US3882050A - Method of depositing a noble metal on a surface of a nickel support - Google Patents
Method of depositing a noble metal on a surface of a nickel support Download PDFInfo
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- US3882050A US3882050A US382069A US38206973A US3882050A US 3882050 A US3882050 A US 3882050A US 382069 A US382069 A US 382069A US 38206973 A US38206973 A US 38206973A US 3882050 A US3882050 A US 3882050A
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- Prior art keywords
- nickel
- palladium
- per cent
- acid
- noble metal
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 65
- 238000000151 deposition Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 17
- 229910000510 noble metal Inorganic materials 0.000 title description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 31
- 230000008021 deposition Effects 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 21
- -1 palladium ions Chemical class 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 24
- 239000006260 foam Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052703 rhodium Inorganic materials 0.000 description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000007514 turning Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910000792 Monel Inorganic materials 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J23/892—Nickel and noble metals
-
- B01J35/56—
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- This invention pertains to massive forms of nickel such as nickel wire, grid, turnings, lath, and foams.
- Such forms of elemental nickel having a noble metal surface deposit are exhaust gas catalysts
- the catalytic reaction of hydrogen with nitric oxide in the presence of oxygen has been studied using a noble supported on alumina; Jones et al., Environmento! Science and Technology, 5, No. 9, September (1971), page 790 et seq.
- the catalytic decomposition of nitric oxide by metallic oxides has also been studied; Winter, Journal of Catalysis, 22, l58-170 (l97l).
- Application of Monel metal to automotive NO emissions control has been reported; Bernstein, Kearby, Raman, Vardi, and Wigg, SAE Paper No. 70014, presented at January 1971 meeting, Detroit, Michigan.
- This invention also pertains to a method of diminishing the amount of components in exhaust gas, which method comprises contacting engine exhaust with nickel having a noble metal dispersed thereon.
- this invention pertains to a method for forming such treated nickel.
- this invention pertains to a method of depositing a noble metal on the surface of nickel, said method comprising contacting said nickel with a liquid containing palladium ions in solution until palladium deposition on the nickel surface has substantially ceased, immersing the treated nickel in nitric acid until its surface is activated, and subsequently immersing the treated nickel surface thereby produced in a liquid containing palladium ions in solution, whereby additional palladium is deposited on said nickel.
- nickel plates will be at least 0.001 inch thick.
- the nickel may be pure, substantially pure, or an alloy of nickel. In general, the alloy should contain at least about 60 per cent nickel and preferably, at least about per cent by weight.
- the nickel coats can be mechanically applied by screws or the like, or can be brazed or welded on.
- the plate or coat can be made by hot sintering, coining, dipping, metallizing, pressure cladding, pouring, and burnishing.
- electrophoresis, electrolytic plating, electrochemical plating, vacuum sputtering, vapor plating, and similar process known in the art can be used.
- Noble metals which may be used in this invention are rhodium, palladium, iridium, and platinum.
- rhodium, palladium, or platinum is used and more preferably rhodium or palladium.
- the concentration of the noble metal salt is not critical. Saturated or more dilute solutions can be used. In general, solutions of concentration of from about 0.5 to about 15 weight per cent are employed. These afford a reasonable deposition rate.
- the solution temperature is not critical. Solutions at ambient or higher or lower temperatures can be employed. Mildly elevated temperatures are preferred. In general, good results are achieved using temperatures from about 25 to about 75C., 48-52C. being preferred.
- acids can be used. Mixtures of applicable acids can be employed. Thus, one may use mixtures of nitric acid and hydrochloric acid, 1:3 to 1:5. In addition, one may use phosphoric acid, 3 volumes, nitric acid, 1 volume, and sulfuric acid, 1 volume. Still another applicable mixture is nitric acid, 3 volumes, sulfuric acid, l volume, orthophosphoric acid, 1 volume, and glacial acetic acid, 5 volumes.
- the time of contacting the metal with the acid is not critical; it is only necessary to activate the metal surface. As a general rule, etching away an excessive amount of metal by acid action is not desirable.
- contacting times within the range of from about 0.25 minutes to about 5 minutes and preferably from about 0.5 minutes to about 2 minutes are used. Shorter and longer times can be employed if desired.
- the acid treatment can be followed with a water wash or rinse, if desired, but use of such wash or rinse is not critical.
- EXAMPLE I A nickel foam with a 30 (0.030 inch) pore size doped using palladium nitrate. For this, a slightly acid HNO solution was used l0 ml in 250 ml of water). To this was added one gram of Pd(NO The salt was difficult to solubilize, therefore, small amounts were added at a time while the solution was warmed (5065C.) and continuously stirred.
- the nickel foam was immersed in the solution for 5 minutes. Within a minute the nickel turned color black grey. After immersion, the foam was dried. Analysis indicated the foam contained 0.07 and 0.09 weight per cent Pd. In a similar manner, rhodium was plated on another sample of nickel foam. The product had 0.2 weight per cent rhodium.
- the foam was redipped in a mix ture of 1 gram Pd(NO 250 H 0, and [0 ml conc. I-INO The foam was redipped for about l520 seconds in the HNO and then dipped in the Pd(NO containing solution for a few minutes again.
- EXAMPLE III Clean nickel turnings, 472 grams, were packed into a 42 cubic inch exhaust emission converter. After packing, the converter with the nickel turnings was dipped in 50 per cent nitric acid, then rinsed with tap water.
- a L500 ml solution of l per cent nitric acid containing l.0 gram of palladium nitrate was prepared.
- the catalyst converter with turnings was then immersed in this solution for 15 minutes. After draining and rinsing, the catalyst and converter were dried at C. overnight.
- Example IV After the nickel catalyst of Example III was tested for exhaust gas catalyst activity in accordance with Example Vl, the entire converter and turnings were cleaned by immersion in 50 per cent nitric acid. Thereafter, the catalyst containing cartridge was immersed for a half hour in a solution of 2 per cent in nitric acid and containing lO grams of palladium nitrate. After draining and rinsing in tap water, the catalyst and converter were air dried. Thereafter, the cartridge and catalyst were placed in a furnace at 540C. and left there overnight.
- EXAMPLE V Roasted nickel turnings, 542 grams, were pressed into a 42 cubic inch capacity converter. The charged converter was rinsed with 50 per cent nitric acid, then rinsed with water and then immersed in a 2 per cent acid solution containing 10 grams of palladium nitrate. The volume of this solution was L500 ml and the immersion time was 30 minutes.
- the cartridge with catalyst was dried at l75C. for 3 hours in circulating air. It was then placed in a furnace at 540C. and kept under nitrogen overnight.
- the engine air flow was about 23.5 lbs per hour.
- lnlet air temperature to carburetor was 145C.
- the A/F ratio was varied from l3.0:l to l7.0:l using a knock test engine carburetor. This range of A/F ratios gave fuel Following the procedures of the above examples, cat- 5 times of 85 to 1 l 1 seconds per 25 ml of fuel.
- the cataalysts are P p from niokol g shoot. at lyst bed was inches from the exhaust port in the Wires. SCfeenS, and foams Such that h y Contain rom head.
- the exhaust pipe and the catalyst converter were 005 to I weight p e t o a metal SeleCled from e both insulated.
- the exhaust temperature into the cataclass consisting of rhodium, iridium, palladium, or platlyst ranged from 1 100] 200F.
- the catalyst converter inum.
- the foams are produced by the procedures of the 10 was fill d i h h catalyst m b md d h d a above-cited patents, for example US. Pat. Nos. pacity of about 22 cubic inches. Another converter or The Solutions which was used had a capacity of 42 cubic inches.
- A/F ratio is itedp i i n is Conducted ing p to seven immorthen varied by adjusting the carburetor and the exhaust sions, oaoh immersion after the first ng pr d d y sampled again after equilibrium, until the range of MP a p in 3, l0 50 P Cent Concentrated- Each ratio is covered by different settings of air fuel ratio.
- the value per cent reduction" pare noble metal-containing catalysts from Monel is obtained as follows: wires, screen saddles, tumings, and foam where the Monel has a composition within the range Concentration Concentration Si 0.5-3.5 weight per cent g d Mn 0.5 .5 weight per cent ML Fe 3.0 weight per cent maximum Percent reducuon X Concentration Cu 28-32 weight per cent before Ni remainder catalyst bed.
- the engine was run at 1340 was conducted using the palladium containing product RPM and a load was applied by an induction motor to of Example I, while Run 3 was conducted using the rhokeep the engine speed substantially constant.
Abstract
Nickel with a surface deposit of palladium is useful as an exhaust gas catalyst. Palladium may be deposited by contacting nickel with a solution of palladium ions. More than one deposition can be used. If a first deposition is followed by contacting the nickel with strong nitric acid, a second palladium deposition will result in an increased amount of palladium on the nickel surface.
Description
D United States Patent 1 1 1 1 11 1 3,882,050 Niebylski 1451 May 6, 1975 (54] METHOD ()F DEPOSITING A NOBLE 3.1 l6,l65 12/1963 Hipp 117/130 R MET L O A SURFACE OF A NICKEL 3,155,536 11/1964 Freeman et 111...... 117/130 R SUPPORT 3,328,271 6/1967 Kneif et a1. 117/130 R 3,719,739 3/1973 Thompson 252/472 Inventor: Leonard R. Niebylski, Birmingham,
Mich.
Assignec: Ethyl Corporation, Richmond, Va.
Filed: July 24, 1973 Appl. N0.: 382,069
Related U.S. Application Data Division of Ser. No. 211.730. Dec. 23. 1971,
abandoned U.S. c1 252/472; 252/477 R; 423/213.5; 117/130 R 1111. c1. B01] 11/12; 1301, 11/22 Field of Search 252/472, 477 R; 423/2135; 23/288 F; 117/130 R References Cited UNITED STATES PATENTS 11/1963 Hipp ..117 130R Primary ExaminerWinston A. Douglas Assistant Examiner-W. J. Shine Attorney, Agent, or FirmDonald L. Johnson; Robert A. Linn [57] ABSTRACT Nickel with a surface deposit of palladium is useful as an exhaust gas catalyst. Palladium may be deposited by contacting nickel with a solution of palladium ions. More than one deposition can be used. lf a first deposition is followed by contacting the nickel with strong nitric acid, a second palladium deposition will result in an increased amount of palladium on the nickel surface.
1 Claim, No Drawings METHOD OF DEPOSITING A NOBLE METAL ON A SURFACE OF A NICKEL SUPPORT This application is a division of application Ser. No. 211,730, filed Dec. 23, 1971, and now abandoned.
BACKGROUND OF THE INVENTION In recent years extensive research has been devoted to the alleviation of air pollution in many metropolitan areas. Part of this effort has been directed to methods of reducing the unburned hydrocarbons and carbon monoxide emitted with the exhaust gas ofintemal combustion engines. Various catalytic converter systems have been proposed to accomplish this purpose. With such systems the exhaust gases are passed through a catalytic bed wherein the noxious materials are converted to an inactive form.
Among the catalysts disclosed in the prior art are the supported nickel catalysts of Gross et al., US. Pat. No. 3,370,914. That patent also teaches emission reduction with certain nickel additives in gasoline.
This invention pertains to massive forms of nickel such as nickel wire, grid, turnings, lath, and foams. Such forms of elemental nickel having a noble metal surface deposit are exhaust gas catalysts The catalytic reaction of hydrogen with nitric oxide in the presence of oxygen has been studied using a noble supported on alumina; Jones et al., Environmento! Science and Technology, 5, No. 9, September (1971), page 790 et seq. The catalytic decomposition of nitric oxide by metallic oxides has also been studied; Winter, Journal of Catalysis, 22, l58-170 (l97l). Application of Monel metal to automotive NO emissions control has been reported; Bernstein, Kearby, Raman, Vardi, and Wigg, SAE Paper No. 70014, presented at January 1971 meeting, Detroit, Michigan.
SUMMARY OF THE INVENTION This invention pertains to massive nickel having a surface deposit thereon of a catalytic quantity of a noble metal. Preferably, the noble metal is rhodium, palladium, or platinum, more preferably rhodium or palladium.
This invention also pertains to a method of diminishing the amount of components in exhaust gas, which method comprises contacting engine exhaust with nickel having a noble metal dispersed thereon.
Also, this invention pertains to a method for forming such treated nickel. As an example, this invention pertains to a method of depositing a noble metal on the surface of nickel, said method comprising contacting said nickel with a liquid containing palladium ions in solution until palladium deposition on the nickel surface has substantially ceased, immersing the treated nickel in nitric acid until its surface is activated, and subsequently immersing the treated nickel surface thereby produced in a liquid containing palladium ions in solution, whereby additional palladium is deposited on said nickel.
DESCRIPTION OF PREFERRED EMBODIMENTS A preferred embodiment of this invention is massive nickel having a surface deposit thereon of a catalytic promoter quantity of a noble metal. Herein, the term massive nickel is used to include nickel in a macroscopic object or objects, and is used to exclude (a) the form or forms of nickel impregnated on catalyst supports and (b) the microscopic nickel particles obtainable by decomposition of nickel compounds in a gaseous or liquid medium. By the term as used herein, is de noted nickel objects having sufficient mass of nickel that common physical properties of nickel. e.g., melting point, are discernible. Thus, the term refers to nickel in a solid state where the mass of nickel is such that the common physical properties and surface characteristics, rather than just surface effects, characterize the metal mass.
The nickel metal may be in many forms such as powders, either fine or coarse, turnings, sheet, lath, wires, screens, sintered objects, foams, etc. The foams can be prepared, for example, by using the process of US. Pat. Nos. 2,983,597, 2,895,819, 3,300,296, 3,297,431, 2,917,384 or 3,111,396. When foaming by use of a metal hydride or similar foaming agent, the mass to be foamed may be made more viscous by using a viscosity increasing amount of a viscosity increasing agent as per the teachings of Belgian Pat. No. 746,135. Likewise, nickel may be plated or coated on such forms of other metals. In general, such nickel plates will be at least 0.001 inch thick. The nickel may be pure, substantially pure, or an alloy of nickel. In general, the alloy should contain at least about 60 per cent nickel and preferably, at least about per cent by weight. The nickel coats can be mechanically applied by screws or the like, or can be brazed or welded on. Likewise, the plate or coat can be made by hot sintering, coining, dipping, metallizing, pressure cladding, pouring, and burnishing. Likewise, electrophoresis, electrolytic plating, electrochemical plating, vacuum sputtering, vapor plating, and similar process known in the art can be used.
Noble metals which may be used in this invention are rhodium, palladium, iridium, and platinum. Preferably, rhodium, palladium, or platinum is used and more preferably rhodium or palladium.
It is only necessary that a promoter quantity of noble metal be present at the surface of the nickel. How this amount is achieved is not critical. One can use objects made of a nickel-noble metal alloy, if desired. However, such forms are usually expensive and accordingly it is desirable from the economic viewpoint to treat the surface of the nickel, rather than compose the whole object of nickel-noble alloy.
One can deposit noble metal such as palladium by contacting the nickel to be treated with a liquid such as water containing palladium ions in solution.
Usually one prefers to use an aqueous solution having a pH less than 7, because acidic solutions tend to keep palladium ions in solution rather than precipitating. In general, one prefers to use a solution having a pH in the range of about 2.0-6.5 but other acid systems can be used. When necessary, the pH can be adjusted to the desired level with acid such as nitric sulfuric or hydrochloric acid or other acid, either organic or inorganic. The nature or composition of the acid used to adjust the pH is not critical.
One can use any convenient source of noble metal ions, such as a salt of such metals. Nitrates, chlorides, and the like can be used; however, the nature of the anion is not critical.
The concentration of the noble metal salt is not critical. Saturated or more dilute solutions can be used. In general, solutions of concentration of from about 0.5 to about 15 weight per cent are employed. These afford a reasonable deposition rate.
The solution temperature is not critical. Solutions at ambient or higher or lower temperatures can be employed. Mildly elevated temperatures are preferred. In general, good results are achieved using temperatures from about 25 to about 75C., 48-52C. being preferred.
The deposition is not pressure dependent, ambient pressures are conveniently employed; greater or lesser pressures can be used if desired. Ambient atmosphere as well as inert atmospheres such as neon or argon blankets can be used.
It has been noted that the deposition of palladium will cease after a while even when using solutions in which palladium ions were still available for deposition. Although not bound by any theory, it appears the nickel surface becomes inert to deposition or passive.
This state can be overcome by immersing or otherwise contacting the nickel being treated in I-INO or other similar oxidizing acid. The nitric acid concentration employed is not critical; but generally is from about volume per cent to about 55 volume per cent, preferably from about 25 volume per cent to about 50 volume per cent; however, greater or lesser amounts can be used. The temperature of the acid can be from about 75 to about 180F., preferably 90 to 120F. Hotter or cooler acids can be used for the temperature is not critical. Acids at ambient and mildly elevated temperature are conveniently used.
Other acids can be used. Mixtures of applicable acids can be employed. Thus, one may use mixtures of nitric acid and hydrochloric acid, 1:3 to 1:5. In addition, one may use phosphoric acid, 3 volumes, nitric acid, 1 volume, and sulfuric acid, 1 volume. Still another applicable mixture is nitric acid, 3 volumes, sulfuric acid, l volume, orthophosphoric acid, 1 volume, and glacial acetic acid, 5 volumes.
Also, one may return the nickel surface to activity by conducting an electrolytic etch in the presence of either per cent phosphoric acid; per cent perchloric acid in ethanol; 10 per cent perchloric acid and 90 per cent acetic acid; 50 per cent sulfuric acid; acetic acid with 7 per cent water and 5 per cent CrO sulfuric acid, l3-l5 weight per cent, plus 56-63 weight per cent orthophosphoric acid, remainder water; sodium chloride, [5 ounces per gallon plus HCl, 0.5 ounce per gallon; or sodium chloride, 7 ounces per gallon plus sodium nitrite, 3 ounces per gallon.
The time of contacting the metal with the acid is not critical; it is only necessary to activate the metal surface. As a general rule, etching away an excessive amount of metal by acid action is not desirable. For the acid concentrations above, contacting times within the range of from about 0.25 minutes to about 5 minutes and preferably from about 0.5 minutes to about 2 minutes are used. Shorter and longer times can be employed if desired.
After acid treatment, recontacting with a solution of noble metal ions of the type and according to the process described above, can be conducted if additional deposition is desired.
The acid treatment can be followed with a water wash or rinse, if desired, but use of such wash or rinse is not critical.
EXAMPLE I A nickel foam with a 30 (0.030 inch) pore size doped using palladium nitrate. For this, a slightly acid HNO solution was used l0 ml in 250 ml of water). To this was added one gram of Pd(NO The salt was difficult to solubilize, therefore, small amounts were added at a time while the solution was warmed (5065C.) and continuously stirred.
The nickel foam was immersed in the solution for 5 minutes. Within a minute the nickel turned color black grey. After immersion, the foam was dried. Analysis indicated the foam contained 0.07 and 0.09 weight per cent Pd. In a similar manner, rhodium was plated on another sample of nickel foam. The product had 0.2 weight per cent rhodium.
EXAMPLE I] A nickel foam of 30 mil pore size which had been doped with 0.l weight per cent Pd was treated with 2530 per cent HNO solution by immersion for approximately 30 seconds and then rinsing in cold running water. This was repeated.
After the acid etch, the foam was redipped in a mix ture of 1 gram Pd(NO 250 H 0, and [0 ml conc. I-INO The foam was redipped for about l520 seconds in the HNO and then dipped in the Pd(NO containing solution for a few minutes again.
After drying, the foam was submitted for chemical analysis which indicated 0.32 weight per cent Pd.
EXAMPLE III Clean nickel turnings, 472 grams, were packed into a 42 cubic inch exhaust emission converter. After packing, the converter with the nickel turnings was dipped in 50 per cent nitric acid, then rinsed with tap water.
A L500 ml solution of l per cent nitric acid containing l.0 gram of palladium nitrate was prepared. The catalyst converter with turnings was then immersed in this solution for 15 minutes. After draining and rinsing, the catalyst and converter were dried at C. overnight.
Thereafter, the temperature of the furnace was raised to 540C. and the converter and catalyst were allowed to stay in this environment for 3 hours.
EXAMPLE IV After the nickel catalyst of Example III was tested for exhaust gas catalyst activity in accordance with Example Vl, the entire converter and turnings were cleaned by immersion in 50 per cent nitric acid. Thereafter, the catalyst containing cartridge was immersed for a half hour in a solution of 2 per cent in nitric acid and containing lO grams of palladium nitrate. After draining and rinsing in tap water, the catalyst and converter were air dried. Thereafter, the cartridge and catalyst were placed in a furnace at 540C. and left there overnight.
Two samples of this catalyst were found to contain 0.29 and 0.42 weight per cent palladium.
EXAMPLE V Roasted nickel turnings, 542 grams, were pressed into a 42 cubic inch capacity converter. The charged converter was rinsed with 50 per cent nitric acid, then rinsed with water and then immersed in a 2 per cent acid solution containing 10 grams of palladium nitrate. The volume of this solution was L500 ml and the immersion time was 30 minutes.
After immersion, the cartridge with catalyst was dried at l75C. for 3 hours in circulating air. It was then placed in a furnace at 540C. and kept under nitrogen overnight.
The engine air flow was about 23.5 lbs per hour. lnlet air temperature to carburetor was 145C. The A/F ratio was varied from l3.0:l to l7.0:l using a knock test engine carburetor. This range of A/F ratios gave fuel Following the procedures of the above examples, cat- 5 times of 85 to 1 l 1 seconds per 25 ml of fuel. The cataalysts are P p from niokol g shoot. at lyst bed was inches from the exhaust port in the Wires. SCfeenS, and foams Such that h y Contain rom head. The exhaust pipe and the catalyst converter were 005 to I weight p e t o a metal SeleCled from e both insulated. The exhaust temperature into the cataclass consisting of rhodium, iridium, palladium, or platlyst ranged from 1 100] 200F. The catalyst converter inum. The foams are produced by the procedures of the 10 was fill d i h h catalyst m b md d h d a above-cited patents, for example US. Pat. Nos. pacity of about 22 cubic inches. Another converter or The Solutions which was used had a capacity of 42 cubic inches. used for doping contain from 0.05 to 10 weight per Af h engine was warmed up, exhaust gas was cent of a chloride or nitrate of the metal to be deposl5 l d b fore and after the catalyst. The A/F ratio is itedp i i n is Conducted ing p to seven immorthen varied by adjusting the carburetor and the exhaust sions, oaoh immersion after the first ng pr d d y sampled again after equilibrium, until the range of MP a p in 3, l0 50 P Cent Concentrated- Each ratio is covered by different settings of air fuel ratio. immersion is 11 Period of from 1 to 60 minutes- Hydrocarbon concentration is measured by a flame similarlywatalysts are p p y p g. ionization detector. Carbon monoxide and No are scribed abflvfi, Palladium, Platinum. iridium, Or 1110- measured by non-dispersive infrared. Oxygen is meadium by this technique on nickel plated steel wires, and Sured larographically. screen where the nickel plate is 1 to l0 mils thick. Simi- Data is given below as per cent reduction for CO, bylarly, the above deposition techniques are used to predrocarbons and NO,. The value per cent reduction" pare noble metal-containing catalysts from Monel, is obtained as follows: wires, screen saddles, tumings, and foam where the Monel has a composition within the range Concentration Concentration Si 0.5-3.5 weight per cent g d Mn 0.5 .5 weight per cent ML Fe 3.0 weight per cent maximum Percent reducuon X Concentration Cu 28-32 weight per cent before Ni remainder catalyst bed.
For the depositions as described above, the dippings in the noble metal ion containing solutions are conducted [n the f ll i table, results f c N01 and HC wlth the SOlutlOn having a temperatur of from (hydrocarbons) are reported for various fuel ratios. 20l0OC. Runs 1, 2, and 3 were conducted using a 22 cubic inch EXAMPLE V1 capacity catalytic converter. Run 1 was conducted using a foam nickel sample having an average pore size T demonstrate emission reduction, Olds Single of 30 microns obtained from General Electric. Run 2 cylinder engine was used. The engine was run at 1340 was conducted using the palladium containing product RPM and a load was applied by an induction motor to of Example I, while Run 3 was conducted using the rhokeep the engine speed substantially constant. The fuel dium containing product of that example. Runs 5, 6, employed was clear lndolene; the engine timing was and 7 were conducted using the product of Examples 10 btc. III, IV, and V respectively.
13.5 14.0 14.5 15.0 15.5 16.0 16.5 Air/Fuel Ratio l. Nickel foam 70 73 35 0 0 0 0 NO,
0 0 O 7 20 33 42 HC 0 0 42 40 33 20 14 CO 2. Nickel foam 29 33 l0 l2 9 0 0 NO,
0.2 per cent 0 3 25 42 29 34 35 HC Rh 3 3 25 35 35 50 CO 3. Nickel foam 45 56 2S 4 0 0 0 NOI 0.3 per 30 54 47 40 39 38 HC cent Pd 0 0 60 33 20 l2 0 (O 4. *Nickel tum- 60 68 30 0 0 0 0 NO ings 0 0 0 0 8 I6 25 HC 0 0 O l2 14 30 28 CO 5. *Nickel turn- 50 6l 30 5 0 0 0 NO,
ings 0.1 per 0 5 20 54 45 3e 30 11c cent Pd 0 2 12 44 34 23 23 CO 6. *Nickel turn- 55 63 69 2 3 4 0 NO,
ings 0.3 0 14 s7 s4 83 )8 HC per cent Pd 0 8 60 66 62 58 53 CO 7. *Nickel tum- 58 67 72 1.7 0 0 0 NO,
ings 0.3 L2 15 8| 82 78 76 HC par cent 0 9 82 83 90 88 CO 42 cu. in. converter cluced with nitric acid until said surface is activated, and thereafter contacting the activated surface thereby produced with an aqueous solution of palladium salt, whereby additional palladium is deposited on said surface.
Claims (1)
1. A METHOD OF DEPOSITING A NOBLE METAL ON A SURFACE OF A NICKEL SUPPORT, SAID METHOD COMPRISING CONTACTING SAID SURFACE OF SAID NICKEL SUPPORT WITH AN AQUEOUS SOLUTION OF A PALLADIUM SALT HAVING A PH LESS THAN 7 UNTIL PALLADIUM DEPOSITION ON SAID SURFACE HAS SUBSTANTIALLY CEASED; SUBSEQUENTLY CONTACTING THE SURFACE THEREBY PRODUCED WITH NITRIC ACID UNTIL SAID SURFACE IS ACTIVATED, AND THEREAFTER CONTACTING THE ACTIVATED SURFACE THEREBY RPODUCED WITH AN AQUEOUS SOLUTION OF PALLADIUM SALT, WHEREBY ADDITIONAL PALLADIUM IS DEPOSITED ON SAID SURFACE.
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US382069A US3882050A (en) | 1971-12-23 | 1973-07-24 | Method of depositing a noble metal on a surface of a nickel support |
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US21173071A | 1971-12-23 | 1971-12-23 | |
US382069A US3882050A (en) | 1971-12-23 | 1973-07-24 | Method of depositing a noble metal on a surface of a nickel support |
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US3882050A true US3882050A (en) | 1975-05-06 |
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US382069A Expired - Lifetime US3882050A (en) | 1971-12-23 | 1973-07-24 | Method of depositing a noble metal on a surface of a nickel support |
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US4515905A (en) * | 1982-11-18 | 1985-05-07 | N. V. Bekaert S.A. | Process for forming a catalyst and the catalytic product produced by the process |
US4552787A (en) * | 1984-02-29 | 1985-11-12 | International Business Machines Corporation | Deposition of a metal from an electroless plating composition |
US4721524A (en) * | 1986-09-19 | 1988-01-26 | Pdp Alloys, Inc. | Non-pyrophoric submicron alloy powders of Group VIII metals |
US5250490A (en) * | 1991-12-24 | 1993-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Noble metal supported on a base metal catalyst |
US6316100B1 (en) * | 1997-02-24 | 2001-11-13 | Superior Micropowders Llc | Nickel powders, methods for producing powders and devices fabricated from same |
US20050100666A1 (en) * | 1997-02-24 | 2005-05-12 | Cabot Corporation | Aerosol method and apparatus, coated particulate products, and electronic devices made therefrom |
US20050097987A1 (en) * | 1998-02-24 | 2005-05-12 | Cabot Corporation | Coated copper-containing powders, methods and apparatus for producing such powders, and copper-containing devices fabricated from same |
US20050262966A1 (en) * | 1997-02-24 | 2005-12-01 | Chandler Clive D | Nickel powders, methods for producing powders and devices fabricated from same |
US20060108290A1 (en) * | 2002-08-23 | 2006-05-25 | Jean-Marie Basset | Removal of metal ions from aqueous effluents |
CN101356347A (en) * | 2006-06-08 | 2009-01-28 | 株式会社电装 | Exhaust heat recovery equipment |
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US4515905A (en) * | 1982-11-18 | 1985-05-07 | N. V. Bekaert S.A. | Process for forming a catalyst and the catalytic product produced by the process |
US4552787A (en) * | 1984-02-29 | 1985-11-12 | International Business Machines Corporation | Deposition of a metal from an electroless plating composition |
US4721524A (en) * | 1986-09-19 | 1988-01-26 | Pdp Alloys, Inc. | Non-pyrophoric submicron alloy powders of Group VIII metals |
US5250490A (en) * | 1991-12-24 | 1993-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Noble metal supported on a base metal catalyst |
US5347027A (en) * | 1991-12-24 | 1994-09-13 | Osi Specialties, Inc. | Noble metal supported on a base metal catalyst |
USRE36330E (en) * | 1991-12-24 | 1999-10-05 | Witco Corporation | Noble metal supported on a base metal catalyst |
EP0548974B1 (en) * | 1991-12-24 | 2001-03-21 | Crompton Corporation | Process for the production of catalyst comprising noble metal supported on a base metal catalyst |
US20050262966A1 (en) * | 1997-02-24 | 2005-12-01 | Chandler Clive D | Nickel powders, methods for producing powders and devices fabricated from same |
US7087198B2 (en) | 1997-02-24 | 2006-08-08 | Cabot Corporation | Aerosol method and apparatus, particulate products, and electronic devices made therefrom |
US20050061107A1 (en) * | 1997-02-24 | 2005-03-24 | Hampden-Smith Mark J. | Coated silver-containing particles, method and apparatus of manufacture, and silver-containing devices made therefrom |
US20050097988A1 (en) * | 1997-02-24 | 2005-05-12 | Cabot Corporation | Coated nickel-containing powders, methods and apparatus for producing such powders and devices fabricated from same |
US20050100666A1 (en) * | 1997-02-24 | 2005-05-12 | Cabot Corporation | Aerosol method and apparatus, coated particulate products, and electronic devices made therefrom |
US7384447B2 (en) | 1997-02-24 | 2008-06-10 | Cabot Corporation | Coated nickel-containing powders, methods and apparatus for producing such powders and devices fabricated from same |
US20050116369A1 (en) * | 1997-02-24 | 2005-06-02 | Cabot Corporation | Aerosol method and apparatus, particulate products, and electronic devices made therefrom |
US6316100B1 (en) * | 1997-02-24 | 2001-11-13 | Superior Micropowders Llc | Nickel powders, methods for producing powders and devices fabricated from same |
US7004994B2 (en) | 1997-02-24 | 2006-02-28 | Cabot Corporation | Method for making a film from silver-containing particles |
US7354471B2 (en) | 1997-02-24 | 2008-04-08 | Cabot Corporation | Coated silver-containing particles, method and apparatus of manufacture, and silver-containing devices made therefrom |
US7083747B2 (en) | 1997-02-24 | 2006-08-01 | Cabot Corporation | Aerosol method and apparatus, coated particulate products, and electronic devices made therefrom |
US20040231758A1 (en) * | 1997-02-24 | 2004-11-25 | Hampden-Smith Mark J. | Silver-containing particles, method and apparatus of manufacture, silver-containing devices made therefrom |
US7097686B2 (en) | 1997-02-24 | 2006-08-29 | Cabot Corporation | Nickel powders, methods for producing powders and devices fabricated from same |
US20050097987A1 (en) * | 1998-02-24 | 2005-05-12 | Cabot Corporation | Coated copper-containing powders, methods and apparatus for producing such powders, and copper-containing devices fabricated from same |
US20060108290A1 (en) * | 2002-08-23 | 2006-05-25 | Jean-Marie Basset | Removal of metal ions from aqueous effluents |
US20110220579A1 (en) * | 2002-08-23 | 2011-09-15 | Centre National De La Recherche Scientifique (C.N.R.S.) | Removal of metal ions from aqueous effluents |
CN101356347A (en) * | 2006-06-08 | 2009-01-28 | 株式会社电装 | Exhaust heat recovery equipment |
US20090293461A1 (en) * | 2006-06-08 | 2009-12-03 | Denso Corporation | Exhaust Heat Recovery Device |
US7946112B2 (en) * | 2006-06-08 | 2011-05-24 | Denso Corporation | Exhaust heat recovery device |
EP2737947A1 (en) * | 2012-11-30 | 2014-06-04 | Eurecat S.A. | Method for preparing supported metal catalysts for the hydrogenation of unsaturated hydrocarbons |
JP2014108427A (en) * | 2012-11-30 | 2014-06-12 | Eurecat Sa | Method for preparing supported metal catalysts for hydrogenating unsaturated hydrocarbons |
US9533288B2 (en) | 2012-11-30 | 2017-01-03 | Eurecat S.A. | Method for preparing supported metal catalysts for hydrogenating unsaturated hydrocarbons |
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