Catalyst for hydrolysis of cellulose and/or reduction of products of hydrolysis of cellulose and method of producing sugar alcohols from cellulose

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalyst for hydrolysis of cellulose or hydrolysis of cellulose and reduction of products of hydrolysis and a method of producing sugar alcohols from cellulose. Described is a catalyst for hydrolysis of cellulose and hydrolysis of cellulose and reduction of hydrolysis products in which a group 8-11 transition metal is deposited on a solid substrate. Described also is a method of producing sugar alcohols involving: hydrolysis of cellulose in the presence of the catalyst in a hydrogen-containing atmosphere at high pressure and reduction of the product of hydrolysis of cellulose.

EFFECT: easy separation of the catalyst from the product, avoiding the need to regulate pH, neutralise acid or alkali when producing alcohols, possibility of recycling a catalyst without activation thereof, obtaining sugar alcohols directly from cellulose using said catalyst.

19 cl, 2 tbl, 8 dwg, 6 ex

 

This application sets the priority of Japanese patent application 2006-54342 filed March 1, 2006, the contents of which are fully included here as a reference.

The technical field

The present invention relates to a catalyst for hydrolysis and recovery of cellulose and to a method for production of cellulose to sugar alcohols. More specifically, the present invention relates to a catalyst, providing sugar alcohols directly from cellulose, and to a method for producing sugar alcohols from cellulose using such a catalyst. Specific sugar alcohols, which are obtained by the present invention are sorbitol and/or mannitol.

The level of technology

Biomass is a renewable resource and plays a role in preventing global warming, reducing the carbon dioxide emissions. In the production of biomass for chemical products (biological treatment) discusses how the conversion of biomass into ethanol, lactic acid and other useful chemical products of enzymatic or chemical means. Currently, the main material used for biological treatment, is a starch derived from corn. From the point of view of the amount of resources the main structural components of plants that can b is to be used, cellulose is present in much larger quantities than starch. However, the methods of transformation of cellulose in a chemically useful products by reducing its molecular weight has not been developed, and this resource is currently not actually used. (See publication Koshijima and others, Functional Cellulose, CMC Publishing Co., Ltd. (2003), and The Japan Institute of Energy, ed., Biomass Handbook, Ohmsha (2002), the contents of which are fully included here as a reference.) For example, a large number of studies conducted in the area of decomposition of cellulose using enzymes. However, there are important problems associated with enzymatic methods, due to the low reaction rates, and the need to enhance the activity of the enzyme and separation from the product. The degradation of cellulose by using catalysts attempted implementation of the methods of obtaining glucose by hydrolysis in the presence of sulfuric acid or hydrofluoric acid. However, such methods have not been implemented in practice due to corrosion of the reactor under the action of acid, risk factors and receipt of large quantities of waste neutralization, imposing a heavy load on the environment.

In previous studies of the chemical conversion of cellulose using catalysts authors Balandin, Vasyunina, etc. for obtaining sorbitol from sulfite pulp wire is whether hydrogenation using deposited on a substrate ruthenium catalyst with a yield of 82% (see the publication of A.A. Balandin, N.A. Vasyunina, G.S. Barysheva, S.V. Chepigo,Izv. Akad. Nauk SSSR, Ser. Khim.,392 (1957), the contents of which are fully included here as a reference). However, this publication does not describe the use as starting material of cellulose per se. In addition, the use in the reaction with sulfuric acid requires the separation of the product, and there are problems in the form of waste neutralization and corrosion of the reactors. The same group of researchers to obtain sorbitol was used as source material silk cellulose, which were treated with alkali and acid, and spent hydrogenation using deposited on a substrate of Raney Nickel in the presence of Nickel sulfate in aqueous solution (see publication N.A. Vasyunina, A.A. Balandin, G.S. Barysheva, S.V. Chepigo, Yu.L. Pogpsov, Z.Prik. Khim.,37, 2725 (1964), the contents of which are fully included here as a reference). And here again we had to pre-process the cellulose, and the selection of the product was not easy. Specht, etc. as the starting material used is a mixture of cellulose and hemicelluloses, which were treated by hydrolysis, and after adjusting the pH of the mixture to 8 or above synthesized sugar alcohols by hydrogenation using deposited on a substrate of the catalyst of Raney Nickel (see patent H.Specht and H. Dewein, DE 1066567 (1959), the content of which is incorporated here fully in to the number of links). However, the required pre-treatment of pulp and pH regulation.

Although cellulose is insoluble in water, most of the starches with similar structure soluble in water. Because hydrolysis and hydrogenation of water-soluble starch proceed without problems in this area have conducted a large number of studies. Corporation Atlas Powder Corp. for the hydrogenation of starch used catalyst Ni/diatomaceous earth and received the polyols (see Atlas Powder, GB 872809 (1961), the contents of which are fully included here as a reference).

Kruse and others for the synthesis of sorbitol from corn starch in two stages used catalyst Ru/USY (see U.S. patent W.M. Kruse and L. W. Wright, US 3963788 (1976), the content of which is incorporated here fully by reference).

Jacobs and others for the synthesis of sorbitol in one stage used the catalyst Ru/USY (see European patent P. Jacobs and H. Hinnekens, EP 0329923 (1989), the Japanese publication of unexamined patent application (KOKAI) Heisei No. 1-268653 or English patent EP 0329923A1, the contents of which are fully included here as a reference). Hydrogenation of the water-insoluble cellulose in the cited publications was conducted. In addition, the catalysts were limited to highly dispersed catalysts with the degree of dispersion of the Ru of 0.58 or higher.

As shown above, in the traditional production of Chernyh alcohols, such as sorbitol, by hydrolysis and hydrogenation of cellulose pulp to increase the solubility in water is always treated with acid or alkali and then used as the reaction substrate; not detected example, when you use water-insoluble cellulose as such. In addition, the need to separate the catalyst and the product, adjust pH to neutralize the acid or alkali and activate the catalyst when reusing create problems in the form of a large load on the environment.

Thus, the purpose of the present invention consists in obtaining a catalyst intended for use in preparation of sugar alcohols by hydrolysis and hydrogenation of cellulose, which provides the use of cellulose without pre-treatment, which provides easy separation of the catalyst from the product and which does not require pH adjustment, neutralization of acid or alkali or activation of the catalyst during repeated use, and in providing a method of producing sugar alcohols from cellulose using such a catalyst.

Description of the invention

To solve the above problems, the authors of the present invention have carried out the reaction in order to reduce the molecular weight of cellulose using solid catalysts. The study led to open the Yu, when conducting reactions of hydrolysis and hydrogenation of cellulose in water under excessive pressure hydrogen deposited on a substrate with a metal catalyst, as shown by the following reaction equation, sugar alcohols (sorbitol and mannitol) are synthesized in one stage.

The present invention includes:

1. The catalyst for the hydrolysis of cellulose and/or recovery of the products of hydrolysis, in which the transition metal 8-11 group is applied to a solid substrate.

2. The catalyst according to claim 1, in which at least a part of the above mentioned solid substrate comprises a porous material.

3. The catalyst according to claim 1 or 2, in which at least a part of the above mentioned solid substrate comprises an inorganic oxide.

4. The catalyst according to any one of points 1 to 3 in which at least a part of the above mentioned solid substrate consists of a material having acidic properties.

5. The catalyst according to any one of points 1 to 4, in which at least a part of the above mentioned solid substrate is at least one representative selected from the group consisting of: silicon dioxide, aluminum oxide, silica-alumina, zeolite, titanium dioxide, zirconium dioxide and activated carbon.

6. The catalyst according to any one of points 1 to 5, in which the aforementioned solid on the spoon is in the form of powder, particle shape, a granular form or in the form of beads; has a cellular structure or extrudable profile; is in the form of annular shape or a columnar shape; has extrudable corrugated profile; or is a corrugated annular shape.

7. The catalyst according to any one of points 1 to 5, in which the mentioned transition metal is at least one representative selected from the group consisting of platinum, ruthenium, rhodium, palladium, iridium, Nickel, cobalt, iron, copper, silver and gold.

8. The catalyst according to any one of points 1 to 7, in which the mentioned transition metal is applied to the surface of the solid substrate with the degree of dispersion of from 0.01 to 60.

9. The catalyst according to any one of points 1 to 8, in which the mentioned transition metal is applied to the substrate at a content of 0.01 to 60 wt.%.

10. The catalyst according to any one of points 1 to 8 in which the catalyst used for the hydrolysis of cellulose.

11. The catalyst according to any one of points 1 to 8 in which the catalyst is used to restore the product of the hydrolysis of cellulose.

12. The catalyst according to any one of points 1 to 8 in which the catalyst used for the hydrolysis of cellulose and to restore the product of the hydrolysis of cellulose.

13. The method of obtaining sugar alcohols, including:

the hydrolysis of cellulose in the presence of the catalyst described in any of clauses 1-9, in a hydrogen-containing atmosphere at an elevated pressure; and

the restoration of the hydrolysis product of cellulose.

14. The way of getting item 13, wherein said cellulose is a α-cellulose crystal structure or having a low degree of crystallinity.

15. A way of getting under item 13 or 14, wherein the hydrolysis and recovery are carried out in the presence of water.

16. The way of getting any PP 13-15, in which the said catalyst is used at a mass ratio of from 0.05 to 5 relative to pulp.

17. The way of getting any PP 13-16, in which the pressure of hydrogen in the hydrogen containing atmosphere is from 1 to 100 MPa.

18. The way of getting any PP 13-17, in which the above-mentioned hydrolysis and recovery is carried out by heating to a temperature of from 150 to 250°C.

19. The way of getting any PP 13-18, in which the aforementioned sugar alcohols are sorbitol and/or mannitol.

20. The way of getting any PP 13-19, wherein after completion of the above-mentioned hydrolysis and recovery of the reaction mixture is subjected to separation into solid and liquid phases and isolated in the form of an aqueous solution containing sugar alcohols, and solids containing at least a catalyst and unreacted cellulose.

Advantages the STV inventions

The present invention is characterized by the following features:

1. For the first time discovered that sugar alcohols (sorbitol and mannitol) can be directly synthesized, using as starting material cellulose. The main component of the sugar alcohol is sorbitol.

2. What additional catalysts were open Pt and Ru catalysts deposited on a substrate with high activity. The catalysts corresponding to the previously patented catalyst Ru/HUSY (Ru/HUSY (2.9, NH3IE) in figure 1), through which the starch synthesized sorbitol, in this reaction involving cellulose exhibit only very low activity (output up 0.7%). Thus, the reaction of cellulose has only been open recently a catalyst. High activity provide a substrate of an inorganic oxide having acid properties in the solid state.

3. The catalyst was separated, can be reused as-is; its processing with the purpose of activation is not needed.

Sorbitol is a sugar alcohol that has three applications. The first area of application corresponds to the sweetener, which is widely distributed in the food industry. The second area is used as intermediate compounds in the synthesis of useful compounds, such as from orbit, propylene glycol, ethylene glycol, glycerol, 1,4-sorbitan and lactic acid. Isosorbide, in particular, is also used in modern processes, such as the copolymerization in the production of polyethylene terephthalate (PET) for the production of polyethyleneterephtalate (PEIT). The PEIT polymer has a higher glass transition temperature than PET, so it is expected to be applied to a transparent plastic containers that can withstand hot water. The third area of application is the use as intermediate compounds in the production of hydrogen and liquid hydrocarbons (containing mainly C5and C6-alkanes)that can be played from biomass. Hydrogen is used in fuel cells, and hydrocarbons are the source material for the petrochemical industry. Although based on research Dumesic and other hydrogen can be obtained from glucose and sorbitol, applying deposited on a substrate of metal catalysts, the use of sorbitol as a source of materials provides greater selectivity of hydrogen and alkanes than glucose (J.A. Dumesic and others,Chern. Commun. 36(2004)). Thus, the application of the results of the present invention provides a hydrogen production for fuel cells and hydrocarbons for petrochemical industry using cellulose as the e of the source material and sorbitol as an intermediate connection.

Mannitol is the isomer (epimer) sorbitol in position C2 and has properties similar to sorbitol.

The preferred embodiment of the invention

Catalyst

The catalyst of the present invention, in which the transition metal 8-11 group is applied to a solid substrate, catalyzes the hydrolysis of cellulose and/or restoration of the hydrolysis product. Referred to "the hydrolysis product" is a product of the hydrolysis of cellulose, specifically represents glucose.

Solid substrate

At least part of the solid substrate used in the catalyst of the present invention, consists of a porous material; it is also suitable for the deposition of the transition metal on its surface.

Thus, the solid substrate used in the catalyst of the present invention, consists of a porous material, at least some part of the surface of which serves as a substrate for the transition metal, and a solid substrate may be entirely of a porous material or may consist of non-porous material, the surface of which is covered with a porous material. The substrate may also consist of another porous material.

At least part of the solid substrate used in the catalyst of the present invention, may consist, in the example, of the inorganic oxide. It is desirable that the inorganic oxide represented the above-described porous material. In addition, it is desirable that at least part of the solid substrate used in the catalyst of the present invention, was in the form of a solid substrate having acid properties, preferably in the form of a solid substrate having acid properties, representing the above-described porous material. Based on the results of research conducted by the authors of the present invention, preferably, the solid substrate is provided the site with the acidic proton on the substrate, on which the hydrogen molecules undergo dissociation under the action of such a metal as Pt.

A specific example of a solid substrate: silicon dioxide, aluminum oxide, silica-alumina, zeolite, titanium dioxide, zirconium dioxide and activated carbon.

Among the silica are examples of amorphous silica: the company Wako Pure Chemical Industries, Ltd.: Wakogels (C-100, C-100E, C-200, C-200E, C-300, C-300E, C-300HG, C-400HG, C-500HG, 50C18, 100C18, DX, FC-40, FC-40FM, G, LP-20 LP-40 LP-60, Q-12, Q-22, Q-23, Q-50, Q-63 and S-1); company Wakosils (C-200, C-300, 25SIL, 25C18, 40SIL and 40C18); company Kanto Chemical Co., Inc.: the silica (60 60N); Merck, Inc.: silica gels (40,60 and 100); Sigma-Aldrich Japan K.K.: silica gels(03, 12, 15, 22, 40, 41, 62, 922, 923, high purity, 70-230 mesh 60 A, 70-270 mesh 60 A, 130-270 m the W 60 A and the 200-400 mesh, 60 A) and silicon dioxide (particle size of 0.5-10 microns); the Fuji Silysia Chemical, Ltd.: CARIACT Q, G and P); the company Grace Davison Co.: Davisil(633, 634, 635, 636, 643, 644, 645, 646 and 710); the company Degussa (Nippon Aerosil Co., Ltd.): Aerosil(90, 130, 150, 200, 300 and 380); the company's NIKKI CHEMICAL CO.,LTD.: dioxidine catalysts (N601, N601A, N601T, N601R3, N601A3, N601T3, N602, N602A, N602T, N608R, N608A and N608T); company Catalysis Society of Japan: standard dioxidine catalysts (JRCS10-1, JRC-SI0-5, JRC-SI0-6, JRC-SI0-7, and JRC-SI0-9A); and Riedel-de Haen Co.: Cabosil M-5.

Examples of mesoporous silica are dioxides with pore diameters of 2 to 50 nm and a specific surface area of 500 to 1500 m2g-1such as FSM-16 (S. Inagaki, and others,J.Chem.Soc.,Chem.Commun.,680 (1993); MCM-41 (C. T. Kresge, and others, Nature, 359, 710 (1992); J.S. Beck and otherSoC.,114, 10834 (1992); SBA-15 (D. Zhao and others,Science,279, 548 (1998); Called Taiyo Co., Ltd.: NPM (nanoporous material, the pore diameter of 1-10 nm); and Sigma-Aldrich Japan K.K.: silicon dioxide (metastructuring, hexagonal lattice, the type MCM-41).

Examples of the aluminum oxide in the form of γ-alumina: the company Wako Pure Chemical Industries, Ltd.: activated alumina; the company Kanto Chemical Co., Inc.: aluminum oxide(α-type,NanoTek, activated); Merck Inc.: aluminum oxide (90, 90 (activated, acid, activity I), 90 (activated, basic, activity I) and 90 (activated, neutral, activity I)); Sigma-Aldrich Japan K.K.: aluminum oxide (to 99.99%, 100 mesh to 99.9%, powder <10 microns, nanopowder, filiform crystals in the form of nanopores is a, -100 mesh 99%, the balls 3 mm in diameter, activated acid Brockmann I, activated subacid Brockmann I, activated basic Brockmann I, activated, neutral, Brockmann I, processed); the company Nishio K.K.: γ-alumina A-11; companies NIKKI CHEMICAL CO.,LTD.: oxytelinae catalysts (N611N, N611N3, N612N and N613N); and the company Catalysis Society of Japan: standard oxytelinae catalysts (JRC-ALO-1, JRC-ALO-2, JRC-ALO-3, JRC-ALO-5, JRC-ALO-1A, JRC-ALO-5A, JRC-ALO-6, JRC-ALO-7 and JRC-ALO-8).

Examples of titanium dioxide include rutile, anatase, and amorphous forms, specifically: the company Wako Pure Chemical Industries, Ltd.: the titanium oxide (IV) (amorphous, in the form of anatase and rutile, 80 nm); the company's Kanto Chemical Co., Inc.: the titanium oxide (IV) (in the form of rutile and anatase, 3N, NanoTek); Sigma-Aldrich Japan K.K.: titanium oxide (IV) (99,999%, 99,99%, mesoporous, with pores 32 angstroms at 99.95%, powder <5 microns to 99.9+%, powder of 99.9+%, -325 mesh 99+%); Japan Aerosil Co., Ltd.: Aeroxide TiO2(NKT90, P25, PF2 and T805); company Sakai Chemical Industry Co., Ltd.: the titanium oxide (SR-1, R-42, R-GL, R-GX, R-GX-2, R-45M, R-650, R-32, R-5N, R-5N-2, R-61N, R-62N, R-7E R-3L, R-3L-SN, R-11P, R-21, R-25, R-310, D-918, A-110, A-150, ST-G A-190, SA-1 and SA-1L); the company Ishihara Sangyo Kaisha, Ltd.: the titanium oxide in the form of ultramontanism particles (TTO-51(A), TIO-51(C), TTO-55(A), TTO-55(B), TTO-55(C), TTO-55(D), TTO-S-1, TTO-S-2, TTO-S-3, MPT-136, TTO-V-3, TTO-V-4, TTO-F-2 and TTO-F-6), neutral Sol of titanium dioxide TSK-5, oxides of titanium as a substrate for catalyst (MC-50, MC-90, MC-150), and the photocatalytic titanium oxide (ST-01, ST-21, ST-31, ST-41 and ST-30L); and comp the Institute of Catalysis Society of Japan: standard dioxidine catalysts (JRC-TIO-1, JRC-TIO-2, JRC-TIO-4, JRC-TIO-S, JRC-TIO-6, JRC-TIO-7, JRC-TIO-8, JRC-TIO-9, JRC-TIO-10, JRC-TIO-11, JRC-TIO-12 and JRC-TIO-13).

Examples of the silica-alumina are products of Sigma-Aldrich Japan K.K.: a substrate for a catalyst of silica-alumina grade 135; companies NIKKI CHEMICAL CO.,LTD.: silicon dioxide-aluminum oxide (N631L, N631HN, N632L, N632HN, N633L and N633HN), and the company Catalysis Society of Japan: standard catalysts on silica-alumina (JRC-SAH-1 and JRC-SAL-2).

Examples of zeolites:

β-type(structural code BEA, hereinafter the same): Catalysis Society of Japan: standard zeolite(β)the catalyst JRC-Z-B25(1), JRC-Z-HB25(1), JRC-HB150(1); company Zeolyst Co.: CP814N*, CP814E*, CP814C*, CP814Q*, CP811E-150, CP811C-300; company Tosoh Corporation: 930NHA, 940NHA and 940HOA;

Y-type (FAU): Sigma-Aldrich Japan K.K.: a substrate for the catalyst in the form of molecular sieves, sodium Y-zeolite powder; the substrate for the catalyst in the form of molecular sieves, ammonium Y zeolite powder; company Catalysis Society of Japan: standard zeolite (Y-type) catalyst JRC-Z-Y4.8, JRC-Z-Y5.6, JRC-Z-HY4.8(2), JRC-Z-Y5.5, JRC-Z-Y5.3, JRC-ZHY5.5 and JRC-Z-HY5.3; UOP LLC: Y-52(NaY), Y-64(NH4Y), Y-74(HY), Y-84(NH4Y) and LZ-15(HY); company Zeolyst Co.: CBV100, CBV300, CBV400, CBV600, CBV712, CBV720, CBV740, CBV760, CBV780 and CBV 901); the company Tosoh. Corporation: 320NAA, 320HOA, 331HSA, 341NHA, 350HUA, 360HUA, 385HUA and 390HUA; and the company's Catalysts &Chemicals Ind. Co., Ltd.: ZCP-50S, ZCP-50, ZCP-150, ZCP-300, ZCP-700, ZCP-1000, ZCP-2000, ZCE-50S, ZCE-50, ZCE-150-2000, ZCB-50S and ZCB-2000. In this application the mentioned price is LTL Y-type are referred to as "USY", if it dealuminated zeolites, Y-type, and just as "Y"if it zeolites that have not undergone such processing. Thus, the zeolites, in which the cation is a proton, referred to as "HUSY" and "HY", respectively.

ZSM-5-type (MFI): Catalysis Society of Japan: standard zeolite (ZSM-5) catalyst JRC-Z5-25H, JRC-Z5-70H, JRC-Z5-1000H, JRC-Z5-70NA, JRC-Z5-1000NA, JRC-Z5-90NA(1) and JRC-Z5-90H(1); and the company Zeolyst Co.: CBV2314, CBV3020E, CBV3024E, CBV5524G, CBV8014 and CBV28014.

Zeolite mordenite (MOR): Catalysis Society of Japan: standard zeolite (mordenite) catalyst JRC-Z-M15(1), JRC-Z-M20(1), JRC-Z-HM20(5), JRC-Z-HM90(1); company Zeolyst Co.: CBV10A, CBV21A, and CBV90A; and the Corporation Tosoh Corporation: 642NAA, 640HOA and 690HOA. Among the above-mentioned zeolite is preferred USY-type processing, carried out for dealumination.

Examples of activated carbon: the company Wako Pure Chemical Industries, Ltd.:activated charcoal (for chromatography, powdered form from 0.2 to 1 mm, the crushed form from 2 to 5 mm, granular form, powder form, the powder, the acid-treated, powder processed with alkali, neutral powder, columnar form); the company's Kanto Chemical Co., Inc.: activated carbon (in the form of particles and powder); Sigma-Aldrich Japan K.K.: granules of activated carbon from 4 to 14 mesh; the company Norit Japan Co., Ltd.: PK, PKDA 10×30 MESH(MRK), ELORIT, AZO, DARCO, HYDRODARCO 3000/4000,DARCO LI, PETRODARCO, DARCO MRX, GAC, GAC PLUS, DARCO VAPURE, GCN, C GRAN, ROW/ROY, RO, ROX, RB/W, R, R.EXTRA, SORBNORIT, GF 40/45,CNR, ROZ, RBAA, RBHG, RZN, RGM, SX, SA, D 10, VETERIHAIR, PN, ZN, SA-SW, W, GL, SAM, HB PLUS, A/B/C EUR/USP, CA, CN, CG, GB, CAP/CGP SUPER, S-51, S-51 A, S-51 HF, S-51 FF, DARCO GFP, HDB/HDC/HDR/HDW, GRO SAFE, DARCO INSUL, FM-1, DARCO TRS, DARCO FGD/FGL/Hg/Hg-LH and PAC 20/200;Japan EnviroChemicals, Ltd.: Shirasagi (A, C, DO-2, DO-5, DO-11, FAC-10, M, P, PHC, Element DC), Aldenite, Carboraffin, Carboraffin DC, cellular carbo Shirasagi, Morshibon resistant Shirasagi, purified Shirasagi supplied by special order Shirasagi, X-7000/X7100, X7000-3/X-7100-3, LPM006, LPM007 and Shirasagi in the form of particles (APRC, C2c, C2x, DC, G2c, G2x, GAAx, GH2x, GHxUG, GM2x, GOC, GOHx, GOX, GS1x, GS2x, GS3x, GTx, GTsx, KL, LGK-100, LGK-400, LGK-700, LH2c, MAC, MAC-W, NCC, S2x, SRCX, TAC, WH2c/W2c, WH2x, WH5c/W5c, WHA, X2M (Morshibon 5A), XRC, X7000H/X7100H, X7000H-3/X7100-3, LGK-700 and " DX7-3); company Kuraray Chemical Co., Ltd: activated carbons in the form of particles for use in the gas phase GG/GS/GA; activated carbons in the form of particles for use in the gas phase GW/GL/GLC/KW/GWC; and activated carbon in powder form PW/PK/PDX; the company Calgon Mitsubishi Chemical Carbon: Diahope (006, 006S, 007, 008, 008B, 008S, 106, 6D, 6MD, 6MW, 6W, S60, C, DX, MM, MZ, PX, S60S, S61, S70, S80, S80A, S80J, S80S, S81, ZGA4, ZGB4, ZGN4, ZGR3, ZGR4, ZS, ZX-4 and ZX-7), Diasorp (F, G4-8, 8-32 W, W 10-30, XCA-C XCA-AS and ZGR4-C) and Calgon (AG 40, AGR, APA, AP3-60, AP4-60, APC, ASC, BPL, BPL 4x10, CAL, CENTAUR 4x6, CENTAUR 8x30, CENTAUR 12x40, CENTAUR HSV, CPG 8x30, CPG 12x40, F-AG 5, Filtrasorb (Filtrasorb) 300, Filtrasorb(Filtrasorb) 400, GRC 20, GRC 20 12x40, GRC 22, HGR, HGR-LH, HGR-P, IVP 4x6, OL 20x50, OLC 20x50, PCB, PCB 4x10, RVG, SGL, STL 820, URC, WS 460, WS 465, WS 480, WS490 and WSC 470); the company Ajinomoto Fine-Techno Co., Inc.: BA, BA-H, CL-H CL-K, F-17, GS A, GS-B, HF, HG, HG-S, HN, HP, SD, Y-180C, Y-4, Y-4S, Y-10S, Y-10SF, YF-4, YN-4, YP and ZN; and the company Cataler Corporation: A-series, BC-9, BFG series, CT series, DSW series, FM-150, FW, FY-series GA PG-series and WA-series. Preferred is an activated carbon with a surface area of from 800 to 1500 m2g-1.

Neither the profile nor the form of the solid substrate is not specifically limited. However, it is possible to apply, for example, the form in powder form, the form in the form of particles, granular form, the form in the form of pellets or a honeycomb shape; extrudable profile; annular shape or a columnar shape; extrudable corrugated profile; or corrugated annular shape. The substrate, which has the form of a powder, particles, granules, or beads, for example, may consist only of the above-described porous material, oxide or the material having acidic properties. In contrast, the substrate of the honeycomb structure may consist of non-porous material, such as a substrate consisting of cordierite, or the surface of which is covered with a porous material, the oxide or the material having acidic properties. Such a substrate may also consist of another porous material.

The transition metal is at least one representative selected from the group consisting of platinum, ruthenium, rhodium, palladium, iridium, Nickel, cobalt, iron, copper, silver and gold. These transition metals can be used singly or in combinations of two or more. From the position of the high catalytic activity is perehodny metal, it is desirable to choose among platinum group metals, consisting of platinum, ruthenium, rhodium, palladium and iridium.

The transition metal is applied to the surface of the solid substrate with the degree of dispersion of from 0.01 to 0.95, preferably from 0.1 to 0.9, and preferably from 0.3 to 0.8. A lower degree of dispersion corresponds to lower the rate of formation of protons from the hydrogen molecules due to aggregation of the metal, thereby reducing the reaction rate. The degree of dispersion of the transition metal can be controlled via the amount of transition metal compounds used as starting material, the temperature conditions (speed of temperature rise and maximum temperature) annealing in oxygen upon receipt of the catalyst and temperature conditions during recovery of hydrogen (the speed of temperature rise and maximum temperature).

The amount of the transition metal, which is applied on a solid substrate, can appropriately be determined in consideration of the type and degree of dispersion of the transition metal, and is suitable, for example, range from 0.01 to 50 wt.%, preferably from 0.01 to 30 wt.%. and more preferably from 0.01 to 10% wt. by weight of the catalyst.

The catalyst according to the present invention can be obtained by using considered traditional methods designed to obtain metal catalysts, applied to terbutaline. For example, you may receive using the impregnation method as follows.

The substrate is dried in vacuum for one hour at 150°C. Then add water to obtain a liquid to form a dispersion. To the resulting add an aqueous solution containing a given amount of metal salt, and the mixture is stirred for 15 hours. Then the water is evaporated under reduced pressure, thus obtaining a solid substance, which is calcined for 2 hours at 400°C in a stream of gaseous oxygen. The product is then recover for 2 hours at 400°C in a stream of hydrogen gas, thus obtaining a catalyst in solid form (see below concept).

Substrate

Catalyst

The catalyst of the present invention is used to restore the product of the hydrolysis of cellulose. That is, it can be used to produce sugar alcohols recovery of glucose, which is the hydrolysis product of cellulose. Alternatively, the catalyst of the present invention is used for hydrolysis of cellulose and recovery product of the hydrolysis of cellulose. That is, it can be used to produce sugar alcohols by hydrolysis of cellulose to obtain glucose and then to restore glucose. Cellulose, which is then subjected to hydrolysis under the action of the catalysate is the RA of the present invention, will be described in detail below in the method of obtaining sugar alcohols.

The method of obtaining sugar alcohols

The method of obtaining sugar alcohols according to the present invention includes a stage of hydrolysis of cellulose in a hydrogen-containing atmosphere in the presence of the above catalyst according to the present invention and recovering the product of the hydrolysis of cellulose.

Cellulose serving as the source material is not specifically limited; commercially available cellulose in powder form can be used as is. Cellulose belongs to the vegetative form and may represent, for example, water-insoluble α-cellulose obtained by bleaching degreased wood flour when handling chlorine to obtain a chemically treated pulp (holocellulose), which is then treated with alkali to remove hemicellulose.

Usually two or more cellulose α-cellulose structural units are joined together by hydrogen bonds and provide its crystalline structure. In the present invention, the cellulose having a crystal structure, can be used as a source material or a crystalline cellulose can be processed for the purpose of lowering the degree of crystallinity and use the resulting cellulose with a low degree Cree is tallinnasta. Cellulose with a low degree of crystallinity can be a cellulose crystallinity which partially reduced, or cellulose, in which the crystalline structure is eliminated completely or almost completely. The type of processing used to reduce the degree of crystallinity, is not specifically limited, but preferred is a method of reducing the degree of crystallinity, providing a splitting of the above-mentioned hydrogen bonds and at least partial receipt of the single-stranded α-cellulose. The use of source material in the form of cellulose at least partially containing single-stranded α-cellulose, significantly increases the efficiency of the hydrolysis.

The method used to reduce the degree of crystallinity of the original cellulose, can be a method of obtaining single-stranded α-pulp physical splitting of hydrogen bonds in α-cellulose, such as processing by grinding in a ball mill (see publication H. Zhao, J.H. Kwak, T. Franz, J.M. White, J. E. Holladay,Energy&Fuels,20,807 (2006), the contents of which are fully included here as a reference), or a method of obtaining single-stranded α-pulp chemical cleavage of hydrogen bonds inαcellulose, for example, such as a treatment of phosphoric acid (see publication Y.H.P. Zhag, J. Cui, L.R. Lynd, L. Kuang,Biomacromolecules,7, 644 (2006), the contents of which are fully included here as a reference). Even when the processing in order to reduce the crystallinity of cellulose crystalline structure of cellulose is not completely eliminated, as described in the embodiment of the invention 7, the efficiency of hydrolysis increases significantly when using as starting material cellulose crystallinity which was partially reduced in comparison with cellulose to such processing.

An additional example of the method of reducing the degree of crystallinity of cellulose is the treatment with hot water under pressure (see publications N. Hayashi, S. Fujita, T. Irie, T. Sakamoto, M. Shibata,J. Jpn. Inst. Energy,83, 805 (2004), and M. Sasaki, Z. Fang, Y. Fukushima, T. Adschiri, K. Arai,Ind. Eng. Chem. Res.,39, 2883 (2000), the contents of which are fully included here as a reference).

Hydrolysis and recovery are carried out in the presence of water. The amount of water present is at least sufficient for hydrolysis of the total amount of cellulose and preferably is, for example, in the range of mass numbers from 5 to 500 relative to the cellulose, if to take into account the characteristics of fluidity and stirring the reaction mixture.

The amount used of the catalyst can be appropriately determined in consideration of the asset the spine of the catalyst and the reaction conditions (such as temperature, the duration and pressure of hydrogen). For example, is suitable mass ratio in the range from 0.05 to 5 relative to pulp.

The reaction atmosphere is a hydrogen-containing atmosphere. For example, a hydrogen-containing atmosphere comprises hydrogen pressure of 1 to 100 MPa, preferably from 1.5 to 50 and more preferably from 2 to 20 MPa.

Hydrolysis and recovery, for example, carried out by heating to a temperature in the range from 150 to 250°C, preferably by heating to a temperature in the range from 180 to 250°C, and more preferably by heating to a temperature in the range from 190 to 210°C.

The duration of the hydrolysis reaction and recovery can be defined, taking into account the scale of the reaction, the reaction conditions used, the amount of catalyst and cellulose, etc. are Usually suitable the duration of the reaction is 1 to 100 hours. The reaction can be performed periodically, continuously, or the like, the Reaction is preferably carried out with stirring of the reaction mixture.

After hydrolysis and recovery over, the reaction mixture can be subjected to separation into solid and liquid phases, an aqueous solution containing sugar alcohols, can be extracted in the form of a liquid phase, and solids comprising at least a catalyst and unreacted C is llulose, can be separated in a solid phase. The method of separation of solid and liquid phase is not specifically limited and can be determined on the basis of conventional methods with respect to the profile and shape of the catalyst, the amount present unreacted cellulose and the like, for Example, you can use techniques such as filtration, centrifugation and sedimentation. The solid containing the catalyst and unreacted cellulose, can be used in the next reaction.

With repeated use of the catalyst according to the present invention does not require any special activation. However, before reuse can be applied, for example, normal activation of the metal catalyst deposited on a solid substrate.

During activation of the catalyst, the catalyst can be washed with water and dried, and the metal and organic compounds remaining on the substrate can be removed by thermal decomposition when heated within 1-5 hours at a temperature of from 200 to 500°C in a stream of hydrogen gas, as the return surface deposited on a substrate metal in the reduced state, that is appropriate for the application.

Embodiments of the invention

The present invention will be described in detail below in koncertnyh embodiments of the invention.

Variant domestic the invention 1

1.1 Obtaining catalysts

Used substrates for catalysts in the form of amorphous silicon dioxide (hereinafter referred to as SiO2: CARIACT 0-10 manufactured by Fuji Silysia Chemical, Ltd.), mesoporous silica (FSM-16, own production (S. Inagaki, etc,J.Chem. Soc., Chem.Commun.,680 (1993))), γ-alumina (γ-Al2O3company K. Nishio K. A-11), titanium dioxide (TiO2, Merck, Inc.), zirconium dioxide (ZrO2company Wako Pure Chemical Industries, Ltd.), silicon dioxide-aluminum oxide (SiO2-Al2O3, Sigma-Aldrich Japan K.K. grade 135), HY (company Zeolyst Co., CBV600, the atomic ratio Si/Al of 2.6), HUSY (company Zeolyst Co., CBV720 (ratio Si/Al 15), 740 (the ratio Si/Al 20), 760 (the ratio Si/Al 30), 780 (ratio Si/Al 40)), HUSY (company Catalysts &Chemicals Ind. Co., Ltd. ZCP-2000, the ratio of Si/Al 100), ZSM-5 (company Zeolyst Co. CBV4024E),H-beta(company Catalysis Society of Japan, the catalyst JRC-ZB25(1)), HMOR (standard catalyst JRC-Z-M15(1) the company Catalysis Society), activated charcoal (company Takeda Pharmaceutical Co., Ltd. (currently, Japan EnviroChemicals, Ltd.), LPM007). Using x-ray fluorescence analysis, it was found that HUSY obtained from NaY (company Union Carbide LZY-52) the method described in patent references 4 and 5, has a ratio Si/Al of 2.9. Further characteristics HUSY will use the atomic ratio Si/Al, which will be indicated by numbers in all the brackets, for example, HUSY (40). To obtain HZSM-5 ZSM-5 was progulivali in air at 550°C for 8 hours. The substrate was pre-treated by heating in vacuum at 150°C for 1 hour and then used to obtain the catalyst. Precursors of the metals was a commercially available hexachloroplatinic acid (H2PtCl6·xH2O), ruthenium chloride (RuCl3·xH2O), chloride hexaammineruthenium ([Ru(NH3)6]Cl3), rhodium chloride (RhCl3·xH2O), palladium chloride (PdCl2), iridium chloride (IrCl3·xH2O) and Nickel chloride (NiCl2·6H2O). As PdCl2insoluble in water, to obtain a water-soluble H2PdCl4added a small amount of hydrochloric acid and was carried out by vacuum distillation in the evaporator. Salts of other metals used as is. The quality of water used water, past the ion exchange processing.

As a method of producing catalyst will be described below is an example of retrieving Pt/HUSY (40). Powder (200 mg) HUSY (40) was heated at 150°C for 1 hour using a vacuum pipeline, and dried (degree of vacuum of approximately 10-3Torr = of 0.13 PA). The mixture was cooled to room temperature and added water (20 ml)to be atomized powder. To the resulting dispersion was added an aqueous solution (5 ml) H2PtCl6·xH O (15 mg) and the mixture was stirred for 15 hours at room temperature. Then the water is evaporated in the evaporator. The obtained powder was dried in vacuum at room temperature for 2 hours using a vacuum manifold. Then the powder was loaded into a U-shaped glass tube and progulivali heating at 400°C for 2 hours in a stream of gaseous oxygen (flow rate 20 ml/minute). After cooling to room temperature, missed nitrogen gas to remove oxygen and restored the mixture in a stream of hydrogen gas (flow rate 20 ml/min) by heating for 2 hours at 400°C. After cooling to room temperature, missed gaseous nitrogen to remove hydrogen and removed the powder. For catalyst Ni/SiO2-Al2O3the amount deposited on a substrate metal in the catalyst was 60 wt.%, although other catalysts it was 2.5% wt. For catalysts in which the substrate HUSY (2,9) inflicted Ru, as the source of the material used [Ru(NH3)6]Cl3for Ru/HUSY (2,9, NH3IE) used ion-exchange (IE) method (patent references 4 and 5). To obtain Ru/HUSY (2,9, NH3, IMP) used the method of impregnation evaporation to dryness (IMP), using [Ru(NH3)6]Cl3for Ru/HUSY (2,9, Cl, IMP) used the method probit and evaporation to dryness, using RuCl3·xH2O. Compare the catalytic activity of these compounds. In addition, the substrate HUSY (20) impregnated RuCl3·xH2O, and for the preparation of the catalyst Ru/HUSY (20, Cl, IMP) for the application used the method of evaporation to dryness.

The degree of dispersion, determined by adsorption of carbon monoxide pulse method (CO/Pt,measured using Chembet-3000 production company Quantachrome Instruments), are shown in table 1. The degree of dispersion of Pt was significantly changed with regard to the substrate. The degree of dispersion of the Ru catalyst of approximately from 0.01 to 0.03, was lower than described in patent references 4 and 5. This is because the surface of the Ru sensitive to air and oxidized small quantities of air that mixes with during the process. However, when such a Ru catalyst used for the hydrolysis and hydrogenation of starch, it has the same high activity described in patent references 4 and 5, and does not show low catalytic performance. Therefore, in the following tests was used without modification.

Table 1
The degree of dispersion of various catalysts according to the results of the adsorption of CO
Catalyst The degree of dispersion (CO/Pt)
Pt/FSM-160,44
Pt/SiO20,08
Pt/γ-Al2O30,50
Pt/HUSY(20)0,41
Pt/C0,03
Pt/ZrO20,08
Pt/TiO20,18
EN/FSM-160,005
Ru/SiO20,02
Ru/HUSY(20, Cl, IMP)0,01
Ru/HUSY(2.9, NH3IE)0,026
Pd/FSM-160,08
Ir/FSM-160,16
Rh/FSM-160,39

1.2 Catalytic reaction

See the procedure for reaction with the catalyst Pt/HUSY (40). In the future, these terms will be referred to as "standard conditions". In an autoclave of stainless steel (Taiatsu Techno Corp., model TPR2, capacity 30 ml) was loaded 0,16g cellulose (Merck, Inc., the microcrystals, 80% or more and a particle diameter of from 20 to 160 microns), the catalyst Pt/HUSY (40) (0,068 g), 20 g of water and a stirrer and a closed autoclave. Here the number of moles S structural units C6H10O5the cellulose was 0.99 mmol, and the total number of C atoms of metal in the catalyst to regulate the ratio of S/C=110. When replacing the catalyst mass of the catalyst is regulated in such a way as to achieve a ratio of S/C=110; used 0,068 g of Pt catalyst, 0.036 g Ru catalyst, 0.037 g of the Rh catalyst, 0.037 g of Pd catalyst, 0,068 g Ir catalyst and 0,009 g of Ni catalyst. Then at room temperature was injected gaseous hydrogen under a pressure of 5 MPa. The autoclave was placed in an oil bath with a temperature of 190°C and reaction was carried out for 24 hours under stirring with a magnetic stirrer. Then, the autoclave was cooled to room temperature, the remaining hydrogen gas is removed, the autoclave was returned to ambient pressure, opened and extracted the contents.

The product was analyzed with a liquid chromatograph (Shimadzu Corp. LC10ATVP, differential refractometric detector, column: Shodex Asahipak NH2P-SO 4E or Shimadzu Shim-pack SPR-Ca). Sugar alcohols (sorbitol and mannitol) were identified using mass spectrometry with liquid chromatography (Shimadzu LCMS-2010A). The output of sorbitol represented the ratio of the number of moles of P obtained with Rita to the number of moles S structural units C 6H10O5loaded cellulose:

the output of sorbitol (percentage) = (number of moles of P obtained sorbitol)/(number of mol's structural units C6H10O5loaded cellulose) × 100. The yield of mannitol was calculated in the same way.

Variant implementation of the invention 2

The results of reactions carried out under standard conditions using various deposited on a substrate of metal catalysts is shown in figure 1. In almost all cases, the hydrolysis of cellulose and the hydrogenation was catalytically, we got sugar alcohols with sorbitol as the main product. For example, the output of sugar alcohols in the presence of a catalyst of Pt/γ-Al2O3was 18%, of which sorbitol was 15% and mannitol 3%. Similar selectivity of the product was provided by other catalysts. In the above reaction conditions, catalysts Pt/HUSY (40) and Pt/SiO2-Al2O3was produced sugar alcohols with outputs of 20% or higher and had high activity. The number of active metals: Pt>EN>Pd>Rh>Ni>Ir. For Pt the number of activity depending on the substrate is shown in figure 2. Sequence represented: HUSY (40), SiO2-Al2O3>HUSY (20), γ-Al2O3>HZSM-5, HUSY (30) >HUSY (15)>HUSY (100),H-β>FSM-16, SiO2HY(2,6), TiO2>ZrO2>C (activated is Gaulle), HUSY (2,9), HMOR. Activity was greatest in HUSY (40) and SiO2-Al2O3, while ZrO2, activated carbon, HUSY (2,9) and HMOR corresponded to low outputs. Taking into account these results it was suggested that effective as a substrate are those inorganic oxides which possess acid properties, although the acid properties are not directly related to the range of the fortress acid properties of the substrate. Thus, the most active site for hydrolysis of cellulose was not the areas with acidic properties, from nature inherent in the substrate. Instead, it is assumed that in conditions of high pressure hydrogen the hydrogen molecules dissociate under the action of Pt and Ru, moving on a substrate (spillover effect) and creating a proton acid sites (Hattori,Shokubai,45, 327 (2003)). In fact, as shown in figure 3, when the reaction was carried out in similar conditions, using different substrates without the deposited metals, received only a small amount of glucose. This result indicates that the hydrolysis promotes the deposition of metals on a substrate.

Deposited on a substrate Ru catalyst possessed activity against catalysis and hydrogenation of cellulose. However, interestingly, the catalyst (patent references 4 and 5), which is used HUSY (2,9), obtained from LZY-52, which is obsoles in the prototype as having high activity in the hydrolysis and hydrogenation of starch, provided extremely low output, equal to 3% or below, regardless of the method of preparation of the catalyst and Ru predecessor. However, the Ru catalyst, using as substrate HUSY (20) provided the output of sugar alcohols, equal to 17%.

Variant implementation of the invention 3

The dependence of the yield of sugar alcohols from the reaction temperature was investigated using catalyst Pt/γ-Al2O3. Used standard conditions except for the reaction temperature. As shown in figure 4, the output of sugar alcohols at 180°C was 14%, increasing to 18% at 190°C. However, at 200°C output decreased to 16%. Thus, 190°C was the optimal temperature.

Variant implementation of the invention 4

The outputs of the sugar alcohols for the duration of the reactions 24 and 72 hours are shown in figure 5. Used standard conditions except for the duration of the reaction. At 72 hours for the three catalysts, the yield of sugar alcohols increased slightly. When the duration of the reaction 72 hours for each catalyst, it was found that the peaks of unidentified by-products in a liquid chromatograph increase.

Variant implementation of the invention 5

Investigated the conditions of re-use of catalysts. The first reaction was carried out under standard conditions, using the image quality is as catalyst Pt/γ-Al 2O3. After the reaction, the reaction mixture was placed in a centrifugal separator, the solids were besieged and was isolated by filtration of the supernatant solution. As shown in Fig.6, the output of the sugar alcohol at one time was 18%. In the selected solid is again added to cellulose, was added water, and reaction was carried out similarly. The output of sugar alcohols comprised in the second reaction 15% in the third reaction is 15%. These values are almost the same as the values in the first reaction. Thus, it was found that the catalyst can be reused without activation processing.

A variant embodiment of the invention 6

Carried out a test in which the number of the boot of the mixture has tripled. The autoclave was loaded 0,4807 g cellulose, 0,209 g of the catalyst Pt/γ-Al2O3and 60 g of water. Hydrogen was introduced at an initial pressure of 5 MPa, and the mixture was subjected to interaction within 24 hours at 190°C. After the reaction, the solid (catalyst and cellulose) was separated from the aqueous phase by centrifugation. Analysis of the aqueous phase using liquid chromatography showed a yield of sugar alcohols 28%, which corresponded to the mass is 0.135, When the aqueous phase was evaporated to dryness, got 0,223 g of oily substance. Thus, the selectivity of the sugar alcohols (based on weight) in aqueous solution was 6%. The remaining by-products are not identified.

Variant implementation of the invention 7

Pre-treatment of cellulose (1)

The processing of phosphoric acid was carried out based on the method described in the publication Y.H. P. Zhang, J. Cui, L. R. Lynd, L.Kuang,Biomacromolecules,7,644 (2006). In a polypropylene bottle (capacity 250 ml) were loaded with 1.0 g of cellulose (Merck, Inc., Avicel, micropowder) and 30 ml of distilled water was injected magnetic stirrer and stirred the mixture for 5 minutes at room temperature. Then added 55 ml of chilled on ice phosphoric acid (Kanto Chemical Co., Ltd., special grade) and the mixture is vigorously stirred, while cooling it with ice to approximately 4°C. the mixing Procedure was carried out by vigorous stirring for 10 minutes, then stop stirring and the mixture giving the opportunity to stand for 2-3 minutes. This procedure was repeated for one hour. When carrying out this procedure after 5 minutes after added phosphoric acid, all of the cellulose was dissolved, giving a homogeneous aqueous solution. Then, when it was added 200 ml of ice water, the cellulose was deposited in the form of white powder, which was isolated by centrifugal separation. The obtained white powder 5 times washed with water; the aqueous solution had a pH of from 2.5 mm to 3,0. Then added 2 ml of 2M aqueous solution of calcium carbonate and repeated washing to neutralize the solution, which resulted in a pH close to 6,0-7,0. Then the white powder 5-6 times washed with water. The resulting white powder was dried at 60°C under reduced pressure in a rotary evaporator and then placed in a desiccator containing silica gel, and dried over night. After drying was obtained 0.96 g of white powder.

Pre-treatment of cellulose (2)

Processing by grinding in a ball mill was carried out based on the method described in the publication of H. Zhao, J.H. Kwak, J. A. Franz, J.M. White, J.E. Holladay,Energy&Fuels,20, 807 (2006). In a ceramic ball mill with a spherical body with a capacity of 900 ml was downloaded 1 kg balls Zirconia (diameter 10 mm) and 10 g of cellulose (Merck Inc., Avicel, micron). The grinding was carried out for 2 hours at 60 rpm using a bench ball mill with a spherical body on a rotating basis (AS ONE Corp., ANZ-51S). No environment, such as water, are not used. After processing the extracted 0.9 g of a powder and used for the implementation of the catalytic reaction.

Figure 7 shows the results of x-ray diffraction analysis of the powder unreacted cellulose treated with phosphoric acid and processed by grinding in a ball mill. In nepareiziem the lice cellulose pronounced peaks, obtained from the crystallographic plane (002) of cellulose I, was observed near the angle=23 degrees. However, after treatment with phosphoric acid or in a ball mill, the peak intensity was significantly decreased, indicating that the crystalline structure is destroyed.

Catalytic reaction

As the reactor used a 100 ml autoclave made of stainless steel (OM Labotech Corp., MMJ-100), and the test was carried out at triple the number of the reaction mixture according to the variant embodiment of the invention 1. Used the following catalysts: catalyst of Pt deposited on a substrate of γ-alumina (Pt/Al2O3, 0.21 g), a catalyst of Pt deposited on a substrate of HUSY zeolite (Si/Al 20) (Pt/HUSY (20) 0.21 g), and catalyst of Ru deposited on a substrate of γ-aluminum oxide (Ru/Al2O3, 0.11 g). These catalysts were obtained by impregnation, using hexachloroplatinic acid or trichloride ruthenium as starting materials according to the method described in the embodiment of the invention 1. Download metal was 2.5% wt.

The reaction was carried out according to the following procedure. Cellulose (Merck Inc., Avicel, of 0.48 g) and distilled water (60 ml) were loaded into the autoclave, the autoclave was closed and at room temperature was injected hydrogen under a pressure of 5 MPa. The ratio of the structural common is C glucose to the number of metal atoms conveyed to the molar ratio of 110 (0,9% mol.). The mixture was heated to 190°C in an electric furnace under stirring with a stirring blade with electric drive in the reactor (600 to 800 rpm) and were subjected to interaction within 24 hours. After the reaction mixture was centrifuged and filtered to separate the solids from the supernatant aqueous solution. The product, in aqueous solution, were analyzed using liquid chromatography (HPLC) and mass spectrometry with a liquid chromatograph (LC-MS).

The results of the catalytic reaction are shown in table 2. When used raw pulp, the total yield of sugar alcohols accounted for 35.4 per cent with the catalyst Pt/Al2O3(sorbitol (1): 27,7%, mannitol (2): 7.7 percent). In the embodiment of the invention 1 in the autoclave was loaded mixer and were mixed with a magnetic stirrer. However, in the present embodiment of the invention, the mixing was carried out with stirring blades, increasing the efficiency to a value, which corresponds to an increased output. On Fig shows a typical liquid chromatogram of products (cellulose, pretreated by grinding in a ball mill, the catalyst Ru/Al2O3). In addition to the peaks corresponding to sorbitol (retention time in 19.3 minutes) and mannitol (retention time of 15.5 minutes), was also attended by large peaks, with the matter of the retention time of 13.9 and 10.8 minutes which reidentification. However, based on LC-MS analysis, it is assumed that the peak corresponding to the retention time of 13.9 min, refers to didehydrothymidine (3), and the peak corresponding to the retention time of 10.8 minutes, refers to anhydromannitol (4). Both are analogous to sorbitol, which of sorbitol removed two oxygen atom or one molecule of water, respectively. The structures of compounds (1)to(4) below. For compounds (3) and (4) the provisions of deoxyadenosine not defined.

The total output of all the above four analogues of sugar alcohols from raw pulp was 46.6% with the catalyst Pt/ Al2O3. In identical conditions, the overall yield with catalyst Ru/Al2O3amounted to 33.9%.

Table 2
Synthesis of sugar alcohols by decomposition of the pre-treated cellulose
Output (%)
Pre-treatment of celluloseCatalystSorbitol
(1)
Mannitol
(2)
Didehydro-sigexit
(3)
The anhydrous-the orbits
(4)
The total yield of sugar alcohols
(1+2)
Total yield analogues sugar alcohols
(1+2+3+4)
No processingPt/Al2O327,77,76,25,035,446,6
No processingRu/Al2O323,75,23,61,428,933,9
Phosphoric acidPt/Al2O349,511,710,8a 4.961,276,9
Phosphoric acidRu/Al2O347,37,63,52,254,960,6
Ball mill Pt/HUSY(20)54,56,3of 5.41,660,867,8
Ball millPt/Al2O341,010,47,2to 12.051,470,6
Ball millRu/Al2O358,311,46,65,669,781,9

Output increased, when the pulp is pre-treated with phosphoric acid. With the catalyst Pt/Al2O3the total yield of sugar alcohols accounted for 61.2%, and the total output of all analogues was 76,9%. With catalyst Ru/Al2O3in the processing of cellulose in phosphoric acid output was also increased.

In the processing of cellulose in a ball mill, we also observed a higher output. With the catalyst Pt/Al2O3the total yield of sugar alcohols was 51,4%, and the total output of all analogues were $ 70.6%. Similar results were obtained with the catalysis of the torus Pt/HUSY(20). In addition, the catalyst Ru/Al2O3the output was increased to the total output of sugar alcohols to 69.7%, and the total output of all analog - to 81.9%. Thus, were achieved extremely high outputs. Accordingly, the degree of conversion of cellulose was 80% or more. The ratio of sorbitol to mannitol was 5.1.

As shown above, in the present embodiment of the invention when used as a starting material cellulose, pretreated phosphoric acid or processed by grinding in a ball mill, in the conditions of hydrogenation and decomposition in water and deposited on a substrate metal catalysts outputs sugar alcohols and analogues constitute 70% or more.

Industrial applicability

The present invention is applicable in the field of methods of obtaining sugar alcohols (sorbitol and mannitol) from cellulosic resources.

Brief description of drawings

Figure 1 shows the output of sugar alcohols from cellulose using various catalysts.

Figure 2 shows the output of sugar alcohols from cellulose using different Pt catalysts.

Figure 3 shows the yield of glucose from cellulose using various substrates.

Figure 4 shows the dependence of the yield of sugar alcohols from the reaction temperature (catalyst: Pt/γ-Al2O3).

Figure 5 pok is explained outputs sugar alcohols during the duration of the reactions 24-hour and 72-hours.

Figure 6 shows the test reuse of the catalyst (catalyst: Pt/γ-Al2O3).

7 shows the results of x-ray diffraction analysis of the powder raw cellulose and cellulose, pretreated phosphoric acid and grinding in a ball mill.

On Fig shows a liquid chromatogram of a typical product (cellulose, processed by grinding in a ball mill, the catalyst Ru/Al2O3), obtained according to the variant embodiment of the invention 7.

1. The catalyst for hydrolysis of the cellulose or the cellulose hydrolysis and recovery of the products of hydrolysis, in which the transition metal 8-11 group is applied to a solid substrate, and the above-mentioned catalyst used for the hydrolysis of cellulose.

2. The catalyst according to claim 1, in which at least a part of the above mentioned solid substrate comprises a porous material.

3. The catalyst according to claim 1 or 2, in which at least a part of the above mentioned solid substrate comprises an inorganic oxide.

4. The catalyst according to claim 1, in which at least a part of the above mentioned solid substrate consists of a material having acidic properties.

5. The catalyst according to claim 1, in which at least a part of the above mentioned solid substrate is at least one representative selected from the group consisting of: dio the sid of silicon, alumina, silica-alumina, zeolite, titanium dioxide, zirconium dioxide and activated carbon.

6. The catalyst according to claim 1, in which the aforementioned solid substrate is in the form of a powder, particulate, granular form or in the form of beads; has a cellular structure or extrudable profile; is of annular shape or a columnar shape; has extrudable corrugated profile; or is a corrugated annular shape.

7. The catalyst according to claim 1, in which the mentioned transition metal is at least one representative selected from the group consisting of: platinum, ruthenium, rhodium, palladium, iridium, Nickel, cobalt, iron, copper, silver and gold.

8. The catalyst according to claim 1, in which the mentioned transition metal is applied to the surface of the solid substrate with the degree of dispersion of from 0.01 to 60.

9. The catalyst according to claim 1, in which the mentioned transition metal is applied to the substrate at a content of 0.01 to 60 wt.%.

10. The method of obtaining sugar alcohols, including:
the hydrolysis of cellulose in the presence of a catalyst according to claim 1 in a hydrogen-containing atmosphere at an elevated pressure; and
the restoration of the hydrolysis product of cellulose.

11. The method of obtaining of claim 10, wherein said cellulose is a α-cellulose crystalline structure of uroi or with a low degree of crystallinity.

12. The method of obtaining of claim 10 or 11, wherein the hydrolysis and recovery are carried out in the presence of water.

13. The method of obtaining of claim 10, wherein the said catalyst is used at a mass ratio of from 0.05 to 5 relative to pulp.

14. The method of obtaining of claim 10, wherein the pressure of hydrogen in the hydrogen containing atmosphere is from 1 to 100 MPa.

15. The method of obtaining of claim 10, in which the above-mentioned hydrolysis and recovery is carried out by heating to a temperature of from 150 to 250°C.

16. The method of obtaining of claim 10, wherein the aforementioned sugar alcohols are sorbitol and/or mannitol.

17. The method of obtaining of claim 10, wherein after completion of the above-mentioned hydrolysis and recovery of the reaction mixture is subjected to separation into solid and liquid phases, and separating the aqueous solution containing sugar alcohols, from solids containing at least a catalyst and unreacted cellulose.

18. The method for claim 11, wherein the α-cellulose with a low degree of crystallinity obtained by pre-treatment of cellulose with phosphoric acid or by grinding in a ball mill.

19. The method of obtaining of claim 10, wherein the cellulose before hydrolysis of pre-treated with phosphoric acid or grind in a ball mill.



 

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4 cl, 10 ex

FIELD: preparative chemistry and technology.

SUBSTANCE: invention relates to a method for separating in fractionating a solution containing betaine and sucrose. Method involves chromatographic fractionation of this solution, nanofiltration and regeneration of fraction enriched with betaine and, possibly, fraction enriched with sucrose. Chromatographic separation is carried out in columns filled with material chosen from cation-exchange and anion-exchange resins, and nanofiltration is carried out with a membrane for nanofiltration chosen from polymeric and inorganic membranes having the limit value of passing through a column from 100 to 2500 g/mole. Solution for fractionation represents a solution prepared from sugar beet, for example, the black syrup solution.

EFFECT: improved method of betaine regeneration.

40 cl, 12 tbl, 3 dwg, 7 ex

Sweetener for food // 2216208
The invention relates to the production of sweeteners for food

The invention relates to food industry, namely breast

The invention relates to the dairy industry and can be used to obtain a dried milk product

The invention relates to a process of crystallization of organic compounds from solutions containing them

The invention relates to the production of xylose, which is used in the confectionery industry, as well as upon receipt of spices and xylitol

The invention relates to the production of xylitol

The invention relates to the production of xylitol
Ruthenium catalysts // 2322293

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.

EFFECT: increased activity and selectivity of catalysts.

16 cl, 4 tbl, 7 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing alkaline- and thermostable composition based on sugar alcohols of the optical density less or equal to 0.100 in S-test. Method involves treatment of sugar-base composition with strong-base anion-exchange resin in hydroxide form at temperature 30-100°C. Method provides decreasing consumption of chemical reagents and providing carrying out the combined a single-step process for alkaline stabilization and decolorizing.

EFFECT: improved preparing method.

18 cl, 7 tbl, 8 ex

FIELD: chemical industry; method of production of the alkali-resistant and thermal-resistant polyols.

SUBSTANCE: the invention is pertaining to the improved method of production of the alkali- resistant and thermal-resistant polyols representing the sugar-alcohol syrups. The method provides for the following stages: hydrogenation of the hydrolysate of the corresponding polysaccharide with formation of the hydrogenated sugar-alcohol syrup, the alkaline and thermal treatment of the hydrogenated syrup for production of the stabilized sugar-alcohol syrup, refining of the stabilized sugar-alcohol syrup by its gating through, at least, one ion-exchange resin, in which the stabilized sugar-alcohol syrup is refined by means of its double gating through the cationic- anionic ion-exchange configuration (CACA) including, at least, the first weak-acid cationic ion-exchange resin and the second strongly-base, medium-base or weak-base anion-exchanging resin. The method allows to have the alkali-resistant and thermal-resistant polyols not having the shortcomings of the polyols of the previous level of the engineering.

EFFECT: the invention ensures production of the alkali-resistant and thermal-resistant polyols not having the shortcomings of the polyols of the previous level of the engineering.

18 cl, 3 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: method includes introduction of first hydrocarbon flow, including olefins and paraffins, which have number of carbon atoms from 4 to 30, into installation of isomerisation, where installation of isomerisation is intended for isomerisation of at least part of linear olefins in first hydrocarbon flow into branched olefins, and where at least part of components of first hydrocarbon flow, that have not reacted, and at least part of obtained branched olefins form second hydrocarbon flow; introduction of at least part of second hydrocarbon flow into installation of hydroformylation, where installation of hydroformylation is intended for hyroformylation of at least part of olefins in second hydrocarbon flow with formation of aliphatic alcohols and where at least part of obtained aliphatic alcohols include branched alkyl group and where at least part of components of second hydrocarbon flow that have not reacted, and at least part of obtained aliphatic alcohols form flow of hydroformilation reaction; separation of at least part of hydroformylation reaction flow in order to obtain flow of product, containing aliphatic alcohols, and flow of paraffins and olefins that have not reacted, and introduction of at lest part of flow of paraffins and olefins that have not reacted into installation of dehydration, where installation of dehydration is intended for dehydration of at least part of paraffins in flow of paraffins and olefins that have not reacted for obtaining olefins and where at least part of obtained olefins leave installation of dehydration forming olefin hydrocarbon flow and introduction of at least part of olefin hydrocarbon flow into installation of isomerisation.

EFFECT: obtained aliphatic alcohols can be used for obtaining surface-active substances, sulphates.

21 cl, 6 tbl, 3 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: proposed method of producing branched olefins involves dehydrogenation of an isoparaffin composition, containing 0.5% or less quaternary aliphatic carbon atoms, on a suitable catalyst. The above mentioned isoparaffin composition contains paraffins with 7 to 35 carbon atoms. These paraffins, or at least part of their molecules, are branched. The average number of branches per paraffin molecule ranges from 0.7 to 2.5, and the branches include methyl and, optionally, ethyl branches. The above mentioned isoparaffin composition is obtained through hydroisomerisation of paraffin, and the above mentioned branched olefins contain 0.5% quaternary carbon atoms or less. The paraffins are produced using Fischer-Tropsch method. The invention also relates to the method of producing a surface active substance from olefins, obtained using the method described above.

EFFECT: improvement of operational characteristics.

5 cl, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes introduction of hydrocarbon Fisher-Tropsch flow, containing olefins and paraffins, said hydrocarbon Fisher-Tropsch flow containing from 5 to 80% of olefins, which have average number of carbon atoms from 10 to 17, and paraffins, into installation of hydration, where hydration installation is made in such way as to hydrate at least part of olefins in hydrocarbon Fisher-Tropsch flow to paraffins, and where at least part of components of hydrocarbon Fisher-Tropsch flow, which did not react, and at least part of hydrated olefins form second hydrocarbon flow; introduction of second hydrocarbon flow into installation of dehydration-isomerisation, where installation of dehydration-isomerisation is made in such way as to hydrate at least part of paraffins in second hydrocarbon flow to olefins, and where installation of dehydration-isomerisation is also made in such way as to isomerize at least part of linear olefins to branched olefins in presence of dehydration-isomerization catalyst, which contains hydrogen form of zeolite, having isotopic lattice structure of ferrierite, and where period duration is such that transformation of paraffins into olefins is lower than 40% mol, and where at least part of second hydrocarbon flow components that did not react, and at least part of products of dehydration and isomerisation reactions form third hydrocarbon flow, and third hydrocarbon flow contains olefins and paraffins, and where at least part of olefins in third hydrocarbon flow represent branched olefins; and introduction of at least part of third hydrocarbon flow into installation of hydroformilation, where installation of hydroformilation is made in such way as to hydroformilate at least part of olefins in third hydrocarbon flow obtaining aliphatic alcohols with average number of carbon atoms from 11 to 18, and where at least part of obtained aliphatic alcohols contain branched alkyl group.

EFFECT: reduction of expenditure.

18 cl, 7 tbl, 5 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of producing aliphatic alcohols. The method involves feeding the first hydrocarbon stream, obtained using the Fischer-Tropsch method, containing olefins and paraffins. The Fischer-Tropsch stream contains 5-80% olefins, with 10-17 average number of carbon atoms. This hydrocarbon stream is fed into the hydrogenation-isomerisation installation, where there is dehydrogenation of at least part of paraffins in the Fischer-Tropsch hydrocarbon stream to olefins. The installation is also made such that, there is isomerisation of at least part of linear olefins to branched olefins, in the presence of a dehydrogenation-isomerisation catalyst, containing zeolite in hydrogen form, with a ferrierite isotope structure. Duration of stay is such that, conversion of paraffins to olefins is lower than 40%, and at least part of unreacted components of the hydrocarbon stream, obtained using the Fischer-Tropsch method and at least, part of products of the dehydration and isomerisation reaction form a second hydrocarbon stream. This second hydrocarbon stream contains olefins and paraffins. At least some of the olefins in the second hydrocarbon stream are branched. The method also involves feeding at least part of the second hydrocarbon stream into a hydroformylation installation. The hydroformylation installation is made such that, at least part of the olefins in the second hydrocarbon stream can be undergo hydroformylation, obtaining aliphatic alcohols with average number of carbon atoms from 11 to 18, and at least part of the obtained aliphatic alcohols contain branched alkyl groups.

EFFECT: invention can be used for producing surface active substances, detergents and sulphates.

9 cl, 7 tbl, 6 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of hydrophormylation of unsaturated olefine compounds with number of carbon atoms from three to sixteen in presence of catalyst in form of rhodium, modified with ligands, selected from group including phosphonites, phosphites, phosphinoxides, phosphines, phosphinites, phosphinines and/or phosphinanes, and is characterized by carrying out hydrophormylation in presence of not less than 0,1-106 mol% per unsaturated olefine compound of not less than one cyclic ether of carbonic acid, selected from group, which includes ethylcarbonate, propylene carbonate, buthylene carbonate and their mixtures.

EFFECT: increasing catalyst stability and output on more preferable terminal aldehydes.

9 cl, 4 ex, 1 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: hydrophormylation is carried out in presence of cyclic ether of carbonic acid, selected from group, which includes ethylene carbonate, propylene carbonate or butylene carbonate or their mixtures, content of carbonic acid ether constituting from 1 wt % to 98 wt % from reaction mixture.

EFFECT: simplicity of catalyst regeneration and low degree of catalyst deactivation.

9 cl, 3 ex, 3 tbl, 2 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to synthesis of aliphatic 1,3-diol, especially 1,3-propanediol from ethylene oxide and syngas in one step. More specifically, invention relates to catalytic composition, which ensures good yield under mild conditions in single-step 1,3-propanediol synthesis process and manifests advantages regarding expenses and efficiency. Catalytic composition comprises cobalt component including one or more non-alloyed cobalt compounds and ruthenium component including mainly ruthenium carbonyl compound alloyed with phospholanoalkane ligand. Single-step 1,3-propanediol synthesis process is carried out in presence of catalytic composition at 30 to 150°C and pressure at least 690 kPa over a period of time long enough to obtain two-phase reaction product mixture including upper phase containing major part of solvent, at least 50% of catalytic composition and unconverted ethylene oxide and lower phase containing major part of 1,3-propanediol.

EFFECT: enhanced process efficiency and reduced expenses.

10 cl, 4 tbl, 17 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved method for preparing 1,3-dioles comprising (i) bringing into contact oxirane, carbon monoxide, and hydrogen at 30 to 150°C and pressure 3 to 25 MPa in essentially water-immiscible solvent in presence of effective amount of homogenous bimetallic hydroformylation cobalt carbonyl-containing catalyst and cocatalyst based on metal selected from ruthenium group and which is bound to phosphine ligand optionally in presence of promoter, wherein molar ratio of ligand to this cocatalyst metal atom is within a range of 0.2:1.0 to 0.4:1.0, under reaction conditions effective to obtain reaction products mixture containing aliphatic 1,3-diol; (ii) adding aqueous solution to reaction product mixture obtained and extracting major part of aliphatic 1,3-diol into said aqueous solution at temperature below 100°C to form aqueous phase containing aliphatic 1,3-diol in higher concentration that that of aliphatic 1,3-diol in reaction product mixture and organic phase containing at least part of bimetallic hydroformylation catalyst; (iii) separating aqueous phase from processing phase; and (iv) optionally recycling at least part of catalyst-containing organic phase to stage (i). Invention also relates to catalyst composition for hydroformylation of ethylene oxide into aliphatic 1,3-propanediol, which composition is obtained via a method comprising (i) preparation of complex A by bringing cocatalyst ruthenium-group metal compound into contact with phosphine ligand at ligand-to-cocatalyst metal atom from 0.2:1.0 to 0.4:1.0; (ii) preparation of complex B by subjecting complex A to redox reaction with cobalt carbonyl.

EFFECT: enabled less costly single-step hydroformylation process.

8 cl, 2 dwg, 4 tbl, 52 ex

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