US3397133A - Apparatus for producing silver nitrate - Google Patents

Apparatus for producing silver nitrate Download PDF

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US3397133A
US3397133A US428001A US42800164A US3397133A US 3397133 A US3397133 A US 3397133A US 428001 A US428001 A US 428001A US 42800164 A US42800164 A US 42800164A US 3397133 A US3397133 A US 3397133A
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band
silver
compartment
electrolyte
bath
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US428001A
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Sooryn Vsevolod
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BENJAMIN B DOCH
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BENJAMIN B DOCH
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver

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  • My present invention relates to a process for producing silver nitrate as more generally disclosed in my co-pending application Ser. No. 779,521 filed Dec. 11, 1958 (now abandoned), of which the present application is a continuation-in-part, and to an apparatus for practicing such process.
  • the aforementioned co-pending application discloses a process wherein crystals of high-purity silver nitrate are produced from metallic silver through the use of a silveroxide intermediary.
  • the latter is deposited at an inert electrode in an alkaline electrolyte and, after its removal therefrom, contacted with nitric acid to be converted to silver nitrate.
  • silver oxide is electrolytically deposited upon a continuous inert but flexible band which passes from the alkaline electrolyte through a water bath to remove traces of alkalinity and thence into a bath of nitric acid in which the silver oxide is stripped ifrom the band and crystals of silver nitrate are precipitated.
  • the band then passes into another water bath wherein excess nitric acid is washed from the band which is thereupon returned to the electrolyte.
  • the bath of preferably concentrated nitric acid (485 B.) is maintained at a temperature in excess of 100 C. to drive off the water resulting from the reaction between the nitric acid and the silver oxide. Only a small proportion of the length of the continuous band is permitted to enter the nitric-acid bath whose volume is kept at a minimum in order to facilitate recovery of the silver-nitrate crystals from the liquor and to limit the erosive action of the acid upon the band.
  • the silver-oxide mass electrodeposited upon the cathodized flexible band tends to adhere thereto as it passes out Of the electrolyte, especially if the mass is compressed against the band as, for example, by a pair of rollers.
  • the latter may also serve to free the oxide mass from electrolyte via a squeegee action.
  • the silver-oxide mass may, therefore, be carried along an extended transport path by the band.
  • FIGURE I show a processing tank 10 divided by partition walls 11, 12 and 13 into a first compartment 14 containing an alkaline electrolyte, a second compartment 15, adjacent thereto, containing a water bath, a third compartment 16 containing a nitric-acid bath, and a fourth compartment 17 containing another water bath.
  • the electrolyte 21 is, preferably, an aqueous solution of an alkali, such as potassium hydroxide, in which a salt having an ion capable of forming soluble silver compounds is dissolved.
  • an alkali such as potassium hydroxide
  • a salt having an ion capable of forming soluble silver compounds is dissolved.
  • An example of such salt is potassium (or sodium) acetate which may be readily dissolved in the electrolyte and which may be present in a proportion up to the point of saturation.
  • the concentration of alkali in the solution is maintained at the value corresponding to maximum conductivity of the electrolyte. Therefore, a 27%-to-30% solution of potassium hydroxide, having a specific gravity between 1.270 and 1.305 at room temperature, will be found to be satisfactory.
  • a pair of silver electrodes 22 are suspended at opposite sides of the band 18 which is brought into an upright position in the compartment 14, as it passes between a pair of vertical rollers 23, so that electrodeposition of silver oxide may occur on both surfaces of the band.
  • a second pair of vertical rollers 24 then serve to compress the silver-oxide mass against the band to limit the flaking off of the mass as the band 18 leaves the compartment 14. As the band leaves this compartment, it passes between a pair of horizontal rollers 25 which further compress the mass and squeeze adherent electrolyte therefrom.
  • the band is guided over an idler roller 26 and into the water bath 27 contained within the compartment 15.
  • the band 18 is led under two rollers 28 immersed in the water bath 27 and, upon emerging therefrom, between another pair of squeegee rollers 29, similar to rollers 25, which serve to extract the water from the mass carried by the band.
  • the compartment 15 is provided with a water inlet 30 and an outlet 31 to permit the water bath 27 to be changed continuously or intermittently as required.
  • the band 18, carrying the silver-oxide mass which has been washed substantially free (from all traces of the alkaline electrolyte in the water bath 27, is then directed over an idler roller 32 between compartments 15 and 16- and down into a nitric acid bath 33 and around a roller 34 immersed therein. Since the reaction between the silver-oxide mass and the nitric acid is rapid, it is not necessary to provide more than a rather shallow bath.
  • the temperature of the bath 3-3 is maintained, with the aid of suitable heating means (not shown) and a thermostat 50, at or slightly above C. to evaporate, as rapidly as it is formed the water resulting from the reaction drawn off in the liquor via outlet 36.
  • hand 18 Upon leaving the nitric-acid bath 33, hand 18 travels between a pair of scraper blades 37, bearing thereupon, which strip adherent silver-nitrate crystals from the band and also wipe off nitric-acid droplets.
  • the band 18 is washed free of acid in the water bath 40 of compartment 17 into which it passes over an idler roller 38.
  • Two rollers 39 immersed in the bath 40 entrain the band 18 beneath the wash liquid. This liquid may be changed through an inlet 42 and an outlet 43 provided in the wall of compartment 17. From the bath 40, the band passes "between two strippers 41 which remove water droplets adhering thereto to prevent dilution of the electrolyte 21 to which the band is guided over rollers 19.
  • the silver electrodes 22 are connected to a directcurrent source 45 to form the anodes, while the band 18 is contacted by a wiper 44 connected to the negative pole of the source 45 and thus forms the cathode.
  • Band 18 is driven by worms 46 and 47 which mesh with worm gears 48 and 49 secured to the vertical rollers 23 and 24 respectively.
  • Rollers 20 and 25 are driven through suitable transmission means (not shown) in synchronism with the rollers 23 and 24 to prevent the band 18 from binding during the transitions from the horizontal lay to the vertical and vice versa.
  • the band is driven sufficiently rapidly to prevent the nitric-acid bath 33 from eroding the exposed electrodeposition surfaces thereof.
  • silver metal goes into solution at the anodes 22 while silver oxide is deposited upon the flexible cathode 18 therebetween.
  • the silver-oxide mass is Washed in the water bath 27 and converted to silver nitrate in compartment 16, while the band, after a subsequent washing, is returned in a continuous process to the alkaline electrolyte 21.
  • Example A stainless-steel band 18, 1 meter in width, is advanced through the compartment 14 at a speed of 3 meters per minute.
  • Silver oxide is deposited upon the band with a current density of 0.45 ampere per square centimeter from a 28.8% solution of potassium hydroxide saturated with potassium acetate and having a specific gravity of approxi mately 1.295 at room temperature.
  • the anodes 22 are positioned 40 centimeters from the band 18 so that a deposition voltage of only about 12 volts is required. After a run of about 25 minutes, 10 kg. of silver nitrate may be removed from compartment 16.
  • An apparatus for making crystals of a metal salt comprising an electrolyte container, a water bath adjacent said electrolyte container, a receptacle ⁇ for a liquid containing anions of said salt adjacent said water bath, an endless conductive band passing successively through said container, said water bath and said receptacle, an anode of said metal in said container, circuit means for maintaining said band at a negative potential relative to said anode whereby a compound containing cations of said metal are formed on said band upon its passage through said container, mechanism -for unidirectionally advancing said band from said container through said water bath and into said receptacle wherein said component reacts with said liquid to form particles of said salt on said band, stripper means for removing said particles from said band upon its passage through said receptacle, horizontal roller means supporting said band outside said container, and vertical roller means holding it substantially upright within said container.
  • An apparatus further comprising a second water bath positioned adjacent said receptacle for traverse by said band immediately upon its emergence from the latter.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

Aug. 13, 1968 v. SOORYN APPARATUS FOR PRODUCING SILVER NITRATE Original Filed March 21, 1960 ukbOmPQmJu Vsevolod Sooryn INVENTOR.
Attorney 3,397,133 APPARATUS FQR PRODUCING SILVER NITRATE Vsevolod Sooryn, Paris, France, assignor to Benjamin B. Doeh, New York, N.Y. Uriginal application Mar. 21, 1960, Ser. No. 16,304, now Patent No. 3,222,128. Divided and this application Dec. 18, 1964, Ser. No. 428,001 2 Claims. (Cl. 204-208) ABSTRACT OF THE DISCLOSURE An apparatus for the production of crystals of a metal salt, especially silver nitrate, wherein an endless inert conductive belt of stainless steel is passed successively through an electrolyte container in which a compound of the metal cation is formed electrolytically on the band, then into This application is a division of application Ser. No. 16,304, filed March 21, 1960 (now US. Patent No. 3,222,128).
My present invention relates to a process for producing silver nitrate as more generally disclosed in my co-pending application Ser. No. 779,521 filed Dec. 11, 1958 (now abandoned), of which the present application is a continuation-in-part, and to an apparatus for practicing such process.
The aforementioned co-pending application discloses a process wherein crystals of high-purity silver nitrate are produced from metallic silver through the use of a silveroxide intermediary. The latter is deposited at an inert electrode in an alkaline electrolyte and, after its removal therefrom, contacted with nitric acid to be converted to silver nitrate.
It is an object of the present invention to provide an eflicient process for the large-scale production of highpurity nitric acid in the manner described above, along with an apparatus for carrying out such process by a continuous operation.
In accordance with a feature of the invention, silver oxide is electrolytically deposited upon a continuous inert but flexible band which passes from the alkaline electrolyte through a water bath to remove traces of alkalinity and thence into a bath of nitric acid in which the silver oxide is stripped ifrom the band and crystals of silver nitrate are precipitated. The band then passes into another water bath wherein excess nitric acid is washed from the band which is thereupon returned to the electrolyte.
According to another feature of the invention, the bath of preferably concentrated nitric acid (485 B.) is maintained at a temperature in excess of 100 C. to drive off the water resulting from the reaction between the nitric acid and the silver oxide. Only a small proportion of the length of the continuous band is permitted to enter the nitric-acid bath whose volume is kept at a minimum in order to facilitate recovery of the silver-nitrate crystals from the liquor and to limit the erosive action of the acid upon the band.
I have found that the silver-oxide mass electrodeposited upon the cathodized flexible band tends to adhere thereto as it passes out Of the electrolyte, especially if the mass is compressed against the band as, for example, by a pair of rollers. The latter may also serve to free the oxide mass from electrolyte via a squeegee action. The silver-oxide mass may, therefore, be carried along an extended transport path by the band.
The above and other objects, features and advantages of the present invention will become more fully apparent from the following description, reference being made to the accompanying drawing in which the sole figure is a schematic, cross-sectional view of a plant for producing silver nitrate by a process according to the invention.
In the FIGURE I show a processing tank 10 divided by partition walls 11, 12 and 13 into a first compartment 14 containing an alkaline electrolyte, a second compartment 15, adjacent thereto, containing a water bath, a third compartment 16 containing a nitric-acid bath, and a fourth compartment 17 containing another water bath. An inert, flexible and conductive band 18, preferably formed from a stainless steel resistant to attack by both the alkaline electrolyte and the nitric-acid bath, passes over guide rollers 19 and between a pair of drive rollers 20, bearing thereupon, into the electrolyte 21 of compartment 14. The electrolyte 21 is, preferably, an aqueous solution of an alkali, such as potassium hydroxide, in which a salt having an ion capable of forming soluble silver compounds is dissolved. An example of such salt is potassium (or sodium) acetate which may be readily dissolved in the electrolyte and which may be present in a proportion up to the point of saturation. Advantageously, the concentration of alkali in the solution is maintained at the value corresponding to maximum conductivity of the electrolyte. Therefore, a 27%-to-30% solution of potassium hydroxide, having a specific gravity between 1.270 and 1.305 at room temperature, will be found to be satisfactory.
A pair of silver electrodes 22 (only one of which is shown) are suspended at opposite sides of the band 18 which is brought into an upright position in the compartment 14, as it passes between a pair of vertical rollers 23, so that electrodeposition of silver oxide may occur on both surfaces of the band. A second pair of vertical rollers 24 then serve to compress the silver-oxide mass against the band to limit the flaking off of the mass as the band 18 leaves the compartment 14. As the band leaves this compartment, it passes between a pair of horizontal rollers 25 which further compress the mass and squeeze adherent electrolyte therefrom.
From the compartment 14, the band is guided over an idler roller 26 and into the water bath 27 contained within the compartment 15. The band 18 is led under two rollers 28 immersed in the water bath 27 and, upon emerging therefrom, between another pair of squeegee rollers 29, similar to rollers 25, which serve to extract the water from the mass carried by the band. The compartment 15 is provided with a water inlet 30 and an outlet 31 to permit the water bath 27 to be changed continuously or intermittently as required.
The band 18, carrying the silver-oxide mass which has been washed substantially free (from all traces of the alkaline electrolyte in the water bath 27, is then directed over an idler roller 32 between compartments 15 and 16- and down into a nitric acid bath 33 and around a roller 34 immersed therein. Since the reaction between the silver-oxide mass and the nitric acid is rapid, it is not necessary to provide more than a rather shallow bath. The temperature of the bath 3-3 is maintained, with the aid of suitable heating means (not shown) and a thermostat 50, at or slightly above C. to evaporate, as rapidly as it is formed the water resulting from the reaction drawn off in the liquor via outlet 36. Upon leaving the nitric-acid bath 33, hand 18 travels between a pair of scraper blades 37, bearing thereupon, which strip adherent silver-nitrate crystals from the band and also wipe off nitric-acid droplets.
The band 18 is washed free of acid in the water bath 40 of compartment 17 into which it passes over an idler roller 38. Two rollers 39 immersed in the bath 40 entrain the band 18 beneath the wash liquid. This liquid may be changed through an inlet 42 and an outlet 43 provided in the wall of compartment 17. From the bath 40, the band passes "between two strippers 41 which remove water droplets adhering thereto to prevent dilution of the electrolyte 21 to which the band is guided over rollers 19.
The silver electrodes 22 are connected to a directcurrent source 45 to form the anodes, while the band 18 is contacted by a wiper 44 connected to the negative pole of the source 45 and thus forms the cathode. Band 18 is driven by worms 46 and 47 which mesh with worm gears 48 and 49 secured to the vertical rollers 23 and 24 respectively. Rollers 20 and 25 are driven through suitable transmission means (not shown) in synchronism with the rollers 23 and 24 to prevent the band 18 from binding during the transitions from the horizontal lay to the vertical and vice versa. The band is driven sufficiently rapidly to prevent the nitric-acid bath 33 from eroding the exposed electrodeposition surfaces thereof.
In operation, silver metal goes into solution at the anodes 22 while silver oxide is deposited upon the flexible cathode 18 therebetween. After compression by rollers 24 and 25, the silver-oxide mass is Washed in the water bath 27 and converted to silver nitrate in compartment 16, while the band, after a subsequent washing, is returned in a continuous process to the alkaline electrolyte 21.
Example A stainless-steel band 18, 1 meter in width, is advanced through the compartment 14 at a speed of 3 meters per minute. Silver oxide is deposited upon the band with a current density of 0.45 ampere per square centimeter from a 28.8% solution of potassium hydroxide saturated with potassium acetate and having a specific gravity of approxi mately 1.295 at room temperature. The anodes 22 are positioned 40 centimeters from the band 18 so that a deposition voltage of only about 12 volts is required. After a run of about 25 minutes, 10 kg. of silver nitrate may be removed from compartment 16.
The invention as described and illustrated is believed to admit of many modifications and variations which are within the ability of persons skilled in the art and are intended to be included within the spirit and scope of the invention, except as further limited by the appended claims.
I claim:
1. An apparatus for making crystals of a metal salt, comprising an electrolyte container, a water bath adjacent said electrolyte container, a receptacle \for a liquid containing anions of said salt adjacent said water bath, an endless conductive band passing successively through said container, said water bath and said receptacle, an anode of said metal in said container, circuit means for maintaining said band at a negative potential relative to said anode whereby a compound containing cations of said metal are formed on said band upon its passage through said container, mechanism -for unidirectionally advancing said band from said container through said water bath and into said receptacle wherein said component reacts with said liquid to form particles of said salt on said band, stripper means for removing said particles from said band upon its passage through said receptacle, horizontal roller means supporting said band outside said container, and vertical roller means holding it substantially upright within said container.
2. An apparatus according to claim 1, further comprising a second water bath positioned adjacent said receptacle for traverse by said band immediately upon its emergence from the latter.
References Cited UNITED STATES PATENTS 1,544,027 6/1925 Mueller 204-204 1,768,358 6/1930 Harrison 204-13 2,433,441 12/ 1947 Davidolf 20413 3,316,160 4/1967 Uchida et a1. 20428 JOHN H. MACK, Prim'az'y Examiner.
W. VAN SISE, Assistant Examiner.
US428001A 1960-03-21 1964-12-18 Apparatus for producing silver nitrate Expired - Lifetime US3397133A (en)

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US16304A US3222128A (en) 1960-03-21 1960-03-21 Process for producing silver nitrate
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014756A (en) * 1976-01-21 1977-03-29 Fromson H A Process for making metal powders
US4093532A (en) * 1977-01-21 1978-06-06 Anken Industries Recovery of silver from photographic film
US5772505A (en) * 1995-06-29 1998-06-30 Peripheral Dynamics, Inc. Dual card scanner apparatus and method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1544027A (en) * 1923-02-01 1925-06-30 Jr John J Mueller Plating device
US1768358A (en) * 1925-05-21 1930-06-24 Florence M Harrison Electrolytic process and apparatus
US2433441A (en) * 1947-12-30 Electrolytic production of thin
US3316160A (en) * 1962-08-16 1967-04-25 Fuji Iron & Steel Co Ltd Process for electrolytic chromium-plating steel strips without a bluish tint while using two or more plating tanks

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2433441A (en) * 1947-12-30 Electrolytic production of thin
US1544027A (en) * 1923-02-01 1925-06-30 Jr John J Mueller Plating device
US1768358A (en) * 1925-05-21 1930-06-24 Florence M Harrison Electrolytic process and apparatus
US3316160A (en) * 1962-08-16 1967-04-25 Fuji Iron & Steel Co Ltd Process for electrolytic chromium-plating steel strips without a bluish tint while using two or more plating tanks

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014756A (en) * 1976-01-21 1977-03-29 Fromson H A Process for making metal powders
US4093532A (en) * 1977-01-21 1978-06-06 Anken Industries Recovery of silver from photographic film
US5772505A (en) * 1995-06-29 1998-06-30 Peripheral Dynamics, Inc. Dual card scanner apparatus and method

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