EP0645466B1 - Catalyst material, based on a titanium-copper alloy and process for producing the same - Google Patents

Catalyst material, based on a titanium-copper alloy and process for producing the same Download PDF

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Publication number
EP0645466B1
EP0645466B1 EP19940114639 EP94114639A EP0645466B1 EP 0645466 B1 EP0645466 B1 EP 0645466B1 EP 19940114639 EP19940114639 EP 19940114639 EP 94114639 A EP94114639 A EP 94114639A EP 0645466 B1 EP0645466 B1 EP 0645466B1
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EP
European Patent Office
Prior art keywords
catalyst material
matrix
intermetallic compound
alloy
producing
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.)
Expired - Lifetime
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EP19940114639
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German (de)
English (en)
French (fr)
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EP0645466A1 (en
Inventor
Tsuyoshi Masumoto
Akihisa Inoue
Katsutoshi Nosaki
Hideo Fukui
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.)
Honda Motor Co Ltd
YKK Corp
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Honda Motor Co Ltd
YKK Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Definitions

  • the present invention provides a highly hard and highly active Ti-Cu based alloy suitable for use as a catalyst material capable of catalyzing, for example, hydrogenation of carbon monoxide.
  • Catalysts for use in the reaction in which carbon monoxide is hydrogenated to produce hydrocarbons and water have pretty widely been investigated, which include ruthenium-bearing alumina and Ti-Cu based alloy catalysts.
  • ruthenium-bearing alumina and Ti-Cu based alloy catalysts have pretty widely been investigated, which include ruthenium-bearing alumina and Ti-Cu based alloy catalysts.
  • An object of the present invention is to provide a Ti-Cu based alloy suitable for use as a catalyst material having increased catalytic activity and improved mechanical properties by further refining the size of the microcrystalline structure and stabilizing the presence thereof in the Ti-Cu based alloy.
  • a Ti-Cu based alloy catalyst material having a composition including at least one element selected from the group consisting of V, Ni, Zr, Cr, Mn, Fe and Co as a partial substitute element for Ti and/or Cu in a composition represented by the general formula Ti 100-a Cu a , wherein "a" is, in atomic %, 30 ⁇ a ⁇ 50, 0.1 to 20 atomic % in the general formula Ti 100-a Cu a being substituted with said at least one element, in which a fine Ti-Cu intermetallic compound having a mean particle size of 10 nm or less is uniformly precipitated in an amorphous phase and/or an ⁇ -Ti matrix.
  • the above intermetallic compound is contained in the alloy catalyst in an amount of 5 to 90% by volume.
  • a process for producing the aforestated Ti-Cu based alloy catalyst material which comprises preparing an alloy having the above-specified Ti 100-a Cu a composition in which 0.1 to 20 atomic % thereof is substituted with at least one element selected from the group consisting of V, Ni, Zr, Cr, Mn, Fe and Co, the alloy having an amorphous phase and/or ⁇ -Ti matrix; and heating the alloy at a temperature ranging from the transformation temperature T x of a non-equilibrium phase minus 50 K (i.e., T x - 50 K) to the transformation temperature T x plus 100 K (i.e., T x + 100 K) so as to precipitate a fine Ti-Cu intermetallic compound in the matrix.
  • the transformation temperature T x of a non-equilibrium phase is referred to "transformation temperature" or "T x " unless otherwise specified.
  • Fig. 1 is a graph indicating the relationship between the particle size of the alloy of Ti 48.5 Cu 48.5 Mn 3 and the reaction rate measured in the hydrogenation of CO.
  • Fig. 2 is a graph indicating the relationship between the volume percentage of the intermetallic compound contained in the same alloy as in Fig. 1 and the reaction rate measured in the hydrogenation of CO.
  • Fig. 3 is a graph indicating the relationship between the heat treatment temperature applied in preparing the same alloy as in Fig. 1 and the particle size of the intermetallic compound.
  • Fig. 4 is a graph indicating the relationship between the heat treatment time taken in the heat treatment of the same alloy as in Fig. 1 at 400°C and the particle size of the intermetallic compound.
  • Fig. 5 is a micrograph showing the crystalline structure of the alloy of Ti 48.5 Cu 48.5 Zr 3 obtained by the present invention.
  • Fig. 6 is a micrograph showing the crystalline structure of the alloy of Ti 48.5 Cu 48.5 Mn 3 obtained by the present invention.
  • Ti and/or Cu in the Ti 100-a Cu a composition is partially substituted with at least one additional element selected from the group consisting of V, Ni, Zr, Cr, Mn, Fe and Co in an amount of 0.1 to 20 atomic % of the composition.
  • fine particles of Ti-Cu intermetallic compound having a mean particle size of 10 nm or less are uniformly precipitated throughout an amorphous phase and/or ⁇ -Ti matrix.
  • intermetallic compounds examples include Ti 2 Cu, TiCu, Ti 2 Cu 3 and TiCu 3 . It is requisite that the precipitated intermetallic compound have a mean particle size of 10 nm or less. When the mean particle size exceeds 10 nm, the mechanical performance and catalytic activity of the alloy catalyst would rapidly be deteriorated with the increase in the particle size.
  • Fig. 1 shows a graph indicating the relationship between the particle size of the alloy of Ti 48.5 Cu 48.5 Mn 3 and the reaction rate measured in the hydrogenation of CO.
  • the intermetallic compound be contained in the matrix in an amount of 5 to 90% by volume.
  • the amount is less than 5% by volume, not only is it too small to cause the resultant catalyst to exhibit desired catalytic activity but also the mechanical strength of the alloy catalyst is likely to be poorer than in the range of 5 to 90% by volume.
  • the amount of the intermetallic compound exceeds 90% by volume, not only is it too large to cause the resultant catalyst to have desired catalytic activity improvement but also the activity lowering by sintering is likely to occur during the use of the catalyst.
  • Fig. 2 shows a graph indicating the relationship between the volume percentage of the intermetallic compound contained in the alloy of Ti 48.5 Cu 48.5 Mn 3 and the reaction rate measured in the hydrogenation of CO.
  • the matrix may be an amorphous phase, a fine Ti matrix phase or a phase of a mixture thereof.
  • the matrix is an amorphous phase, a structure in which fine Ti crystals and a Ti-Cu intermetallic compound have been precipitated would result.
  • the matrix consists of fine Ti crystals, a structure in which a Ti-Cu intermetallic compound has been precipitated therein would result.
  • the above alloy having an amorphous phase and/or ⁇ -Ti matrix may be prepared by rapid solidification in which the cooling rate is 10 4 to 10 6 K/sec.
  • the cooling rate is lower than 10 4 K/sec, any alloy having the composition according to the present invention and having the desired matrix cannot be obtained.
  • the cooling rate exceeding 10 6 K/sec cannot be attained by any industrial quenching means utilizing the currently available liquid quenching, etc.
  • the heat treatment for precipitating a Ti-Cu intermetallic compound must be conducted at a temperature ranging from the transformation temperature T x minus 50 K to the transformation temperature T x plus 100 K.
  • the transformation temperature is the crystallization temperature of the amorphous phase.
  • the temperature is lower than the transformation temperature T x minus 50 K, it is hard to attain precipitation of the Ti-Cu intermetallic compound which effectively acts in the catalytic activity desired in the present invention, so that the heat treatment takes a prolonged period of time.
  • such a heat treatment is not practical and makes it difficult to form the intermetallic compound at a desirable volume percentage.
  • Fig. 3 shows a graph indicating the relationship between the heat treatment temperature applied in preparing the alloy of Ti 48.5 Cu 48.5 Mn 3 and the particle size of the intermetallic compound.
  • Fig. 4 shows a graph indicating the relationship between the heat treatment time taken in the heat treatment of the alloy of Ti 48.5 Cu 48.5 Mn 3 at 400°C and the particle size of the intermetallic compound.
  • the heat treatment time be at least 0.01 hr.
  • the heating must be conducted at a temperature of at least T x plus 100 K for obtaining effective particle size. It is industrially difficult to achieve particle size control by uniformly heating within the above short period of time.
  • the reason for limiting the substitution with at least one additional element in the Ti 100-a Cu a composition to 0.1 to 20 atomic % is that an amorphous phase and/or ⁇ -Ti matrix required to form the desired microcrystalline structure can be obtained by the limitation, and that, outside the above range, it is difficult to stably obtain such a matrix.
  • Heating at 400°C in a vacuum for 1 hr converts a Ti-Cu based amorphous alloy to a crystalline structure of Ti-Cu intermetallic compound phase having a coarse particle size as large as about 1 to 2 ⁇ m.
  • the addition of the above additional element to the amorphous alloy suppresses the growth of crystal grains, so that a crystalline structure results which has a size of about 1/10 to 1/1000 of that of the crystalline structure formed when no such additional element is added.
  • This crystalline structure is a Ti-Cu intermetallic compound phase corresponding to the respective compositional proportions of Ti and Cu.
  • the refining of the crystalline structure as indicated above catalytically activates and improves the properties of the alloy to thereby render the same excellent as a catalyst material.
  • An alloy having a given composition was prepared by the use of an arc melting furnace.
  • the alloy was inserted into a silica tube having a small opening at its tip, and heated to melt the alloy.
  • the silica tube was placed just above a 200-mm roll, and the molten alloy was injected through the small opening of the silica tube under an argon pressure of 0.7 kg/cm 2 while rotating the roll at a speed as high as 4000 rpm so as to cause the injected alloy to contact the roll surface, thereby effecting quench solidification of the alloy.
  • a thin ribbon having a width of about 1 mm was obtained.
  • the thin ribbon was heated at 400°C for 1 hr in a vacuum to thereby crystallize the same.
  • Tables 1 and 2 show data on the catalysts in which Zr and Mn were employed as the additional elements.
  • the present invention provides a Ti-Cu based alloy catalyst material which is excellent in mechanical properties and catalytic activity.
  • the Ti-Cu based alloy catalyst effectively catalyzes chlorofluorocarbon decomposition, benzene hydrogenation, carbon monoxide hydrogenation, alcohol dehydration and other reactions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP19940114639 1993-09-29 1994-09-16 Catalyst material, based on a titanium-copper alloy and process for producing the same Expired - Lifetime EP0645466B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5265701A JPH07163879A (ja) 1993-09-29 1993-09-29 Ｔｉ−Ｃｕ系合金触媒材料及びその製造方法
JP265701/93 1993-09-29

Publications (2)

Publication Number Publication Date
EP0645466A1 EP0645466A1 (en) 1995-03-29
EP0645466B1 true EP0645466B1 (en) 1998-07-08

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EP19940114639 Expired - Lifetime EP0645466B1 (en) 1993-09-29 1994-09-16 Catalyst material, based on a titanium-copper alloy and process for producing the same

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EP (1) EP0645466B1 (ja)
JP (1) JPH07163879A (ja)
DE (1) DE69411483T2 (ja)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4011316B2 (ja) * 2000-12-27 2007-11-21 独立行政法人科学技術振興機構 Ｃｕ基非晶質合金
DE10224722C1 (de) * 2002-05-30 2003-08-14 Leibniz Inst Fuer Festkoerper Hochfeste, plastisch verformbare Formkörper aus Titanlegierungen
WO2015072817A1 (ko) * 2013-11-18 2015-05-21 코닝정밀소재 주식회사 산화 촉매, 그 제조방법 및 이를 포함하는 배기가스 정화용 필터
KR101555924B1 (ko) * 2013-11-18 2015-09-30 코닝정밀소재 주식회사 산화 촉매, 그 제조방법 및 이를 포함하는 배기가스 정화용 필터

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH660130A5 (de) * 1984-07-27 1987-03-31 Lonza Ag Verfahren zur herstellung von katalytisch wirksamen, glasig erstarrten metallen.

Also Published As

Publication number Publication date
EP0645466A1 (en) 1995-03-29
DE69411483T2 (de) 1999-02-18
DE69411483D1 (de) 1998-08-13
JPH07163879A (ja) 1995-06-27

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