491 results about "Formylation reaction" patented technology

The present invention relates to catalyst system for propylene hydrogenation and formylation and process of catalytically synthesizing butyl aldehyde. The catalyst system is triaryl phosphine-Rh(I) catalyst system with proper additive, such as bisphosphite ester, in proper amount. Compared with similar available catalyst, the catalyst system has obviously higher catalytic acitivity, higher selectivity, higher stability and raised n-butyl aldehyde / isobutyl aldehyde ratio in the catalytically synthesized product.

A modified activated carbon supported rhodium type catalyst for high carbene hydrocarbon hydrogen formylation reaction is provided. The preparation of the catalyst comprises the techniques such as carrier pretreatment-activity rhodium solid-phase bound reagent combination, and used for gas-liquid-solid three phase catalyst system, which is characterized in that: a certain amount of alkali or alkaline earth metal hydroxide and salt modification activated carbon is used as a carrier, and the supported rhodium catalyst is prepared by using multiple impregnation method. The catalyst of the present invention is high in activity and selectivity. The catalyst is easy to be separated from products after reaction, capable of being used repeatedly, stable in performance, and suitable for the production process of high carbene hydrocarbon or mixed olefin hydrogen formylation made high carbon aldehyde, which has good industrial application value.

The invention relates to a preparation method of a compound with general formula (I), the preparation method includes: (1) the compound with general formula (II) and the formylation reagent are carried out the formylation reaction with the presence of Lewis acid and the organic base at -20 DEG C to 100 DEG C, and then the tertiary amine is added for reaction for a period of time; (2) the product of step (1) is carried out the methylation reaction with the inorganic base and the methylation reagent at -10 DEG C to 100 DEG C, so as to get the compound with general formula (I).

The invention relates to a propylene hydroformylation catalyst system and a method for catalyzing synthesis of butyraldehyde. In the present invention, in the propylene hydroformylation reaction system catalyzed by triarylphosphine-Rh(I), by using appropriate types and quantities of additives, such as bisphosphite, the performance of the Rh(I) / triarylphosphine catalyst can be significantly improved The activity and the positive-iso ratio of butyraldehyde in the product (molar ratio of n-butyraldehyde / isobutyraldehyde>20), and significantly prolong the service life of the bisphosphite ligand, and significantly reduce the amount of triarylphosphine. This type of catalyst system is characterized by higher activity and selectivity than third-generation Rh(I) / triphenylphosphine catalysts and better stability than fourth-generation Rh(I) / bisphosphite catalysts, so The novel catalyst system provided by the present invention can overcome the shortcomings of the third and fourth generation catalysts, reduce the cost of industrialized production of propylene hydroformylation, and provide a new catalyst technology for its industrial application.

The invention discloses a supported metal catalyst under double modification of an anchoring ligand and an auxiliary and a preparation method and application thereof. The catalyst comprises an active component, an auxiliary, a carrier and a ligand, wherein the active component is one or more of metals Rh, Ru and Co; the auxiliary is one or more of Al, K, Zn, Cu and Ag; the carrier is a molecular sieve SiO2, Al2O3, MCM-41 or SBA-15; the ligand is an N or P-containing organic ligand capable of acting with silicon hydroxyl. In the catalyst, the metal component and the auxiliary are directly fixed on the carrier, and then the anchoring ligand and the metal generate a coordination action to in-situ generate an active species; due to the double modification of the ligand and the auxiliary, the activity and stability of the catalyst are remarkably improved. The catalyst can be applied to alkene hydroformylation to prepare various organic aldehydes, has relatively high catalytic activity and excellent stability, and is easy to separate.

The invention relates to a method for preparing aldehyde through linear chain olefin hydroformylation. According to the method, a continuous reaction mode is used for performing olefin hydroformylation reaction in a homogeneous catalyst system; a catalyst is a composite catalysis system composed of a rhodium complex, a biphenyl backbone or biphenyl backbone diphosphine ligands and triphenylphosphine or triphenyl phosphate monophosphorous ligands; a reaction solvent comprises butyraldehyde, valeraldehyde, toluene or isodecanol; when the catalyst system uses propylene or butene-1 as raw materials under the condition of a low molar ratio of the diphosphine ligands to the rhodium complex, contents of the aldehyde generated by hydroformylation of the propylene and the butene-1 is larger than 97% and 95% respectively; and when the catalyst system uses a mixture of the butene-1 and butene-2 as raw materials, and the content of n-valeraldehyde in hydroformylation reaction products can reach above 85%.

The invention discloses a high-selectivity method for preparing linear-chain aldehyde. According to the method disclosed by the invention, a phosphine-containing organic polymer self-loaded type high-dispersity metal catalyst is used, and olefin hydroformylation reaction is used for preparing the linear-chain aldehyde in a high-selectivity manner. The organic polymer self-loaded type catalyst takes one, two and three of metal Rh, Co, Pd, Ir and Rt as active components and a phosphine-containing organic polymer is used as a carrier, wherein the phosphine-containing organic polymer carrier is formed by co-polymerizing or self-polymerizing a multi-dentate organic phosphine ligand and a single-dentate organic phosphine ligand. The phosphine-containing organic polymer self-loaded type high-dispersity metal catalyst provided by the invention is applied to reactors including fixed beds, slurry beds, bubbling beds, trickle beds and the like. The method disclosed by the invention has very goodpresentation in the olefin hydroformylation reaction and can be used for producing a target product linear-chain aldehyde in the high-selectivity manner.

The invention relates to a method for an olefin hydroformylation reaction of olefin through adopting a solid heterogeneous catalyst. The method is characterized in that the method adopts the solid heterogeneous catalyst, the solid heterogeneous catalyst is composed of a metal component and an organic ligand polymer with a hierarchical pore structure, the metal component is one or more of Rh, Ir and Co, the organic ligand polymer is a polymer formed by polymerizing an organic ligand monomer containing P, an alkylene group and optional N, and the metal component and the P atom or N in the skeleton of the organic ligand polymer form a coordination bond and exist in a monoatomic dispersion state. The olefin hydroformylation reaction of an olefin raw material and a CO / H2 mixed gas is carried out in the presence of the solid heterogeneous catalyst in a reactor. The method adopting the novel solid heterogeneous catalyst has the advantages of simple reaction process and apparatus, stable hydroformylation performance of the catalyst, high activity and yield, and wide industrial application prospect.

The invention relates to a catalyst combination used for propylene hydrogen formylation reaction, comprising the components: rhodium, bis-phosphite and single-phosphite. The effects that the activation of Rh / phosphite catalyst is kept and the normal / isomeric ratio of outcome butyraldehyde is suitably adjusted are achieved by adding single-phosphite or bis-phosphite in the propylene hydrogen formylation reaction system catalyzed by the phosphite / Rh; furthermore, highe normal / isomeric ratio and reaction rate are still remained on the basis that the dosage of bis-phosphite is reduced and sub-pressure CO: H2 is more than 1.

The invention relates to a method for producing high carbon aldehyde through using an olefin hydroformylation reaction. The method is characterized in that the olefin hydroformylation reaction of a C6-C20 olefin raw material and synthetic gas is carried out in the presence of a solid heterogeneous catalyst in a trickle bed, the solid heterogeneous catalyst is composed of a metal component and an organic ligand polymer, the metal component is one or more of Rh, Ir and Co, the organic ligand polymer is a polymer having a large specific surface area and a hierarchical pore structure and formed by polymerizing an organic ligand monomer containing P, an alkylene group and optional N through a solvothermal polymerization technology, and the metal component and the P atom or N in the skeleton of the organic ligand polymer form a coordination bond and exist in a monoatomic dispersion state. The method has the advantages of simple and easy reaction process, suitableness for industrial large-scale production, excellent reaction activity and selectivity, and high normal / isomeric ratio of the product aldehyde.

A process for preparing high-C aldehyde from high-C olefin by hydroformylation in a two-phase system consisting of the quaternary ammonium salt ion liquid containing ethoxy chain and the non-polar (or weak-polar) organic solvent features high-temp mixing and dissolving, ordinary-temp phase separation, temp control, homogeneous reaction and two-phase separation. Its advantages are high catalytic activity, selectivity and output rate, and long cyclic life of catalyst (at least 9 cycles).

The invention relates to a preparation method for a material, specifically to a catalyst used for hydroformylation of olefin and a preparation method thereof. The catalyst is prepared from a rhodium complex and bidentate phosphoramidite or phosphite phosphine ligand and used for hydroformylation of olefin. The invention provides synthesis of 2,2-dihydroxymethyl-1,1'-biphenyl skeleton bidentate phosphine ligand with better flexible deformation performance; and when the ligand-modified catalyst is applied to hydroformylation of olefin-containing structures, the catalyst has better activity at low temperature compared with conventional catalysts, and selectivity of aldehyde is improved through improvement of the flexibility of the ligand for the first time.

The invention discloses a heterogeneous catalyst adopting a hierarchical pore structure and adopting phosphine-containing organic mixed polymer-metal as well as preparation and an application of the heterogeneous catalyst in production of aldehyde with a high normal / isomeric ratio through internal olefin hydroformylation. In the heterogeneous catalyst, one, two or three of metal Rh, Co and Ir are taken as active components, and a phosphine-containing organic mixed polymer adopting the hierarchical pore structure is taken as a carrier and is prepared from multidentate organic phosphine ligands containing alkylene and monodentate organic phosphine ligands through copolymerization. The coordinate bond type heterogeneous catalyst is applicable to a fixed bed reactor, a slurry bed reactor, a bubble column reactor, a trickle-bed reactor and other reactors. The provided heterogeneous catalyst has good presentation in the internal olefin hydroformylation reaction, internal olefins are firstly isomerized to be terminal-group olefins under the action of the catalyst, a hydroformylation reaction is performed, corresponding normal aldehyde is selectively generated, accordingly, the normal / isomeric ratio of the product aldehyde is high and can be higher than 15, and the content of alkane in the obtained product is lower than 1%.

The invention relates to a catalyst for hydroformylation reaction and a preparation method of the catalyst. The catalyst comprises a rhodium complex and a novel bis-phosphoramidite ligand and is prepared by the rhodium complex and the novel bis-phosphoramidite ligand with molar ratio of 2:1-1:10 through mixed reaction. The catalyst can be applied to the hydroformylation reactions of compounds with unsaturated C-C double-bonded structure at any end position and can improve the yield of linear-chain aldehyde in a product, and the service life of the catalyst is remarkably prolonged.

The invention relates to a separation method of an olefin hydroformylation reaction liquid-phase discharged material. The invention belongs to the field of hydroformylation reaction aldehyde preparation. The method comprises the steps that: (1) decompression is carried out upon a C2-C4 olefin hydroformylation liquid-phase discharged material; (2) the decompressed C2-C4 olefin hydroformylation liquid-phase discharged material is subjected to multi-level heating evaporation separation, wherein the pressure after decompression is corresponding to the evaporation temperature, and the evaporation temperature is no higher than 140 DEG C; (3) gas-phase materials obtained in each level of evaporation separation are condensed, such that a liquid-phase aldehyde product is obtained; and (4) a catalyst-containing liquid-phase material obtained through the multi-level evaporation separation is recycled to the reactor. With the technical scheme provided by the invention, the separation of the hydroformylation reaction product and a catalyst solution can be carried out under a relatively low temperature. With leveled evaporation, the retention time of the materials in a hot area in the separation process can be effectively controlled, such that the heat-sensitive rhodium catalyst can be protected.

The invention relates to a method for preparing aldehyde through olefin hydrogen formylation and mainly solves the technical problems of low raw material conversion rate and low objective product selectivity in the reaction process of the olefin hydrogen formylation existing in the prior art. With the adoption of the technical scheme that the method for preparing the aldehyde through the olefin hydrogen formylation comprises the following steps that: C2-C8 olefin, CO and hydrogen are taken as raw materials, rhodium-contained liquid solution is taken as a catalyst, and under the conditions that the reaction temperature is 40-160 DEG C, the reaction pressure is 0.5-5.0 MPa, the molar ratio of olefin to rhodium is (0.5-30):1, the raw materials are in contact with the rhodium-contained liquid solution catalyst in a highly-efficient reactor for reaction to generate a liquid effluent containing the aldehyde, wherein the high-performance reactor selects a rotating packed bed reactor, so the problems are better solved. The method can be used in the industrial production for preparing the aldehyde through the olefin hydrogen formylation.

The invention discloses a method for generating corresponding arabino compounds through hydroformylation of light olefin compounds, carbon monoxide and hydrogen under proper temperature and pressure conditions by taking imidazole, bis-imidazole, quaternary phosphonium, quaternary amine or guanidine ionic liquid as a solvent in the presence of a noble metal complex catalyst and a phosphine ligand system. The ionic liquid solvent is interacted with an Rh catalyst in reaction or forms a novel complex, the formation of a low-activity Rh cluster compound is inhibited, the structure of the Rh catalyst is stabilized, and the activity and stability of the catalyst are improved. After the hydroformylation is finished, most products are separated through simple flashing; and the flashed ionic liquid and homogeneous complex catalyst can be circularly used for the hydroformylation. The method has the advantages of environmental friendliness, simple process and the like.

The invention provides a synthesis method of propionaldehyde by low-pressure carbonyl of ethylene, belonging to a preparation method of saturated compound which contains -CHO group and is connected with a noncyclic carbon atom. The synthesis method comprises the steps of: taking ethylene, carbon monoxide and hydrogen as raw materials, adopting a rhodium / phosphonium complex catalyst system, and synthesizing the propionaldehyde by ethylene hydrogen formylation reaction. The synthesis method is characterized by comprising a synthesis operating unit and a rectification operating unit, wherein thesynthesis operating unit comprises a compressor, a synthesis reactor, a coarse propionaldehyde collecting tank and a gas stripping column; an entrainment separator is respectively arranged above the synthesis reactor and the coarse propionaldehyde collecting tank; and an iron-free propionaldehyde solution catalyst system of metal rhodium catalyst and ligand triphenylphosphine is used, the rhodiumconcentration in the catalyst solution is 80ppm-150ppm, and the weight percentage concentration of the triphenylphosphine is 1.5%-3%. The synthesis method of the propionaldehyde by the low-pressure carbonyl of the ethylene is simple in equipment, less in investment, simple in technological operation, and small in catalyst consumption. Counting as the ethylene, the raw material conversion rate is more than or equal to 90%, and the propionaldehyde product content is more than or equal to 99.5%.

The invention relates to a method for preparing aldehyde through alkene hydroformylation reaction and mainly solves the problems in the prior art that the reaction activity of a rhodium catalyst based on a phosphine ligand is low, the iso-to-n ratio of a product is low and the stability of a rhodium catalyst based on a phosphite ester ligand is poor. The problems are solved by adopting the method for preparing aldehyde through the alkene hydroformylation reaction; and according to the method, alkene, carbon monoxide and hydrogen enter a hydroformylation reactor to come into contact with a catalyst at the reaction temperature of 70-120 DEG C under the reaction pressure of 1.0-4.0 Mpa to generate a product which comprises the aldehyde, wherein the catalyst comprises a rhodium-containing catalyst precursor, a double-teeth phosphine ligand and a double-teeth phosphite ester ligand. The method disclosed by the invention can be used in the alkene hydroformylation reaction.

The invention relates to a rhodium / carbon nanotube catalyst of rhodium nanoparticle supported in a tube chamber of a carbon nanotube used for an olefin hydrogen formylation reaction, the catalyst takes the carbon nanotube as a carrier, the rhodium nanoparticle can be dispersed in the tube chamber, the size is uniform and the particle size is 1-3nm; the rhodium / carbon nanotube catalyst appears higher activity by comparing with other carrier supported catalyst in the hydrogen formylation reaction of styrene, the highest TOF value can reach more than 300h<-1>, when an appropriate phosphite ester ligand is added in the reaction system, activity is increased, the highest TOF value can reach more than 1000h<-1> which is the highest intrinsic reaction activity obtained in the styrene hydrogen formylation reaction of a heterogeneous catalyst; the selectivity of product aldehyde generated by catalysis of the catalyst is high and can reach more than 99%, the selectivity for producing branched chain aldehyde can reach 94%; and 42% of enantioselectivity can be obtained in the presence of the chiral ligand.

The invention provides a method for synthesizing propyl aldehyde by ethylene hydroformylation. The invention belongs to preparation of a saturated compound which contains a -CHO group which is connected to an acyclic carbon atom. In the method, the ethylene, carbon monoxide and hydrogen are taken as raw materials. The method comprises the following steps: adopting a rhodium phosphine complex catalyst system and ethylene hydroformylating to synthesize propyl aldehyde. The invention is characterized in that the system comprises a synthesis operating unit, a separation recovery operating unit and a rectification operating unit; and in the method, the complete separation of the synthesized propyl aldehyde product from the catalyst is realized; and the method has the advantages of low catalystconcentration, low consumption, low reaction temperature, long service life of the catalyst, high raw material conversion, less impurities in the propyl aldehyde product and high propyl aldehyde content. The synthesized propyl aldehyde product is completely separated from the catalyst, thus avoiding catalyst loss, reducing catalyst consumption, avoiding decomposition of the catalyst and prolonging the service life of the catalyst. A double-synthesis reactor is adopted, raw materials are recycled, feed gas conversion rate counted by ethylene is more than or equal to 95%, and propyl aldehyde content is more than or equal to 99.9%.

The invention relates to a preparation method of a monoatomic rhodium catalyst used for catalyzing alkene hydroformylation reaction to generate branched chain aldehydes and olefine aldehydes. Applications of the monoatomic rhodium catalyst are capable of realizing a whole new reaction approach, tandem of alkene hydroformylation reaction and aldol condensation reaction is realized without adding ofadditional acid or base, and one-step of production of branched chain aldehydes and olefine aldehydes from alkenes and synthetic gas is realized. The main active component of the monoatomic rhodium catalyst is rhodium; rhodium is dispersed on a carrier in atom grade; the mass amount of rhodium accounts for 0.005 to 2wt% of the total mass amount of the monatomic rhodium catalyst. The monoatomic rhodium catalyst is relatively high in catalytic activity and stability in alkene hydroformylation reaction; under the optimum reaction conditions, branched chain aldehyde product selectivity is 95% orhigher. The monoatomic rhodium catalyst is low in economical and environment cost; production separation is convenient; post-treatment is simple; and the application prospect is promising.

The invention discloses a method for high selectively preparing an aldehyde by using an olefin. According to the method, an organic polymer self-load type catalyst is used, an olefin hydroformylationreaction is applied to high selectively preparation of an aldehyde. According to the organic polymer self-load catalyst, one, two or three metals selected from a group consisting of Rh, Co, Pd and Irare used as active components, and a phosphine-containing organic copolymer is used as a carrier, wherein the phosphine-containing organic copolymer carrier is formed by copolymerization of a polydentate organic phosphine ligand and a monodentateorganic phosphine ligand. The organic polymer self-load catalyst provided by the invention is suitable for reactors such as fixed beds, slurry beds, bubbling beds, trickle beds and the like, and has good performance in a reaction of high selectively preparing the aldehyde through the olefin hydroformylation reaction; the aldehyde with a high normal-specific ratio can be produced, wherein the positive-specific ratio can reach 25 or above; side reactions are few; and the alkane content of an obtained product is 1% or below. The multi-phase catalyst is good in stability, and the separation of the catalyst from the reactants and products is simple and efficient.

The invention relates to a multi-phase catalyst for preparing propionaldehyde by ethene hydroformylation and a fixed bubbling bed reaction technology using the catalyst. More specifically, the multi-phase catalyst is formed by self-loading a transitional metal component by an organic ligand polymer carrier; the organic ligand polymer carrier is formed by polymerizing organic ligand monomers containing P, randomly selected N and alkenyl by a solvent thermal polymerization method and adopts a multistage pore structure; the transitional metal component is one or more of Rh, Ir and Co; furthermore, the content of the transitional metal component is 1-20.0 percent based on the total weight of the catalyst. The preparation method for the catalyst and a reaction technology and a reaction device which apply the catalyst are simple; propionaldehyde prepared by ethene hydroformylation of the catalyst is stable in performance and high in activity and yield; ethene hydroformylation reaction with strong reaction heat is realized; the multi-phase catalyst has wide industrial application prospect.

The invention discloses a catalyst composition for reducing the normal-to-isomer ratio of aldehyde products which are obtained through a hydroformylation reaction of olefin. The catalyst composition comprises a solvent, a catalyst active component, a cocatalyst, an assistant A and an assistant B, wherein the catalyst active component is a rhodium salt, the cocatalyst is triphenylphosphine, the assistant A is a phosphine-containing alkyl ligand, and the assistant B is indole structure-containing doped benzene. The catalyst composition is applied to hydroformylation of olefin, the normal-to-isomer ratio in the products can be reduced, and the selectivity and stability of a catalyst under the condition of a low normal-to-isomer ratio of less than 10 can be improved.

The invention relates to a substitutive bidentate phosphoramidite ligand of a diphenyl ketone framework in the catalysis of hydroformylation and Isomerization-hydroformylation of isomerised olefins. In an atmosphere of an inert gas or N2, the ligand is reacted with an Rh salt in an organic solvent to obtain a ligand / Rh catalyst. In the atmosphere of the inert gas or N2, an olefin substrate is added into solution of the ligand / Rh salt catalyst, CO and H2 are charged into the solution respectively to undergo a raction to form the a hydroformylated product, namely a compound having formyls, wherein the conversion rate of the reaction is high; and the selectivity of the n-alkanal product is high. The substitutive bidentate phosphoramidite ligand of the diphenyl ketone framework has a structural formula below.

The invention discloses a method for preparing an enamine ketone compound, wherein the enamine ketone compound with two substituents on a nitrogen atom is prepared through an enolate intermediate. A formylation reaction is carried out by using a ketone compound with alpha-methyl or alpha-methylene as a substrate to obtain enolate; and a dehydration-condensation reaction of the enolate and dimethylamine hydrochloride is further carried out to obtain the enamine ketone compound. A reaction formula is as shown in the figure. The raw materials adopted by the method are all ordinary and easily obtained materials, and the method has simple preparation process and mild reaction condition, does not need large expensive equipment and is adaptable to industrialized large-scale production; moreover, the reaction selectivity is high, and the prepared enamine ketone has high yield, is easy to separate and purify and has broad application prospect.

The invention discloses a preparation method for a highly-dispersed supported catalyst. The preparation method comprises the following steps: adding tannic acid and a carrier into an active metal precursor solution, adjusting a pH value of an obtained solution to 8 to 11, carrying out a reaction for 1 to 3 h, and carrying out filtering, drying and reducing so as to obtain the highly-dispersed supported catalyst. Due to the chelating and stabilizing actions of the tannic acid, the universality of the carrier is high, and an oxide carrier with defects is no longer limited. The above-mentioned method is simple and effective and has easily-available raw materials, low cost and important industrial application prospects. The invention also discloses the highly-dispersed supported catalyst prepared by using the above-mentioned method provided by the invention. The highly-dispersed supported catalyst has high active metal dispersity and high atom utilization rate. The invention also disclosesan application of the highly-dispersed supported catalyst in a hydroformylation reaction of olefin and a hydroesterification reaction of unsaturated hydrocarbon. The highly-dispersed supported catalyst provided by the invention has high catalytic efficiency and good selectivity; and compared with a conventional homogeneous catalyst, the highly-dispersed supported catalyst provided by the invention is easy to be separated from a hydroformylation reaction system and a hydroesterification reaction system, so the cost of recovery is reduced.

The invention relates to an olefin hydroformylation catalyst. The problems of low reaction activity, low normal-to-iso ratio in products, and poor stability of phosphine ligand based rhodium catalysts in the prior art are solved. The olefin hydroformylation catalyst comprising a rhodium-containing catalyst precursor, a bidentate phosphine ligand and a bidentate phosphite ligand well solves the problems, and can be used in olefin hydroformylation reactions.

The invention relates to a synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds, which comprises the following steps: by using phenylmethyl acetate with or without substituting groups as a raw material, carrying out formylation reaction at -20-100 DEG C for 4-6 hours in a nitrogen atmosphere in the presence of Lewis acid in an aprotic solvent neutralized formylation reagent, dissociating with an organic base, hydrolyzing with hydrochloric acid, and stratifying, wherein the organic layer is an intermediate; carrying out methylation reaction on the intermediate, benzyltriethylammonium chloride, a methylation reagent and an inorganic base at 20-100 DEG C for 1-3 hours; after the reaction finishes, washing with water, desolventizing, and recrystallizing or distilling while depressurizing to obtain the product. The invention has the advantages of fewer processing steps (the methylation reaction can be directly carried out without purifying and separating the intermediate product), favorable selectivity, higher yield and low cost; and the reaction process is easy to control, and is safe and easy to amplify.