33 results about "Hydrocyanation" patented technology

The invention relates to the technical field of hydrocyanic acid production, in particular to a high-yield hydrocyanic acid chemical process which comprises the following steps: 1) respectively pretreating ammonia gas, natural gas and air, mixing according to a ratio, and inputting into a hydrocyanic acid reactor; (2) carrying out oxidation reaction on the raw material gas under a certain condition under the catalytic action of a platinum alloy net to prepare ammonia-containing hydrocyanic acid gas; 3) performing ammonia removal treatment on the hydrocyanic acid gas to obtain purified hydrocyanic acid gas and an ammonium sulfate solution containing cyanide; 4) carrying out cyanogen removal treatment on the ammonium sulfate solution to obtain mixed gas containing hydrocyanic acid and a cyanogen-free ammonium sulfate solution; according to the method, the area of a platinum alloy net capable of being contained is increased, the reaction area playing a catalytic role is increased, then the reaction efficiency is improved, and the single-line productivity is improved.

A process for the hydrocyanation of an organic compound containing at least one olefinic group comprising reacting the organic compound with hydrogen cyanide in the presence of a catalyst complex comprising at least one transition metal and a phosphorus-containing ligand comprising a calixarene backbone and at least two aryl phosphite or aryl phosphoramidite groups chemically bonded to the backbone.

This invention discloses a method for pretreatment and purification of crude adiponitrile prepared by butadiene hydrocyanation, belonging to the field of organic chemical product refining technology. The method includes: continuous multi-stage countercurrent washing of crude adiponitrile containing metal compound impurities using a brine solution; transferring the metal compound impurities to the aqueous phase through extraction; after oil-water separation, adjusting the pH of the aqueous phase to precipitate the metal compounds; obtaining a solid metal compound and a filtrate through solid-liquid separation; recycling the filtrate as washing liquid; dehydrating the oil phase to obtain a dehydrated adiponitrile solution suitable for entering a distillation system; and distilling the dehydrated adiponitrile solution to obtain qualified adiponitrile. This invention can efficiently remove residual metal compounds from crude adiponitrile, with a removal rate greater than 99%, and the metal content in the oil phase after treatment is less than 10 ppm. It does not introduce nitrogen-containing impurities such as ammonia / amines, resulting in high product purity. The process is simple, energy consumption is low, the washing liquid can be recycled, and metal resources are easily recovered, showing good prospects for industrial application.

The application provides a hydrocyanation reaction method, which is carried out in a reaction system containing an aromatic amine under the action of a nickel-monodentate phosphite ligand catalyst, and the structure of the aromatic amine is: wherein, X 1 - X 3 groups and Y 1 - Y 3 groups each include any one of hydrogen, an alkyl group, an alkoxy group, an alkylamine group, a hydroxyl group and an amino group. The hydrocyanation reaction method of the application includes the nickel-monodentate phosphite ligand catalyst and the aromatic amine with a specific structure, so that the hydrocyanation reaction method can be catalyzed to be shortened in time, the accumulation of ligand hydrolysis products can be significantly reduced or eliminated, and the catalyst loss in the reaction can be reduced. The hydrocyanation reaction method of the application has high reaction efficiency, stable catalyst performance, high raw material conversion rate and high product selectivity, and can be used for the preparation process of preparing adiponitrile by directly hydrocyanating a large amount of butadiene.

Provided in the present invention is a hydrocyanation method. The hydrocyanation method is carried out in a reaction system containing an aromatic amine under the action of a nickel-monodentate phosphite ligand catalyst. The structure of the aromatic amine is as shown in formula I, wherein X1-X3 groups and Y1-Y3 groups separately comprise any one of hydrogen, an alkyl group, an alkoxy group, an alkylamino group, a hydroxyl group and an amino group. The hydrocyanation method of the present invention comprises the nickel-monodentate phosphite ligand catalyst and the aromatic amine having a specific structure; therefore, the time of the hydrocyanation method can be catalytically shortened, the accumulation of a ligand hydrolysate can be substantially reduced or eliminated, and the loss of the catalyst during the reaction can also be reduced. In the hydrocyanation method of the present invention, the reaction efficiency is high, the performance of the catalyst is stable, and the conversion rate of the raw materials and the selectivity of the product are higher; therefore, the hydrocyanation method can be used in a preparation process for large-scale preparation of adiponitrile from butadiene by means of a direct hydrocyanation method.

A process for the hydrocyanation of an organic compound containing at least one olefinic group comprising reacting the organic compound with hydrogen cyanide in the presence of a catalyst complex comprising at least one transition metal and an organic ligand containing at least one P—N linkage, wherein the P and N atoms of the P—N linkage are cach bonded to two other atoms.

The application provides a hydrocyanation reaction method, which is carried out in a reaction system containing an aromatic amine under the action of a nickel-bidentate phosphite ligand catalyst, and the structure of the aromatic amine is: wherein, X 1 - X 3 groups and Y 1 - Y 3 groups each include any one of hydrogen, an alkyl group, an alkoxy group, an alkylamine group, a hydroxyl group and an amino group. The hydrocyanation reaction method provided by the application not only has high reaction efficiency, but also can significantly reduce or eliminate the accumulation of ligand hydrolysis products, and stabilize the effective content of the catalyst in the reaction system; in addition, the hydrocyanation reaction method provided by the application has high reaction efficiency, few side reactions, high raw material conversion rate and high product selectivity, and can meet the needs of a large-scale production process of adiponitrile prepared by directly hydrocyanating butadiene.

The application discloses a calcium carbide furnace tail gas deep purification process. The calcium carbide furnace tail gas is firstly subjected to wet desulfurization and dehydrocyanation and TSA treatment, and then sequentially enters a de-fluorine and de-hydrocyanation reactor, a hydrolysis desulfurization reactor, a fine desulfurization reactor, a de-phosphorus and de-arsenic reactor, a de-oxygen reactor and a de-hydrocarbon reactor. After the treatment process, the HCl content in the gas is less than 0.1 ppm, the HF content is less than 0.1 ppm, the HCN content is less than 0.1 ppm, the total sulfur content is less than 0.1 ppm, the AsH3 content is less than 5 ppb, the PH3 content is less than 5 ppb, the oxygen content is less than 10 ppm, and the unsaturated hydrocarbon content is less than 0.1 ppm, thereby meeting the separation and purification requirements of subsequent processes, and the pressure drop of the whole process is not more than 100 kPa. The process can remove oxygen and unsaturated hydrocarbons in the gas under low-temperature conditions, thereby reducing the occurrence of side reactions, and has the characteristics of reasonable process design, high purification precision, low energy consumption and low operation cost.

The application provides a method for isomerizing cis-2-pentenenitrile into 3-pentenenitrile, which comprises isomerizing cis-2-pentenenitrile into 3-pentenenitrile in a supercritical fluid under the action of a catalyst and a ligand; wherein the catalyst is a rare earth metal oxide or a rare earth metal halide, and the ligand is a monodentate phosphite or a polydentate phosphite. By selecting a rare earth metal oxide or a rare earth metal halide and combining a specific monodentate phosphite or a polydentate phosphite, cis-2-pentenenitrile is isomerized into 3PN in a supercritical fluid, the catalytic process has high raw material conversion rate and high 3PN selectivity, cis-2-pentenenitrile can be efficiently converted into 3PN in the second hydrocyanation step in the industrialization process of butadiene hydrocyanation to adiponitrile, thereby eliminating the poisoning effect of cis-2-pentenenitrile on the catalyst, improving the process efficiency, saving the cost, and improving the economic benefit.

The invention belongs to the field of organic chemical synthesis, and relates to a process for preparing butanediamine by using acrylonitrile and hydrocyanic acid through a one-pot method, which comprises the following steps: placing acrylonitrile, hydrocyanic acid, a hydrocyanation catalytic component and a hydrogenation catalytic component in the same reactor, and reacting in a nitrogen atmosphere, the preparation method comprises the following steps: carrying out a hydrocyanation addition reaction on acrylonitrile and hydrocyanic acid under the action of a hydrocyanation catalytic component to generate a succinonitrile intermediate, adding hydrogen into a reaction system for boosting without separation treatment, carrying out a catalytic hydrogenation reaction under the action of a hydrogenation catalytic component, and carrying out separation treatment to obtain butanediamine. According to the method, two-step reaction is integrated into a single reactor and intermediate separation is avoided, so that the process is fundamentally simplified, the equipment investment and the operation cost are reduced, meanwhile, the material loss caused by unstable intermediates is reduced, the production efficiency and the total yield of products are improved, and the method is suitable for industrial production. And the transfer of toxic materials is reduced, so that the process safety is improved.

Provided are a method and device for preparing adiponitrile. The method of the present disclosure comprises the steps of a first hydrocyanation reaction, an isomerization reaction and a second hydrocyanation reaction, wherein online Raman spectroscopy is used for detecting the content of a specific component in the system; and the reaction conditions are regulated based on the detection results, so as to achieve precise control of the materials in each step of the reaction system. The method of the present disclosure can reduce an amount of butadiene, thereby reducing the subsequent energy consumption needed for recycling butadiene and equipment investment after reaction; by monitoring the content of hydrocyanic acid in real time, the residue of hydrocyanic acid is reduced to a lower level, and the operation safety and the stability of a catalyst during reaction are improved; and the loss of the catalyst is reduced.

The invention relates to the technical field of hydrocyanic acid production, in particular to a hydrocyanic acid reactor with a flexible tube plate structure, which comprises a tank body, an air inlet and an air outlet are fixedly mounted at the upper end and the lower end of the tank body respectively, a catalyst net is arranged in the top end of the tank body, and an exciter is fixedly mounted on the outer side of the tank body; the distributor is arranged above the catalyst net; the bottom end of the heat exchange tube is fixedly connected with the inner wall of the tank body, a tube plate is fixedly arranged in the tank body, the top end of the heat exchange tube is connected with the tube plate, the tube plate is arranged below the distributor, and the tube plate is a flexible plate; the cooling part is arranged below the tube plate; the manifold part is mounted on the outer side of the tank body, and the manifold part is communicated with the cooling part through a pipeline; according to the invention, the possibility of stress concentration of the tube plate under the action of thermal stress can be reduced, the possibility of pull crack damage of the tube plate is reduced, and the service life of the hydrocyanic acid reactor is further prolonged.

A bidentate phosphite ligand which comprises a backbone having an a,a,a,a-tetrahydrocarbyl-1,3-dioxolane-4,5-dimethanol structure in which the hydrogen atoms of the hydroxyl groups on the methanol substituents have each been replaced by a P(OR1)2 group, where R1 is an aryl radical and wherein the 1,3-dioxolane ring in the α,α,α,α-tetrahydrocarbyl-1,3-dioxolane-4,5-dimethanol backbone is optionally substituted at the 2-position with one or more alkyl groups. When combined with a transition metal, such as nickel, the ligand provides a catalyst complex useful in hydrocyanation and other reactions.

The invention provides a method for preparing aromatic nitrile from an alkyl-substituted phenolic compound, and belongs to the technical field of compound synthesis, the method comprises the following steps: dissolving the alkyl-substituted phenolic compound in a nitrile solvent, adding phosphorus trihalide, and stirring to obtain a first solution; dissolving nickel salt and zinc salt in a nitrile solvent, stirring, adding cyanide, stirring for the second time, and dehydrating to obtain a second dehydrated solution; and under the condition of introducing ammonia gas, adding the second dehydration solution and a reaction auxiliary agent into the first solution, and carrying out hydrocyanation reaction to prepare the aromatic nitrile compound. According to the method, the alkyl substituted phenolic compound is used as a raw material, efficient synthesis of aromatic nitrile is achieved through cooperation of all the steps, the phenolic compound in the industrial waste liquid is converted into a high-value chemical, and a new technical path is provided for treatment and resource utilization of the phenolic waste liquid.

The invention relates to a method and a device for generating 3-pentenenitrile through hydrocyanation of 1, 3-butadiene. The device comprises a reaction area and a discharge port located below the reaction area, and the reaction area sequentially comprises an upper portion, a lower portion, a lower portion and a material inlet from top to bottom, a middle upper part in which a plug flow reaction is performed; a middle lower part in which a circulation flow reaction is carried out; and a lower portion in which a plug flow reaction is performed. According to the device and the method provided by the invention, the conversion rate of hydrogen cyanide can be effectively improved, no residue exists, and the generation amount and the accumulation amount of a deactivated catalyst are effectively inhibited, so that the stability of a reaction system is improved, the equipment investment is saved, and the generation benefit is improved.

This application relates to the field of catalyst regeneration technology, and more particularly to a method and system for recycling catalysts used in the butadiene-to-adiponitrile synthesis process. The butadiene-to-adiponitrile synthesis process includes a cyclic reaction flow comprising a primary hydrocyanation reaction, an isomerization reaction, and a secondary hydrocyanation reaction. The method includes: obtaining pre-conversion and pre-selectivity data for each reaction in the first reaction flow, and post-conversion and post-selectivity data for each reaction in the Nth reaction flow; obtaining conversion change data and selectivity change data for each reaction from these data; determining the amount of catalyst to be recovered for each reaction based on these data; and processing the recovered catalyst based on these recovery amounts to obtain a regenerated catalyst. This method directly determines the amount of catalyst to be recovered by using the conversion change data and selectivity change data for each reaction, achieving accurate catalyst recovery and effectively improving the catalytic performance of the catalyst.

The invention discloses a helicene bisphosphite ligand as shown in a formula 1, a preparation method of the helicene bisphosphite ligand, a nickel-based catalyst containing the helicene bisphosphite ligand and a preparation method of the nickel-based catalyst. The ligand compound can be used as a ligand of a homogeneous metal catalyst, and can be used in organic reactions such as hydrocyanation reactions of olefins. A catalyst prepared from the helicene bisphosphite ligand is used for preparing nitrile substances, not only is high in catalytic activity, high in yield and high in stability, but also is high in product position selectivity, so that a linear addition product of anti-Markov addition can be obtained more easily, and the helicene bisphosphite ligand has a wide industrial application prospect. Formula 1

A bidentate phosphite ligand comprises a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR1)2 group, where R1 is an aryl radical. When combined with a transition metal, such as nickel, the ligand provides a catalyst complex useful in hydrocyanation and other reactions.

A multidentate phosphite ligand is used in the catalytic synthesis of adiponitrile. The ligand is represented by the following general formula (I). The method of catalytic synthesis of adiponitrile comprises primary hydrocyanation, isomerization, and secondary hydrocyanation reactions, wherein the catalyst adopted each comprises a phosphite ligand-nickel complex composed of a nickel precursor and a multidentate phosphite ligand. The ligand molecule has a higher electron cloud density, and the phosphorus content capable of participating in coordination in the ligand molecule per unit mass is higher, so that the catalytic activity of the catalyst is improved, and the amount of the catalyst is reduced.

The invention provides a preparation method of 3-pentenenitrile, which comprises the following steps: S1, preparing crude hydrogen cyanide gas by a formamide pyrolysis method: under the conditions that the reduced pressure is 5-200mbar and the pyrolysis temperature is 250-650 DEG C, introducing the raw material formamide gas into a columnar catalyst bed layer, and reacting in a hydrocyanic acid fixed bed synthesizer to generate the crude hydrogen cyanide gas and a pyrolysis product; s2, preparation of acetone cyanohydrin: cooling the crude hydrogen cyanide gas and the pyrolysis product so as to condense the product with the boiling point higher than that of the hydrogen cyanide gas; removing ammonia and water from the crude hydrogen cyanide gas by using acid, and then feeding the crude hydrogen cyanide gas into an adsorption tower to carry out chemical adsorption reaction with acetone in the presence of a catalyst, so as to prepare acetone cyanohydrin; and S3: preparation of 3-pentenenitrile: preparing a catalyst by using the phosphite ligand and nickel, and under the condition that Lewis acid is used as a cocatalyst, preparing 3-pentenenitrile by taking acetone cyanohydrin as a cyanogen source and hydrocyanating 1, 3-butadiene.

The present invention provides a method for isomerizing cis-2-pentenenitrile to 3-pentenenitrile. The method comprises: in a supercritical fluid, subjecting cis-2-pentenenitrile to an isomerization reaction under the action of a catalyst and a ligand to generate 3-pentenenitrile, wherein the catalyst is a rare earth metal oxide or a rare earth metal halide, and the ligand is a monodentate phosphite or a multidentate phosphite. The present invention uses the rare earth metal oxide or the rare earth metal halide in combination with the specific monodentate phosphite or multidentate phosphite to catalyze the isomerization of cis-2-pentenenitrile in the supercritical fluid to generate 3PN. The catalytic process has a high starting material conversion rate and a high 3PN selectivity, and enables efficient conversion of cis-2-pentenenitrile into 3PN in the second hydrocyanation step of an industrial process for preparing adiponitrile by a butadiene hydrocyanation method, thereby eliminating the poisoning effect on the catalyst, improving the process efficiency, saving costs, and improving economic benefits.

This invention relates to a method for preparing 3-pentenonitrile by isomerization of 2-pentenonitrile. In this method, polyvinylpyridine porous microspheres are used as a catalyst. The polyvinylpyridine porous microspheres comprise polystyrene porous microspheres and a polyvinylpyridine polymer supported on the polystyrene porous microspheres. The catalyst used in this method possesses high catalytic activity, high selectivity, long service life, easy separation and recovery, and low cost, enabling efficient and highly selective isomerization of 2-pentenonitrile to 3-pentenonitrile. Therefore, when applied to the method of preparing adiponitrile by hydrocyanation of butadiene, the byproduct 2-pentenonitrile can be selectively isomerized to the target product 3-pentenonitrile, thus protecting the hydrocyanation catalyst and improving the yield of the target product.

The present invention relates to a bidentate phosphorus ligand catalyst composition and a preparation method and application thereof, the catalyst composition comprises a bidentate phosphorus ligand, a nickel catalyst and at least one Lewis acid accelerator, the bidentate phosphorus ligand has a 3, 3-bis (methoxy)-5, 5-dimethyl-2, 2-bisphenol structural skeleton, and the nickel catalyst has at least one Lewis acid accelerator, and the at least one Lewis acid accelerator has a 3, 3-bis (methoxy)-5, 5-dimethyl-2, 2-bisphenol structural skeleton and a 3, 3-bis (methoxy)-5, 5-dimethyl-2, 2-bisphenol structural skeleton. Hydrogen of hydroxyl is respectively substituted by monophosphine and mononite to form a chelating structure. The catalyst composition can be prepared by mixing a bivalent nickel compound and a ligand in an inert atmosphere to form a complex, then adding a reducing agent for reduction to obtain a zero-valent nickel catalyst. The catalyst composition can be used for catalyzing the hydrocyanation reaction of olefin, and is especially suitable for the reaction of 3-pentenenitrile and hydrocyanic acid to prepare an adiponitrile product with high added value. The catalyst system provided by the invention has high reaction activity and selectivity and good catalyst stability, is suitable for an industrial continuous reaction process, and significantly improves the production efficiency of adiponitrile and reduces the use cost of the catalyst.

The invention discloses a miloabalin key intermediate and a preparation method thereof. The invention provides a preparation method of a compound 8, which comprises the following step: in a solvent, carrying out the following reaction on a compound 7 and a Nagata reagent to obtain the compound 8. According to the method disclosed by the invention, the compound 8 is synthesized by adopting a Nagata hydrocyanation reaction, so that the use of NaCN is avoided, and the addition stereoselectivity of the product is better. # imgabs0 #

A bidentate phosphite ligand comprises a backbone having a structure of acenaphthene-1,2-diol in which the hydrogen atoms of the hydroxyl groups have each been replaced by a P(OR1)2 group, where R1 is an aryl radical. When combined with a transition metal, such as nickel, the ligand provides a catalyst complex useful in hydrocyanation and other reactions.

The invention provides a catalyst for a hydrocyanation reaction and a preparation method of a nitrile compound. The catalyst comprises rare earth metal serving as an active component, a monodentate phosphite ligand and a polydentate phosphite ligand, wherein the monodentate phosphite ligand and the polydentate phosphite ligand serve as ligands; according to the catalyst, a one-molecule polydentate phosphite ligand is bridged with two-molecule rare earth metal active centers, and each rare earth metal active center and a three-molecule monodentate phosphite ligand form a stable four-coordination structure; in a water-containing hydrocyanation reaction system, the catalyst can be coordinated with an auxiliary agent and water at a first temperature to form a hydration catalytic compound so as to realize water locking, and the hydration catalytic compound can be dehydrated at a second temperature so as to realize recycling of the catalyst; wherein the first temperature is lower than the second temperature. The catalyst provided by the invention can avoid catalyst inactivation caused by hydrolysis of phosphite ligands, and continuously and stably exerts catalytic activity; and the hydration catalytic compound can be dehydrated to recover the original configuration so as to be recycled, so that the method has a good application prospect.

A process for the hydrocyanation of an organic compound containing at least one olefinic group comprising reacting the organic compound with hydrogen cyanide in the presence of a catalyst complex comprising a bidentate phosphite ligand having one of the following structures: (I) and (II) and at least one transition metal.

The invention relates to the technical field of organic synthetic chemistry, in particular to a phosphite ligand, a chiral quaternary carbon nitrile derivative, a preparation method and application. The structural formula of the phosphite ligand is shown in the specification, and the phosphite ligand introduces a 7, 7 '-site substituent on a binaphthol skeleton with only 3, 3'-site substituent traditionally. The structural modification can effectively change the dihedral angle of a binaphthol skeleton and enhance the overall rigidity of the binaphthol skeleton, thereby providing good space support for coordination of a ligand and a metal center and weak interaction between substituents. The phosphite ligand and a zero-valent nickel catalyst form a catalytic system to catalyze the asymmetric hydrocyanation reaction of polysubstituted olefin and hydrocyanic acid equivalent, so that the chiral quaternary carbon nitrile derivative is successfully prepared, the problems of high reaction temperature and low enantioselectivity in the prior art are solved, and the chiral quaternary carbon nitrile derivative has excellent practical value and popularization prospect.

The invention provides a pyrazine phosphine ligand compound as well as a preparation method and application thereof, and relates to the technical field of catalysts. According to the preparation method disclosed by the invention, the raw materials are subjected to lithiation reaction and then react with different monochlorophosphine compounds to generate corresponding pyrazine phosphine ligand compounds, and the preparation method is simple, few in separation steps, high in yield and suitable for industrial production. The invention also relates to a catalytic system formed by complexing a series of pyrazine phosphine ligand compounds serving as ligands and a metal center, and the catalytic system is used for catalyzing olefin hydroformylation reaction, hydrocarboxylation reaction and hydrocyanation reaction. Particularly, the catalytic system has good activity and selectivity in a reaction for preparing methyl propionate through an alkoxycarbonylation reaction of ethylene.

The present application provides a kind of formula I shows that the pillar aromatic double phosphite ligand and its preparation method and application, and the outer rim of pillar aromatic bonding phosphorus compound is prepared pillar aromatic double phosphite compound, can be used as novel ligand of homogeneous metal catalyst, for olefin hydrocyanation etc. Organic reaction. The catalyst prepared using the ligand of the present application is used for the preparation of nitrile, not only high catalytic activity, high yield, and the position selectivity of product is high, it is advantageous to obtain the product of anti-masashi linear addition.