CN1847206A - A kind of synthetic method of cyclohexanone and cyclohexanol - Google Patents

Abstract

The present invention relates to synthesis process of cyclohexanone and cycloexanol, especially through hydrogenating phenol. Phenol material, C1-C2 fatty alcohol and water in the weight proportion of 1 to 2.5-40 to 10-160 are reacted in one step at 100-300 deg.c temperature and 1-10 MPa pressure and in the action of Renny Ni catalyst or active carbon supported palladium catalyst to synthesize cyclohexanone and cycloexanol. The present invention features no need of outer hydrogen supply for hydrogenating phenol and the use of relatively cheap Renny Ni catalyst, and has the advantages of high safety, simplified technological process, low production cost, high phenol converting rate, high total cyclohexanone and cycloexanol selectivity near 100 %, no side product and easy product separation.

Description

A kind of synthetic method of cyclohexanone and cyclohexanol

(1) Technical field

The invention relates to a synthesis method of cyclohexanone and cyclohexanol, in particular to a method for synthesizing cyclohexanone and cyclohexanol by hydrogenation of phenol.

(2) Background technology

Cyclohexanone and cyclohexanol (KA oil) are important organic chemical raw materials, the main raw materials of monomer caprolactam and adipic acid of synthetic fiber nylon 6 and nylon 66, and also important intermediates of fine chemicals such as medicine, paint, dyes, etc. It is also a raw material for the preparation of spices, rubber anti-aging agents, fruit anti-fungal agent phenylphenol, etc. It can also be used as an auxiliary agent for fine chemicals, and it is also very useful in printing and recycling of plastics. The existing KA oil industrial production methods include: benzene hydrogenation-cyclohexane air oxidation method, phenol hydrogenation method, benzene partial hydrogenation-cyclohexene hydration method.

The benzene hydrogenation-cyclohexane oxidation method uses benzene as the starting material. The benzene is first hydrogenated to produce cyclohexane, and then the cyclohexane is oxidized to obtain cyclohexanone and cyclohexanol (KA oil). This method is an industrial The most widely used method. The oxidation of cyclohexane to prepare cyclohexanone and cyclohexanol (KA oil) includes catalytic oxidation and non-catalytic oxidation. The catalytic oxidation method usually uses cobalt salt as a catalyst, and carries out liquid phase reaction at 125-165°C and 0.8-1.5MPa to oxidize cyclohexane into cyclohexanone and cyclohexanol (KA oil). A variety of oxidation by-products are easily generated during the catalytic oxidation of cyclohexane, so a method with low conversion rate (generally <10%) and high selectivity (about 80%) is adopted. Another important issue of the cyclohexane air oxidation method is its safety. The contact of cyclohexane with air may cause an explosion. In addition, a large amount of by-product organic acid waste liquid needs to be treated, and a large amount of unreacted cyclohexane needs to be recovered and recycled due to the low conversion rate process of cyclohexane, and the carboxylic acid generated during the reaction is easy to react with the catalyst to form carboxylic acid. Cobalt acid salt remains on equipment and pipelines, and slagging blocks pipelines and valves, shortening the start-up period of the device. The cyclohexane air oxidation method using boric acid or metaboric acid as a catalyst can improve the selectivity (about 90%) of cyclohexane conversion rate and cyclohexanone and cyclohexanol, but the reaction product of boric acid oxidation is very complicated, and the The organic phase must also be further processed to remove impurities, and the process is complicated. The non-catalytic oxidation method was first developed by the Rhone-Ponlene company in France. It is characterized in that the reaction is divided into two steps. The first step is to directly oxidize cyclohexane into cyclohexyl hydroperoxide by air under the condition of 160-170°C. The second step is to decompose cyclohexyl hydroperoxide into cyclohexanone and cyclohexanol under alkaline conditions and catalyst action. The advantage of this process is that the reaction is carried out step by step, no catalyst is used in the oxidation stage, the problem of slagging in the oxidation reactor is avoided, the device can run continuously under the conditions allowed by the equipment, and the yield of cyclohexyl hydroperoxide in the oxidation process can reach above 95. Its disadvantage is that the selectivity of cyclohexanone and cyclohexanol is less than 90% in the decomposition process of cyclohexyl hydroperoxide, and a large amount of alkali is needed. Because the single-pass conversion rate of cyclohexane in this process is low, the process flow is long and the energy consumption is high. high. Under the catalysis of iron porphyrin or cobalt porphyrin, under appropriate temperature and pressure, the conversion rate of cyclohexane can reach more than 7%, and the selectivity of cyclohexanol and cyclohexanone can reach more than 87%.

The partial hydrogenation of benzene-cyclohexene hydration process for producing cyclohexanol was first successfully developed by Asahi Kasei in the 1980s. The process uses benzene as the starting material, under the conditions of 100-180°C, 3-10MPa, and ruthenium catalyst, benzene undergoes incomplete hydrogenation reaction to prepare cyclohexene, the conversion rate of benzene is 50-60%, and cyclohexene is selected The property is 80%, and 20% of the by-product is cyclohexane. Under the action of the catalyst, the cyclohexene is further hydrated to generate cyclohexanol, the single-pass conversion rate of the cyclohexene is 10-15%, and the selectivity of the cyclohexanol can reach 99.3%. The process has low consumption, the carbon yield is almost 100%, the hydrogen consumption is about 2/3 of the traditional method, and the waste lye produced in the cyclohexane oxidation process is effectively avoided, which reduces the pressure on environmental protection and has obvious advantages. Prospects. The disadvantage of this process is that the precious metal catalyst Ru is used in the partial hydrogenation of benzene, and the reaction is carried out in a batch reactor, which greatly reduces the production capacity. In addition, because the organic phase of the product of the reaction contains cyclohexene, cyclohexane, unreacted benzene and a small amount of water, the difference between the boiling points of these components is very small (80.1°C for benzene, 81°C for cyclohexane, and 83.19°C for cyclohexene ), which are difficult to separate by ordinary distillation methods. Although extraction and distillation with polar solvents have a better separation effect, problems such as the corrosion of the extraction agent to the device must be considered. The hydration reaction includes homogeneous catalytic reaction and heterogeneous catalytic reaction. The homogeneous catalytic reaction is carried out under the action of strong inorganic acid and its salt, the corrosion problem is serious, and the separation of products and the recovery of catalyst are difficult. The heterogeneous catalytic reaction adopts a high silica zeolite catalyst, and under the conditions of a reaction temperature of 100° C. and a reaction time of 120 minutes, the conversion rate of cyclohexene is 18%, and the selectivity of cyclohexanol is 99%.

The Dutch National Mining Company (DSM) first realized the industrialization of one-step hydrogenation of phenol to produce cyclohexanone and cyclohexanol. There are two methods of hydrogenation of phenol to produce cyclohexanone and cyclohexanol in one step: gas phase and liquid phase. The main product of the phenol liquid-phase catalytic hydrogenation process developed and put into use by Allied Chem. (United Chemical) Company of the United States is cyclohexanone. The conversion rate of phenol is 95%, the yield of cyclohexanone is 97%, and the dehydrogenation process of cyclohexanol can be omitted. Liquid-phase hydrogenation is to pass hydrogen through molten phenol suspended with platinum-group metal catalysts. The process includes filtering and removing the catalyst from the reaction product. Not only is the operation troublesome, the device is complicated, and the loss of expensive platinum-group metals is difficult to avoid. The gas-phase hydrogenation method can overcome the above-mentioned shortcomings. This method usually uses 3 to 5 reactors in series, with methanol as the solvent, at a temperature of 140-170 °C and a pressure of 0.1 MPa. The yield of cyclohexanone and cyclohexanol can be It reaches 90-95%, the equipment can be made of carbon steel, and no waste water and waste gas are produced. The quality of cyclohexanone and cyclohexanol produced by phenol hydrogenation is better (the total selectivity of ketone alcohol is about 90%, and the main by-products include: benzene, cyclohexane, cyclohexene, anisole, o-cresol, etc. ), this process is safer than cyclohexane oxidation. But the existing methods all use noble metal catalysts (the main catalysts of phenol hydrogenation reaction are Pd _, Y, Ru, etc.; the carrier mainly contains Al ₂ O ₃ , SiO ₂ , activated carbon, MgO _, etc.; TiO ₂ as a carrier), the production cost of cyclohexanone and cyclohexanol is higher, and the surface of the catalyst is also prone to carbon deposition, resulting in a decrease in catalyst activity and shortened life, so the application is limited. The Supercritical Fluid Research Center of Japan Advanced Institute of Industrial Technology has successfully developed the use of supercritical carbon dioxide to extract solvents, and 100% hydrogenation of phenol to cyclohexanone and cyclohexanol (KA oil) under the action of a supported rhodium catalyst at a temperature of 55°C . And with the change of carbon dioxide and hydrogen pressure, the composition ratio of cyclohexanone and cyclohexanol can be freely controlled. This synthesis method does not use organic solvents, and the reaction conditions are mild, so the catalyst is not easy to age, and carbon dioxide is easy to recycle, which greatly reduces environmental protection costs. But this method uses a more expensive supported rhodium catalyst.

(3) Contents of the invention

The purpose of the present invention is to provide a kind of method that adopts Raney nickel or activated carbon supported palladium as catalyst to synthesize cyclohexanone and cyclohexanol with high selectivity by phenol one-step method, and catalyst cost is low, is a green synthetic route.

The technical scheme that the present invention adopts is as follows:

A synthesis method of cyclohexanone and cyclohexanol, using phenol as raw material, in the aqueous solution of C1～C2 aliphatic alcohol, under the action of Raney nickel or activated carbon supported palladium catalyst, at the temperature of 100～300 ℃, 1.0 Under the pressure of ~10.0MPa, cyclohexanone and cyclohexanol are synthesized by one-step reaction, and the substance ratio of phenol:fatty alcohol:water is 1:2.5~40:10~160.

The one-step reaction includes a hydrogen production reaction of aliphatic alcohol and a hydrogenation reduction reaction of phenol in situ occurring simultaneously in a reactor. The hydrogen production reaction of fatty alcohol is a hydrogen production reaction by decomposition of fatty alcohol or a hydrogen production reaction by aqueous phase reformation of fatty alcohol and water.

In this reaction, a catalytic aqueous phase reforming reaction occurs between fatty alcohol and water, and the hydrogen generated in situ reduces phenol to cyclohexanone and cyclohexanol, no external supply of hydrogen is needed; the catalyst is both fatty alcohol and water to generate water The catalyst for the phase reforming reaction is also the catalyst for the hydrogenation of phenol to synthesize cyclohexanone and cyclohexanol, and the aqueous solution of fatty alcohol is also used as a solvent for the reaction.

Further, in the synthesis method of cyclohexanone and cyclohexanol, the reaction is carried out in a fixed-bed reactor, the amount of the catalyst is 1 to 3 g, and the hourly space velocity of the mixed liquid of fatty alcohol, water and phenol is 0.5 ~6.0 hours ⁻¹ , the hourly space velocity of the liquid is the ratio of the volume feed rate of the mixed liquid of all fed reaction substances to the bulk volume of the catalyst in the reactor.

Still further, the reaction temperature is 160-240° C., the reaction is carried out at a pressure of 1.0-4.2 MPa, and the fatty alcohol is methanol.

In the method, it is recommended to use a Raney nickel catalyst as the catalyst, which is commercially available or self-made. The Raney nickel catalyst used in the embodiment of the present invention is prepared according to the following steps: slowly add a strong alkali solution, such as NaOH solution, to the nickel aluminum alloy powder , Of course, other strong alkali solutions, such as KOH, can also be used. The temperature of the strong alkali solution is preferably 20-50°C, and the concentration is 15-25%. After the feeding is completed, the temperature is raised to 75-85°C and kept for 2-3 hours to extract the aluminum in the nickel-aluminum alloy and then discharge it. Stand still, remove the solution, and wash with water until the pH value is 8-9 to obtain the Raney nickel catalyst. Usually, it is preferred to wash with water at 70-80°C first, and then wash with water at room temperature. The prepared catalyst should be preserved with absolute ethanol. The catalyst prepared in the scope of the above-mentioned parameter condition variation has little influence on the present invention.

The activated carbon-supported palladium catalyst of the present invention has a palladium loading of 2 wt%, which can be commercially available or self-made according to methods well known to those of ordinary skill in the art. The activated carbon-supported palladium catalyst in the embodiment of the present invention is prepared by the following method: take the coconut shell activated carbon used to prepare the catalyst, prepare the above-mentioned activated carbon into a slurry with a temperature of 60-90 ° C, and slowly add it dropwise according to the palladium loading of 2 wt%. H ₂ PdCl ₄ solution, fully stirred evenly, then adjust the pH value of the solution to 7.1-9 with 10% NaOH solution, and lower the temperature to room temperature, filter, wash the filter cake with deionized water until neutral, and then put the filter cake in Prepare a slurry at 30°C, add 85% hydrazine hydrate solution dropwise, stir, filter, wash the filter cake with deionized water until neutral, and finally dry it in the air at room temperature, and take a wet sample to obtain the activated carbon load palladium catalyst.

Raney nickel catalysts are preferred among the catalysts.

Specifically, the synthesis method of cyclohexanone and cyclohexanol is as follows: add 1.5 grams of Raney nickel catalyst into the fixed bed reactor, according to the molar ratio of phenol:methanol:water is 1:2.5～20:20 ～80 feed, react at a temperature of 200～240°C and a pressure of 2.4～4.2MPa, the hourly space velocity of the mixed liquid is 1.76～5.3 hours ^-1 , more preferably the hourly space velocity is 3～3.6 hours ^-1 , the reactor outlet The liquid product is separated, and cyclohexanone and cyclohexanol are obtained after excess methanol is removed.

In the invention, the conversion rate of phenol reaches 50-90%, and the selectivity of cyclohexanone and cyclohexanol is close to 100%.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

The hydrogenation reduction process of phenol does not require external supply of hydrogen, but utilizes the hydrogen produced by the catalytic aqueous phase reforming reaction between methanol and water to reduce phenol to cyclohexanone and cyclohexanol in situ, eliminating the existing In the method, special steps such as hydrogen preparation, storage and transportation are required to avoid safety problems in the process of using hydrogen, and meanwhile, the process is simplified and the production cost is reduced. Further the present invention preferably uses Raney nickel as catalyst, does not use noble metal catalyst, significantly reduces the cost of catalyst and consumption; The present invention's phenol conversion rate is high, and the total selectivity of cyclohexanone and cyclohexanol is close to 100%, basically no The formation of by-products is a green synthetic route; methanol and water undergo aqueous phase reforming reaction to produce hydrogen, which effectively utilizes the hydrogen in water and has a high utilization rate of hydrogen; methanol, water, phenol and cyclohexanone, cyclohexanol The difference in boiling point is relatively large (methanol 64.65°C, phenol 182°C, cyclohexanone 155.7°C, cyclohexanol 161°C), the product separation is convenient, and high-purity cyclohexanone and cyclohexanol can be obtained directly by ordinary distillation.

In summary, the present invention is a green synthesis route with simple process, safe production process, low production cost, high product selectivity, and no environmental pollution, and can be produced continuously or intermittently.

(4) Specific implementation methods:

The technical scheme of the present invention is described below with specific examples, but protection scope of the present invention is not limited thereto:

The Raney nickel catalyst in the following implementation one to thirty-six is obtained as follows: in the nickel-aluminum alloy powder that the mass ratio of nickel to aluminum is 55: 45, slowly add the strong alkali NaOH solution that mass concentration is 15～25%, gradually simultaneously Raise the temperature from room temperature to 75-85°C, and keep it for 2-3 hours to extract the aluminum in nickel-aluminum alloy until the mass content of aluminum is less than 6%. ℃ water, and then washed with normal temperature water until the pH value is 8-9 to obtain the Raney nickel catalyst.

Embodiment 1

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 2.5: 20 is ^3.53 hours in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 16.41%, the selectivity of cyclohexanol is 81.62%, and the selectivity of by-product benzene and o-cresol is 1.97% and 0%, respectively.

Example 2

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, phenol, methyl alcohol, the mixed liquid that the molar ratio of water substance is 1: 10: 80 is ^3.53 hours in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 16.36%, the selectivity of cyclohexanol is 83.33%, and the selectivity of by-products benzene and o-cresol are 0.23% and 0.07%, respectively.

Example Three

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 10: 160 is ^3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 19.67%, the selectivity of cyclohexanol is 79.95%, and the selectivity of by-products benzene and o-cresol are 0.38% and 0%, respectively.

Embodiment 4

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is ^1.76 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 22.48%, the selectivity of cyclohexanol is 76.9%, and the selectivity of by-products benzene and o-cresol are 0.23% and 0.4%, respectively.

Example 5

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 80 is ^3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 14.44%, the selectivity of cyclohexanol is 85.32%, and the selectivity of by-products benzene and o-cresol are 0.24% and 0%, respectively.

Embodiment Six

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 10: ⁴⁰ is 3.53 hours in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 26.5%, the selectivity of cyclohexanol is 72.55%, and the selectivity of by-products benzene and o-cresol are 0.22% and 0.73%, respectively.

Example 7

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 40: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 18.23%, the selectivity of cyclohexanol is 80.68%, and the selectivity of by-products benzene and o-cresol are 0.36% and 0.73%, respectively.

Embodiment Eight

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:5:20 is 1.76 hours ^-1 joins in the reactor with the liquid hourly space velocity, adjusts reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 29.52%, the selectivity of cyclohexanol is 69.83%, and the selectivity of by-products benzene and o-cresol are 0.65% and 0%, respectively.

Example 9

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 20: 40 is 3.52 hours ^-1 feed rate joins reactor with liquid hourly space velocity In the process, the reaction temperature is adjusted to be 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol was 80.6%, the selectivity of cyclohexanone was 17.18%, the selectivity of cyclohexanol was 81.8%, and the selectivity of by-products benzene and o-cresol were 0.87% and 0.15%, respectively.

Example 10

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is 3.52 hours ^-1 join in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 21.53%, the selectivity of cyclohexanol is 76.9%, and the selectivity of by-products benzene and o-cresol are 0.73% and 0.84%, respectively.

Example 11

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 20: 40 is 3.52 hours ^-1 feed rate joins reactor with liquid hourly space velocity In the process, adjust the reaction temperature to 240°C and the reaction pressure to 2.4MPa. The product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol was 80.8%, the selectivity of cyclohexanone was 18.26%, the selectivity of cyclohexanol was 79.4%, and the selectivity of by-products benzene and o-cresol were 0.64% and 1.7%, respectively.

Example 12

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1:20:80 is 1.76 hours ^-1 join in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 20.84%, the selectivity of cyclohexanol is 78.77%, and the selectivity of by-products benzene and o-cresol are 0.28% and 0.1%, respectively.

Embodiment Thirteen

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 160°C, the reaction pressure is 1.0MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 36.26%, the selectivity of cyclohexanol is 59.54%, and the selectivity of by-product benzene and o-cresol is 4.2% and 0%, respectively.

Embodiment Fourteen

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is ^3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 180°C and the reaction pressure is 1.6MPa. The liquid product at the outlet of the reactor is separated by a gas-liquid separator. The liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 25.06%, the selectivity of cyclohexanol is 72.6%, and the selectivity of by-products benzene and o-cresol are 2.34% and 0%, respectively.

Example 15

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is ^3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 33%, the selectivity of cyclohexanol is 67%, and the selectivity of by-products benzene and o-cresol is 0%.

Example 16

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 40.93%, the selectivity of cyclohexanol is 58.04%, and the selectivity of by-products benzene and o-cresol are 1.03% and 0%, respectively.

Example 17

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 240°C and the reaction pressure is 4.2MPa. The liquid product at the outlet of the reactor is separated by a gas-liquid separator. The liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 22.31%, the selectivity of cyclohexanol is 76.28%, and the selectivity of by-products benzene and o-cresol are 0.88% and 0.53%, respectively.

Embodiment 18

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 240°C and the reaction pressure is 3.0MPa. The liquid product at the outlet of the reactor is separated by a gas-liquid separator. The liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 26.24%, the selectivity of cyclohexanol is 72.34%, and the selectivity of by-products benzene and o-cresol are 0.75% and 0.67%, respectively.

Embodiment 19

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 240°C, the reaction pressure is 2.0MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 35.2%, the selectivity of cyclohexanol is 60.61%, and the selectivity of by-products benzene and o-cresol are 2.09% and 2.10%, respectively.

Example 20

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 240°C, the reaction pressure is 5.0MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 20.69%, the selectivity of cyclohexanol is 78.69%, and the selectivity of by-products benzene and o-cresol are 0% and 0.61%, respectively.

Example 21

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is 0.71 hour ^-1 to join in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 80.4%, the selectivity of cyclohexanone is 14.52%, the selectivity of cyclohexanol is 85.49%, and the selectivity of by-products benzene and o-cresol is 0%.

Example 22

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1:20:40 is ^5.29 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 56.92%, the selectivity of cyclohexanol is 38.83%, and the selectivity of by-products benzene and o-cresol are 4.28% and 0%, respectively.

Example 23

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 10: 40 is ^1.76 hours in the reactor with liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 27.59%, the selectivity of cyclohexanol is 71.68%, and the selectivity of by-products benzene and o-cresol are 0.3% and 0.26%, respectively.

Example 24

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 10: 80 is ^1.76 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 40.72%, the selectivity of cyclohexanol is 58.64%, and the selectivity of by-products benzene and o-cresol are 0.52% and 0.12%, respectively.

Example 25

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1: 2.5: ²⁰ is 1.76 hours in the reactor with liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 18.91%, the selectivity of cyclohexanol is 79.36%, and the selectivity of by-products benzene and o-cresol are 1.71% and 0%, respectively.

Example 26

Add 1.5 grams of Raney's nickel catalysts in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 10: 160 is 1.76 hours ^-1 joins in the reactor with the liquid hourly space velocity, adjusts reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 25.12%, the selectivity of cyclohexanol is 74.39%, and the selectivity of by-products benzene and o-cresol are 0.49% and 0%, respectively.

Example 27

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methyl alcohol, water substance is 1:20:80 is 1.76 hours ^-1 join in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 11.88%, the selectivity of cyclohexanone is 25.74%, the selectivity of cyclohexanol is 73.23%, and the selectivity of by-products benzene and o-cresol are 1.02% and 0%, respectively.

Example 28

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:5:10 is 3.53 hours ^-1 join in the reactor with liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 31.4%, the selectivity of cyclohexanol is 61.42%, and the selectivity of by-products benzene and o-cresol are 4.61% and 2.56%, respectively.

Example 29

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:5:10 is 1.76 hours ^-1 join in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 44.68%, the selectivity of cyclohexanol is 53.39%, and the selectivity of by-products benzene and o-cresol are 1.57% and 0.39%, respectively.

Example Thirty

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:40:40 is ^1.76 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C and the reaction pressure is 2.4MPa. The liquid product at the outlet of the reactor is separated by a gas-liquid separator. The liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 31.42%, the selectivity of cyclohexanol is 62.35%, and the selectivity of by-products benzene and o-cresol are 4.55% and 1.73%, respectively.

Example 31

Add 1.5 grams of Raney nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:5:20 is 3.53 hours ^-1 join in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 3.5MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 29.52%, the selectivity of cyclohexanol is 69.84%, and the selectivity of by-products benzene and o-cresol are 0.65% and 0%, respectively.

Example Thirty-two

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1:5:20 is 1.76 hours ^-1 joins in the reactor with the liquid hourly space velocity, adjusts reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 46.49%, the selectivity of cyclohexanol is 51.93%, and the selectivity of by-products benzene and o-cresol are 0.91% and 0.7%, respectively.

Example 33

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 160°C and the reaction pressure is 2.4MPa. The liquid product at the outlet of the reactor is separated by a gas-liquid separator. The liquid product is analyzed by AGilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 21.96%, the selectivity of cyclohexanol is 77.84%, and the selectivity of by-product benzene and o-cresol is 0.2% and 0%, respectively.

Example Thirty-Four

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 22.89%, the selectivity of cyclohexanol is 76.31%, and the selectivity of by-products benzene and o-cresol are 0.2% and 0.6%, respectively.

Example Thirty-five

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: 40 is ^3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 220°C, the reaction pressure is 2.4MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 30.66%, the selectivity of cyclohexanol is 68.14%, and the selectivity of by-products benzene and o-cresol are 0.3% and 0.9%, respectively.

Example Thirty-six

Add 1.5 grams of Raney's nickel catalyst in the fixed bed reactor, the mixed liquid that the molar ratio of phenol, methanol, water substance is 1: 20: ⁴⁰ is 3.53 hours in the reactor with the liquid hourly space velocity, adjust reaction The temperature is 200°C, the reaction pressure is 1.7MPa, the product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator, and the liquid product is analyzed by Agilent-GC-MS after removing excess methanol. The conversion rate of phenol The selectivity of cyclohexanone is 28.14%, the selectivity of cyclohexanol is 70.36%, and the selectivity of by-products benzene and o-cresol are 0.9% and 0.6%, respectively.

Example Thirty-seven

In the fixed-bed reactor, adding palladium load is 1.0 grams of 2wt% palladium-carbon catalyst, and the mixed liquid with the molar ratio of phenol, methanol and water is 1:10:40 with the liquid hourly space velocity as ^1.76 hours In the reactor, adjust the reaction temperature to 220°C and the reaction pressure to 3.5MPa. The product at the outlet of the reactor is separated from the liquid product by a gas-liquid separator. Analysis showed that the conversion rate of phenol was 43.39%, the selectivity of cyclohexanone was 43.37%, the selectivity of cyclohexanol was 54.05%, and the selectivity of by-product benzene and o-cresol were 0% and 2.57% respectively.

Claims (10)

1. the synthetic method of pimelinketone and hexalin, it is characterized in that with phenol being raw material, in the aqueous solution of C1～C2 Fatty Alcohol(C12-C14 and C12-C18), under the effect of Raney's nickel or activated carbon supported palladium catalyst, under 100～300 ℃ temperature, 1.0～10.0MPa pressure, single step reaction synthesizing cyclohexanone and hexalin, described phenol: Fatty Alcohol(C12-C14 and C12-C18): the amount of substance ratio of water is 1: 2.5～40: 10～160.

2. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, it is characterized in that described being reflected in the fixed-bed reactor carry out, described catalyst levels 1～3g, the space-time speed of described Fatty Alcohol(C12-C14 and C12-C18), water and phenol mixing liquid is 0.5～6.0 hour ^-1, the space-time speed of described liquid is the volume feeding rate of all reactive material mixed solutions that feed intake and the ratio of the stacking volume of described catalyzer in reactor.

3. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described temperature of reaction is 160～240 ℃.

4. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described being reflected under pressure 1.0～4.2MPa carry out.

5. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, it is characterized in that described catalyzer is a Raney's nickel, described catalyzer prepares as follows: slowly add strong base solution in Nickel Aluminium Alloy Powder, described strong base solution temperature is controlled at 20～50 ℃, concentration is 15～25%, be warming up to 75～85 ℃ behind reinforced the finishing, and keep extracting in 2～3 hours to go out discharging behind the aluminium in the alumel, leave standstill then, remove the solution after washing to pH value 8～9, promptly get Raney's nickel catalyst.

6. the synthetic method of pimelinketone as claimed in claim 1 and hexalin, the loading that it is characterized in that palladium in the described activated carbon supported palladium catalyst is 2wt%, described activated carbon supported palladium catalyst adopts laxative remedy to make: take by weighing the cocoanut active charcoal that is used to prepare catalyzer, above-mentioned gac is mixed with the slurries of 60～90 ℃ of temperature, is that 2wt% slowly drips H by the palladium loading ₂PdCl ₄Solution stirs, again with 10% NaOH solution regulator solution pH value to 7.1～9, and cool the temperature to room temperature, filter, filter cake to neutral, is configured to slurries with filter cake with deionized water wash again under 30 ℃, drip 85% hydrazine hydrate solution, stir, filter, filter cake is extremely neutral with deionized water wash, at last in room temperature in air through preliminarily dried, get wet sample and promptly get described activated carbon supported palladium catalyst.

7. the synthetic method of pimelinketone as claimed in claim 2 and hexalin is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is a methyl alcohol.

8. the synthetic method of pimelinketone as claimed in claim 2 and hexalin, it is characterized in that described synthetic method is: in fixed-bed reactor, add 1.5 Cray Buddhist nun nickel catalyzators, according to phenol: methyl alcohol: the amount ratio of water substance is 1: 2.5～20: 20～80 to feed intake, temperature at 200～240 ℃, 2.4 the pressure of～4.2MPa is reaction down, the space-time speed of mixing liquid is 1.76～5.3 hours-1, the product liquid of reactor outlet is separated, promptly get pimelinketone and hexalin after removing excessive methanol.

9. the synthetic method of pimelinketone as claimed in claim 1 and hexalin is characterized in that described single step reaction is included in hydrogen production reaction and the phenol add in-place hydrogen reduction reaction that Fatty Alcohol(C12-C14 and C12-C18) takes place in the reactor synchronously.

10. the synthetic method of pimelinketone as claimed in claim 9 and hexalin is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) hydrogen production reaction is the reaction of Fatty Alcohol(C12-C14 and C12-C18) decomposing hydrogen-production or Fatty Alcohol(C12-C14 and C12-C18) and water generation aqueous phase reforming hydrogen production reaction.