43 results about "Nitrocyclohexane" patented technology

The invention relates to a nitrocyclohexane hydrogenation catalyst and a preparation method thereof, and relates to a method for nitrocyclohexane hydrogenation by using the catalyst. Carbon nano tubes are used as a carrier in the catalyst and carry the following components: at least one VIII family metal and at least one alkali metal in the element periodic table. The catalyst can be used for preparing cyclohexane oxime by nitrocyclohexane hydrogenation; and according to the method, the preparation flow is short, the yield is high, comprehensive cost is low, resources are saved and no waste slag, waste gas or waste liquid is discharged; and the method is a pollution-free production process.

The invention relates to a method for synthesizing cyclohexanone-oxime and caprolactam, particularly a method for synthesizing cyclohexanone-oxime and caprolactam by performing catalytic hydrogenation on nitrocyclohexane used as a raw gas phase. The method has the advantages of high controllability, low cost, environmental protection, higher conversion ratio of raw materials and higher yield, and has industrialization application prospects. The reaction process is simple, no coproduct ammonium sulfate is generated in the reaction process, and no wastewater or waste gas is generated to pollute the environment, and thus, the method is an environment-friendly production technique.

The invention discloses a preparation method of a nitrogen-carbon doping modified nickel-based catalyst and application thereof for catalyzing nitrocyclohexane hydrogenation reaction. According to the invention, a catalyst is firstly subjected to nitrogen doping modification, and then is loaded with nickel, and the obtained catalyst is applied to the nitrocyclohexane hydrogenation reaction. An N doped carbon support is capable of improving the dispersibility of reactive metal remarkably, the particle size of metal is reduced and the specific surface of metal is increased, so that cheap metal Ni is used to replace noble metal as reactive metal, high selectivity of cyclohexanone-oxime can be ensured and the cost is remarkably reduced. The application process is environmentally friendly and simple and has mild conditions, and the yield of cyclohexanone-oxime is obviously improved by improvement of the reaction conditions and the catalyst.

The invention provides a preparation method of an Fe-doped nickel-based activated carbon catalyst and application thereof in hydrogenation reaction of nitrocyclohexane. According to the preparation method, activated carbon is acidified first, then the acidified activated carbon is used as a carrier to be loaded with nickel and iron simultaneously, and then the Fe-doped nickel-based activated carbon catalyst is applied to the hydrogenation reaction of nitrocyclohexane. The preparation method uses Fe for carrying out doping modification, has low cost and low pollution, cannot corrode equipment, and adopts the non-noble metal nickel as the active component and activated carbon as the carrier, thus obviously reducing the cost; and the prepared catalyst is used in the hydrogenation reaction of the nitrocyclohexane and can improve the conversion rate of nitrocyclohexane and the selectivity of cyclohexanone-oxime in relatively mild reaction conditions, thereby realizing production of high-quality cyclohexanone-oxime with a low-cost catalyst.

The invention discloses a method for preparing cyclohexanone oxime by catalysis of transferring and hydrogenating of nitrocyclohexane. The method comprises the following steps: adding catalyst cupper-nickel-loaded activated carbon, nitrocyclohexane and an amine borane compound in a reactor according to the mass ratio of 0.1-0.4 to 1 to 2-20.8; reacting for 6 to 12 hours at 50 to 80 DEG C under stirring conditions to obtain a reaction liquid; filtering and separating the obtained reaction liquid to obtain the cyclohexanone oxime. According to the method, hydrogenation reaction of the nitrocyclohexane is catalyzed by taking a hydrogen storage material as a hydrogen donor; a preparation process can be completed through a common glass instrument without the equipment, such as a high-pressure reaction kettle, so that the cost of a reaction device is reduced, the operation of the reaction is simplified, and the safety of a reaction process is improved.

The invention relates to a catalyst used in synthesis of nitrocyclohexane by nitrifying a cyclohexane liquid phase, a preparation method and application thereof. In the catalyst, a zirconium-aluminum composite oxide is taken as a carrier, and sulfuric acid is loaded on the carrier by taking an immersion method to form solid acid. The catalyst is used for catalyzing a liquid-phase nitration reaction between cyclohexane serving as a raw material and nitric acid under a certain condition to synthesize nitrocyclohexane. By adopting the method disclosed by the invention, the process can be simplified greatly, the cost is lowered, the catalyst is very easy to separate after the reaction, the problems of a large quantity of byproducts caused by mixed acid nitration in the conventional nitration,difficulty in treating waste acid and environmental pollution are solved, and the resource utilization ratio can be effectively increased.

The invention discloses a process for synthesizing nitrocyclohexane by liquid phase nitration. The process comprises the following steps: feeding cyclohexane, nitric acid, distilled water and an acidic ionic liquid catalyst into a high-pressure reaction kettle, wherein the mole ratio of the cyclohexane to the nitric acid to the distilled water to the acidic ionic liquid catalyst is 1:1:12:(0.025-0.1), the reaction temperature is 115-135 DEG C, the reaction time is 6-24 hours, and the nitrocyclohexane is finally prepared. The mass percentage of the nitric acid is 65-68%. The acidic ionic liquid catalyst is a quaternary ammonium salt acidic ionic liquid catalyst which is prepared from a tertiary amine compound and acid in a one-step neutralization synthesis mode, or is a functionalized quaternary ammonium salt acidic ionic liquid catalyst which is synthesized from the tertiary amine compound and the acid in alkylation and neutralization two-step synthesis modes. The acidic ionic liquid catalyst for synthesizing the nitrocyclohexane from cyclohexane by liquid phase nitration has high catalysis activity, and meanwhile the function of a phase transfer catalyst is achieved, the reaction temperature is low, and no organic solvents are added.

The invention relates to a method for the high-selectivity co-production of nitrocyclohexane and adipic acid, which adopts nitrogen oxide NOx as the nitrating and oxidizing agent, carrys out continuous gas-phase catalysis or non-catalytic nitration and oxidation reaction on cyclohexane. By effectively setting the conditions of the concentration ratio, the reaction temperature and the reaction time of the reactants and optimizing the reaction pressure as well as catalysts and assistants, the invention realizes the simultaneous high-selectivity co-production of the nitrocyclohexane and the adipic acid of different ratios, and the reduction product NO generated by the nitration and oxidation reaction can be recycled for cyclic utilization. The method of the invention has high resource efficiency, less waste generation, simple process flow and device and low production cost, and is an environment-friendly synthetic method.

The present invention relates to a method for high selectivity co-production of adipic acid and nitrocyclohexane. According to the present invention, a nitrogen oxide NOx is adopted as an oxidant and a nitrating agent to carry out one step high selectivity conversion of cyclohexane into adipic acid and nitrocyclohexane, and adjustments of a reactant ratio, a reaction temperature, a reaction pressure, a type and an amount of a catalyst or an induction agent, and other conversion conditions are adopted to achieve regulation of a production ratio of the adipic acid and the nitrocyclohexane; and NO produced from the reaction can be recycled and then reacts with oxygen to be converted into NOx so as to be recycled.

The invention discloses a preparation method of a supported cigarette butt porous carbon material catalyst and application of the supported cigarette butt porous carbon material catalyst in nitrocyclohexane hydrogenation reaction. The method comprises the following steps: carrying out water carbonization treatment on polluted waste cigarette butts, activating with sylvite to prepare a porous carbon material, carrying out active metal loading by using the porous carbon material as a carrier, and applying the obtained supported cigarette butt porous carbon material catalyst to nitrocyclohexane hydrogenation reaction. The porous carbon material is prepared by taking the harmful waste cigarette butts as a raw material and is used as the catalyst carrier, so that reasonable conversion and application of low-economic-value polluted wastes are realized, and metal with hydrogenation catalytic activity is used as an active component to prepare the supported cigarette butt porous carbon materialcatalyst. The obtained catalyst is used in nitrocyclohexane hydrogenation reaction, the conversion rate of nitrocyclohexane and the selectivity of cyclohexanone-oxime can be improved under the relatively mild reaction condition, and therefore high-quality cyclohexanone-oxime can be produced through the waste resource recycling type catalyst.

The invention discloses an application of a metal-free hydrogenation catalyst in catalytic nitrocyclohexane hydrogenation reaction, wherein the metal-free hydrogenation catalyst adopted by the application is a nitrogen doped carbon nanotube prepared by taking melamine as a nitrogen source through an impregnation method or a nitrogen doped carbon nanotube prepared by taking ammonia gas a nitrogen source through an in-situ synthesis process; and the obtained catalyst is applied to nitrocyclohexane hydrogenation reaction. According to the application, the nitrogen doped carbon nanotube is used as a nitrocyclohexane hydrogenation catalyst, and any metal active ingredient is not loaded, so that the purpose of hydrogenation catalysis is achieved by only utilizing a nitrogen doped modifying method. The whole reaction process avoids use of noble metals, so that the cost is reduced, the environment is not polluted, and the catalyst can be repeatedly used. The catalyst disclosed by the invention is simple in preparation method, is low in production cost, is good in hydrogenation effect, and is easy to control in reaction; and the catalyst is environment-friendly, does not cause secondary pollution to the environment, and can be widely applied to various hydrogenation reactions.

The invention discloses a preparation method of an N-doped Cu-modified nickel-based activated carbon catalyst and application of the N-doped Cu-modified nickel-based activated carbon catalyst in nitrocyclohexane hydrogenation reaction. The preparation method comprises the following steps: performing acid modification on activated carbon, taking the modified activated carbon as a carrier, performing N doping and nickel-copper loading at the same time, and applying the obtained N-doped Cu-modified nickel-based activated carbon catalyst to nitrocyclohexane hydrogenation reaction. Cu is used for modification, nickel acetate is used as a nickel source, the cost is low, pollution is small, equipment corrosion is avoided, non-noble metal nickel is used as an active component, melamine and urea are used as nitrogen sources, and activated carbon is used as a carrier, so that the cost can be obviously reduced. The obtained catalyst is used in nitrocyclohexane hydrogenation reaction, the conversion rate of nitrocyclohexane and the selectivity of cyclohexanone-oxime can be improved under relatively mild reaction conditions, and therefore the purpose that high-quality cyclohexanone-oxime is produced through the low-cost catalyst is achieved.

The invention discloses a preparation method and an application of a Pd-Ni bimetallic catalyst supported by N-doped acid-activated sepiolite. The preparation method comprises the following steps: sepiolite is subjected to acid activation or acid modification firstly, then subjected to N-doping treatment and subjected to impregnation to support Ni and Pd. Non-noble metal Ni is taken as a dominant active component and is modified with a small amount of Pd for preparation of the Pd-Ni bimetallic catalyst, so that noble metal is prevented from being used as the only active component, the cost of the catalyst is reduced greatly, a technology for preparing cyclohexanone-oxime from nitrocyclohexane through liquid-phase hydrogenation is enabled to be more environment-friendly by means of the catalyst, the technology is simple, conditions are mild, and quite high nitrocyclohexane conversion rate and cyclohexanone-oxime with high selectivity can be obtained by optimizing the reaction conditions and preparing the catalyst.

The invention provides a method for synthesizing caprolactam in one step by liquid phase hydrogenation of nitrocyclohexane, wherein caprolactam is synthesized in one step setting out from nitrocyclohexane and under the action of hydrogen pressure of 0.1-2.0MPa and a composite catalytic system; and the composite catalytic system is the supported catalyst and the mixture composed of triazine compounds and formamide compounds. The method of the invention has temperate reaction conditions and simplifies the technology substantially.

The invention relates to a method for the high-selectivity co-production of nitrocyclohexane and adipic acid, which adopts nitrogen oxide NOx as the nitrating and oxidizing agent, carrys out continuous gas-phase catalysis or non-catalytic nitration and oxidation reaction on cyclohexane. By effectively setting the conditions of the concentration ratio, the reaction temperature and the reaction time of the reactants and optimizing the reaction pressure as well as catalysts and assistants, the invention realizes the simultaneous high-selectivity co-production of the nitrocyclohexane and the adipic acid of different ratios, and the reduction product NO generated by the nitration and oxidation reaction can be recycled for cyclic utilization. The method of the invention has high resource efficiency, less waste generation, simple process flow and device and low production cost, and is an environment-friendly synthetic method.

Synthesis of nitrocyclohexane is carried out by nitrofication reacting cyclohexane with NOX under protection of nitrogen and obtain final product. X is 1.5-2.5. It's simple, cheap and has friendly environment.

The invention belongs to the technical field of organic synthesis, aims at solving the problems that an existing synthesis method of oseltamivir is multiple in reaction steps, low in overall yield and high in cost. The invention provides a synthesis method of oseltamivir. The method comprises the following steps of (1) adopting 3-pentyloxy acetaldehyde and nitroolefin as substrates and reacting under catalysis of a catalyst in the presence of lewis acid to obtain an aldehyde intermediate A; (2) reacting the obtained aldehyde intermediate A with 2-diethoxy oxygen-phosphorus acrylic acid ethyl ester under the action of an alkali catalyst to obtain a cyclohexenyl intermediate B; (3) reacting the cyclohexenyl intermediate B with thiocresol to obtain a cyclohexane intermediate C; (4) preparing a compound D from the cyclohexane intermediate C under the action of zinc powder and trimethylchlorosilane; and (5) obtaining a final product oseltamivir from the intermediate D obtained in the step (4) under the action of an ammonia gas and potassium carbonate. The method has the characteristics that the route is short and the catalyst is easy to recover.

The invention relates to a temperature-sensitive polyvinylidene fluoride / precious metal nanoparticle hybrid membrane and a preparation method thereof. With combination of hydrophilicity and temperature sensitive of a polymer gel, high catalytic activity of precious metal nanoparticles, and corrosion resistance and good film-forming property of polyvinylidene fluoride, the hybrid membrane with good anti-pollution ability, temperature-sensitive catalytic activity and separation property is prepared. The temperature-sensitive polyvinylidene fluoride / precious metal nanoparticle hybrid membrane can be used for catalyzing a reduction reaction of nitro in amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyano nitrobenzene, chloronitrobenzene, vinyl nitrobenzene, nitrocyclohexane and other molecules to transform nitro into amino.

The invention relates to the field of preparation of fluorescein probes with specific selectivity, and particularly discloses a preparation method of a fluorescein probe with specific selectivity. The method comprises the following steps: (1) mixing 4-nitrophthalic anhydride, resorcinol, nitrocyclohexane and anhydrous cobalt chloride, conducting heating and melting, adding zinc chloride, conducting reacting, then adding hydrochloric acid for reflux, and conducting filtering, washing and drying; (2) mixing a reducing solution containing Na2S and Na2SO3 with a product obtained in the step (1), conducting reacting, then dropwise adding glacial acetic acid until complete precipitation, and conducting filtering, washing and drying; and (3) mixing a mixed solvent containing methanol and triethylamine with a product obtained in the step (2), dropwise adding CS2, conducting reacting, dropwise adding a copper chloride aqueous solution, continuing reacting after dropwise adding, adjusting the pH value of the system to 1-2 by using hydrochloric acid, and carrying out reduced pressure distillation, washing, drying and column chromatography purification. According to the method, the conversion rate and the yield of the 5-fluorescein isothiocyanate are greatly improved.

The invention relates to a polyvinylidene fluoride / gold nanoparticle hybrid hollow fiber membrane and a preparation method thereof. With combination of hydrophilicity of a polymer gel, high catalytic activity of gold nanoparticles, and corrosion resistance and good film-forming property of polyvinylidene fluoride, the hybrid hollow fiber membrane with good anti-pollution ability, high catalytic activity and good separation property is prepared. The hollow fiber membrane can be used for catalyzing a reduction reaction of nitro in amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyano nitrobenzene, chloronitrobenzene, vinyl nitrobenzene, nitrocyclohexane and other molecules to transform nitro into amino. At the same time, the hollow fiber membrane also can be used for separation of different-size substances in a liquid mixture.

The invention discloses a copper-based catalyst for catalyzing partial hydrogenation of nitrocyclohexane to prepare cyclohexanone-oxime as well as a preparation method and application of the copper-based catalyst. The catalyst comprises a main active component and an auxiliary active component, the main active component is copper, the auxiliary active component is selected from one or more of titanium, vanadium, chromium, molybdenum, zirconium, cadmium, indium, tin, antimony, niobium, silver, iron, zinc, magnesium, aluminum, bismuth, manganese, lanthanum, gold or lead, the total molar ratio of the copper to the auxiliary active component is (100-1): 1, and the catalyst is prepared by adopting a coprecipitation method or a supported impregnation-coprecipitation method. And the process is simple and green. Under mild conditions, the catalyst can realize the conversion rate gt of nitrocyclohexane; the selectivity of cyclohexanone-oxime is greater than or equal to 99%, and the method is obviously superior to the existing non-noble metal system, and is low in cost, good in stability and suitable for industrial production of green synthesis of caprolactam.

The invention relates to a method for co-producing adipic acid and cyclohexanone-oxime from cyclohexane. The method comprises the following steps: (1) carrying out oxidation nitration on cyclohexane and NOx to generate adipic acid, nitrocyclohexane, nitrogen oxides and a byproduct-A, and separating to obtain crude adipic acid and nitrocyclohexane; (2) carrying out catalytic hydrogenation on the obtained nitrocyclohexane and hydrogen to generate cyclohexanone-oxime and a small amount of cyclohexylamine, separating to obtain crude cyclohexanone-oxime and cyclohexylamine, and enabling cyclohexylamine to be directly used as a byproduct or to be continuously converted into cyclohexanone-oxime. and (3) partially oxidizing the cyclohexylamine obtained in the previous step with molecular oxygen to obtain an oxidation reaction product consisting of cyclohexanone-oxime, a byproduct B and possibly unconverted cyclohexylamine, and then separating the oxidation reaction product without separation, or firstly separating part or all of water in the oxidation reaction product, carrying out hydrogenation amination reaction under the action of a catalyst, or carrying out hydrogenation and amination reaction, or only carrying out hydrogenation reaction, and then separating to obtain the cyclohexanone-oxime. The method can realize high-selectivity co-production of adipic acid and cyclohexanone-oxime, and is short in process flow, low in equipment investment and low in material consumption, energy consumption and cost.

The invention discloses a process for synthesizing nitrocyclohexane by liquid phase nitration. The process comprises the following steps: feeding cyclohexane, nitric acid, distilled water and an acidic ionic liquid catalyst into a high-pressure reaction kettle, wherein the mole ratio of the cyclohexane to the nitric acid to the distilled water to the acidic ionic liquid catalyst is 1:1:12:(0.025-0.1), the reaction temperature is 115-135 DEG C, the reaction time is 6-24 hours, and the nitrocyclohexane is finally prepared. The mass percentage of the nitric acid is 65-68%. The acidic ionic liquid catalyst is a quaternary ammonium salt acidic ionic liquid catalyst which is prepared from a tertiary amine compound and acid in a one-step neutralization synthesis mode, or is a functionalized quaternary ammonium salt acidic ionic liquid catalyst which is synthesized from the tertiary amine compound and the acid in alkylation and neutralization two-step synthesis modes. The acidic ionic liquid catalyst for synthesizing the nitrocyclohexane from cyclohexane by liquid phase nitration has high catalysis activity, and meanwhile the function of a phase transfer catalyst is achieved, the reaction temperature is low, and no organic solvents are added.

The present invention provides a supported catalyst, a preparation method and applications thereof. The supported catalyst comprises two parts such as an active component and a carrier, wherein the active component is a Pt-based catalyst containing a Pt-In2O3-x or Pt-SnO2-x structure unit, and the supported catalyst is used for catalyzing nitro cyclohexane hydrogenation to prepare cyclohexanone-oxime. According to the invention, the catalyst containing Pt-In2O3-x and Pt-SnO2-x structural units has ideal nitrocyclohexane hydrogenation activity and selectivity, the preparation process of the catalyst is simple, side reactions possibly introduced can be reduced, the production and operation cost is effectively reduced, the complex degree of cyclohexanone-oxime production and the emission of solid-liquid wastes can be reduced, and the used active components are environment-friendly and pollution-free.

The invention relates to a polyvinylidene fluoride / gold nanoparticle hybrid hollow fiber membrane and a preparation method thereof. With combination of hydrophilicity of a polymer gel, high catalytic activity of gold nanoparticles, and corrosion resistance and good film-forming property of polyvinylidene fluoride, the hybrid hollow fiber membrane with good anti-pollution ability, high catalytic activity and good separation property is prepared. The hollow fiber membrane can be used for catalyzing a reduction reaction of nitro in amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyano nitrobenzene, chloronitrobenzene, vinyl nitrobenzene, nitrocyclohexane and other molecules to transform nitro into amino. At the same time, the hollow fiber membrane also can be used for separation of different-size substances in a liquid mixture.

The invention provides a method for synthesizing caprolactam in one step by liquid phase hydrogenation of nitrocyclohexane, wherein caprolactam is synthesized in one step setting out from nitrocyclohexane and under the action of hydrogen pressure of 0.1-2.0MPa and a composite catalytic system; and the composite catalytic system is the supported catalyst and the mixture composed of triazine compounds and formamide compounds. The method of the invention has temperate reaction conditions and simplifies the technology substantially.

The invention relates to a polyvinylidene fluoride / silver nanoparticle hybrid hollow fiber membrane and a preparation method thereof. With combination of hydrophilicity of a polymer gel, high catalytic activity of silver nanoparticles, and corrosion resistance and good film-forming property of polyvinylidene fluoride, the hybrid hollow fiber membrane with good anti-pollution ability, high catalytic activity and good separation property is prepared. The hollow fiber membrane can be used for catalyzing a reduction reaction of nitro in amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyano nitrobenzene, chloronitrobenzene, vinyl nitrobenzene, nitrocyclohexane and other molecules to transform nitro into amino. At the same time, the hollow fiber membrane also can be used for separation of different-size substances in a liquid mixture.

The invention discloses a method for preparing cyclohexanone oxime by catalytic transfer hydrogenation of nitrocyclohexane. According to the mass ratio of 0.1~0.4:1:2~20.8, the present invention adds activated carbon supported by catalyst copper nickel, nitrocyclohexane, amine borane compound into the reactor; reacts at 50~80°C for 6~ The obtained reaction solution was obtained after 12 hours; the obtained reaction solution was filtered and separated to obtain cyclohexanone oxime. The method uses the hydrogen storage material as the hydrogen donor to catalyze the hydrogenation reaction of nitrocyclohexane, and the preparation process can be completed through ordinary glass instruments, without the need for high-pressure reactors and other equipment, which reduces the cost of the reaction device and simplifies the reaction operation. The safety of the reaction process is increased.

The invention provides a method for synthesizing nitroalkane at low temperature, which is carried out in a miniature reaction kettle by taking normal hexane or cyclohexane as a raw material, tributyl phosphate as a solvent and nitric acid as a nitrating agent. By controlling the reaction temperature to be 100-130 DEG C, the concentration of nitric acid to be 2-10 mol / L and the reaction time to be 4-12 h, three nitration products can be obtained from n-hexane, and the yields of 1-nitrohexane, 2-nitrohexane and 3-nitrohexane are 5.9-9.9%, 33.1-37.9% and 26.3-30.6% respectively; the nitration product of cyclohexane is nitrocyclohexane, and the yield of the nitration product is 25.5-40.1%. The preparation method provided by the invention has two advantages: (1) the reaction can be carried out at a lower temperature and a lower nitric acid concentration; (2) the yield of nitroalkane can be adjusted within a certain range; and (3) few by-products are generated in the reaction.

The invention relates to a polyvinylidene fluoride / palladium nanoparticle hybrid hollow fiber membrane and a preparation method thereof. With combination of hydrophilicity of a polymer gel, high catalytic activity of palladium nanoparticles, and corrosion resistance and good film-forming property of polyvinylidene fluoride, the hybrid hollow fiber membrane with good anti-pollution ability, high catalytic activity and good separation property is prepared. The hollow fiber membrane can be used for catalyzing a reduction reaction of nitro in amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyano nitrobenzene, chloronitrobenzene, vinyl nitrobenzene, nitrocyclohexane and other molecules to transform nitro into amino. At the same time, the hollow fiber membrane also can be used for separation of different-size substances in a liquid mixture.