US3843491A - Process for the preparation of silver base catalyst - Google Patents

Process for the preparation of silver base catalyst Download PDF

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Publication number
US3843491A
US3843491A US00319060A US31906072A US3843491A US 3843491 A US3843491 A US 3843491A US 00319060 A US00319060 A US 00319060A US 31906072 A US31906072 A US 31906072A US 3843491 A US3843491 A US 3843491A
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US
United States
Prior art keywords
silver
cathode
preparation
catalyst
useful
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Expired - Lifetime
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US00319060A
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English (en)
Inventor
M Piro
L Rivola
B Notari
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SnamProgetti SpA
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SnamProgetti SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen

Definitions

  • the present invention refers to an improved process for the preparation of silver base catalysts which are useful in the synthesis of ethylene oxide.
  • the present invention refers to a process for the electrochemical preparation of silver base catalysts.
  • silver production might be possible with high yields and in a reproducible way when using systems of electrochemic deposition of such metal; but it is also known that the electrolysis of silver solutions gives rise to a metal having a compact shape or, in any case, high particle sizes that render them unusable in the industrial process for the production of ethylene oxide by ethylene oxidation.
  • the detaching of stored silver from the cathode may be eifected by mechanical methods or by ultra-sonic vibrations.
  • Helpful uses can be made of the following mechanical techniques: employment of brushes sliding on the cathode and vice versa, employment of a vibrating or oscillating cathode, jets of liquid under pressure onto the cathode, violent stirring of the electrolytic solution.
  • the silver compounds usefully employable as electrolytic solution in the process of our invention can be selected from salts such as silver nitrates, silver sulphate, silver acetate, silver halides, silver oxalate, or complexed basic compounds such as ammoniacal silver hydroxides.
  • the silver salts be complexed with ammonia or with fluoboric ions.
  • Electrolysis is generally carried out in the presence of protector colloids such as cellulose derivatives, for instance carboxymethylcellulose.
  • protector colloids such as cellulose derivatives, for instance carboxymethylcellulose.
  • the electrolytic operation is generally performed at low temperatures, between 10 and 50 C.
  • the current density may vary over a large range: however use is preferably made of values ranging between 2 mampers/cm. and 50 mampers/cmfi.
  • the following working examples illustrate the. invention but are not limitative thereof.
  • EXAMPLE 1 100 g. of AgNo 750 g. of borax (N B O 1O H 0), 400 g. of NaOH were dissolved in distilled water and diluted upto a 10011 volume. Thereto were added 600 cc. of aqueous ammonia solution (28 Be.) and 10 g. of carboxymethylcellulose (before solubilized on another side). 3.5 liters of the aforesaid solution were poured into the electrolytic all shown in 'FIG. 1 with an anode consisting of compact graphite 1 and a cathode consisting of a silver plate 2.
  • the cell was provided with the system of mechanical removal of the deposited silver consistuted by two plastic brushes 3,3 whose speed of rotation may range over large limits by means of a geared motor 4.
  • the brushes were arranged so as to lap the cathode surface.
  • the electrolysis was carried out at constant current by means of an amperostat.
  • a reference electrode saturated calomel contacted to cathode to measure the electrode potential.
  • the electrodeposition was carried out under the follow: ing conditions:
  • the electric energy consumption was about 0.7 kwh. per kg. of produced silver, the yield was close to
  • the produced silver having average sizes of 800 A., was washed with water made free from ions, dried in an oven at 80 C. and then deposited, by suitable technics, on a ceramic carrier in order to carry out a test of catalyst activity.
  • the catalyst constituted by' carrier and silver in an amount of 15%, was introduced into a 2.4 cm. pipe, equipped with "an external jacket allowing the thermostating liquidto circulate.
  • the catalytic bed heighflwas aboutlm.v
  • a gaseous mixture was fed into the reactor at atmospheric pressure having the following composition: 5% ethylene, 6.5% C0 5% 0 83.5% N
  • the feed flow was 210 Nl/h. and the contact time was about 4.6 sec.
  • the energy consumption was about 3 kwh. per kg. of produced silver.
  • EXAMPLE 3 An electrolysis was carried out on the solution of Example 1 by using ultra-sonic vibrations for detaching silver.
  • the experimental conditions were the following ones:
  • Anode Compact graphite Anode surface 100 cmfl.
  • the sound head of ultra-sonic vibrations was electrically connected to the cathode so as to avoid possible corrosion processes.
  • the silver obtained under the aforesaid experimental conditions had sizes of about 800 A. and gave rise to conversion and selectivity values, in the ethylene-ethylene oxide reaction, of 25% and 78%.
  • EXAMPLE 4 This example relates to one of the possible industrial processes for preparing silver base catalyst by an electrodeposition from silver nitrate solutions with continuous current and continuous detaching of the electrodepositated material in an electrolytic cell of bipolar type.
  • a process for the preparation of silver useful as a catalyst by silver electrochemical deposition comprising: complexing a silver compound with a member selected from the group consisting of ammonic and fluoboric ions, electrolytically depositing the silver compound on a cathode, and concurrently removing the deposited silver from said cathode whereby the removed silver has a size of less than 1500- A.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)
US00319060A 1971-12-28 1972-12-27 Process for the preparation of silver base catalyst Expired - Lifetime US3843491A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT33010/71A IT944424B (it) 1971-12-28 1971-12-28 Procedimento per la preparazione di catalizzatori a base di argento

Publications (1)

Publication Number Publication Date
US3843491A true US3843491A (en) 1974-10-22

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US00319060A Expired - Lifetime US3843491A (en) 1971-12-28 1972-12-27 Process for the preparation of silver base catalyst

Country Status (23)

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US (1) US3843491A (instruction)
JP (1) JPS5511895B2 (instruction)
AR (1) AR196221A1 (instruction)
AT (1) AT333702B (instruction)
AU (1) AU476492B2 (instruction)
BE (1) BE792890A (instruction)
BR (1) BR7208712D0 (instruction)
CA (1) CA1028276A (instruction)
CH (1) CH556915A (instruction)
CS (1) CS162787B2 (instruction)
DD (1) DD103269A5 (instruction)
DE (1) DE2263883C3 (instruction)
ES (1) ES410294A1 (instruction)
FR (1) FR2186541B1 (instruction)
GB (1) GB1400758A (instruction)
HU (1) HU165610B (instruction)
IT (1) IT944424B (instruction)
LU (1) LU66759A1 (instruction)
NL (1) NL7217691A (instruction)
RO (1) RO58869A (instruction)
TR (1) TR17434A (instruction)
YU (1) YU36103B (instruction)
ZA (1) ZA727973B (instruction)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302319A (en) * 1978-08-16 1981-11-24 Katsyguri Ijybi Continuous electrolytic treatment of circulating washings in the plating process and an apparatus therefor
US5413987A (en) * 1994-01-24 1995-05-09 Midwest Research Institute Preparation of superconductor precursor powders
US5462647A (en) * 1994-09-09 1995-10-31 Midwest Research Institute Preparation of lead-zirconium-titanium film and powder by electrodeposition
US5785837A (en) * 1996-01-02 1998-07-28 Midwest Research Institute Preparation of transparent conductors ferroelectric memory materials and ferrites
WO2001051685A3 (en) * 2000-01-10 2002-09-19 Michael John Sole Removal of metals from solution
CN101579889B (zh) * 2009-06-05 2010-10-13 黎永健 陶瓷粉料下料装置及其下料方法
US20130075251A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for the production thereof
US20130075249A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for production thereof
CN103060854A (zh) * 2013-01-11 2013-04-24 东南大学 一种电化学连续合成胶体银溶液的方法
CN104492428A (zh) * 2014-11-28 2015-04-08 东莞市青麦田数码科技有限公司 一种掺杂银或铋的二氧化锆纳米管及其制备方法和用途

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2715856C2 (de) * 1977-04-06 1984-04-12 Duval Corp., 77002 Houston, Tex. Verfahren und Vorrichtung zur kontinuierlichen Gewinnung von Metallen, insbesondere Kupfer, in Form eines teilchenförmigen kristallinen Materials
NL8503090A (nl) * 1985-11-11 1987-06-01 Harshaw Chemie Bv Werkwijze voor het bereiden van gedragen katalysator systemen.
JPH04131393A (ja) * 1990-09-21 1992-05-06 Power Reactor & Nuclear Fuel Dev Corp 電解法によるパラジウムの回収方法および回収装置
US6024855A (en) * 1997-08-15 2000-02-15 Sachem, Inc. Electrosynthesis of hydroxylammonium salts and hydroxylamine using a mediator
JP4395257B2 (ja) * 1997-08-15 2010-01-06 サッチェム， インコーポレイテッド 触媒フィルム、触媒フィルムの作製方法、および触媒フィルムを用いる化合物の電気的合成
RU2255150C1 (ru) * 2003-12-04 2005-06-27 Федеральное государственное унитарное предприятие "Научное конструкторско-технологическое бюро "Феррит" Способ получения порошка серебра
DE102014204372A1 (de) 2014-03-11 2015-09-17 Bayer Materialscience Ag Verfahren zur Herstellung von katalytisch aktiven Pulvern aus metallischem Silber oder aus Mischungen aus von metallischem Silber mit Silberoxid zur Herstellung von Gasdiffusionselektroden
RU2558325C1 (ru) * 2014-06-17 2015-07-27 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Способ электролитического получения мелкодисперсных порошков серебра

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB501278A (en) * 1937-08-21 1939-02-21 Bataafsche Petroleum Process for manufacturing catalysts and for bringing about catalytic reactions therewith

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302319A (en) * 1978-08-16 1981-11-24 Katsyguri Ijybi Continuous electrolytic treatment of circulating washings in the plating process and an apparatus therefor
US5413987A (en) * 1994-01-24 1995-05-09 Midwest Research Institute Preparation of superconductor precursor powders
WO1995020063A1 (en) * 1994-01-24 1995-07-27 Midwest Research Institute Preparation of superconductor precursor powders
US5789348A (en) * 1994-01-24 1998-08-04 Midwest Research Institute Preparation of superconductor precursor powders
US5462647A (en) * 1994-09-09 1995-10-31 Midwest Research Institute Preparation of lead-zirconium-titanium film and powder by electrodeposition
US5785837A (en) * 1996-01-02 1998-07-28 Midwest Research Institute Preparation of transparent conductors ferroelectric memory materials and ferrites
WO2001051685A3 (en) * 2000-01-10 2002-09-19 Michael John Sole Removal of metals from solution
CN101579889B (zh) * 2009-06-05 2010-10-13 黎永健 陶瓷粉料下料装置及其下料方法
US20130075251A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for the production thereof
US20130075249A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for production thereof
US9118082B2 (en) * 2011-09-23 2015-08-25 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for the production thereof
US9163318B2 (en) * 2011-09-23 2015-10-20 Bayer Intellectual Property Gmbh Oxygen-consuming electrode and process for production thereof
CN103060854A (zh) * 2013-01-11 2013-04-24 东南大学 一种电化学连续合成胶体银溶液的方法
CN104492428A (zh) * 2014-11-28 2015-04-08 东莞市青麦田数码科技有限公司 一种掺杂银或铋的二氧化锆纳米管及其制备方法和用途
CN104492428B (zh) * 2014-11-28 2016-09-14 东莞市莞信企业管理咨询有限公司 一种掺杂银或铋的二氧化锆纳米管及其制备方法和用途

Also Published As

Publication number Publication date
JPS5511895B2 (instruction) 1980-03-28
AT333702B (de) 1976-12-10
NL7217691A (instruction) 1973-07-02
TR17434A (tr) 1975-07-23
DE2263883A1 (de) 1973-07-19
RO58869A (instruction) 1975-11-15
YU325672A (en) 1981-04-30
ZA727973B (en) 1973-09-26
AU476492B2 (en) 1976-09-23
DD103269A5 (instruction) 1974-01-12
CA1028276A (en) 1978-03-21
CS162787B2 (instruction) 1975-07-15
IT944424B (it) 1973-04-20
AR196221A1 (es) 1973-12-10
FR2186541A1 (instruction) 1974-01-11
ATA1110772A (de) 1976-04-15
YU36103B (en) 1982-02-25
FR2186541B1 (instruction) 1976-01-30
JPS4873387A (instruction) 1973-10-03
LU66759A1 (instruction) 1973-02-27
DE2263883B2 (de) 1974-10-10
GB1400758A (en) 1975-07-23
ES410294A1 (es) 1976-01-01
DE2263883C3 (de) 1975-05-28
CH556915A (fr) 1974-12-13
BR7208712D0 (pt) 1973-09-20
AU4866372A (en) 1974-05-09
BE792890A (fr) 1973-03-30
HU165610B (instruction) 1974-09-28

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