WO2012149865A1 - 一种环己烷氧化制环己醇的方法 - Google Patents

一种环己烷氧化制环己醇的方法 Download PDF

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WO2012149865A1
WO2012149865A1 PCT/CN2012/074283 CN2012074283W WO2012149865A1 WO 2012149865 A1 WO2012149865 A1 WO 2012149865A1 CN 2012074283 W CN2012074283 W CN 2012074283W WO 2012149865 A1 WO2012149865 A1 WO 2012149865A1
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cyclohexane
rectification column
molecular sieve
column
hydrogen peroxide
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PCT/CN2012/074283
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English (en)
French (fr)
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蒋卫和
林民
屈铠甲
何嘉勇
杨浴
汪燮卿
舒兴田
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岳阳昌德化工实业有限公司
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Publication of WO2012149865A1 publication Critical patent/WO2012149865A1/zh

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a process for the oxidation of cyclohexane to cyclohexanol. 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, are required to be more than 2 million tons per year worldwide.
  • titanium silicalite there are many factors influencing the oxidation of cyclohexane by titanium silicalite, such as the nature of titanium silicalite itself, the nature of oxidant hydrogen peroxide H 2 0 2 , the choice of solvent, the reaction conditions (such as temperature, raw material ratio, reaction pressure, etc. Etc., in order to improve the selectivity of cyclohexanone in the oxidation of cyclohexane, the researchers focused on the development of more efficient titanium-silicon molecular sieve catalysts, and optimized the reaction conditions in the process to achieve the aforementioned objectives.
  • An object of the present invention is to provide a process for the continuous oxidation of cyclohexane having a higher yield of cyclohexanol for cyclohexanol.
  • 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 current research seems to be based on the total weight of the reaction liquid in the cyclohexane oxidation reaction in the titanium silicalite/H 2 0 2 system.
  • the solvent usually accounts for 30 to 90% by weight, so although the reaction is efficiently carried out because the addition of the solvent is effective, the large addition of the solvent adds trouble and cost to the subsequent separation, thereby reducing its industrial application prospect.
  • 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.
  • cyclohexane oxidation is divided into two steps. The first step is the oxidation of cyclohexane to cyclohexanol, and the second step is the oxidation of cyclohexanol.
  • the present invention provides a method for oxidizing cyclohexane to cyclohexanol, which comprises feeding cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from a feed port to an aliquot under an oxidation reaction condition.
  • a method for oxidizing cyclohexane to cyclohexanol which comprises feeding cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from a feed port to an aliquot under an oxidation reaction condition.
  • the method for oxidizing cyclohexane to cyclohexanol of the present invention is oxidized in a rectification column (ie, under rectification conditions), and the latent heat of the reaction is fully utilized to achieve energy saving;
  • the selectivity of the alcohol to cyclohexanone i.e., the yield of cyclohexanol is greatly increased
  • relatively direct oxidation to cyclohexanone which not only saves half of the amount of hydrogen peroxide, but also dehydrogenates the cyclohexanol to cyclohexanone.
  • Hydrogen resources are generated, which further strengthens its application prospects in the industry.
  • the present invention can be separated by the oxidation reaction of cyclohexane in the rectification column so that the oxidation product can be reacted with the raw material cyclohexane side, thereby saving the subsequent separation cost.
  • the present invention provides a method for the oxidation of cyclohexane to cyclohexanol, which comprises contacting cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from a feed port into a rectification column under oxidation reaction conditions. And obtaining all or most of the oxidation products from the bottom of the rectification column, wherein some or all of the fillers in the rectification column are catalysts containing titanium silica molecular sieves, and the organic solvent has a boiling point of 40 ° C - 250 Nitrile and / or halogenated hydrocarbons at °C.
  • the oxidation product it is preferred that 95 to 100% by weight of the oxidation product is obtained from the bottom of the rectification column.
  • 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 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; wherein
  • the number of trays or the number of theoretical plates between a feed port and the bottom of the column accounts for 50-100%, more preferably 80-100%, of the total number of plates or the number of theoretical plates in the distillation 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%, more preferably 30-70% of the total number of plates or the number of theoretical plates in the rectification column.
  • 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 selectively fed from the second feed port, so that a stable rectification state can be formed, which can be known to those skilled in the art, and will not be further described herein, in the specific implementation of the present invention. The example is no longer specifically emphasized.
  • the invention has no special requirement for the titanium silicon molecular sieve catalyst, and can be various shaped titanium silicon molecular sieve catalysts which can be applied to the rectification column.
  • the catalyst containing the titanium silicon molecular sieve comprises a carrier and a titanium silicon molecular sieve.
  • the content of the carrier is from 10 to 90% by weight based on the total weight of the catalyst, and the content of the titanium silicon molecular sieve is from 10 to 90% by weight.
  • the optional range of the amount of the titanium-silicon molecular sieve catalyst contained in the filler is wide, but if the amount of the catalyst is too large, the reaction tends to be too fast, and subsequent separation is not easily achieved. If the amount of the catalyst is too small, The reaction is too slow and is not advantageous for industrial applications, and therefore it is preferred that the filler contains 30 to 100% by weight, more preferably 30 to 70% by weight, of the catalyst containing titanium silicalite.
  • the filler containing the titanium silicalite catalyst in the present invention is preferably a mixed filler obtained by uniformly mixing a conventional filler with a titanium silicalite 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.
  • a Raschig ring Raschig ring
  • Pall ring Pall ring
  • step ring an arc saddle
  • a saddle saddle
  • metal ring saddle filler 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 titanium silicon molecular sieve in the titanium silicon molecular sieve catalyst may be a conventional titanium silicon molecular sieve, which may be modified or unmodified, preferably an MFI structure titanium silicon molecular sieve (such as TS-1). At least one of a titanium-silicon molecular sieve of a MEL structure (such as TS-2) and a titanium-silicon molecular sieve of a BETA structure (such as Ti- ⁇ ); more preferably having a structural formula of xTiO Si0 2 , wherein X is 0.0001-0.04, A titanium silicon molecular sieve of preferably 0.01 to 0.03, more preferably 0.015 to 0.025.
  • the titanium silicon molecular sieve is commercially available or can be prepared, and a method for preparing the titanium silicon molecular sieve is known to those skilled in the art.
  • a method for preparing the titanium silicon molecular sieve is known to those skilled in the art.
  • the titanium silicon molecular sieve in the titanium silicon molecular sieve catalyst is an MFI structure
  • the titanium silicon molecular sieve crystal grain is a hollow structure
  • the hollow portion of the hollow structure has a radial length of 5 to 300 nm
  • the titanium silicon Molecular sieves at 25.
  • C, P/Po 0.10
  • the adsorption amount of benzene measured under the condition of adsorption time of 1 hour is at least 70 mg/g, and there is a hysteresis loop between the adsorption isotherm of the low-temperature nitrogen adsorption of the titanium-silicon molecular sieve and the desorption isotherm.
  • the titanium silicon molecular sieve having the above structure and properties is generally referred to as a hollow titanium silicon molecular sieve, and its commercial brand number is HTS.
  • the relevant parameters and preparation methods thereof can be referred to CN1301599A.
  • the solvent is mainly through various factors such as electronic effect, steric hindrance effect, solvent polarity, physical diffusion and distribution, solvent oxidation side reaction, catalyst deactivation and solubility. Affect the reaction. Many researchers have studied the solvent effects of propylene epoxidation and cyclohexanone ammoximation. Some researchers have pointed out that methanol and other protic solvents are effective solvents for epoxidation of propylene and other low-carbon olefins. The present inventors have unexpectedly discovered that halogenated hydrocarbons and nitrile solvents can substantially increase the conversion of cyclohexane to cyclohexanol.
  • the organic solvent is a halogenated hydrocarbon and/or nitrile solvent having a boiling point of 50 to 140 ° C, preferably 60 to 13 CTC.
  • the inventors of the present invention have also unexpectedly discovered during the course of the research that when the nitrile and the halogenated hydrocarbon are mixed as an organic solvent, the conversion of cyclohexane and the yield of cyclohexanol can be greatly improved, that is,
  • the organic solvent is a mixture of a nitrile and a halogenated hydrocarbon, preferably a mass ratio of the nitrile solvent to the halogenated hydrocarbon solvent of from 0.1 to 10:1.
  • the conversion of cyclohexane and the yield of the target product cyclohexanol were further improved by using two solvents, The solvent reaction system will bring trouble to the subsequent separation work.
  • the nitrile is a C1-C10 mononitrile and/or a dibasic nitrile, preferably Further preferably, the C1-C8 mononitrile and/or the dinitrile, the nitrile is one or more of acetonitrile, propionitrile and valeronitrile, preferably acetonitrile and/or propionitrile;
  • the present invention has no particular requirements on the oxidation reaction conditions, as long as the object of the present invention can be achieved.
  • the oxidation reaction conditions include a distillation column bottom temperature of 55-170 ° C, preferably 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, The reflux ratio will be specifically described.
  • the total number of trays or the number of theoretical plates in the rectification column is from 20 to 45, more preferably from 30 to 40.
  • 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 present invention has no special requirement on the mass ratio of the cyclohexane, hydrogen peroxide, water and organic solvent, and can be selected by referring to the ratio of each substance in the catalytic oxidation of the cyclohexane system by the conventional titanium silica molecular sieve.
  • the mass ratio of cyclohexane, hydrogen peroxide, water and organic solvent during the reaction is preferably adjusted. Is 1:0.03-3:0.1-3:0.5-30, It is preferably 1:0.3-1.5:0.1-2:3-15.
  • 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.
  • the rectification column in the actual reaction process, in order to prevent the collapse of the packed bed of the catalyst containing the titanium silicon molecular sieve in the rectification column, the rectification column can be divided into a plurality of sections, and each section can be directly used.
  • the conventional 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, and is generally 5-20 cm, preferably 8-15 cm.
  • the preparation method of the titanium silicon molecular sieve catalyst can be carried out by a technique known in the art, and can be prepared according to a conventional method for molding a catalyst, mainly including steps of beating, granulating, etc., and the present invention has no special requirements for this. , will not repeat them here.
  • the present invention has no special requirement for the carrier in the catalyst containing titanium silica molecular sieve, and may be a carrier of various commonly used shaped catalysts, for example, may be a porous heat-resistant inorganic oxide and/or silicate, for example, for example, It is one or more of alumina, silica, titania, magnesia, zirconia, cerium oxide, cerium oxide and clay. More preferably, the support is one or more of alumina, silica, magnesia and zirconia.
  • the method of the present invention further comprises: feeding cyclohexane, an aqueous hydrogen peroxide solution and an organic solvent from the feed port to the rectification column for contact.
  • the organic solvent and unreacted cyclohexane and an aqueous hydrogen peroxide solution are returned from the feed port to the rectification column for contacting.
  • 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 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 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. Save on production costs.
  • the amount of hydrogen peroxide in the aqueous phase in the above-described discharge in the present invention means the amount of hydrogen peroxide in the aqueous phase after removal of the organic matter.
  • the reagents used in the comparative examples and the examples were all commercially available chemically pure reagents.
  • the content of the hollow titanium silicon molecular sieve (HTS) was 50% and the content of silica was 50% based on the total weight of the catalyst.
  • the conventional titanium silicalite (TS-1) content was 50% and the silica content was 50% based on the total weight of the catalyst.
  • the amount of benzene adsorbed was 78 mg/g measured under the conditions, and the content of titanium oxide was 2.5% by weight.
  • the conventional titanium silicon molecular sieve (TS-1) used in the comparative example 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 hydrogen peroxide used in the examples and comparative examples was a commercially available 27.5 wt% hydrogen peroxide.
  • the conventional fillers in the examples and in the comparative examples were purchased from Tianjin Kaimet Chemical Technology Co., Ltd.
  • the catalysts containing titanium silicalite (TS-1 or HTS) in the examples were all 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 Indicator.
  • y cyclohexanol s cyclohexanol x ⁇ cyclohexane
  • X is the conversion ratio
  • s is the selectivity (s! s means the total selectivity of the ketol, or simply the ketol selectivity);
  • the ratio of the ratio of 1:1.72:15 in the reaction is from the feed port of the rectification column.
  • the feed amount per hour of hydrogen peroxide per kg of hollow titanium silicon molecular sieve (HTS) catalyst is 0.05 kg, wherein cyclohexane is fed from the second feed port, hydrogen peroxide and solvent 1,2-dichloropropane
  • the first feed port is fed, the bottom temperature of the control tower 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 first The number of theoretical plates between the 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 a hollow titanium silicon molecular sieve (HTS) catalyst. 40% by weight of 9 rings.
  • the ratio of the ratio of 1:1.72:15 is from the feed port of the rectification column.
  • Material, and relative to each kilogram of titanium silicon The sieve (HTS) catalyst feeds 0.5 kg per hour of hydrogen peroxide, wherein cyclohexane is fed from the second feed port, and hydrogen peroxide and solvent 1,2-dichloropropane are fed from the first feed port; wherein the control
  • the temperature at the bottom of the column is 140 ° C, and the top of the distillation column is discharged into water and then enters the second feed port for recycling.
  • the number of theoretical plates of the rectification column is 35, and the first feed port is between the bottom and the bottom of the column.
  • the number of theoretical plates is 30, the number of theoretical plates between the second feed port and the bottom of the column is 10; the filler contains 60% by weight of a hollow titanium silicon molecular sieve (HTS) catalyst, 40% by weight of 9 rings.
  • the column material is discharged from the discharge port at the bottom of the distillation column. After 18 hours of stable operation, samples were taken from the outlet of the bottom of the column.
  • the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • the feed is fed from the feed port of the rectification column, and relative to each The kilogram of titanium silicon molecular sieve (HTS) catalyst feeds 0.1 kg per hour of hydrogen peroxide, 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 is At 110 ° C, the top of the distillation column is discharged into water and then enters the second feed port for recycling.
  • HTS titanium silicon molecular sieve
  • the number of theoretical plates of the distillation column is 35, and the theoretical tray between the first feed port and the bottom of the column The number is 30, the number of theoretical plates between the second feed port and the bottom of the column is 10, the filler contains 60% by weight of titanium silicalite (HTS) catalyst, 40% by weight of anthracene ring.
  • HTS titanium silicalite
  • the outlet of the bottom of the tower was discharged. After 18 hours of stable operation, the sample was taken from the outlet of the bottom of the column for analysis.
  • the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • cyclohexane to hydrogen peroxide concentration: 27.5% by weight
  • solvent acetonitrile boiling point 81. ⁇ , the ratio of 1:2.26:10
  • the titanium silicon molecular sieve (HTS) catalyst feeds 0.2 kg per hour of hydrogen peroxide, wherein cyclohexane and solvent acetonitrile are fed from the second feed port, and hydrogen peroxide is fed from the first feed port, wherein the bottom temperature is 88. °C, the top of the distillation column is discharged and then enters the second feed port for recycling.
  • 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, the filler contains 30% by weight of titanium silicon molecular sieve (HTS) catalyst, 70% by weight of 9 ring.
  • the column material is from the distillation tower The discharge port of the bottom was discharged. After 18 hours of stable operation, the sample was taken from the bottom outlet, and the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 8 The same procedure as in Example 2 except that the solvent 1,3-dichloropropane was replaced by a mixed solvent of 1,2-dichloropropane and propionitrile, and the mass ratio of the two was 1:1, cyclohexane.
  • the conversion, total ketol selectivity and cyclohexanol yield are shown in Table 1.
  • Example 9 The same procedure as in Example 3 except that the solvent propionitrile was replaced by a mixed solvent of 1,2-dichloropropane and propionitrile, and the mass ratio of 1,2-dichloropropane to propionitrile was 1:9, The conversion of hexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 9 The conversion of hexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 10 The same procedure as in Example 4 except that the solvent acetonitrile was replaced by acetonitrile and 1,3-dichloropropane, and the mass ratio of acetonitrile to 1,3-dichloropropane was 1:9, the conversion of cyclohexane, The total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 10 The total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 11 The procedure was the same as in Example 1, except that the solvent 1,2-dichloropropane was replaced by 1-chloropropane, and the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 11 The procedure was the same as in Example 1, except that the solvent 1,2-dichloropropane was replaced by 1-chloropropane, and the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 11 The procedure was the same as in Example 1, except that the solvent 1,2-dichloropropane was replaced by 1-chloropropane, and the conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1.
  • Example 11 The procedure was the same as in Example 1, except that the solvent 1,2-dichloropropane was replaced by 1-chloropropane,
  • Example 1 The procedure was the same as in Example 1, except that the catalyst was a catalyst containing a conventional titanium silica molecular sieve (TS-1). The conversion of cyclohexane, the total selectivity of ketol and the yield of cyclohexanol are shown in Table 1. Comparative example 1

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Description

一种环己院氧化制环己醇的方法 技术领域
本发明涉及一种环己烷氧化制环己醇的方法。 背景技术
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， 全世界每年的需求量都在 200万吨以上。
针对上述需求， 国内外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。
钛硅分子筛催化氧化环己烷反应的影响因素很多， 如钛硅分子筛本身的性质， 氧化 剂过氧化氢 H202的性质， 溶剂的选择， 反应条件 （如温度、 原料配比、 反应压力等） 等等， 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， 以及优化该过程中的反应条件来实现前述目标。
虽然目前已有较多的钛硅分子筛催化氧化环己烷反应的研究，但大部分仅停留在实 验室阶段的研究，仍无法实现连续化工业生产。究其原因要么是对设备的要求过于苛刻， 要么是能耗高、 但产率低等。
因此，如何开发一套适用于工业连续化生产的钛硅分子筛催化氧化环己烷反应的工 艺将是日后关于钛硅分子筛 /H202体系内环己烷氧化反应的研究的重点努力方向。 发明内容
本发明的目的是为了提供一种适用于工业应用的连续进行，且环己醇收率较高的环 己烷氧化制环己醇的方法。
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。
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。 此外， 现有技术一 直致力于如何提高该过程中环己烷转变为环己酮的收率。 然而， 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 是环己醇氧化制备环己酮的过程，而在整个过程中，因为环己醇较环己烷更容易被氧化， 因此如何提高环己醇在该过程中的收率是提高后续环己酮收率的关键。 并且， 提高环己 醇收率的另一个优势在于， 现有的醇脱氢氧化制备酮的工艺已非常成熟， 例如采用金属 催化环己醇脱氢即可获得很高的环己酮收率， 并且在脱氢过程中还可以产生氢气资源， 同时还可以避免环己醇氧化制备环己酮的过程也在昂贵的钛硅分子筛催化作用下进行 并多消耗一倍的双氧水， 从而可以大幅度的降低生产成本。 因此， 本发明的发明人打破 现有技术的思维定势， 在钛硅分子筛 /H202体系中由环己烷氧化生成环己酮收率难以进 一步提高的情况下， 着力于提高环己烷氧化生成环己醇的收率， 后续可以通过成熟的脱 氢技术来低成本、 高收率的获得环己酮。 基于这种设想制造了本发明。
为了实现上述目的， 本发明提供了一种环己烷氧化制环己醇的方法， 该方法包括在 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 全部填料为含有钛硅分子筛的催化剂， 所述有机溶剂为沸点 40°C -250°C的腈和 /或卤代 烃。
本发明的环己烷氧化制环己醇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； 二是意外发现提高了环己醇相对环己酮的 选择性 （即环己醇的收率大大提高）， 相对直接氧化成环己酮， 这不仅节约了一半的双 氧水用量， 而且生产的环己醇再脱氢成环己酮时会产生氢气资源， 这进一步加强了其在 工业中的应用前景。 同时， 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。
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。 具体实施方式
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。
本发明提供了一种环己烷氧化制环己醇的方法， 该方法包括在氧化反应条件下， 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含有钛硅 分子筛的催化剂， 所述有机溶剂为沸点 40°C-250°C的腈和 /或卤代烃。
根据本发明， 优选氧化产物的 95-100重量％从精馏塔的塔底得到。
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， 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%。
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， 可以选择将 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。
本发明对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， 优选情况下， 所述含有钛硅分子筛的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％。
根据本发明， 所述填料中含有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％的所述含有钛硅分子筛的催化剂。 本发明中所述含有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。
根据本发明， 所述钛硅分子筛催化剂中的钛硅分子筛可以为常规的钛硅分子筛， 可 以为改性的也可以为非改性的， 优选为 MFI结构的钛硅分子筛 （如 TS-1 )、 MEL结构 的钛硅分子筛 （如 TS-2)、 BETA结构的钛硅分子筛 （如 Ti- β ) 中的至少一种； 更优选 为具有结构式为 xTiO Si02， 其中， X 为 0.0001-0.04， 优选为 0.01-0.03， 更优选为 0.015-0.025的钛硅分子筛。
在本发明中， 所述钛硅分子筛可以商购得到， 也可以制备得到， 制备所述钛硅分子 筛的方法已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 CN 101279959A中公开的制备催 化剂的方法制得。
更优选为，所述钛硅分子筛催化剂中的钛硅分子筛为 MFI结构，钛硅分子筛晶粒为 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为至少 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， 其商品牌号为 HTS, 其相关参数及其制备方法 可以参见 CN1301599A。
一般来说， 对于 TS-1/H202体系， 溶剂主要是通过电子效应、 空间位阻效应、 溶剂 极性、物理扩散和分配、溶剂氧化副反应、催化剂失活和溶解度等多种因素影响反应的。 目前已有很多研究者研究了丙烯环氧化和环己酮氨肟化反应中的溶剂效应。部分研究者 指出甲醇和其他质子型溶剂是丙烯环氧化和其它低碳烯烃氧化的有效溶剂。而本发明则 意外地发现， 卤代烃和腈类溶剂可以大幅提高环己烷向环己醇的转化。 优选情况下， 所 述有机溶剂为沸点为 50-140°C， 优选为 60-13CTC的卤代烃和 /或腈溶剂。
本发明的发明人在研究过程中还意外的发现， 将所述腈和卤代烃混用为有机溶剂 时， 能够使得环己烷的转化率及环己醇收率获得很大的提高， 即特别优选情况下， 所述 有机溶剂为腈和卤代烃的混合物， 优选为腈溶剂和卤代烃溶剂的质量比为 0.1-10:1。 尽 管采用两种溶剂时， 环己烷的转化率、 目标产物环己醇的收率有进一步的提高， 然而两 种溶剂的反应体系， 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。
采用腈和 /或卤代烃作为有机溶剂时均可实现本发明的前述有益效果，而本发明的发 明人进一步研究发现， 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、 丙腈和戊腈中的一种或多种， 优选为乙腈和 /或丙腈； 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的 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， 效果能够更进一步。
本发明对所述氧化反应条件无特殊要求， 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。
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。
本发明中，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。 本发明中， 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。
根据本发明，本发明对所述环己烷、过氧化氢、水与有机溶剂的质量比无特殊要求， 可以参照常规的钛硅分子筛催化氧化环己烷体系内的各物质的配比进行选择， 同时可以 根据所需获得的目标产物以及要实现的目标进行相应的调变， 优选情况下， 反应过程中 (即为接触过程中）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。
根据本发明， 在实际的反应过程中， 可以依据具体情况， 为了防止精馏塔内含有钛 硅分子筛的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， 一般为 5-20cm， 优选为 8-15cm。
本发明中， 所述钛硅分子筛催化剂的制备方法可以采用本领域公知的技术进行， 可 以按照常规的成型催化剂的方法进行制备， 主要包括打浆、 造粒等步骤， 本发明对此均 无特殊要求， 在此不再赘述。 本发明对所述含有钛硅分子筛的催化剂中的载体无特殊要求，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。 更 优选地， 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。
根据本发明的方法， 为了有效利用反应原料， 优选情况下， 本发明的方法还包括： 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后所得的有机 溶剂和未反应的环己烷以及过氧化氢水溶液返回从所述进料口送入精馏塔中进行接触。
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。
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。
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。 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。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。
下面的实施例将对本发明予以进一步的说明， 但并不因此而限制本发明。
除非特别说明， 对比例和实施例中所用到的试剂均为市售的化学纯试剂。
实施例中含有空心钛硅分子筛 （HTS ) 的催化剂中， 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%。
对比例中含有钛硅分子筛 （TS-1 ) 的催化剂中， 以催化剂总重量为基准， 常规钛硅 分子筛 （TS-1 ) 的含量为 50%， 二氧化硅的含量为 50%。
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％。
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行中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％。
实施例和对比例中采用的双氧水均为市售的 27.5重量％的双氧水。
实施例中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。
实施例中含有钛硅分子筛 （TS-1或 HTS ) 的催化剂均为 40目。
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。
本发明中， 环己烷的转化率计算公式如下:
m环己烷 _m环己烷
X环己烷 χ100%
°环己烷
组分选择性的计算公式如下:
η环己醇 + w环己酮
S酮醇总 =~5 χ100%
n 环己烧 — n环己烷 己醇 = 0 ^ X匪
n 环己烷 — n环己烷
组分收率的计算公式如下:
y环己醇 =s环己醇 x ^环己垸
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）；
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
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的比例从精馏塔的进料口进料，且相对于每千克空心钛硅 分子筛（HTS)催化剂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， 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。 实施例 2
按照反应过程中环己烷与双氧水 （浓度为 27.5重量％) 及溶剂 1,3-二氯丙烷 （沸点 125 °C ) 的质量比为 1:1.72:15的比例从精馏塔的进料口进料， 且相对于每千克钛硅分子 筛 （HTS) 催化剂每小时双氧水的进料量为 0.5千克， 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 140°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。 实施例 3
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 （沸点 97.ΓΟ 的质量比为 1:1.72:10的比例从精馏塔的进料口进料，且相对于每千克钛硅分子筛 (HTS) 催化剂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 60 重量％的钛硅分子筛 (HTS)催化剂， 40重量％的 Θ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。 实施例 4
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 （沸点 81.ΓΟ 的质量比为 1:2.26:10的比例从精馏塔的进料口进料，且相对于每千克钛硅分子筛 (HTS) 催化剂每小时双氧水的进料量为 0.2千克， 其中环己烷及溶剂乙腈从第二进料口进料， 双氧水从第一进料口进料，其中塔底温度为 88°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。 实施例 5
与实施例 1的方法相同， 不同的是， 溶剂为三氯甲烷。 实施例 6
与实施例 1的方法相同， 不同的是， 溶剂为 1,2,3-三氯丙烷。 实施例 7
与实施例 2的方法相同， 不同的是， 溶剂 1,3-二氯丙烷由 1,2-二氯丙烷和丙腈的混合 溶剂代替，且二者的质量比为 1:1，环己烷的转化率、酮醇总选择性及环己醇收率见表 1。 实施例 8
与实施例 3的方法相同，不同的是溶剂丙腈由 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， 环己烷的转化率、酮醇总选择性及环己醇收率见 表 1。 实施例 9
与实施例 4的方法相同， 不同的是溶剂乙腈由乙腈和 1,3-二氯丙烷代替， 且乙腈与 1,3-二氯丙烷的质量比为 1:9， 环己烷的转化率、 酮醇总选择性及环己醇收率见表 1。 实施例 10
与实施例 1的方法相同， 不同的是溶剂 1,2-二氯丙烷由 1-氯丙烷代替， 环己烷的转 化率、 酮醇总选择性及环己醇收率见表 1。 实施例 11
与实施例 1的方法相同，不同的是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、 酮醇总选择性及环己醇收率见表 1。 对比例 1
与实施例 3的方法相同， 不同的是溶剂为丙酮， 环己烷的转化率、 酮醇总选择性及环己 醇收率见表 1。 对比例 2
与实施例 3的方法相同， 不同的是溶剂为乙酸， 环己烷的转化率、 酮醇总选择性及 环己醇收率见表 1。 表 1
Figure imgf000013_0001
由表 1可以看出， 采用本发明的方法， 环己烷的转化率及环己醇的收率均较高， 并且本 发明因为在精馏塔中进行反应， 有效的利用了氧化体系中产生的热量， 节约了能耗。
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。
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。
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。

Claims

权利要求
1、 一种环己烷氧化制环己醇的方法， 该方法包括在氧化反应条件下， 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含有钛硅分子筛的 催化剂， 所述有机溶剂为沸点 40°C-250°C的腈和 /或卤代烃。
2、 根据权利要求 1所述的方法， 其中， 氧化产物的 95-100重量％从精馏塔的塔底 得到。
3、 根据权利要求 1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%。
4、 根据权利要求 1-3中任意一项所述的方法， 其中， 所述填料中含有 20-100重量 %, 优选含有 30-70重量％的所述含有钛硅分子筛的催化剂。
5、 根据权利要求 1-3中任意一项所述的方法， 其中， 所述含有钛硅分子筛的催化 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％。
6、 根据权利要求 5所述的方法， 其中， 所述钛硅分子筛为 MFI结构， 钛硅分子筛 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为至少 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。
7、根据权利要求 1-3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 60-13CTC ; 更优选为腈和卤代烃， 腈和卤代烃的质量比为 0.1-10:1。
8、 根据权利要求 7所述的方法， 其中， 所述腈为乙腈、 丙腈和戊腈中的一种或多 种， 优选为乙腈和 /或丙腈； 所述卤代烃为氯代烃和 /或氟氯二代烃， 优选为氯代烃， 更 优选为二氯代烃和 /或三氯代烃； 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。
9、 根据权利要求 8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。
10、 根据权利要求 1-3中任意一项所述的方法， 其中， 接触过程中环己烷、 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。
11、 根据权利要求 1-3中任意一项所述的方法， 其中， 该方法还包括： 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后所得的有机溶剂和未 反应的环己烷以及过氧化氢水溶液返回从所述进料口送入精馏塔中进行接触。
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CN111662171B (zh) * 2019-03-06 2024-03-12 中国石油化工股份有限公司 一种脱除环己醇中环己酮和中间组分的方法
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