EP1699539A1 - Verfahren zur abreicherung von schwefel und/oder schwefelhaltigen verbindungen aus einer biochemisch hergestellten organischen verbindung - Google Patents

Verfahren zur abreicherung von schwefel und/oder schwefelhaltigen verbindungen aus einer biochemisch hergestellten organischen verbindung

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Publication number
EP1699539A1
EP1699539A1 EP04804187A EP04804187A EP1699539A1 EP 1699539 A1 EP1699539 A1 EP 1699539A1 EP 04804187 A EP04804187 A EP 04804187A EP 04804187 A EP04804187 A EP 04804187A EP 1699539 A1 EP1699539 A1 EP 1699539A1
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EP
European Patent Office
Prior art keywords
sulfur
zeolite
ppm
weight
range
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Application number
EP04804187A
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German (de)
English (en)
French (fr)
Inventor
Till Gerlach
Johann-Peter Melder
Bram Willem Hoffer
Anton Meier
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a process for the depletion of sulfur and / or sulfur-containing compounds from a biochemically produced organic compound, ethanol which can be prepared by this process and its use
  • Examples of these renewable resources are alcohols such as ethanol, butanol and methanol, diols such as 1,3-propanediol and 1,4-butanediol, triols such as glycerol, carboxylic acids such as lactic acid, acetic acid, propionic acid, citric acid, butyric acid, formic acid, Malonic acid and succinic acid.
  • alcohols such as ethanol, butanol and methanol
  • diols such as 1,3-propanediol and 1,4-butanediol
  • triols such as glycerol
  • carboxylic acids such as lactic acid, acetic acid, propionic acid, citric acid, butyric acid, formic acid, Malonic acid and succinic acid.
  • bioethanol instead of synthetic ethanol, which is mainly produced by hydrating ethylene, ethanol from biological sources, so-called bioethanol, can also be used for many applications.
  • 1,3-propanediol which is predominantly produced by hydrolysis of acrolein to 3-hydroxypropanal under acidic catalysis followed by metal-catalyzed hydrogenation or by hydroformylation of ethylene oxide (Industrial Organic Chemistry, Weissermel and Arpe, 2003)
  • 1,3-propanediol from biological sources, so-called bio-1,3-propanediol, can also be used (US Pat. No. 6,514,733, DE-A-3829 618).
  • lactic acid from biological sources can also be used for many applications (K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, p. 306).
  • Edible oils and animal fats can be transesterified to biodiesel.
  • a glycerin fraction is formed.
  • Applications for glycerin include those in the chemical industry, for example the production of pharmaceuticals, cosmetics, polyether isocyanates, glycerol tripolyethers (K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, p. 303 ).
  • the applications for ethanol include those in the chemical industry, such as the production of ethylamines, the production of ethyl esters from carboxylic acids (esp.
  • 1,3-propanediol include those in the chemical industry, for example the production of pharmaceuticals, polyesters, polytrimethylene terephthalates, fibers.
  • Lactic acid is used in the food industry and in the production of biodegradable polymers.
  • biochemically produced compounds such as bioethanol, bio-1, 3-propanediol or lactic acid, in particular in a particularly pure form, would be more advantageous and less expensive in many of these applications.
  • the purification or isolation of the biochemically produced compounds is often carried out by distillation in complex, multi-stage processes.
  • the advantage of the corresponding biochemically produced compound is frequently impaired by the fact that the compound contains sulfur and / or sulfur-containing compounds, in particular specific sulfur compounds, in small amounts, even after the known cleaning processes, and the sulfur or which often interferes with the sulfur-containing compounds in the respective applications.
  • the sulfur content of bioethanol when used in the amination to ethylamines, has a disruptive effect by poisoning the metal catalyst.
  • the alcohol amination is carried out on an industrial scale, in particular heterogeneous, hydrogenation / dehydrogenation catalysts by reacting the corresponding alcohol with ammonia, primary or secondary amines at elevated pressure and elevated temperature in the presence of hydrogen.
  • aliphatic Amines Production from alcohols'.
  • the catalysts usually contain transition metals, such as Group VIII and IB metals, often copper, as catalytically active components, which are often supported on an inorganic support such as aluminum oxide, silicon dioxide, titanium dioxide, carbon, zirconium oxide, zeolites, hydrotalcites and the like, known to the person skilled in the art Materials that are applied.
  • transition metals such as Group VIII and IB metals, often copper
  • an inorganic support such as aluminum oxide, silicon dioxide, titanium dioxide, carbon, zirconium oxide, zeolites, hydrotalcites and the like, known to the person skilled in the art Materials that are applied.
  • the catalytically active metal surface of the heterogeneous catalysts gradually becomes more and more covered with the sulfur or sulfur compounds introduced by the bio-alcohol. This leads to an accelerated catalyst deactivation and thus to a significant impairment of the economy of the respective process.
  • the sulfur content of bioethanol also has a negative effect due to catalyst poisoning, e.g. in steam reforming processes for the production of hydrogen and in fuel cells (fuel cells).
  • the sulfur content of chemicals from natural raw materials will have a negative impact on their implementation, for example as described by sulphurizing metallic centers and thereby deactivating them, or by occupying acidic or basic centers, by entering or catalyzing side reactions, by deposits in production facilities as well as through contamination of the products.
  • WO-A-2003020850, US-A1-2003070966, US-A1 -2003 113598 and US-B1 -6,531,052 relate to the removal of sulfur from liquid hydrocarbons (petrol).
  • Chemical Abstracts No. 102: 222463 (M.Kh. Annagiev et al., Doklady - Akademiya Nauk Azerbaidzhanskoi SSR, 1984, 40 (12), 53-6) describes the depletion of S compounds from technical grade ethanol (not bioethanol ) from 25-30 to 8-17 mg / l by contacting the ethanol at room temperature with zeolites of clinoptilolite and mordenite type, these zeolites having previously been conditioned at 380 ° C. for 6 h and in some Cases with metal salts, especially Fe 2 ⁇ 3, were treated.
  • the depleted S compounds are H 2 S and alkylthiols (R-SH).
  • the object of the present invention was to provide an improved economical process for the treatment of biochemically produced organic compounds, such as bio-alcohols, e.g. Bioethanol, through which the corresponding treated compound is obtained in high yield, space-time yield and selectivity, which when used, e.g. in chemical synthesis processes, e.g. in the production of ethylamines, especially mono-, di- and triethylamine, from bioethanol and also for other uses, e.g. in the chemical, cosmetic or pharmaceutical industry or in the food industry, has improved properties.
  • biochemically produced organic compounds such as bio-alcohols, e.g. Bioethanol
  • bio-alcohols e.g. Bioethanol
  • the use of a treated bioethanol should enable extended catalyst service lives in the synthesis of ethylamines.
  • ethanol was produced with a specific specification (see below), which can be produced by the above.
  • the method according to the invention is particularly suitable for the depletion of sulfur or a sulfur-containing compound from a compound produced by fermentation.
  • the sulfur-containing compounds are inorganic or organic compounds, especially symmetrical or unsymmetrical C 2- ⁇ 0 - dialkyl sulfides, especially C 2 -6-dialkyl sulfides, such as Diethylsulfide Di-n-propyl sulfide, di-isopropyl sulfide, very particularly dimethyl sulfide, C 2- ⁇ o-dialkyl sulfoxides, such as dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, 3-methylthio-1-propanol and / or S-containing amino acids, such as methionine and S-methyl-methionine.
  • the biochemically produced organic compound is preferably an alcohol, ether or a carboxylic acid, in particular ethanol, 1,3-propanediol, 1,4-butanediol, 1-butanol, glycerin, tetrahydrofuran, lactic acid, succinic acid, malonic acid, citric acid , Acetic acid, propionic acid, 3-hydroxypropionic acid, butyric acid, formic acid or gluconic acid.
  • a silica gel, an activated aluminum oxide, a zeolite with hydrophilic properties, an activated carbon or a carbon membrane are preferably used as adsorbers.
  • silica gels examples include silicon dioxide, boehmite, gamma, delta, theta, kappa, chi and alpha alumina for usable aluminum oxides, and charcoals made of wood, peat, coconut shells, or also synthetic carbons are used for activated carbons Carbon blacks, made from natural gas, petroleum or derived products, or polymeric organic materials that also contain heteroatoms such as Nitrogen can be used, and for usable carbon molecular sieves, molecular sieves are made of anthracite and "hard coal” by partial oxidation, and are described, for example, in the Electronic Version of Sixth Edition of Ullmann's Encyclopedia of Industrial Chemistry, 2000, Chapter Adsorption, Paragraph, Adsorbents ,
  • the adsorber is manufactured as a shaped body, for example for a fixed bed process, it can be used in any shape.
  • Typical moldings are spheres, strands, hollow strands, star strands, tablets, grit, etc. with characteristic diameters from 0.5 to 5 mm, or also monoliths and similar structured packings (see Ullmann's Encyclopedia, Sixth Edition, 2000 Electronic Release, Chapter Fixed-Bed Reactors, Par.2: Catalyst Forms for Fixed-Bed Reactors).
  • the adsorber is used in powder form. Typical particle sizes in such powders are 1 - 100 ⁇ m, but particles significantly smaller than 1 ⁇ m can also be used, for example when using soot.
  • the filtration can be carried out discontinuously in suspension processes, for example by deep filtration. Cross-flow filtration is an option in continuous processes.
  • Preferred adsorbers are zeolites, in particular zeolites from the group of natural zeolites, faujasite, X zeolite, Y zeolite, A zeolite, L zeolite, ZSM 5 zeolite, ZSM 8-zeolite, ZSM 11-zeolite, ZSM 12-zeolite, mordenite, beta-zeolite, pentasil zeolite, and mixtures thereof, which contain ion-exchangeable cations.
  • MOFs Metal Organic Frameworks
  • the cations of the zeolite are preferably completely or partially replaced by metal cations, in particular transition metal cations. (Loading of the zeolites with metal cations).
  • the metals are preferably applied to the zeolite by ion exchange since, as recognized according to the invention, they then have a particularly high dispersion and thus a particularly high sulfur adsorption capacity.
  • the cation exchange is e.g. possible starting from zeolites in the alkali metal, H or ammonium form. Such ion exchange techniques for zeolites are described in detail in Catalysis and Zeolites, J. Weitkamp and L. Puppe, Eds., Springer, Berlin (1999).
  • Preferred zeolites have a modulus (molar SiO 2 : Al 2 O 3 ratio) in the range from 2 to 1000, particularly 2 to 100.
  • adsorbers in particular zeolites, are very particularly used which contain one or more transition metals, in elemental or cationic form, from groups VIII and IB of the periodic table, such as Fe, Co, Ni, Ru, Rh, Pd, Os , Ir, Pt, Cu, Ag and / or Au, preferably Ag and / or Cu, contain.
  • the adsorber preferably contains 0.1 to 75% by weight, in particular 1 to 60% by weight, particularly 2 to 50% by weight, very particularly 5 to 30% by weight (in each case based on the total mass of the adsorber ) of the metal or metals, in particular the transition metal or the transition metals.
  • Very preferred adsorbers are: Ag-X zeolite with an Ag content of 10 to 50% by weight (based on the total mass of the adsorber) and
  • Cu-X zeolite with a Cu content of 10 to 50 wt .-% (based on the total mass of the adsorber).
  • the adsorber is generally brought into contact with the organic compound at temperatures in the range from 0 ° C. to 200 ° C., in particular from 10 ° C. to 50 ° C.
  • the contacting with the adsorber is preferably carried out at an absolute pressure in the range from 1 to 200 bar, in particular 1 to 5 bar.
  • the corresponding organic compound is in the liquid phase, i.e. in liquid form or dissolved or suspended in a solvent or diluent, brought into contact with the adsorber.
  • Particularly suitable solvents are those which are able to dissolve the compounds to be purified as completely as possible or which mix completely with them and which are inert under the process conditions.
  • suitable solvents are water, cyclic and alicyclic ethers, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxy propane, dimethyldiethylene glycol, aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol, carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, and aliphatic ether alcohols such as methoxypropanol.
  • the concentration of compound to be purified in the liquid, solvent-containing phase can in principle be chosen freely and is frequently in the range from 20 to 95% by weight, based on the total weight of the solution / mixture.
  • a variant of the method according to the invention is that it is carried out, unpressurized or under pressure, in the presence of hydrogen.
  • the process can be carried out in the gas or liquid phase, fixed bed or suspension procedure, with or without backmixing, continuously or batchwise in accordance with the processes known to the person skilled in the art (for example described in Ullmann's Encyclopedia, sixth edition, 2000 electronic release, chapter “Adsorption ").
  • the method according to the invention enables in particular the depletion of
  • the process according to the invention enables in particular the depletion of sulfur and / or sulfur-containing compounds from the respective compound to a residual content of ⁇ 2, particularly ⁇ 1, very particularly from 0 to ⁇ 0.1 ppm by weight (calculated in each case S), e.g. determined according to Wickbold (DIN EN 41).
  • the bioethanol which is preferably used in the process according to the invention is generally produced from agricultural products such as molasses, cane sugar juice, corn starch or from products of wood saccharification and from sulfite waste liquors by fermentation.
  • Bioethanol is preferably used that was obtained by fermentation of glucose with elimination of CO 2 (K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, p. 194; Electronic Version of Sixth Edition of Ullmann's Encyclopedia of Industrial Chemistry, 2000, Chapter Ethanol, Paragraph Fermentation).
  • the ethanol is usually obtained from the distillation process Fermentation broths won: Electronic Version of Sixth Edition of Ullmann's Encyclopedia of Industrial Chemistry, 2000, Chapter Ethanol, Paragraph Recovery and Purification.
  • the ethanol produced by the process found is used advantageously
  • the present invention also relates to an ethanol which can be produced by the process according to the invention
  • the content of C 3 ⁇ -alkanols, methanol, ethyl acetate and 3-methyl-butanoI-1 is determined, for example, by means of gas chromatography (30 m DB-WAX column, inner diameter: 0.32 mm, film thickness: 0.25 ⁇ m, FID- Detector, temperature program: 35 ° C (5 min.), 10 ° C / min. Heating rate, 200 ° C (8 min.).
  • the Ag / ZSM-5 adsorber was produced by ion exchange of the Na-ZSM-5 with an aqueous AgN0 3 solution (50 g ZSM-5, 1.94 g AgNO 3 , 50 ml impregnation solution).
  • aqueous AgN0 3 solution 50 g ZSM-5, 1.94 g AgNO 3 , 50 ml impregnation solution.
  • the catalyst was then dried at 120 ° C.
  • the Ag / SiO 2 adsorber was produced by impregnating SiO 2 (BET approx. 170 m 2 / g, Na 2 O content: 0.4% by weight) with an aqueous AgNO 3 solution (40 g SiO 2 , 1.6 g AgNO 3 , 58 ml impregnation solution). The catalyst was then dried at 120 ° C and calcined at 500 ° C.
  • the Ag / Al 2 O 3 adsorber was produced by impregnating gamma-Al 2 O 3 (BET approx. 220 m 2 / g) with an aqueous AgNO 3 solution (40 g Al 2 O 3> 1.6 g AgNO 3 , 40 ml impregnation solution). The catalyst was then dried at 120 ° C and calcined at 500 ° C.
  • the ethanol / adsorber suspension was transferred to a 4-neck glass flask into which nitrogen was introduced for inerting for about 5 minutes. The flask was then closed and the suspension was stirred for 5 h at room temperature. After the experiment, the adsorber was filtered through a pleated filter. The sulfur content of the filtrate and possibly also of the adsorber was determined coulometrically:
  • the materials CuO-ZnO / AI 2 O 3 and NiO / SiO 2 / AI 2 ⁇ 3 / Zr ⁇ 2 are suitable for desulfurization, but less well than, for example, a silver-doped zeolite, even if at elevated temperature and with addition was worked by hydrogen. If palladium on carbon is used, sulfur is taken up from ethanol.
  • a continuous fixed bed system with a total volume of 192 ml was filled with 80.5 g of Ag-13X balls (15.9% by weight of Ag, 2.7 mm balls, described in Example 2).
  • About 80 ppm dimethyl sulfide (> 99%, Merck) (corresponds to about 40 ppm sulfur) were added to the feed ethanol (absolute ethanol,> 99.8%, Riedel de Haen).
  • the feed was passed over the adsorber in a swamp mode. During the sampling, the sample bottle was always cooled with an ice / salt mixture.
  • the sulfur determination in the entry and exit was carried out (in all examples) coulometrically (DIN 51400 part 7) with a detection limit of 2 ppm.
  • Example 1 The preparation of the Ag-13X is described in Example 1.
  • CBV100 and CBV720 are Zeolite-Y systems.
  • the doping with metals was carried out by cation exchange as in Example 1, using AgNO 3 or CuNO 3 solutions.
  • the Cu-CPV720 was then calcined at 450 ° C in N 2 .
  • the ethanol / adsorber suspension was transferred to a 4-neck glass flask and stirred without pressure for 24 h at room temperature. After the experiment, the adsorber was filtered through a pleated filter. The sulfur content of the filtrate and possibly also of the adsorber was determined coulometrically:
  • the table shows that both silver-doped zeolites and copper-doped zeolites are able to desulfurize ethanol.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
EP04804187A 2003-12-23 2004-12-22 Verfahren zur abreicherung von schwefel und/oder schwefelhaltigen verbindungen aus einer biochemisch hergestellten organischen verbindung Withdrawn EP1699539A1 (de)

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DE10361508A DE10361508A1 (de) 2003-12-23 2003-12-23 Verfahren zur Abreicherung von Schwefel und/oder schwefelhaltigen Verbindungen aus einer biochemisch hergestellten organischen Verbindung
PCT/EP2004/014591 WO2005063354A1 (de) 2003-12-23 2004-12-22 Verfahren zur abreicherung von schwefel und/oder schwefelhaltigen verbindungen aus einer biochemisch hergestellten organischen verbindung

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US (1) US20070167530A1 (enrdf_load_stackoverflow)
EP (1) EP1699539A1 (enrdf_load_stackoverflow)
JP (1) JP2007515448A (enrdf_load_stackoverflow)
DE (1) DE10361508A1 (enrdf_load_stackoverflow)
IN (1) IN2006CH02676A (enrdf_load_stackoverflow)
WO (1) WO2005063354A1 (enrdf_load_stackoverflow)
ZA (1) ZA200606041B (enrdf_load_stackoverflow)

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DE102005012209A1 (de) * 2005-03-15 2006-09-28 Basf Ag Verfahren zur Herstellung eines Ethylamins
US7749376B2 (en) * 2005-08-15 2010-07-06 Sud-Chemie Inc. Process for sulfur adsorption using copper-containing catalyst
DE102005043440A1 (de) * 2005-09-13 2007-03-15 Basf Ag Verfahren zur Herstellung eines Ethylamins aus vergälltem Ethanol
JPWO2007055361A1 (ja) 2005-11-14 2009-04-30 三井化学株式会社 バイオマス由来の炭素を含むプロピレンの製造方法
DE102006036332A1 (de) * 2006-08-03 2008-02-07 Süd-Chemie AG Verfahren zur Herstellung von Biodieselkraftstoff
WO2008021194A2 (en) * 2006-08-10 2008-02-21 The University Of Houston System Adsorbent composition for desulfuring a fluid, method and apparatus for its use
JP2009143853A (ja) * 2007-12-14 2009-07-02 Jgc Corp アルコール類の製造方法およびそのアルコール類の製造方法を用いた水素または合成ガスの製造方法、アルコール類
CN101481627B (zh) * 2008-01-09 2012-11-14 中国石油化工股份有限公司 一种烃油脱硫吸附剂及其应用方法
WO2010003903A2 (de) * 2008-07-08 2010-01-14 Basf Se Verfahren zur entfernung von schwefelhaltigen verbindungen aus kraftstoffen
JP2010070512A (ja) * 2008-09-19 2010-04-02 Jgc Corp アルコール類の製造方法およびそのアルコール類の製造方法を用いた水素または合成ガスの製造方法、アルコール類
DE102009029567A1 (de) 2008-10-02 2010-04-08 Basf Se Verfahren zur Abreicherung von Schwefel und/oder schwefelhaltigen Verbindungen aus einer biochemisch hergestellten organischen Verbindung
US9000236B2 (en) 2008-11-28 2015-04-07 Total Research & Technology Feluy Purification of alcohols prior to their use in the presence of an acid catalyst
US8974675B2 (en) * 2009-02-09 2015-03-10 Allan J. Jacobson Porous solids, selective separations, removal of sulfur compounds, adsorption
CN102617281A (zh) * 2011-01-28 2012-08-01 株式会社大赛璐 从醇中除去硫化合物的方法
CN104587962B (zh) * 2013-10-31 2017-04-05 上海工程技术大学 聚烯烃提纯用脱色吸附剂及其制备方法
WO2015098762A1 (ja) * 2013-12-25 2015-07-02 ニッカウヰスキー株式会社 飲料に含まれる不要成分を除去する方法及び装置
TWI656210B (zh) * 2013-12-25 2019-04-11 Idemitsu Kosan Co., Ltd. 酒類用金屬載持沸石及酒類之製造方法
JP6335813B2 (ja) 2015-02-16 2018-05-30 出光興産株式会社 酒類用金属担持ゼオライトの製造方法、酒類用金属担持ゼオライト、及び酒類の製造方法
JP6673563B2 (ja) * 2015-06-18 2020-03-25 出光興産株式会社 蒸留酒の製造方法、及び金属担持イオン交換樹脂を含む処理部材
JP6733093B1 (ja) * 2019-05-09 2020-07-29 株式会社三井Ｅ＆Ｓマシナリー ゼオライト膜に供する被処理流体の処理方法
CN116350521A (zh) * 2023-02-22 2023-06-30 中国人民解放军北部战区总医院 一种口腔修复抗菌材料

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT395983B (de) * 1986-03-10 1993-04-26 Vogelbusch Gmbh Verfahren zur herstellung von aethanol aus zuckerhaeltigen rohstoffen sowie anlage zur durchfuehrung des verfahrens
US6136577A (en) * 1992-10-30 2000-10-24 Bioengineering Resources, Inc. Biological production of ethanol from waste gases with Clostridium ljungdahlii
DE10045939B4 (de) * 2000-09-16 2016-05-04 Caterpillar Inc. Sensor zur Bestimmung der Konzentration von Schwefelverbindungen in einer Flüssigkeit
US6531052B1 (en) * 2000-10-05 2003-03-11 Alcoa Inc. Regenerable adsorbent for removing sulfur species from hydrocarbon fluids
EP1283072A1 (en) * 2001-08-08 2003-02-12 The Procter & Gamble Company Doped adsorbent materials with enhanced activity
DE10149060A1 (de) * 2001-10-05 2003-04-30 Daimler Chrysler Ag Verfahren zur Reformierung flüssiger Kohlenwasserstoffgemische
US20030113598A1 (en) * 2001-12-19 2003-06-19 Ballard Power Systems Inc. Method and apparatus for removing sulfur from a hydrocarbon fuel
JP2003277779A (ja) * 2002-03-27 2003-10-02 Mitsubishi Heavy Ind Ltd バイオガスの脱硫装置
JP4101696B2 (ja) * 2003-05-16 2008-06-18 三菱重工業株式会社 ガス精製装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005063354A1 *

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WO2005063354A1 (de) 2005-07-14
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US20070167530A1 (en) 2007-07-19
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