio of cyclohexane, hydrogen peroxide, water to an organic solvent in the first contact reaction is 1:0.03-3:0.1-3:0.5-30, preferably It is 1:0.3-1.5:0.1-2:3-15.
16、根据权利要求 1所述的方法，其中，所述第二接触反应在固定床反应器中进行， 所述第二接触反应的条件包括： 温度为 150-280 °C， 压力为 0.3-3.2MPa， 重时空速为 0.35-0.5511-1 , 所述脱氢催化剂含有以下组份： 16. The method of claim 1 wherein said second contacting reaction is carried out in a fixed bed reactor, said second contacting reaction conditions comprising: a temperature of from 150 to 280 ° C and a pressure of from 0.3 to 3.2 MPa, a weight hourly space velocity of 0.35-0.5511- 1, the dehydrogenation catalyst comprises the following components:
a)铜或铜的氧化物 20-74重量％;  a) copper or copper oxide 20-74% by weight;
b)钯和 /或铂或钯和 /或铂的氧化物 0.001-2.0重量％;  b) palladium and / or platinum or palladium and / or platinum oxides 0.001 - 2.0% by weight;
c)除铜、 钯和铂之外的其他金属或该其他金属的氧化物 24-78重量％， 所述其他金 属为选自锌、 镁、 钙、 锶、 钡、 硅、 铝、 铬、 锰、 镍、 锆和钛中的至少一种。  c) 24 to 78% by weight of other metals than copper, palladium and platinum selected from the group consisting of zinc, magnesium, calcium, strontium, barium, silicon, aluminum, chromium, manganese At least one of nickel, zirconium and titanium.
17、 根据权利要求 1所述的方法， 其中， 该方法还包括步骤 （3 ): 将步骤 （2) 所 得氢气通过蒽醌法合成过氧化氢， 并将该过氧化氢用于步骤 （1 ) 的所述第一接触反应 中。 17. The method according to claim 1, wherein the method further comprises the step (3): synthesizing the hydrogen obtained in the step (2) by hydrogen peroxide, and using the hydrogen peroxide in the step (1). The first contact reaction.
PCT/CN2012/074285 2011-04-29 2012-04-18 Process for oxidizing cyclohexane WO2012146145A1 (en)

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CN201110111332.3A CN102757306B (en) 2011-04-29 2011-04-29 Preparation method of cyclohexanone
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CN2011101158540A CN102766031A (en) 2011-05-05 2011-05-05 Oxidation method of cyclohexane
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (en) * 1999-12-24 2001-07-04 中国石油化工集团公司 Titanium-silicon molecular sieve and its preparing method
CN1381434A (en) * 2001-04-18 2002-11-27 中国石油化工股份有限公司 Process for preparing cyclohexanone by dehydrogenating cyclohexanol
CN101137608A (en) * 2004-12-07 2008-03-05 罗狄亚化学公司 Method for the production of cyclohexanone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (en) * 1999-12-24 2001-07-04 中国石油化工集团公司 Titanium-silicon molecular sieve and its preparing method
CN1381434A (en) * 2001-04-18 2002-11-27 中国石油化工股份有限公司 Process for preparing cyclohexanone by dehydrogenating cyclohexanol
CN101137608A (en) * 2004-12-07 2008-03-05 罗狄亚化学公司 Method for the production of cyclohexanone

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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