Chinese Academy of Sciences

Uop Lcc

Other

Dalian Institute of Chemical Physics

Mingyuan Zheng

Tao Zhang

Aiqin Wang

Xiaodong Wang

Jifeng Pang

Na Ji

Jingguang Chen

Tom N Kalnes

Joseph A Kocal

John Qianjun Chen

Yu Jiang

Yuying Shu

Changzhi Li

Zhijun Tai

Hui Xing Wang

Weizhen Li

Yanhua Zhang

Likun Zhou

Aigin Wang

Shuo Al

Ruiyan Sun

Hui Wang

This invention provides a method for catalytic conversion of carbohydrates to low-carbon diols using alloy catalysts. In the process, carbohydrates as the feedstock are subjected to one-step catalytic conversion to realize the highly efficient and selective production of ethylene glycol etc. under hydrothermal conditions, with an alloy catalyst composed of tin, and a transition metal such as iron, cobalt, nickel, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof. The reaction is carried out in water at a temperature range of 120-300&#xb0; C., with a hydrogen pressure range of 1-13 MPa. Compared with the present petroleum based synthesis technology of ethylene glycol, the method in this invention possesses advantages of using renewable feedstock, high atom economy and environmental friendly. Besides, compared with other technologies using biomass as feedstock to produce ethylene glycol, the alloy catalyst in this invention possesses the advantages of few leaching amount, good hydrothermal stability and easy to recycle.

Method of catalytic conversion of carbohydrates to low-carbon diols by using alloy catalysts

This invention discloses an approach for the separation of the close-boiling mixture of polyols. The raw material is ethylene glycol containing miscellaneous polyols (such as 1,2-propylene glycol and 1,2-butanediol). Over an acid catalyst, these miscellaneous polyols, through (1) a dehydration reaction, (2) pinacol rearrangement, and (3) acetalization or ketalization reaction, are converted into aldehydes (small amounts), acetals, and ketals (trace amount), which are simultaneously and readily separated via distillation. Meanwhile, after the reaction, the mixture is further separated to obtain an ethylene glycol product at a high purity. The invention provides a technique to remove the miscellaneous polyols from ethylene glycol via liquid-phase dehydration reactions under mild conditions, with low energy consumption. In particular, this approach is markedly effective for the removal of 1,2-butanediol that is difficult to be removed via conventional techniques. The purity of the resulting ethylene glycol product is high, and value-added acetals or ketals are co-produced.

Method for separation of close-boiling mixture of polyols

This invention provides methods for producing ethylene glycol from polyhydroxy compounds such as cellulose, starch, hemicellulose, glucose, sucrose, fructose, fructan, xylose and soluble xylooligosaccharides. The methods uses polyhydroxy compounds as the reactant, a composite catalyst having active components comprising one or more transition metals of Groups 8, 9, or 10, including iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, as well as tungsten oxide, tungsten sulfide, tungsten hydroxide, tungsten chloride, tungsten bronze oxide, tungsten acid, tungstate, metatungstate acid, metatungstate, paratungstate acid, paratungstate, peroxotungstic acid, pertungstate, heteropoly acid containing tungsten. Reacting at a temperature of 120-300&#xb0; C. and a hydrogen pressure of 1-13 MPa under hydrothermal conditions to accomplish one-step catalytic conversion. It realizes efficient, highly selective, high yield preparation of ethylene glycol and propylene glycol from polyhydroxy compounds. The advantage of processes disclosed in this invention include renewable raw material and high atom economy. At the same time, compared with other technologies that converts biomass raw materials into polyols, methods disclosed herein enjoy advantages including simple reaction process, high yield of targeted products, as well as easy preparation and low cost for the catalysts.

Methods for preparing ethylene glycol from polyhydroxy compounds

This invention provides a method for highly efficient catalytic conversion of cellulosic raw materials to glycols. In the process, cellulosic compounds such as crop stalk, wood powder and etc., as feedstock are subjected to one-step catalytic conversion with a ternary composite catalyst composed of organic acid or inorganic acid which does not contain tungsten, a transition metal from Groups 8, 9 or 10 such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, or a mixture thereof, and a tungsten oxide, a tungsten sulfide, a tungsten chloride, a tungsten hydroxide, tungsten bronze, tungstic acid, a tungstate, a metatungstate acid, a metatungstate, a paratungstate acid, a paratungstate, a peroxotungstic acid, pertungstate and heteropoly tungstate, or a mixture thereof. The reaction is carried out under hydrothermal conditions at a temperature between 120-300&#xb0; C. with hydrogen pressure between 1-13 MPa.

Process for highly efficient catalytic conversion of cellulose raw material to diol

A supported tungsten carbide catalyst comprises tungsten carbide as its active component and a mesoporous carbon as its support, wherein tungsten carbide is highly dispersed on the surface and in the channels of the mesoporous carbon, and the content of tungsten element is in the range from 30% to 42% by mass based on the mesoporous carbon. This catalyst can be prepared by impregnation process. This catalyst can be used for the direct catalytic conversion of cellulose to ethylene glycol under the hydrothermal conditions and at a temperature of 245&#xb0; C. and the hydrogen pressure of 6 MPa with high reactivity, selectivity and stability.

Mesoporous carbon supported tungsten carbide catalysts, preparation and applications thereof

Tungsten carbide catalysts are used in preparation of ethylene glycol by hydrogenating degradation of cellulose. The catalyst includes tungsten carbide as main catalytic active component, added with small amount of one or more transition metals such as nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, and copper as the second metal, supported on one or more porous complex supports such as active carbon, alumina, silica, titanium dioxide, silicon carbide, zirconium oxide, for conversion of cellulose to ethylene glycol. The catalyst realizes high efficiency, high selectivity, and high yield in the conversion of cellulose to ethylene glycol at the temperature of 120-300&#xb0; C., hydrogen pressure of 1-10 MPa, and hydrothermal conditions. Compared to the existing industrial synthetic method of ethylene glycol using ethylene as feedstock, the invention has the advantages of using renewable raw material resources, environment friendly process, and excellent atom economy.

Methods of using tungsten carbide catalysts in preparation of ethylene glycol

A catalytic process for generating at least one polyol from a feedstock comprising cellulose is performed in a continuous manner. The process involves, contacting, continuously, hydrogen, water, and a feedstock comprising cellulose, with a catalyst to generate an effluent stream comprising at least one polyol, water, hydrogen, and at least one co-product. The water, hydrogen, and at least one co-product are separated from the effluent stream and recycled to the reaction zone. The polyol is recovered from the effluent stream.

Continuous catalytic generation of polyols from cellulose with recycle

A catalytic process for generating at least one polyol from a feedstock comprising cellulose is performed in a continuous manner using a catalyst comprising nickel tungsten carbide. The process involves, contacting, continuously, hydrogen, water, and a feedstock comprising cellulose, with the catalyst to generate an effluent stream comprising at least one polyol and recovering the polyol from the effluent stream.

Continuous catalytic generation of polyols from cellulose

A method for producing ethylene glycol, including (a) adding a polyhydroxy compound and water to a sealed high-pressure reactor, (b) removing air and introducing hydrogen, and (c) allowing the polyhydroxy compound to react in the presence of a catalyst while stiffing. The catalyst includes a first active ingredient and a second active ingredient. The first active ingredient includes a transition metal of Group 8, 9, or 10 selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, and/or a mixture thereof. The second active ingredient includes a metallic state of molybdenum and/or tungsten, or a carbide, nitride, or phosphide thereof. The method is carried out at a hydrogen pressure of 1-12 MPa, at a temperature of 120-300&#xb0; C. for not less than 5 min in a one-step catalytic reaction. The efficiency, selectivity, and the yield of ethylene glycol are high. The preparation process is simple and the materials used are renewable.

Method for producing ethylene glycol from polyhydroxy compound

A method for preparing ethylene glycol from cellulose uses the cellulose as the feed for the reaction. The cellulose conversion is performed over catalysts which are composed of the metallic state, carbides, nitrides, or phosiphides of molybdenum or tungsten, and metallic cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum of the group 8, 9, or 10 transition metals. The catalytic conversion of cellulose is conducted at 120 to 300&#xb0; C. and hydrogen pressure 1 to 12 MPa under the hydrothermal conditions to achieve the high efficiency, high selectivity, and high yield of ethylene glycol. Compared to the existing method of preparing ethylene glycol from ethylene, the method, using the renewable raw material for the reaction, is friendly to the environment, and has high atom economy.

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Dalian, China

Mingyuan Zheng