US3721615A - Process for the production of hydroquinone - Google Patents

Process for the production of hydroquinone Download PDF

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Publication number
US3721615A
US3721615A US00226124A US3721615DA US3721615A US 3721615 A US3721615 A US 3721615A US 00226124 A US00226124 A US 00226124A US 3721615D A US3721615D A US 3721615DA US 3721615 A US3721615 A US 3721615A
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US
United States
Prior art keywords
benzene
hydroquinone
quinone
recycle stream
sulfuric acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00226124A
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English (en)
Inventor
M Fremery
H Hover
G Schwarzlose
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Union Rheinische Braunkohlen Kraftstoff AG
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Union Rheinische Braunkohlen Kraftstoff AG
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    • 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
    • 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

  • Dilute sulfuric acid optionally with the addition of some sodium sulfate is generally used as the electrolyte. Since the electrolyte mixture is a two-phase mixture, emulsifiers were added despite the fact that they can give rise to disadvantages in so far as they may take part in the reaction and have an adverse effect upon separation of the hydroquinone.
  • the present invention provides a process for the production of hydroquinone by the electrochemical oxidation of benzene to quinone and electrochemical reduction of the quinone to hydroquinone.
  • a finely dispersed recycle stream of benzene, dilute sulfuric acid and quinone whose quinone content is no higher than 2 percent related to the benzene is passed at high speed through the anode compartment of an electrolytic cell.
  • Fresh benzene is added to this recycle stream before it is introduced into the anode compartment, removing a corresponding proportion of the anode recycle stream after the anode compartment.
  • the sulfuric acid is separated from this proportion and returned to the anode recycle stream.
  • the residual benzene-quinone mixture containing no more than about 2 percent of quinone is added to a finely dispersed cathode recycle stream of benzene, dilute sulfuric acid, and hydroquinone before it is introduced into the cathode compartment of an electrolytic cell.
  • a corresponding proportion of the cathode recycle stream is removed after the cathode compartment, separating the benzene from this proportion and returning it to the anode recycle stream.
  • the hydroquinone is separated from the residual hydroquinone sulfuric acid mixture, and the acid thus obtained is returned to the cathode recycle stream before it is introduced into the cathode compartment.
  • a filter is installed in the pipe 1.
  • solid secondary products from the anode compartment such as lead oxid, lead sulfate or sulfonated products of benzene and quinone polymers, are removed from the recycle stream.
  • the rate of flow of the recycle stream is adjusted so that turbulence is maintained in the cell.
  • a Reynolds number of 2,000 should be exceeded in order to mix thoroughly the two liquid phases of electrolyte and organic compounds.
  • Part of the recycle stream for example from 5 to 30 percent is delivered to separator B through pipe 7.- In the separator B, the sulfuric acid is separated from the benzene solution and returned through pipe 8 to the recycle stream.
  • the benzene solution should contain no more than about 2 percent of quinone.
  • a recycle stream consisting of dilute sulfuric acid, benzene, and small amounts of hydroquinone is also passed through the cathode compartment C (through pipes l0, ll, 12, 9).
  • the ratio of benzene to sulfuric acid is between 1:2 and 1:8 advantageously between 1:4 and 1:6, where 5 25 percent, for example 10 percent sulfuric acid is used.
  • the hydroquinone content can amount to be between about 5 and 15 percent corresponding to the solubility at the temperatures used.
  • Part of the cathode recycle stream for example 10 percent, is delivered through pipe 13 to separator D. A smaller or larger proportion of the recycle stream can of course also be removed depending upon the equilibrium.
  • the recycle benzene containing only very small quantities of hydroquinone corresponding to the solubility, for example 0.1 percent, is separated from the sulfuric acid solution. It is returned to the process through pipe 6.
  • the sulfuric acid solution containing the hydroquinone is delivered through pipe 14 for recovery of hydroquinone in E, for example by crystallization at low temperatures, optionally under reduced pressure.
  • the sulfuric acid containing dissolved hydroquinone is returned through pipe 15 to the cathode recycle stream.
  • the mother liquor from the crystallization can also be introduced there.
  • electrolytic cell having a diaphragma of conventional material separating the anode from the cathode may be used. Also, anodes and cathodes of conventional material may be used, although titan clad with lead dioxide is preferred.
  • the electrolytic cell may be operated in an usual manner, the current density and the quantity of electricity being maintained over a wide range.
  • the process can be made very simple pertaining to apparatus used.
  • the hydroquinone obtained is very pure because no impurities from the anode compartment enter the cathode recycle stream.
  • EXAMPLE 1 A mixture of 9 liters of benzene containing 1.5 percent of quinone and 18 liters of 20 percent sulfuric acid was passed as recycle stream through an anode compartment of an electrolytic cell with a volume of approximately 2 liters. Electrolysis was carried out at 7.5 V, 600A and 35C. Part of the reaction mixture obtained, having a quinone content of 2 percent, was added to the recycle stream passed through the cathode compartment consisting of approximately 20 liters of percent sulfuric acid, 7 liters of benzene and small quantities of hydroquinone. The hydroquinone concentration rose to approximately 80 g/l in the cathode compartment.
  • a proportion of the reaction mixture thus obtained corresponding to the benzene solution delivered to the anode compartment was removed and separated into a benzene solution and a sulfuric acid solution.
  • a quantity of fresh benzene corresponding to the benzene reacted was delivered to the anode compartment.
  • l-lydroquinone was recovered from the sulfuric acid solution by crystallization at 0C.
  • the residual sulfuric acid which still contained approximately 35 g/l of hydroquinone was returned to the recycle stream passed through the cathode compartment.
  • the hydroquinone obtained was 99.5 percent pure.
  • the yield based on the benzene used was 5.2 percent, and the current efficiency based on hydroquinone 37.5 percent.
  • a process for the production of hydroquinone by the electrochemical oxidation of benzene to quinone and the electrochemical reduction of quinone to hydroquinone which comprises passing a finely dispersed recycle stream of benzene, dilute sulfuric acid and quinone whose quinone content is no higher than 2 percent related to the benzene, at high speed through the anode compartment of an electrolytic cell, passing a finely dispersed recycle stream of benzene, dilute sulfuric acid and hydroquinone, substantially free of quinone, at high speed through the cathode compartment of an electrolytic cell, removing a part of the anode recycle stream after the anode compartment, adding a corresponding amount of benzene to the anode recycle stream before it is introduced into the anode compartment, separating the sulfuric acid from the said part and returning it to the anode recycle stream, adding the residual benzene quinone mixture containing no more than about 2 percent of quinone, to the cathode

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00226124A 1971-02-24 1972-02-14 Process for the production of hydroquinone Expired - Lifetime US3721615A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2108623A DE2108623C3 (de) 1971-02-24 1971-02-24 Verfahren zur Herstellung von Hydrochinon durch elektrochemische Umwandlung von Benzol

Publications (1)

Publication Number Publication Date
US3721615A true US3721615A (en) 1973-03-20

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ID=5799606

Family Applications (1)

Application Number Title Priority Date Filing Date
US00226124A Expired - Lifetime US3721615A (en) 1971-02-24 1972-02-14 Process for the production of hydroquinone

Country Status (12)

Country Link
US (1) US3721615A (enExample)
JP (1) JPS5644153B1 (enExample)
AT (1) AT314502B (enExample)
BE (1) BE778521A (enExample)
CA (1) CA943902A (enExample)
CH (1) CH573376A5 (enExample)
DE (1) DE2108623C3 (enExample)
FR (1) FR2126195B1 (enExample)
GB (1) GB1365643A (enExample)
IT (1) IT948679B (enExample)
NL (1) NL7201196A (enExample)
NO (1) NO136836C (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884776A (en) * 1973-05-15 1975-05-20 Du Pont Preparation of hydroquinone
US3895326A (en) * 1973-06-07 1975-07-15 Siemens Ag Transit time tube with a coil-like delay line
US3909376A (en) * 1974-12-04 1975-09-30 Basf Ag Electrolytic manufacture of alkyl-substituted hydroquinones
US4133726A (en) * 1976-12-29 1979-01-09 Monsanto Company Electrolytic flow-cell apparatus and process for effecting sequential electrochemical reaction
US4464236A (en) * 1982-05-10 1984-08-07 The Dow Chemical Company Selective electrochemical oxidation of organic compounds
US4689124A (en) * 1985-09-13 1987-08-25 The Dow Chemical Company Flow-through electrolytic cell

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5973983A (ja) * 1982-10-21 1984-04-26 Mitsubishi Electric Corp プリンタ装置
IT1233936B (it) * 1988-03-24 1992-04-22 Mini Ricerca Scient Tecnolog Sintesi elettrochimica di 2 arilidrochinoni.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884776A (en) * 1973-05-15 1975-05-20 Du Pont Preparation of hydroquinone
US3895326A (en) * 1973-06-07 1975-07-15 Siemens Ag Transit time tube with a coil-like delay line
US3909376A (en) * 1974-12-04 1975-09-30 Basf Ag Electrolytic manufacture of alkyl-substituted hydroquinones
US4133726A (en) * 1976-12-29 1979-01-09 Monsanto Company Electrolytic flow-cell apparatus and process for effecting sequential electrochemical reaction
US4464236A (en) * 1982-05-10 1984-08-07 The Dow Chemical Company Selective electrochemical oxidation of organic compounds
US4689124A (en) * 1985-09-13 1987-08-25 The Dow Chemical Company Flow-through electrolytic cell

Also Published As

Publication number Publication date
FR2126195A1 (enExample) 1972-10-06
FR2126195B1 (enExample) 1975-10-24
CA943902A (en) 1974-03-19
NO136836C (no) 1977-11-16
GB1365643A (en) 1974-09-04
NO136836B (no) 1977-08-08
CH573376A5 (enExample) 1976-03-15
DE2108623A1 (de) 1972-08-31
DE2108623B2 (de) 1978-11-16
BE778521A (fr) 1972-05-16
NL7201196A (enExample) 1972-08-28
JPS5644153B1 (enExample) 1981-10-17
IT948679B (it) 1973-06-11
AT314502B (de) 1974-04-10
DE2108623C3 (de) 1979-07-19

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