WO2013124392A1 - Metal powderdous catalyst for hydrogenation processes - Google Patents

Metal powderdous catalyst for hydrogenation processes Download PDF

Info

Publication number
WO2013124392A1
WO2013124392A1 PCT/EP2013/053512 EP2013053512W WO2013124392A1 WO 2013124392 A1 WO2013124392 A1 WO 2013124392A1 EP 2013053512 W EP2013053512 W EP 2013053512W WO 2013124392 A1 WO2013124392 A1 WO 2013124392A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal alloy
catalyst
total weight
catalyst according
metal
Prior art date
Application number
PCT/EP2013/053512
Other languages
English (en)
French (fr)
Inventor
Werner Bonrath
Axel Buss
Original Assignee
Dsm Ip Assets B.V.
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 Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to IN7057DEN2014 priority Critical patent/IN2014DN07057A/en
Priority to BR112014020919-7A priority patent/BR112014020919B1/pt
Priority to JP2014558110A priority patent/JP6312609B2/ja
Priority to KR1020147026524A priority patent/KR102096118B1/ko
Priority to CN201380010934.7A priority patent/CN104136115A/zh
Priority to US14/380,892 priority patent/US9238218B2/en
Priority to EP13705766.7A priority patent/EP2817093B1/en
Publication of WO2013124392A1 publication Critical patent/WO2013124392A1/en

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B01J37/0226—Oxidation of the substrate, e.g. anodisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

Definitions

  • the present invention is related to a new metal powder catalytic system (catalyst) comprising a Fe-alloy as a carrier, its production and its use in hydrogenation processes.
  • Powderous catalysts are well known and used in chemical reactions. Important types of such catalysts are i.e. the Lindlar catalysts.
  • a Lindlar catalyst is a heterogeneous catalyst which consists of palladium deposited on a calcium carbonate carrier which is also treated with various forms of lead.
  • the goal of the present invention was to find a powderous catalyst with improved properties.
  • the powderous catalysts according to the present invention do have a metal (or metal alloy) as carrier material, instead of a calcium carbonate carrier.
  • This metal alloy is coated by a metal oxide layer on which palladium (Pd) is deposited. Furthermore the new catalyst according to the present invention is free from lead (Pb).
  • the present invention relates to a powderous catalytic system (I) comprising a metal alloy carrier comprising
  • the said metal alloy is coated by a metal oxide layer and impregnated with Pd.
  • the catalytic system is in the form of a powder.
  • This new catalyst has numerous advantages: o
  • the catalyst is easy to recycle (and to remove) after the reaction. This can be done i.e. by filtration,
  • the catalyst can be used more than once (re-usable),
  • the catalyst as such is a very stable system. It is i.e. stable in regard to acids as well as to water,
  • the catalyst is easy to handle.
  • the catalyst is free from lead.
  • the catalyst shows high selectivity in hydrogenation reactions.
  • the metal alloys used are iron/nickel/cobalt/molybendum alloys. Such alloys are known as maraging steels and can be bought commercially from companies such as Matthey SA (Switzerland) and EOS GmbH (Germany). Such steels are avaibale under the tradenames of Durnco or EOS Maraging Steel MS1 .
  • the metal alloys can comprise further metals, such as i.e. Cu, Cr, Mn, Si, Ti, Al and/or Nb.
  • metal alloy can comprise carbon as well.
  • the present invention relates to a powderous catalytic system (II) comprising a metal alloy carrier comprising
  • the said metal alloy is coated by a metal oxide layer and impregnated with Pd.
  • the present invention also relates to a powderous catalytic system (III), wherein catalytic system (I) or (II) comprises at least one further metal chosen from the group consisting of Cu, Cr, Mn, Si, Ti, Al and Nb.
  • the present invention also relates to a powderous catalytic system ( ⁇ ), wherein the powderous catalytic system (III) comprises carbon. Furthermore, the present invention also relates to a powderous catalytic system (III"), wherein the metal alloy of the catalytic system (I), (II), (III) or (III * ) is maraging steel.
  • the metal oxide layer which coats the metal alloy, is non-acidic (preferably basic or amphoteric).
  • Suitable non-acidic metal oxide layers comprise Zn, Cr, Mn, Cu or Al.
  • the oxide layer comprise ZnO and optionally at least one further metal oxide wherein the metal is chosen from the group consisting of Cr, Mn, Mg, Cu and Al. Therefore the present invention also relates to a powderous catalytic system (IV), wherein powderous catalytic system (I), (II), (III), (III * ) and/or (III”) the metal oxide layer is basic or amphoteric.
  • a powderous catalytic system which is powderous catalytic system (IV), wherein the non-acidic metal oxide layer comprises Zn, Cr, Mn, Cu and/or Al (more preferably the oxide layer comprise ZnO and optionally at least one further metal oxide wherein the metal is chosen from the group consisting of Cr, Mn, Mg, Cu and Al).
  • the metal alloy is preferably coated with a thin layer of ZnO (0.5 - 3.5 ⁇ thickness) and optionally at least one further metal (Cr, Mn, Mg, Cu and/or Al) oxide.
  • the present invention also relates to a powderous catalytic system (V), which is powderous catalytic system (I), (II), (III), (III'), (III"), (IV), (IV) and/or (IV"), wherein the metal alloy is coated with a thin layer of ZnO and optionally at least one further metal (Cr, Mn, Mg, Cu and/or Al) oxide.
  • the coating of the metal alloy is done by commonly known processes, such as i.e. dip-coating.
  • the catalytic system (catalyst) of the present invention comprises between 0.1 wt-% and 50 wt-%, based on the total weight of the catalyst, of ZnO, preferably between 0.1 wt-% and 30 wt-%, more preferably between 1 .5 wt-% and 10 wt-% and most preferably between 2 wt-% and 8 wt-%.
  • the present invention also relates to a powderous catalytic system (VI), which is powderous catalytic system (I), (II), (III), (III'), (III"), (IV), (IV), (IV") and/or (V), wherein the catalyst comprises between 0.1 wt-% and 50 wt-%, based on the total weight of the catalytic system, of ZnO (preferably between 0.1 wt-% and 30 wt-%, more preferably between 1 .5 wt-% and 10 wt-% and most preferably between 2 wt-% and 8 wt-%).
  • ZnO preferably between 0.1 wt-% and 30 wt-%, more preferably between 1 .5 wt-% and 10 wt-% and most preferably between 2 wt-% and 8 wt-%.
  • the non-acidic metal oxide layers comprises ZnO and at least one further metal oxide wherein the metal is chosen from the group consisting of Cr, Mn, Mg, Cu and Al.
  • non-acidic metal oxide layer comprises ZnO and AI 2 O 3 .
  • the present invention also relates to a powderous catalytic system (VII), which is powderous catalytic system (I), (II), (III), (III'), (III"), (IV), (IV), (IV"), (V) and/or (VI), wherein the non-acidic metal oxide layer comprises ZnO and AI 2 O 3 .
  • ZnO : AI 2 O 3 is from 2:1 to 1 :2 (preferably 1 :1 ).
  • the present invention also relates to a powderous catalytic system (VII'), which is powderous catalytic system (VII), wherein the ratio of ZnO : AI 2 O 3 is from 2:1 to 1 :2 (preferably 1 :1 ).
  • the coated metal alloys are then impregnated by Pd-nanoparticles.
  • the nanoparticles are synthesized by commonly known methods, i.e. by using PdCI 2 as a precursor, which is then reduced by hydrogen.
  • the Pd-nanoparticles which are on the non-acidic metal oxide layer, have an average particle size of between 0.5 and 20 nm, preferably of between 2 and 15 nm, more preferably of between 5 and 12 nm and most preferably of between 7 to 10 nm. (The size is measured by light scattering methods).
  • the present invention also relates to a powderous catalytic system (VIII), which is powderous catalytic system (I), (II), (III), (III'), (III"), (IV), (IV), (IV"), (V), (VI), (VII) and/or (VII'), wherein the Pd-nanoparticles have an average particle size of between 0.5 and 20 nm (preferably of between 2 and 15 nm, more preferably of between 5 and 12 nm and most preferably of between 7 to 10 nm).
  • the catalyst according to present invention comprises between 0.001 wt-% and 5 wt-%, based on the total weight of the catalyst, of the Pd- nanoparticles, preferably between 0.01 wt-% and 2 wt-% more preferably between 0.05 wt-% and 1 wt-%.
  • the present invention also relates to a powderous catalytic system (IX), which is powderous catalytic system (I), (II), (III), (III'), (III"), (IV), (IV), (IV"), (V), (VI), (VII), (VII') and/or (VIII), wherein the catalyst comprises between 0.001 wt-% and 5 wt-%, based on the total weight of the catalyst, of the Pd- nanoparticles (preferably between 0.01 wt-% and 2 wt-% more preferably between 0.05 wt-% and 1 wt-%).
  • the catalyst comprises between 0.001 wt-% and 5 wt-%, based on the total weight of the catalyst, of the Pd- nanoparticles (preferably between 0.01 wt-% and 2 wt-% more preferably between 0.05 wt-% and 1 wt-%).
  • the catalyst is usually activated before the use.
  • the activation is done by using well known processes, such thermoactivation in H 2 .
  • the catalyst of the present invention is used in selective catalytic hydrogenation of organic starting material, especially of organic starting material comprising a carbon-carbon triple bond, more especially of alkynol compounds. Therefore the present invention also relates to the use of a powderous catalytic system (catalyst) (I), (II), (III), (III'), (III"), (IV), (IV), (IV”), (V), (VI), (VII), (VII'), (VIII) and/or (IX) in selective catalytic hydrogenation of organic starting material, especially of organic starting material comprising a carbon-carbon triple bond, more especially of alkynol compounds.
  • the present invention relates to a process of reacting a compound of formula (I)
  • R 1 wherein R-i is linear or branched C 5 -C 35 alkyl or linear or branched C 5 -C 35 alkenyl moiety, wherein the C chain can be substituted, and
  • R 2 is linear or branched Ci-C 4 alkyl, wherein the C chain can be substituted, with hydrogen in the presence of a catalyst (I), (II), '), (III"), (IV), (IV), (IV"), (V), (VI), (VII), (VII'), (VIII) and/or (IX). Hydrogen is usually used in the form H 2 gas.
  • Preferred compounds of formula (I) are the following:
  • Example 1 Synthesis of the catalyst (maraging steel coated by A O ⁇ ZnO and Pd deposition)
  • Step 1 Thermal pre-treatment
  • the stainless steel powder (EOS Maraging Steel MS1 ® commercially available from EOS GmbH, Germany) was subjected to a thermal pre-treatment at 450°C for 3 h.
  • Step 2 Deposition of ZnO + Al 2 0 3 (coating of the metal alloy carrier)
  • the powder was then filtered off via a membrane filter and dried in air at 40° C and 125 mbar for 2h followed by a calcination step at 450° C for 1 h.
  • the stirring- drying-calcination cycle was repeated 3 times.
  • the powder support was calcined in air at 550° C for 1 h.
  • the Pd° suspension was formed by bubbling hydrogen through the precursor solution for 1 h in a glass cylinder at room temperature.
  • the powder catalyst obtained from step 3 was subjected to a temperature treatment at 300° C for 4 h under H 2 -Ar flow. Then, it was cooled down to room temperature under the same H 2 -Ar flow.
  • Example 2 Selective hydrogenation of MBY to MBE
  • the new powderous catalyst has excellent properties as a catalyst for selective hydrogenations.
  • the new powderous catalyst has excellent properties as a catalyst for selective hydrogenations.
  • the new powderous catalyst has excellent properties as a catalyst for selective hydrogenations.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Crystallography & Structural Chemistry (AREA)
PCT/EP2013/053512 2012-02-24 2013-02-22 Metal powderdous catalyst for hydrogenation processes WO2013124392A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
IN7057DEN2014 IN2014DN07057A (forum.php) 2012-02-24 2013-02-22
BR112014020919-7A BR112014020919B1 (pt) 2012-02-24 2013-02-22 sistema catalítico em pó para processos de hidrogenação
JP2014558110A JP6312609B2 (ja) 2012-02-24 2013-02-22 水素化プロセスのための金属粉末状触媒
KR1020147026524A KR102096118B1 (ko) 2012-02-24 2013-02-22 수소화 공정을 위한 금속 분말형 촉매
CN201380010934.7A CN104136115A (zh) 2012-02-24 2013-02-22 用于氢化工艺的金属粉末状催化剂
US14/380,892 US9238218B2 (en) 2012-02-24 2013-02-22 Metal powderdous catalyst for hydrogenation process
EP13705766.7A EP2817093B1 (en) 2012-02-24 2013-02-22 Metal powderdous catalyst for hydrogenation processes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12156823.2 2012-02-24
EP12156823 2012-02-24

Publications (1)

Publication Number Publication Date
WO2013124392A1 true WO2013124392A1 (en) 2013-08-29

Family

ID=47748607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/053512 WO2013124392A1 (en) 2012-02-24 2013-02-22 Metal powderdous catalyst for hydrogenation processes

Country Status (8)

Country Link
US (1) US9238218B2 (forum.php)
EP (1) EP2817093B1 (forum.php)
JP (1) JP6312609B2 (forum.php)
KR (1) KR102096118B1 (forum.php)
CN (2) CN108246288A (forum.php)
BR (1) BR112014020919B1 (forum.php)
IN (1) IN2014DN07057A (forum.php)
WO (1) WO2013124392A1 (forum.php)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620778A (zh) * 2021-08-17 2021-11-09 万华化学集团股份有限公司 一种炔丙醇类化合物还原制备烯丙醇类化合物的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6238211B2 (ja) * 2012-04-18 2017-11-29 ディーエスエム アイピー アセッツ ビー．ブイ． 水素化反応に有用な装置（ｉｉｉ）
CN104245113B (zh) * 2012-04-18 2018-03-20 帝斯曼知识产权资产管理有限公司 适用于氢化反应(i)的装置
CN106391044A (zh) * 2015-07-28 2017-02-15 江苏吉华化工有限公司 一种催化剂
WO2018202639A1 (en) * 2017-05-01 2018-11-08 Dsm Ip Assets B.V. Metal powderdous catalyst for hydrogenation processes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008101603A2 (en) * 2007-02-19 2008-08-28 Dsm Ip Assets B.V. Catalysts based on sintered metal fibers coated by zinc oxide layer impregnated with palladium nanoparticles for the hydrogenation of alkynols
WO2011092280A1 (en) * 2010-01-28 2011-08-04 Dsm Ip Assets B.V. Hydrogenation process
WO2012001166A1 (en) * 2010-07-01 2012-01-05 Dsm Ip Assets B.V. Novel structured catalyst

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1578122A (en) * 1976-02-11 1980-11-05 Johnson Matthey Co Ltd Catalytic hydrogenation of fatty oils
GB1568391A (en) * 1976-04-14 1980-05-29 Atomic Energy Authority Uk Catalysts having metallic substrates
AU3715597A (en) * 1996-05-14 1997-12-05 E.I. Du Pont De Nemours And Company Catalyst compositions of nanoparticulate metal on a refractory support
US20070053784A1 (en) * 2005-09-06 2007-03-08 Crucible Materials Corp. Maraging steel article and method of manufacture
JP2011251951A (ja) * 2010-06-03 2011-12-15 Mitsubishi Chemicals Corp 水素化芳香族化合物の製造方法及び有機化合物の製造方法
CN104245117A (zh) * 2012-04-18 2014-12-24 帝斯曼知识产权资产管理有限公司 适用于氢化反应(ii)的装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008101603A2 (en) * 2007-02-19 2008-08-28 Dsm Ip Assets B.V. Catalysts based on sintered metal fibers coated by zinc oxide layer impregnated with palladium nanoparticles for the hydrogenation of alkynols
WO2011092280A1 (en) * 2010-01-28 2011-08-04 Dsm Ip Assets B.V. Hydrogenation process
WO2012001166A1 (en) * 2010-07-01 2012-01-05 Dsm Ip Assets B.V. Novel structured catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SEMAGINA ET AL: "Structured catalyst of Pd/ZnO on sintered metal fibers for 2-methyl-3-butyn-2-ol selective hydrogenation", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US, vol. 251, no. 1, 7 September 2007 (2007-09-07), pages 213 - 222, XP022235097, ISSN: 0021-9517, DOI: 10.1016/J.JCAT.2007.06.028 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620778A (zh) * 2021-08-17 2021-11-09 万华化学集团股份有限公司 一种炔丙醇类化合物还原制备烯丙醇类化合物的方法

Also Published As

Publication number Publication date
IN2014DN07057A (forum.php) 2015-04-10
CN108246288A (zh) 2018-07-06
EP2817093A1 (en) 2014-12-31
BR112014020919B1 (pt) 2020-10-27
KR20140134300A (ko) 2014-11-21
JP2015513456A (ja) 2015-05-14
CN104136115A (zh) 2014-11-05
US9238218B2 (en) 2016-01-19
US20150011791A1 (en) 2015-01-08
KR102096118B1 (ko) 2020-04-02
JP6312609B2 (ja) 2018-04-18
EP2817093B1 (en) 2020-03-25

Similar Documents

Publication Publication Date Title
EP2528882B1 (en) Hydrogenation process
EP2817093B1 (en) Metal powderdous catalyst for hydrogenation processes
JP6447940B2 (ja) 新規な触媒システム
EP2817092B1 (en) Metal powderdous catalyst comprising a fe-alloy
EP2817095B1 (en) Use of a metal powderdous catalyst comprising a cocrmo-alloy
EP3618957A1 (en) Metal powderous catalyst for hydrogenation processes
JP7098863B2 (ja) 水素化プロセスのための金属粉末状触媒

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13705766

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014558110

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 14380892

Country of ref document: US

Ref document number: 2013705766

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147026524

Country of ref document: KR

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112014020919

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112014020919

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20140825