US3193484A - Electrolytic conversion of acidic compounds - Google Patents

Electrolytic conversion of acidic compounds Download PDF

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Publication number
US3193484A
US3193484A US138282A US13828261A US3193484A US 3193484 A US3193484 A US 3193484A US 138282 A US138282 A US 138282A US 13828261 A US13828261 A US 13828261A US 3193484 A US3193484 A US 3193484A
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Prior art keywords
phthalocyanine
electrolytic
compound
conversion
solution
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US138282A
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English (en)
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William K T Gleim
Bremanis Elmars
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Universal Oil Products Co
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Universal Oil Products Co
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Priority to BE666363A priority patent/BE666363A/xx
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the electrolytic conversion of mercapto compounds is exemplified by the regeneration of used alkali metal hydroxide solutions containing mercaptides as described in Yabroff et al. Patent 2,140,194, Gaylor Pat ent 2,654,706 and others.
  • This process is described in further detail in a paper entitled Electrolytic Regeneration of Treating Solutions, by Zandona and Ripple, which paper was presented at the Seventeenth Mid-Year Meeting of the American Petroleum Institutes Division of Refining at San Francisco, California, on May 14, 1952.
  • a later paper, entitled Economic Aspects of the ADC Electrolytic Mercaptan Process was presented by Miller and Fiske at the regional meeting of the Western Petroleum Refineries Association in Alma, Michigan, in June of 1954.
  • references described above are directed to the regeneration of used alkali metal hydroxide solutions, it is understood that the improvement of the present invention is used in any electrolytic process for the conversion of acidic compounds and particularly of mercapto compounds.
  • An example of another use of such a process is the conversion of mercaptans, either alone or dissolved in an organic substrate such as hydrocarbon distillate.
  • hydrocarbon distillate For example, sour hydrocarbon distillate, including gasoline, kerosene, jet fuel, etc. is subjected to electrolytic conversion to convert the mercaptans contained in the hydrocarbon distillate into disulfides.
  • the present invention is used for the oxidation of hydrogen sulfide and salts thereof such as ammonium sulfide, sodium sulfide, potassium sulfide, etc., either as such or in admixture with hydrocarbon gases, hydrocarbon liquids, water, etc.
  • Other acidic compounds also are converted by the present process including, for example, phenols, cresols, xylenols, etc.
  • the electrolyzer consists of 60 electric cells in series, through which the spent or used caustic soda solution is passed and is regenerated by an applied direct electric current.
  • the electrodes are nickel plated cast iron, 24" to 36" square by 1" thick, separated by rubber gasketedvulcanized asbestos diaphragms.
  • Each unit consists of an anode oxidation plate and a cathode hydrogen plate separated by an asbestos diaphragm.
  • Each plate has a hole in each corner through which the caustic flows.
  • the spent caustic enters the lower port and flows upward and diagonally to the top port before it enters the anode outlet header.
  • a similar set of ports is provided for the cathode hydrogen plates, which permit circulation of spent caustic solution and release of hydrogen gas.
  • the electrolytic cell described in detail in the Yabroif et al. patent referred to above is of cylindrical type and contains a rotatable cylindrical anode. This patent also states that a series of alternating positive and negative electrode plates in rectangular cell also has given satisfactory results.
  • the oxygen required for the conversion is generated in situ.
  • the mercaptide solutions contain entrained oxygen and the oxygen either may be removed or may be allowed to remain in the charge to the electrolytic cell.
  • oxygen from an extraneous source may be supplied to the electrolytic cell to furnish the oxygen required for the conversion of the mercapto compound. This embodiment is particularly desirable when substantially all of the anode current is utilized to effect the electro-chemical conversion of the mercaptide ion and the available current will not be used for the decomposition of the water.
  • the electrolytic conversion may be effected at any suitable temperature which may range from 0 C. to C. or higher and preferably from about 15 to about 50 C.
  • the electrical current required for the process will depend upon the concentration of mercapto compounds in the charge to the electrolytic cell. In the process described in the above publications, it is presumed that 240 volts 3-phase AC. power is available. The power required for the conversion of 225 pounds per day of mercaptan sulfur is estimated to be 63 kilowatts. For the conversion of 500 pounds per day of mercaptan sulfur the power required is estimated to be 136 kilowatts.
  • the process of the present invention may be used in various arrangements.
  • the hydrocarbon distillate comprises gasoline
  • the alkaline solution containing the extracted mercaptans then is converted electrically as described herein.
  • the extracted gasoline still contains a minor concentration of mercaptans and this gasoline also may be treated hydroxide.
  • a preferred reagent comprises anaqueous solution of an alkali metal hydroxide such as sodium hydroxide (caustic), potassium hydroxide, etc.
  • alkali metal hydroxide such as sodium hydroxide (caustic), potassium hydroxide, etc.
  • Other alkaline solutions include aqueous solutions of lithium hydroxide, rubidium hydroxide, cesiurnhydroxide, etc., although, in general, these hydroxides are more expensive and therefore generally are not preferred for commercial use.
  • a preferred alkaline solution is an aqueous solution of from about 1% to about 50% and more preferably 5% to by weight concentration of sodium hydroxide or potassium While aqueous solutions are preferred, it
  • eluding for example, alcohols, ketones, etc., or mixtures thereof, either as such or diluted with water.
  • electrolytic conversion of acidic compounds is effected in the presence of a phthalocyanine compound.
  • a phthalocyanine compound As hereinbefore set forth, this results in a reduction in the polarization of the electrodes and accordingly in a decrease in the voltage requirements. This in turn results in a reduction in the cost of the process and also in reducing side reactions which would occur at the increased voltage which otherwise would be required.
  • the present invention relates to an improvement in a process for the electrolytic conversion of an acidic compound, which comprises effecting said electrolytic conversion in the presence of a phthalocyanine compound.
  • the present invention relates to an improvement in a process for the regeneration of used alkaline reagent, which comprises effecting said electrolytic regeneration in the presence of cobalt phthalo cyanine sulfonate.
  • the present invention relates to an improvement in the electrolytic sweetening of a sour hydrocarbon fluid, which comprises effecting said sweetening in the presence of vanadium phthalo cyanine carboxylate.
  • any suit able phthalocyanine compound may be used in the present invention and preferably comprises a metal phthalocyanine.
  • Particularly preferred metal phthalocyanines include cobalt phthalocyanine and vanadium phthalocyanine.
  • Other metal phthalocyanines include iron phthalocyanine, copper phthalocyanine, nickel phthalocyanine, molybdenum phthalocyanine, chromium phthalocyanine, tungsten phthalocyanine, etc.
  • the metal phthalocyanine in general is not readily .soluble in aqueous solvents and, therefore, when used in an aqueous alkaline solution or for ease of compositing with a solid carrier, a derivative of the phthalocyanine is preferred.
  • a particularly preferred derivative is the sulfonated derivative.
  • an especially preferred phthalocyanine compound is cobalt phthalocyanine sulfonate.
  • Such a compound is available commercially and comprises cobalt phthalocyanine disulfonate and also contains cobalt phthalocyanine monosulfonate
  • Another preferred compound comprises vanadium phthalocyanine sulfonate.
  • These compounds are obtained from any suitable source or are prepared in any suitable manner as, for example, by reacting cobalt or vanadium phthalocyanine with 2550% fuming sulfuric acid. While the sufonic acid derivatives are preferred, it is understood 'cured inthe range of about 0.8 v. to 0.0 v.
  • Other derivatives include particularly the carboxylated derivative which may be prepared, for example, by the action of trichloroacetic acid on the metal phthalocyanine or by the action of phosgene and aluminum chloride. In the latter reaction the acid chloride is formed and may be converted to the desired carboxylated derivative by conventional hydrolysis.
  • the phthalocyanine compound may be used as a solution in an alkaline reagent or other charge being subjected to electrolytic conversion.
  • the phthalocyanine compound may be composited with a solid support and utilized as finely divided particles entrained in the alkaline solution or other charge.
  • the phthalocyanine compound is composited with any suitable support which preferably comprises activated charcoal, coke or other suitable forms of carbon.
  • the support may comprise silica, alumina, magnesia, etc., or mixtures thereof.
  • the solid catalyst is prepared in any suitable manner.
  • preformed particles of the solid support are soaked in a solution containing the phthalocyaninecompound, after which excess solution is drained off and the composite is used as such or is subjected to a drying treatment, mild heating, blowing'with air, hydrogen, nitrogen,'etc., or successive treatments using two or more of these operations, prior to use;
  • a solution of the phthalocyanine compound may be sprayed or poured over the particles of the solid support, or such particles may be dipped, suspended, im-
  • the concentration of phthalocyanine compound in the composite may range from 01% to 10% by weightor more of the composite.
  • the phthalocyanine compound is used in any suitable concentration. Generally this is used in comparatively lowconcentrations which may range from 1 to parts per million of phthalocyanine compound based upon the charge to the electrolytic converter. However, it
  • a larger concentration of phthalocyanine may be used when desired and may range up to 5000 parts per million or more.
  • Example I was 0.003 M n-heptyl mercaptan and 1 N NaOH.
  • mercaptan was prepared as a methanolic solution and added in this manner to the sodium hydroxide.
  • the platinum Wire electrode then was coatedwith cobalt phthalocyanine monosulfonate by dipping the electrode into a solution of the phthalocyanine compound.
  • the current rose to 120 microamperes, indicating a high rate of mercaptan oxidation.
  • Example II This evaluation was made using the same equipment described in Example I except that the applied potential was kept constant at -O.25 v. and a solution containing one part per million of cobalt phthalocyanine monosulfonate in dilute sodium hydroxide was included in the test solution.
  • the test solution containing the phthalocyanine compound resulted in a rapid current rise to about 120 microamperes in about 1 /2 minutes. This indicates that the phthalocyanine compound was adsorbed rapidly on the platinum wire electrode. Accordingly, this run demonstrates the improved conversion of the mercaptan compound when the electrolysis is efiected in the presence of the phthalocyanine compound.
  • Example III Thermally cracked gasoline containing hydrogensulfide and mercaptans is first prewashed with a 5% aqueous sodium hydroxide solution to remove the hydrogen sulfide.
  • the prewashed gasoline then is treated with 20% aqueous potassium hydroxide solution containing parts per million of vanadium phthalocyanine sulfonate.
  • the potassium hydroxide solution containing mercaptides and phthalocyanine compound then is subjected to electrolytic conversion in a filter-press electrolytic cell as described in the publications hereinbefore set forth.
  • approximately 215 pounds of mercaptan sulfur are removed and converted in the manner described above.
  • the regenerated potassium hydroxide solution then is recycled for further use in treating sour cracked gasoline.
  • Example IV A fractionator overhead in a refinery contains ammonia and hydrogensulfide. Upon cooling the vapors, ammonium sulfide is formed. Water is supplied during the condensing and dissolves the ammonium sulfide. The water containing ammonium sulfide then is subjected to electrolytic oxidation in the presence of cobalt phthalocyanine carboxylate in the manner described hereinbefore. This serves to oxidize the ammonium sulfide and permits removal of the sulfur from the water.
  • a process for the electrolytic oxidation of a sulfur compound which comprises passing a direct current through an alkaline electrolyte bath containing a compound selected from the group consisting of mercaptans, mercaptides, hydrogen sulfide and salts thereof in contact with an anode and a cathode, said electrolyte bath also containing a phthalocyanine compound.
  • a process for the electrolytic oxidation of a sulfur compound which comprises passing a direct current through an aqueous alkaline electrolyte bath containing a compound selected from the group consisting of mercaptans, mercaptides, hydrogen sulfide and salts thereof in contact with an anode and a cathode, said electrolyte bath also containing a phthalocyanine compound.
  • a process for the electrolytic oxidation of a mercapto compound which comprises passing a direct current through an aqueous alkaline electrolyte bath containing a mercapto compound in contact with an anode and a cathode, said electrolyte bath also containing a phthalocyanine compound.
  • a process for the electrolytic oxidation of a mercaptide which comprises passing a direct current through an aqueous alkali metal hydroxide solution containing a mercaptide in contact with an anode and a cathode, said solution also containing a phthalocyanine compound.
  • a process for the electrolytic oxidation of a mercap tide which comprises passing a direct current through an aqueous caustic solution containing a mercaptide in contact with an anode and a cathode, said solution also containing a phthalocyanine compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US138282A 1961-09-15 1961-09-15 Electrolytic conversion of acidic compounds Expired - Lifetime US3193484A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673070A (en) * 1970-06-22 1972-06-27 Petrolite Corp Process for removing and concentrating acidic organic material from water
US4127454A (en) * 1976-10-05 1978-11-28 Ouchi Shinko Kagaku Kogyo Kabushiki Kaisha Preparation of benzothiazolylsulfenamides
US4861555A (en) * 1985-03-11 1989-08-29 Applied Automation, Inc. Apparatus for chromatographic analysis of ionic species
RU2101320C1 (ru) * 1996-03-26 1998-01-10 Александр Васильевич Зосимов Способ очистки жидкого углеводородного сырья от сероорганических соединений
US5723039A (en) * 1996-04-11 1998-03-03 Catalytic Sciences, Ltd. Process for removal of organo-sulfur compounds from liquid hydrocarbons
US6338788B1 (en) 1999-06-11 2002-01-15 Exxonmobil Research And Engineering Company Electrochemical oxidation of sulfur compounds in naphtha
US6837980B2 (en) 2000-12-21 2005-01-04 Olin Corporation Bond enhancement antitarnish coatings
RU2342422C2 (ru) * 2006-08-24 2008-12-27 Яков Григорьевич Бродянский Способ очистки жидких углеводородов от серы и установка для его осуществления
US11441230B2 (en) * 2018-11-29 2022-09-13 Championx Usa Inc. Preparation of disulfide corrosion inhibitors by electrochemical methods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2654706A (en) * 1949-12-10 1953-10-06 Charles W Rippie Electrolytic regeneration of spent caustic
US2794768A (en) * 1955-05-09 1957-06-04 Sun Oil Co Refining process, including regeneration of alkaline treating agents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2654706A (en) * 1949-12-10 1953-10-06 Charles W Rippie Electrolytic regeneration of spent caustic
US2794768A (en) * 1955-05-09 1957-06-04 Sun Oil Co Refining process, including regeneration of alkaline treating agents

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673070A (en) * 1970-06-22 1972-06-27 Petrolite Corp Process for removing and concentrating acidic organic material from water
US4127454A (en) * 1976-10-05 1978-11-28 Ouchi Shinko Kagaku Kogyo Kabushiki Kaisha Preparation of benzothiazolylsulfenamides
US4861555A (en) * 1985-03-11 1989-08-29 Applied Automation, Inc. Apparatus for chromatographic analysis of ionic species
RU2101320C1 (ru) * 1996-03-26 1998-01-10 Александр Васильевич Зосимов Способ очистки жидкого углеводородного сырья от сероорганических соединений
US5723039A (en) * 1996-04-11 1998-03-03 Catalytic Sciences, Ltd. Process for removal of organo-sulfur compounds from liquid hydrocarbons
US6338788B1 (en) 1999-06-11 2002-01-15 Exxonmobil Research And Engineering Company Electrochemical oxidation of sulfur compounds in naphtha
US6837980B2 (en) 2000-12-21 2005-01-04 Olin Corporation Bond enhancement antitarnish coatings
RU2342422C2 (ru) * 2006-08-24 2008-12-27 Яков Григорьевич Бродянский Способ очистки жидких углеводородов от серы и установка для его осуществления
US11441230B2 (en) * 2018-11-29 2022-09-13 Championx Usa Inc. Preparation of disulfide corrosion inhibitors by electrochemical methods

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