US3645799A - Method of activating nickel-based catalysts - Google Patents

Method of activating nickel-based catalysts Download PDF

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Publication number
US3645799A
US3645799A US733076A US3645799DA US3645799A US 3645799 A US3645799 A US 3645799A US 733076 A US733076 A US 733076A US 3645799D A US3645799D A US 3645799DA US 3645799 A US3645799 A US 3645799A
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metal
nickel
annealing
alloy
aluminum
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US733076A
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English (en)
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Bernard Goue
Claude Edon
Louis Guitard
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Alcatel Lucent SAS
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Compagnie Generale dElectricite SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • ABSTRACT A method for activating nickel-based catalysts and the products resulting therefrom, which comprises annealing and hardening a nickel-based alloy prior to mechanical shaping, mechanically shaping said alloy, annealing and hardening said alloy a second time, isothermally annealing said alloy and thereafter cooling said alloy to about room temperature.
  • This invention relates to a method for preparing and activating the catalytic properties of certain nickel-base binary alloys. These alloys are especially useful as electrodes with hydrogenated fuel for fuel cells. Further, the products of this invention can be utilized generally as catalysts for hydrogenation reactions.
  • a catalyst comprising a binary supersaturated solution of a metal, such as beryllium or aluminum, in nickel is activated for fuel cell and other applications.
  • a metal such as beryllium or aluminum
  • the particular alloy selected for this invention is based upon the following conditions:
  • the solubility of the second metal in the nickel must vary as a function of temperature
  • the second metal must form with nickel an intermetallic compound or an intermediate phase
  • the proportion of the second metal in the resulting alloy must be between a lower limit corresponding to the maximum content leading to a single solid solution, at ambient temperature and an upper limit, corresponding to the intermetallic compound or the intermediate phase mentioned above.
  • This binary alloy is activated by a series of mechanical treatments which are performed while the alloy is being shaped into the desired configuration for its ultimate end use. Specifically, the alloy is subjected to annealing and hardening, shaping to the desired configuration, annealing and hardening a second time, isothermal annealing and finally cooling.
  • FIG. I is a diagram of a melting furnace according to the invention.
  • FIG. 2 shows the results of activation treatment applied to a sample of nickel-beryllium subjected to tempering at the temperature of 450 C.
  • FIG. 3 shows the results of activation treatment applied to a sample of nickel-aluminum subjected to tempering at a temperature of 600 C.
  • One condition necessary for catalytic activity of the type involved here is the capability of the catalyst to chemically absorb one of the reagents, which form an intermediate compound on the surface of the catalyst corresponding to the reagent and the catalyst. These intermediate compounds then give rise to ions in the solution.
  • This special feature can be used in order to catalyze, for example, one or the other of the two inverse oxygen or reduction reactions, by varying the conditions under which the reaction is to take place.
  • molecular hydrogen is generated.
  • oxidation ionized oxygen is generated.
  • the method involved in this invention is precisely intended, after the preparation of the primary alloy as such, to, modify the structure of the electrodes which are drawn from the alloy during the course of the shaping. These modifications occur in such a way that the catalytic activity of these electrodes is increased.
  • the alloy In shaping the alloy for use as an electrode, the alloy is subjected to a variety of heat treatments. These heat treatments necessarily have a direct effect on the catalytic properties of the metal.
  • the method involved in this invention is thus intended to make the electronic factors of the bodies present more favorable.
  • the metals which catalyze hydrogenation are so-called transition metals whose basic feature is that they have removable d" orbitals.
  • a catalyst for example, an electrode of the type visualized in this invention, in terms of the activation energy with respect to the conversion of parahydrogen into orthohydrogen.
  • the electrocatalytic activity may be characterized by the intensity corresponding to the ionization of hydrogen in a solution of potash at a fixed potential, with respect to a reference electrode.
  • the appearance of structural defects and especially the appearance of defects intentionally introduced to activate the electrode can also be detected and its evolution can be made noticeable by measuring the hardness of the alloy obtained.
  • One means used in the present method to activate nickel consists in displacing the atoms situated in the immediate vicinity of the surface of the metal, while they are in their equilibrium position; the displacements in question can be obtained from the interior of the metal.
  • This type of displacement causes favorable modifications in the electronic coupling conditions which occur between the activating gas molecules and the metallic atoms on the surface thereby increasing the catalytic and electrocatalytic activities of the metal.
  • the abovementioned structural modification must, if it is to be favorable, take place during heat treatment consisting in raising the temperature; this is done so that the resultant activation can be maintained during the heat treatments which will have to be undertaken afterward in order to prepare the electrodes.
  • one such favorable treatment consists in precipitating or mixture separating, starting with a solid binary solution which is supersaturated and very rich in nickel.
  • the precipitation is characterized by the presence of a relatively small quantity of precipitate which is-very highly enriched in solute, within a matrix that is much less rich.
  • mixture separation is used herein as denoting the presence of a large quantity of a precipitate which is relatively poor in terms of solute, as compared to the matrix.
  • Another characteristic of mixture separation is that the matrix and the precipitate have a crystal lattice which are generally of the same nature and whose parameters differ only slightly.
  • nickel-beryllium alloys to show the precipitation method
  • nickel-aluminum alloys to show mixture separation
  • composition of binary alloys is kept between the limits indicated above.
  • the metals are fused preferably in a vacuum.
  • the alloy so formed is mechanically worked and hardened.
  • the temperature is either higher than the critical solubility temperature of the second metal or is not greater than that of the solidus point.
  • the alloy is kept at the temperature selected during the time required for the maximum solution of the second metal in the nickel.
  • the metal On the basis of this temperature, the metal is hardened at sufficient speeds and ambient temperatures, precipitated or mixture separated by means of suitable tempering which is performed at temperatures which are lower than the critical solutility temperatures.
  • the alloy is hardened during the tempering operations which are normally referred to as structural hardening.”
  • Ni-Be nickel-beryllium
  • Ni -Al nickel-aluminum phase
  • tempering process is tied in with the germination process. After tempering, which follows hardening, structures which are in a higher energy state than equilibrium because of the dispersion in the impoverished solution of precipitates or heterogeneous elements with weak interfacial energy, is obtained. That is to say, they are totally or partially coherent with the matrix.
  • the catalytic activity of a metal such as nickel
  • a metal such as nickel
  • the catalytic activity of a metal may be attributed to the fact that, since the atoms are displaced from their equilibrium position, a certain number of defects in the structure of this metal are obtained.
  • metal having sufficient purity, for example 99.9 percent nickel, 99.97 percent beryllium, and 99.99 percent aluminum. 7
  • quartz tubes constituting the interiors of the various furnaces used will be cleaned by means of a baththat might have the following composition:
  • Hydrofluoric acid 50% 40 cm.” Fuming nitric acid, 48 Be 60 cm. Acetic acid, I00% 40 cm. Bromine a few drops This cleaning is followed by abundant rinsing with deionized water.
  • the nickel preferably in the form of fine balls, is degreased, for example, in acetone, and then is dried and deoxidized, for example, in a 50 percent solution of hydrochloric acid, brought to a temperature of 50 C.
  • the balls are subjected for a short time (4-6 seconds), to the action of a bath of 50 percent fuming nitric acid, brought to a temperature of 70 C.; this is followed by abundant rinsing, still using deionized water. Finally, the balls are dried in argon.
  • Prior fusion in a vacuum is performed in a furnace such as shown in FIG. 1.
  • the crucible is made of very pure recrystallized alumina capable of withstanding temperatures of up to l,950 while still suitably resisting heat shocks.
  • the walls of the crucible are quite thin, for example, for a content of about 50 cm., the weight of the crucible is about 300 g.
  • the crucible is placed onto a plate 2 likewiseimade of alumina which is insulated from the crucible by the quartz support 3.
  • a tube 4 consisting of transparent quartz and not containing any boron, concentrically surrounds the crucible and the plate.
  • a guide sleeve 5 likewise made of alumina, is fitted to hold the crucible l.
  • the winding coils 6 provide high-frequency heating energy.
  • the other parts of the furnace have not been shown because they are all known (the cooled head, the upper portion of tube 4, the thermocouple, the neutral gas, circulation device, the pumping unit, which can generate pressures on the order of 5X10 mm. Hg, the secondary silicone oil diffusion pump, the vacuum measurement gauge, etc.).
  • the nickel balls which have been degreased and deoxidized as indicated above, are placed into crucible 1.
  • the second metal is then introduced.
  • a vacuum of up to about 7X10 mm. Hg is created and the I high-frequency heating system is started taking care to achieve a progressive temperature rise. Local overheating which might cause the crucible to burst is avoided and the operation is controlled with the degassing gauge.
  • a slide valve not shown, makes it possible to insulate the furnace from the beginning of fusion.
  • argon is slowly introduced until a static pressure of about l00 g. above the atmosphere is reached.
  • the evaporation of the components can thereby be limited.
  • the bar When using aluminum, the bar is not introduced into the bath until the complete melting of the nickel which takes about minutes before the nickel-aluminum bath reaches sufficient homogeneity. A i W 7 The melt is then solidified gradually by increasing the flow rate of the cooling gas up to about 60 liters per hour. The chamber is again placed under a secondary vacuum until the cooling is complete.
  • the next operation involves hardening which must be performed in a minimum amount of time (not to exceed 34 seconds).
  • the piece is placed in a baffle which is immediately subjected to a water shower under pressure, at ambient temperature. 7 g
  • the piece then becomes sufficiently malleable so as make the first mechanical transformations possible (cutting, laminating, wire-drawing) which is done cold.
  • the plates or wires in the desired dimensions are thus prepared.
  • the semifinished products which have undergone mechanical transformation are then removed or the samples prior to annealing are annealed by means of dissolving annealing. These operations likewise take place in a vacuum for periods of 2-5 hours, at temperatures between 1,100 and l,350 C.
  • the piece After the so-called dissolving annealing, the piece is again hardened with water at ambient temperature.
  • p v V V V V The conditions must be known here with great precision and this applies to the temperature, which for example, is measured with the help of a Pt/PtRh thermocouple.
  • the exact duration of annealing must also be known. The annealing is terminated by air cooling of the nickel-beryllium alloys and by' water showering the nickel-aluminum alloys.
  • FIGS. 2 and 3 summarize the results obtained, respectively, 7
  • FIG. 2 have been plotted, The first two, each characterize the evolution of the structure of the material as a function of the duration of isothermal annealing at 450 C. on the nickelberyllium sample as described above.
  • the structural characteristics, whose evolution is indicated by the first two curves are the electrical resistance (curve R) and the Vickers hardness (curve D).
  • the resistance and hardness of each sample was measured by known methods.
  • the intensity corresponding to the electrochemical release of hydrogen is concerned, its variations are indicated as a function of the linear growth of the electric voltage applied to the sample, with respect to a reference electrode.
  • the intensity selected is the intensity which corresponds to a polarization of 920 mv., with respect to an l-lg HgO electrode and for a scanning speed of l v./minute. This characteristic furthermore expresses a rather qualitative aspect'of the evolution of the electrocatalytic activity of the alloy studiedin terms of time.
  • the paraorthohydrogen conversion reaction test was studied under a dynamic regime.
  • the hydrogen contained in a bottle, is expanded by a double-cutoff manometer.
  • a needle valve keeps its flow rate constant.
  • the gas is conducted over a bed of activated charcoal which is kept at the temperature of liquid nitrogen.
  • the proportion in the mixture of each of the two paraand orthohydrogen isomers is fixed at about 50 percent.
  • the mixture is then conducted into the first branch of a twobranch conductivity cell; these two branches constitute the two arms of a Wheat-stone bridge. Due to the effect of the catalyst, the proportion of the two isomers in the mixture is modified and this leads to a corresponding modification of the conductivity of the gas mixture passing into the second branch, which throws the bridge out of equilibrium.
  • the two magnitudes R and D enable, to different degrees, the determination of the direction of evolution of the structure of the alloy being treated, in terms of time.
  • the intensity of hydrogen release As far as the intensity of hydrogen release is concerned, it varies in a direction opposite to the activation energy, thereby indicating, the fluctuations in the latter which, as all of the experiments have shown, goes through a more or less regular $9992. 2? ai m m a ums
  • the intensity reveals two maximums, respectively, around the 50th and the 650th minutes.
  • the activation energy reveals two minimums, the first one at about the 50th minute and the second one atthe 450th minute, roughly. m n
  • the activation maximums occur at approximately the 30th and the th minutes. It should be noted that the duration maximum is reached only at about the l,l00th minute, that is to say, quite a bit after the second activation maximum.
  • FIG. 3 which pertains to the above-mentioned sample of nickel-aluminum, we have shown the only two results concerning the variations in the Vickers hardness and the intensity of hydrogen release. I it can be seen that the latter presents four maximums, the last of which is the biggest; it corresponds to a treatment dura- 'tion of about 100 hours.
  • a method for preparing an activated nickel-based binary catalyst which comprises:
  • nickel with from about 1 percent to-about 9 percent by weight of a second metal selected from the group consisting of aluminum and beryllium, said second metal being present in an amount of at least the maximum quantity which will form a unique solid solution in nickel, and an amount not more than the quantity corresponding to an intermediate phaseof said second metal and nickel, homogenization annealing and hardening said catalyst in a first operation, shaping said catalyst, annealing said catalyst at a temperature of about l,l C. to about 1,350 C. and hardening said catalyst in a second operation, isothermally annealing said catalyst, and cooling said catalyst to at least room temperature.
  • tion is homogenization annealing and is performed at temperatures of from about l,l00-l,300 C. for approximately hours.
  • said second annealing procedure is a dissolving annealing operation wherein the alloy is annealed for about 2 to 5 hours.

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  • Engineering & Computer Science (AREA)
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US733076A 1967-05-29 1968-05-29 Method of activating nickel-based catalysts Expired - Lifetime US3645799A (en)

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BE (1) BE715763A (enrdf_load_stackoverflow)
CA (1) CA925843A (enrdf_load_stackoverflow)
CH (1) CH491670A (enrdf_load_stackoverflow)
DE (1) DE1767622A1 (enrdf_load_stackoverflow)
FR (1) FR1589362A (enrdf_load_stackoverflow)
GB (1) GB1226768A (enrdf_load_stackoverflow)
LU (1) LU56162A1 (enrdf_load_stackoverflow)
NL (1) NL6807607A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4221610A (en) * 1978-02-24 1980-09-09 The United States Of America As Represented By The United States Department Of Energy Method for homogenizing alloys susceptible to the formation of carbide stringers and alloys prepared thereby
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
US9452409B2 (en) 2011-04-22 2016-09-27 Vanderbilt University Para-hydrogen polarizer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4487818A (en) * 1982-07-19 1984-12-11 Energy Conversion Devices, Inc. Fuel cell anode based on a disordered catalytic material

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1675264A (en) * 1924-03-17 1928-06-26 Gen Electric Treatment of nickel-copper-aluminum alloys
US1915473A (en) * 1930-12-31 1933-06-27 Raney Murray Method of preparing catalytic material
US1941368A (en) * 1931-12-22 1933-12-26 Beryllium Corp Nickel alloys
US2062130A (en) * 1934-03-24 1936-11-24 Heraens Vacuumschmelze A G Heat treatable nickel-beryllium alloys
US2289566A (en) * 1937-06-30 1942-07-14 Perosa Corp Nickel-beryllium alloy
US2848360A (en) * 1953-05-21 1958-08-19 Lorraine Carbone Method of treating nickel-beryllium alloys
US2850384A (en) * 1956-09-26 1958-09-02 Driver Co Wilbur B Electrical resistance alloys
US3021211A (en) * 1959-06-05 1962-02-13 Westinghouse Electric Corp High temperature nickel base alloys
US3343949A (en) * 1965-03-01 1967-09-26 Brush Beryllium Co Nickel-beryllium alloy and method of heat treating same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1675264A (en) * 1924-03-17 1928-06-26 Gen Electric Treatment of nickel-copper-aluminum alloys
US1915473A (en) * 1930-12-31 1933-06-27 Raney Murray Method of preparing catalytic material
US1941368A (en) * 1931-12-22 1933-12-26 Beryllium Corp Nickel alloys
US2062130A (en) * 1934-03-24 1936-11-24 Heraens Vacuumschmelze A G Heat treatable nickel-beryllium alloys
US2289566A (en) * 1937-06-30 1942-07-14 Perosa Corp Nickel-beryllium alloy
US2848360A (en) * 1953-05-21 1958-08-19 Lorraine Carbone Method of treating nickel-beryllium alloys
US2850384A (en) * 1956-09-26 1958-09-02 Driver Co Wilbur B Electrical resistance alloys
US3021211A (en) * 1959-06-05 1962-02-13 Westinghouse Electric Corp High temperature nickel base alloys
US3343949A (en) * 1965-03-01 1967-09-26 Brush Beryllium Co Nickel-beryllium alloy and method of heat treating same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4221610A (en) * 1978-02-24 1980-09-09 The United States Of America As Represented By The United States Department Of Energy Method for homogenizing alloys susceptible to the formation of carbide stringers and alloys prepared thereby
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
US9452409B2 (en) 2011-04-22 2016-09-27 Vanderbilt University Para-hydrogen polarizer

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CH491670A (fr) 1970-06-15
NL6807607A (enrdf_load_stackoverflow) 1968-12-02
DE1767622A1 (de) 1971-10-07
BE715763A (enrdf_load_stackoverflow) 1968-11-28
FR1589362A (enrdf_load_stackoverflow) 1970-03-31
CA925843A (en) 1973-05-08
GB1226768A (enrdf_load_stackoverflow) 1971-03-31
LU56162A1 (enrdf_load_stackoverflow) 1970-01-14

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