EP1981917A1 - Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren - Google Patents

Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren

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Publication number
EP1981917A1
EP1981917A1 EP07704054A EP07704054A EP1981917A1 EP 1981917 A1 EP1981917 A1 EP 1981917A1 EP 07704054 A EP07704054 A EP 07704054A EP 07704054 A EP07704054 A EP 07704054A EP 1981917 A1 EP1981917 A1 EP 1981917A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenation
megaporous
carbon nanofibers
hydrogenation catalyst
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07704054A
Other languages
German (de)
English (en)
French (fr)
Inventor
Bram Willem Hoffer
Ekkehard Schwab
Jochem Henkelmann
Zsolt Jozsef Szarka
Hubertus Peter Bell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07704054A priority Critical patent/EP1981917A1/de
Publication of EP1981917A1 publication Critical patent/EP1981917A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Definitions

  • the present invention relates to a process for the hydrogenation of polymers having C-C double bonds or C-N multiple bonds using a hydrogenation catalyst comprising a megaporous substrate and a hydrogenation catalyzing metal or its precursor deposited on carbon nanofibers.
  • a hydrogenation catalyst comprising a megaporous substrate and a hydrogenation catalyzing metal or its precursor deposited on carbon nanofibers.
  • Carbon nanofibers are also referred to as carbon nanofibers.
  • polymers having saturated side chains for example those side chains comprising an ethyl group or an amino methyl group.
  • Such polymers can be used, for example, for the production of cosmetics, for temporary corrosion protection, as crosslinkers for adhesives or for dye fixing in laundry.
  • preparation of such polymers in one step is usually not easy.
  • monomers such as, for example, 3-aminopropene or 1-butene are poorly free-radically polymerizable.
  • Immobilized catalysts can be used, for example, in suspension, as fixed bed catalysts or in the form of monoliths.
  • EP-A 1 040 137 it is proposed to prepare hydrogenation catalysts based on a monolith with megapores.
  • Monoliths are known for high (hydrogen) gas / liquid mass transfer rates with low energy input.
  • a catalytically active metal is deposited on a monolith with megapores.
  • the space-time yield of the corresponding catalyst is unsatisfactory. If one attempts to deposit a finer-pored material by means of a so-called washcoat on the monolith, unsatisfactory conversions are found due to diffusion.
  • pores having an average diameter below 2 nm are also referred to as micropores, pores having an average diameter in the range from 2 to 50 nm and also as mesopores and pores having an average diameter in the range from 50 nm to 1 ⁇ m also as macropores designated.
  • the average diameter of megapores is preferably in the range of 0.1 to 10 mm, preferably 0.5 to 2 mm, determined, for example, visually or by microscopic methods.
  • the process according to the invention can be carried out as a process for the partial or preferably quantitative hydrogenation of polymers which have CC double bonds or CN multiple bonds.
  • the process according to the invention is preferably carried out as a process for the quantitative or almost complete hydrogenation of polymers which have C-C double bonds or C-N multiple bonds, for example C-N double bonds and in particular nitrile groups, ie less than 5 mol%, particularly preferably 0, 01 to 1 mol% of im
  • the employed CC double bonds or CN multiple bonds remain intact.
  • the process according to the invention can be carried out by starting from a polymer which has C-C double bonds and C-N multiple bonds and selectively hydrogenating the C-N multiple bonds.
  • the hydrogenation agent used is preferably gaseous hydrogen.
  • polymers comprising CC double bonds or CN multiple bonds include not only homopolymers, but also copolymers of those monomers which have CC double bonds or CN multiple bonds which are not due to the actual polymerization or copolymerization involved.
  • monomers are isoprene, chloroprene and in particular acrylonitrile and 1, 3-butadiene.
  • Polymers which have C-C double bonds or C-N multiple bonds are understood in the context of the present invention to mean those polymers which on average have at least one C-C double bond or C-N multiple bond per molecule.
  • aromatics such as phenyl rings, which can be introduced into polymers by (co) polymerization of, for example, styrene or ⁇ -methylstyrene, do not belong to C-C double bonds.
  • the process according to the invention is preferably a process for the selective hydrogenation of polymers which have C-C double bonds or C-N multiple bonds in such a way that olefinic C-C double bonds or C-C multiple bonds are hydrogenated when carrying out the process according to the invention, however, aromatic systems such as phenyl rings are not.
  • polymers having CC double bonds or CN multiple bonds have a molecular weight Mw in the range of 2,000 to 2,000,000 g / mol, preferably 3,500 to 1,000,000 g / mol, more preferably 4,000 to 250,000 g / mol.
  • the process according to the invention is carried out using at least one hydrogenation catalyst.
  • the hydrogenation catalyst used can comprise one or more catalytically active species. Catalytically active species can be derived from one or more different metals.
  • a hydrogenation catalyst comprises: a megaporous substrate, carbon nanofibers, and hydrogenation catalyzing metal or its precursor deposited on carbon nanofibers.
  • megaporous substrates are known as such.
  • megaporous substrates are preferably those substrates which are dimensionally stable not only at room temperature but also at temperatures up to 300 ° C., preferably up to 500 ° C., ie. when heated to up to 300 ° C, preferably up to 500 ° C do not change the shape, determined for example by visual inspection.
  • Megaporous substrates in the sense of the present invention are generally constructed like a foam, i. they have predominantly open-cell pores, which can be shaped like channels.
  • the average diameter of the pores of megaporous substrates in the context of the present invention is preferably in the range from 0.1 to 10 mm, preferably from 0.5 to 2 mm, determined, for example, visually or by microscopic methods.
  • the shape of the megapores of megaporous substrates may be regular or irregular, each different or predominantly similar.
  • a megaporous substrate comprises a plurality of packed films at a distance, for example, spaced by spacers, which films may be flat or corrugated, and wherein the films may be stacked or rolled one on top of the other.
  • the megaporous substrate is a monolith, i.
  • the megaporous substrate used is a monolith.
  • Monoliths and their use in the preparation of catalysts are known per se, see, for example, A. Cybulski et al., Catal. Rev. - Be. Closely. 1994, 36, 179-270.
  • Monoliths in the context of the present invention may be metallic or preferably ceramic material and comprise a plurality of parallel tubes, for example 10 to 1000 parallel tubes, whose walls are permeable or preferably impermeable to solutions of polymer to be hydrogenated may, more preferably as a wire mesh honeycomb monolith structure or as a foam monolith structure.
  • the megaporous substrate is abrasion resistant, i. with the fingernail, scratching can loosen or remove less than 1% by weight of the megaporous material.
  • the megaporous substrate is a monolith of ceramic material, for example silicon carbide or silicon nitride, and in particular ceramic oxidic material, for example aluminum oxide, in particular OC-Al 2 O 3, SiO 2, titanium dioxide, zirconium, molybdenum, spinels, mixed oxides of For example, lithium and aluminum or aluminum and titanium, and in particular Cor dierit, 2 MgO-5 Si ⁇ 2-2 Al2O3.
  • ceramic oxidic material for example aluminum oxide, in particular OC-Al 2 O 3, SiO 2, titanium dioxide, zirconium, molybdenum, spinels, mixed oxides of For example, lithium and aluminum or aluminum and titanium, and in particular Cor dierit, 2 MgO-5 Si ⁇ 2-2 Al2O3.
  • Another preferred substrate is essentially carbon, see, for example, Vergunst et al., Catal. Rev. - Be. Closely. 2001, 43, 291.
  • the megaporous substrate has a porosity in the range of 30 to 95%, preferably 70 to
  • megaporous substrate has a cell density in the range of up to 20 tubes per linear cm, as determined on the cross-section of the megaporous substance, preferably 5 to 10 tubes per linear cm.
  • the tubes of megaporous substance have an average diameter in the range of 0.1 to 10 mm, preferably 0.5 to 2 mm, and an average length in the range of 5 cm to 2 m, preferably 10 cm up to 1 m.
  • Hydrogenating catalysts in the context of the present invention furthermore include carbon nanofibers.
  • Carbon nanofibers in the context of the present invention consist essentially of carbon. Carbon nanofibers in the sense of the present invention have a thread-like shape, wherein the threads can be stretched or preferably entangled.
  • carbon nanofibers may have a mean diameter in the range of 3 to 100 nm and an average length in the range of 0.1 to 1000 ⁇ m, the average length being generally greater than the average diameter, preferably at least twice as big.
  • Carbon nanofibers can be prepared by processes known per se.
  • a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such
  • Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • the decomposition of volatile carbon-containing compound is carried out in the presence of a decomposition catalyst, for example Fe, Co, or preferably Ni, deposited on the megaporous substance.
  • a decomposition catalyst for example Fe, Co, or preferably Ni, deposited on the megaporous substance.
  • a decomposition catalyst for example Fe, Co, or preferably Ni, deposited on the megaporous substance.
  • a decomposition catalyst for example, 0.5 to 50 wt .-%, preferably from 2 to 20 wt .-% decomposition catalyst Deposited on the megaporous substance, based on megaporous substance.
  • Fe, Co and in particular Ni can be deposited by impregnating the megaporous substrate with a preferably aqueous solution of a compound of Fe, Co or in particular Ni, for example the sulfate, nitrate, chloride or acetate, for example by spraying and preferably by impregnation, then reacted with a reducing agent such as urea (others) and then calcined, for example at temperatures in the range of 400 to 700 0 C.
  • a reducing agent such as urea (others)
  • hydrogenation catalysts comprise a monolith as a megaporous substrate on which carbon nanofibers are deposited, for example in a layer which is on average 100 nm to 5 ⁇ m thick, preferably 200 nm to 2 ⁇ m.
  • Hydrogenation catalysts in the context of the present invention furthermore comprise at least one hydrogenation-catalyzing metal or its precursor deposited on carbon nanofibers.
  • the metals of the 7th to 11th group of the Periodic Table of the Elements preferably Mn, Re, Rh, Fe, Co, Ni, Pd, Pt, Ru, Ag, Au and in particular Ru and mixtures of the abovementioned metals.
  • hydrogenation catalysts in the context of the present invention comprise at least one further metal or its precursor as cocatalyst, likewise deposited on the carbon nanofibers, for example groups 6 to 7 of the Periodic Table of the Elements.
  • precursors compounds of the particular hydrogenation catalyzing or cocatalysting metal which are themselves not catalytically active but are converted into the catalytically active phase under the conditions of the process according to the invention.
  • the hydrogenation catalyzing metal may be the same as the decomposition catalyst, or preferably different.
  • the hydrogenation-catalyzing metal and optionally cocatalyst are deposited on carbon nanofibers.
  • carbon nanofibers are contacted with a preferably aqueous solution of a metal catalyzing the hydrogenation, for example impregnated, preferably by spraying and more preferably by impregnation, and then reduced with the aid of a reducing agent to the relevant metal or optionally its precursor. Then you can heat, for example, to temperatures in the range of 200 to 500 ° C.
  • the hydrogenation catalyst is substantially free of micropores, ie no micropores can be detected by ISb adsorption methods.
  • the process according to the invention is carried out at temperatures in the range from 100 to 300.degree. C., preferably from 150 to 250.degree.
  • the process according to the invention is carried out at a pressure in the range from 50 to 300 bar, preferably 100 to 250 bar.
  • the process of the invention is carried out using a solvent that is liquid under the process conditions.
  • a solvent that is liquid under the process conditions.
  • Particularly suitable are, for example, toluene, ethylbenzene, ethers such as tetrahydrofuran (THF) and 1, 4-dioxane, and alcohols such as methanol and ethanol, especially so-called anhydrous alcohols.
  • mixtures of two or more solvents which are preferably both liquid under the process conditions, for example mixtures of ethylbenzene and toluene.
  • the process according to the invention is carried out by dissolving polymer which has C-C double bonds or C-N multiple bonds in a solvent which is liquid under the process conditions.
  • a solvent which is liquid under the process conditions.
  • Hydrogen is pressed on and the resulting solution is passed through hydrogenation catalyst prepared as described above, for example with an average contact time in the range from 10 to 24 hours, preferably 14 to 18 hours.
  • the hydrogenation catalyst is introduced in an autoclave and polymer solution is added and a Hydrogen pressure of about 50 bar sets. Thereafter, the temperature is raised to the preferred reaction temperature, for example from 100 to 300 ° C, preferably 150 to 250 ° C. The pressure can then be set, for example, in the range of 50 to 300 bar.
  • the process according to the invention can be carried out particularly well in continuous form.
  • the hydrogenation catalyst is prepared by a process comprising the following steps:
  • step (c) For depositing carbon nanofibers in step (c), one can proceed as described above.
  • step (f) For calcining in step (f), for example, over a period of
  • the hydrogenation catalyst is prepared by a process which prior to step (c) comprises a step
  • step (a) it is possible, for example, to carry out a washcoat with a material suspended in an organic or inorganic solvent, in particular in water, which forms macropores, for example after thermal treatment.
  • Suitable materials for step (a), which form macropores, especially after thermal treatment, are AbC 1 -aq, TiO 2 -aq, SiO 2 -aq, ZrO 2 aq.
  • step (a) and subsequent thermal treatment a layer of material forming macropores is formed, which layer may be in the range of 1 to 300 ⁇ m thick, preferably up to 100 ⁇ m.
  • the hydrogenation catalyst is prepared by a process comprising the steps
  • step (c) before step (c) and optionally after step (a). Further one leads step (c)
  • step (b) particularly preference is given to impregnating in step (b) with a compound of Fe, Co or, in particular, Ni.
  • Fe, Co and in particular Ni can be deposited by passing the megaporous substrate, optionally after carrying out step (a), with a preferably aqueous solution of a compound of Fe, Co or, in particular, Ni, for example the sulfate, nitrate, chloride or Acetate, impregnated, for example, by spraying and preferably by impregnating bringing into contact, then with a reducing agent such as urea (others) and then calcined, for example at temperatures in the range of 400 to 700 ° C.
  • a reducing agent such as urea (others)
  • mineral acid such as, for example, hydrochloric acid, nitric acid, sulfuric acid, more preferably aqueous mineral acid, most preferably concentrated nitric acid or concentrated sulfuric acid.
  • step (d) for example, acid is treated for 10 minutes to 12 hours, preferably one to 3 hours.
  • step (d) for example, a temperature in the range from 30 to 150 ° C., preferably around 100 ° C., is treated.
  • the process of the invention makes it possible to obtain hydrogenated polymers having, for example, CH 2 NH 2 groups or ethyl side groups in good space-time yield. If the process according to the invention is carried out, it is observed in particular only a slight reduction in the molecular weight of the hydrogenated polymer. Furthermore, it is observed that in the case of the implementation of polymers which have CC double bonds or CN multiple bonds and continue to attack aromatic groups such as phenyl rings, the phenyl rings are not attacked.
  • Tests of the hydrogenation catalysts can be carried out either in continuous apparatus. However, it is also possible to crush finished hydrogenation catalysts and test them as debris with a mean diameter of 125 ⁇ m in a batch experiment. The comparability of the results in the present cases is not affected by the different experimental setup.
  • the mixture was then polymerized at an internal temperature of 100 ° C over a period of two hours and then distilled for 2 hours at an external temperature of 100 ° C excess residual monomer under reduced pressure (50 to 500 mbar), wherein the pressure was regulated so that Excessive foaming was avoided. Distillation also resulted in a certain proportion of 1,4-dioxane.
  • Tetrahydrofuran (THF, 810 g) was heated to boiling point in a 2 l HWS vessel under a nitrogen atmosphere (65 ° C.). Feed 1 was then added simultaneously, consisting of 795 g of methyl acrylate, 490 g of acrylonitrile and 244 g of THF and Feed 2, a solution of 19.25 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (commercially available as Azo Starter V-65 from Wako Chemicals GmbH), in 244 g of THF. The dosage lasted 3 hours each.
  • the mixture was then polymerized for two hours at an internal temperature of 65 ° C and distilled for two hours at an external temperature of 65 ° C excess residual monomer under reduced pressure (50 to 500 mbar), while the pressure was regulated so that excessive foaming Ver ⁇ was avoided. Distillation also resulted in a certain amount of THF.
  • Each was based on a cordierite ceramic monolith, 2 MgO-5 SiO 2-2Al 2 O 3, 3.75 cm long and 1.8 cm in diameter and having a cell density of 400 cpsi (cells per square inch), one length of 3.75 cm and a diameter of 1, 8 cm.
  • the porosity was 74%, the average tube diameter 1.1 mm and the inner surface 2710 m 2 / m 3 .
  • steps 11.1 to II.6 the entire amount of monolith was further processed in each case.
  • Monolith from step 11.1 was covered in a 1000 ml glass flask with 500 ml of distilled water at a temperature of 90 ° C.
  • Ni (NO3) 2-6 H2O was adjusted to a pH of 3.5 with nitric acid. Thereafter, 0.72 g of urea was added. It was allowed to stand for 16 hours at 90 ° C without stirring, then cooled to room temperature and filtered. The filter residue was washed three times with distilled water, dried at 120 ° C. for 16 hours and calcined at 600 ° C. in a rotary tube over a period of 3 hours.
  • Monolith from step II.2 was inserted into a quartz tube (dimensions: diameter: 23 mm, length 860 mm) and reduced in a gas stream of a gas mixture of 20 l / h of hydrogen and 5 l / h of nitrogen.
  • the gas stream was heated to 550 ° C over two hours and then held at 550 ° C for 3 hours. Then it was purged with nitrogen and cooled to room temperature.
  • Monolith from step II.3 was boiled with 500 ml of 65 wt .-% aqueous nitric acid over a period of two hours at reflux, then removed and washed three times with one liter of water.
  • Monolith from step II.4 was slurried in 500 ml of distilled water (90 ° C) and adjusted to pH 3.5 with nitric acid. 0.2 g of ruthenium nitrosyl nitrate (Ru (NO) (NO 3 ) SH 2 O) and 0.132 g of urea were added. It was allowed to stand for 16 hours at 90 ° C without stirring, then cooled to room temperature and poured off the liquid. The monoliths thus treated were washed three times with distilled water, dried at 120.degree. C. for 16 hours, reduced in water
  • a hydrogenation catalyst was obtained, also referred to as hydrogenation catalyst from step II.5.
  • the hydrogenation catalyst from step II.5 had a content of Ru of 0.32 wt .-%, based on monolith, and of 3.8 wt .-%, based on carbon nanofibers.
  • Hydrogenation catalyst from step II.5 could be passivated, for example by storage in air. The activation then took place during the first minutes of the
  • the autoclave was rendered inert with nitrogen. Hydrogen was introduced into the autoclave through a Büchi station and a pressure of 50 bar was set at room temperature. It was heated to 200 ° C and pressed 200 bar of hydrogen. The mixture was allowed to react for 16 hours, then cooled to room temperature and the autoclave was released.
  • the hydrogenation catalyst was filtered off using a pleated filter and the THF was distilled off on a rotary evaporator (60 ° C. ⁇ 100 ° C., 300 mbar ⁇ 10 mbar). This gave a polymer P1 (red.) which no longer had nitrile groups. All phenyl rings were intact; for example, no cyclohexyl groups were detected.
  • 150 g of polymer P2 were filled as a 10% by weight solution in THF in a 300 ml autoclave with stirrer and gas inlet tube.
  • 2 g of hydrogenation catalyst from step II.5 were crushed into small pieces (average particle diameter d p about 125 microns) and also filled into the autoclave.
  • the autoclave was rendered inert with nitrogen.
  • Hydrogen was introduced into the autoclave through a Büchi station and a pressure of 50 bar was set at room temperature. It was heated to 200 ° C and pressed 200 bar of hydrogen. The mixture was allowed to react for 16 hours, then cooled to room temperature and the autoclave was released.
  • the hydrogenation catalyst was filtered off using a pleated filter and the THF was distilled off on a rotary evaporator (60 ° C. ⁇ 100 ° C., 300 mbar ⁇ 10 mbar).
  • COOCH3 groups were intact, for example, no CH2OH groups were detected.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP07704054A 2006-01-30 2007-01-22 Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren Withdrawn EP1981917A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07704054A EP1981917A1 (de) 2006-01-30 2007-01-22 Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06101016 2006-01-30
EP07704054A EP1981917A1 (de) 2006-01-30 2007-01-22 Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren
PCT/EP2007/050586 WO2007085581A1 (de) 2006-01-30 2007-01-22 Verfahren zur hydrierung von polymeren und dafür geeignete hydrierkatalysatoren

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EP1981917A1 true EP1981917A1 (de) 2008-10-22

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US (1) US20100227979A1 (enExample)
EP (1) EP1981917A1 (enExample)
JP (1) JP2009525356A (enExample)
CN (1) CN101374869A (enExample)
WO (1) WO2007085581A1 (enExample)

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US20110313186A1 (en) * 2009-02-09 2011-12-22 Basf Se Hydrogenation catalysts, the production and the use thereof
WO2010089266A2 (de) * 2009-02-09 2010-08-12 Basf Se Verfahren zur verbesserung der katalytischen aktivität von monolithischen katalysatoren
CN119793501A (zh) * 2024-12-29 2025-04-11 浙江工业大学 一种Pd-Cu-M/α-Si3N4负载型金属催化剂及其制备和应用

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US6087455A (en) * 1997-12-19 2000-07-11 Shell Oil Company Process for hydrogenation of macromolecular organic substrates
FR2832649B1 (fr) * 2001-11-23 2004-07-09 Sicat Composites a base de nanotubes ou nanofibres de carbone deposes sur un support active pour application en catalyse
EP1465836A2 (en) * 2001-12-21 2004-10-13 Battelle Memorial Institute Structures containing carbon nanotubes and a porous support, methods of making the same, and related uses

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CN101374869A (zh) 2009-02-25
JP2009525356A (ja) 2009-07-09
WO2007085581A1 (de) 2007-08-02

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