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WO1990012753A1 - Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique - Google Patents

Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique Download PDF

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Publication number
WO1990012753A1
WO1990012753A1 PCT/US1989/001597 US8901597W WO9012753A1 WO 1990012753 A1 WO1990012753 A1 WO 1990012753A1 US 8901597 W US8901597 W US 8901597W WO 9012753 A1 WO9012753 A1 WO 9012753A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
sulfuric acid
stream
sulfur dioxide
gas
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.)
Ceased
Application number
PCT/US1989/001597
Other languages
English (en)
Inventor
John E. Stauffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to CA000587323A priority Critical patent/CA1332372C/fr
Priority claimed from CA000587323A external-priority patent/CA1332372C/fr
Application filed by Individual filed Critical Individual
Priority to DE68919362T priority patent/DE68919362T2/de
Priority to EP89907403A priority patent/EP0422066B1/fr
Priority to PCT/US1989/001597 priority patent/WO1990012753A1/fr
Priority to AU38472/89A priority patent/AU622372B2/en
Priority to JP1507097A priority patent/JPH03505613A/ja
Publication of WO1990012753A1 publication Critical patent/WO1990012753A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • 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
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation

Definitions

  • the present invention concerns a process for removing sulfur dioxide from a waste gas stream such as effluent vent, flue or exhaust gas, for purposes of economy, for achieving a useful by-product, and for minimizing environmental pollution.
  • the invention concerns a process for removing sulfur dioxide from effluent vent or flue gas, by subjecting the gas cyclically to scrubbing in an acid stream and to electrolysis.
  • the process comprises the steps of scrubbing the gas in a confined scrubbing zone with an aqueous sulfuric acid stream to remove sulfur dioxide from the gas and convert the thus removed sulfur dioxide to sulfurous acid, subjecting the sulfuric acid stream containing the thus produced sulfurous acid to electrolysis in an electrolytic cell comprising an anode and a cathode, applying a potential across said electrodes in the range from about 0.6 volts to about 1.7 volts, to oxidize the sulfurous acid to sulfuric acid, recycling the sulfuric acid stream resulting from the electrolysis step to the scrubbing zone, and maintaining the recycled sulfuric acid within a predetermined range of concentration by means of make-up water or acid.
  • the range of concentration of sulfuric acid in the acid stream is determined largely by electrical conductivities.
  • concentration of sulfuric acid in the acid stream is determined largely by electrical conductivities.
  • dilute aqueous sulfuric acid from under 5 weight percent acid up to the concentration of oil of vitriol, namely, 93.19 weight percent acid, the conductivities in mho/cm 2 x 10 4 at 18oC, are greater than 1000.
  • the values of conductivities exceed 2000, and within the limits of 20 weight percent and 40 weight percent the values are above 6500.
  • the scrubbing zone conveniently is the chamber contained within an absorber or scrubbing column of conventional design or modified design for passage of a stream of effluent gas therethrough.
  • the scrubbing column contains packing material that provides gas-liquid contact surface for the gas stream and the aqueous acid stream.
  • the design of the packing material is critical in order to minimize channeling and thereby achieve greater scrubbing efficiency.
  • the packing material is electrically conductive and serves both as a gas-liquid contact surface for scrubbing and as the electrochemically active surface of the electrolytic cell.
  • the by-product sulfuric acid is withdrawn in desired quantity from the acid stream. This is done, for example, while adding or making-up with water to lower the acid concentration to a predetermined level.
  • the dissolved sulfur dioxide in the acid stream is kept at a minimum concentration by operating at a low current density which in turn is accomplished by employing an anode with increased area, preferably by employing an anode comprising electrically conductive packing in the scrubbing column.
  • FIGURE 1 is a diagrammatic view of a scrubber and an electrolytic cell in series with a pump for acid-stream-processing of flue gas through the scrubber and cycling the acid stream via the cell back to the scrubber;
  • FIGURE 2 is a similar view in which the anode of the electrolytic cell is located as gas-liquid contact packing with the scrubber.
  • Electrolysis according to the invention is an effective and efficient method of converting sulfurous acid (as well as SO 2 ), to sulfuric acid. No additive is introduced which might contaminate the by-product acid produced. There are no catalysts which may become fouled. Because the electrochemical potential for the reaction is relatively low, the cost of power is moderate. In short, the present electrolytic process has the important advantage that it is direct and simple to operate.
  • S is the unit cost
  • E is the cell voltage
  • C is the cost of electricity
  • U is the fixed cost, i.e. amortization, insurance, maintenance, etc.
  • R is credit given for by-product acid.
  • the capacity of a pollution control unit to remove sulfur dioxide by the present invention is readily adjustable so that upsets can be handled. For example, any surge in the volume of vent gas or increase in sulfur dioxide concentration can adequately be met. This result is accomplished by raising the applied voltage thus causing an increase in electrode current density. To cope with emergencies or irregularities the potential across the electrodes can be raised as high as 1.7 volts, which is the potential where nascent oxygen begins to form. The applied cell voltage would thus be equal to the potential across the electrodes plus the potential through the electrolyte. The latter value is dependent on the acid conductivity and cell geometry.
  • Vent or flue gases are contacted at ambient temperature or higher but below the acid's boiling point in an absorber or scrubbing column with a downstream of dilute aqueous sulfuric acid.
  • This acid stream strips the sulfur dioxide from the gas stream.
  • the acid containing the absorbed sulfur dioxide is passed to an electrolytic cell which converts the SO 2 as sulfurous acid to more sulfuric acid. Hydrogen is vented from the cell.
  • the electrodes must stand up to the corrosive conditions and therefore are fabricated from suitable inert electrode material such as lead, graphite, platinum, palladium, or ruthenium.
  • a preferred modification of the process provides an improvement in its efficiency.
  • the dissolved sulfur dioxide in the acid must be maintained at a minimum concentration. This result, as indicated, can be achieved by increasing the area of the anode.
  • a further advantage of increasing the anode area is that the overvoltage can thereby be reduced as the current density drops.
  • the packing in the scrubbing column for the dual purposes of providing gas-liquid contact surface and also serving as the anode.
  • This design has the further advantage of improving the transport of sulfite ions through the diffusion layer.
  • the packing must be made of an electrically conductive material such as graphite, graphite treated with a noble metal, or platinum-plated zirconium.
  • Figure 2 shows the layout of the process in which the column packing functions as the anode.
  • the weak acid with or without nitrogen values may be used in the production of fertilizer.
  • the acid may be concentrated and purified by procedures well known to the trade. This concentrated acid may be used for many industrial purposes, thus improving the economics of the pollution control process.
  • the potential applications of the present invention are numerous, but four uses stand out as being particularly significant.
  • the process can be applied to the cleaning of flue gases from power plants that burn high sulfur coal or fuel oil. Environmental pollution including acid rain are thereby reduced.
  • Another application is in the control of sulfur dioxide from smelters that roast sulfide ores.
  • the process can be used to clean the vent gases from contact sulfuric acid plants.
  • the process controls excessive emissions of sulfur dioxide during plant start-up and any upsets in the operation. It also allows greater utilization of plant capacity without contributing additional emissions of sulfur dioxide to the atmosphere.
  • the weak acid produced by the process is recycled to the acid plant for fortification.
  • the process is used to treat flue gases from waste incinerators.
  • the potential sources of sulfur dioxide include high sulfur fuel used to operate the incinerator, vulcanized rubber goods, and certain plastics.
  • an oxidizing agent such as dichromate or permangante into the scrubbing solution in a odor-inhibiting quantity (e.g. 4 wt. %) odors form traces of organic substances can be minimized.
  • the oxidizing agent is rejuvenated by the electric current during the electrolysis step.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

L'invention concerne un procédé combiné d'épuration à l'acide et d'électrolyse, permettant d'extraire le dioxyde de soufre d'un courant de gaz résiduels provenant par exemple d'un évent de gaz de fumée; ce procédé économique permet d'obtenir un produit dérivé utile contribuant à limiter la pollution.
PCT/US1989/001597 1988-12-30 1989-04-14 Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique Ceased WO1990012753A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA000587323A CA1332372C (fr) 1988-12-30 1988-12-30 Extraction de dioxyde de soufre
DE68919362T DE68919362T2 (de) 1988-12-30 1989-04-14 Beseitigung von schwefeldioxyd aus abfallgasen und wiedergewinnung als schwefelsäure.
EP89907403A EP0422066B1 (fr) 1988-12-30 1989-04-14 Elimination du dioxyde de soufre (s0 2?) de gaz residuels et recuperation sous forme d'acide sulfurique
PCT/US1989/001597 WO1990012753A1 (fr) 1988-12-30 1989-04-14 Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique
AU38472/89A AU622372B2 (en) 1988-12-30 1989-04-14 Removal of sulfur dioxide from waste gases and recovery as sulfuric acid
JP1507097A JPH03505613A (ja) 1989-04-14 1989-04-14 廃ガスからの二酸化硫黄（ｓｏ↓２）の除去及び硫酸としての回収方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA000587323A CA1332372C (fr) 1988-12-30 1988-12-30 Extraction de dioxyde de soufre
PCT/US1989/001597 WO1990012753A1 (fr) 1988-12-30 1989-04-14 Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique

Publications (1)

Publication Number Publication Date
WO1990012753A1 true WO1990012753A1 (fr) 1990-11-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/001597 Ceased WO1990012753A1 (fr) 1988-12-30 1989-04-14 Elimination du dioxyde de soufre (s02) de gaz residuels et recuperation sous forme d'acide sulfurique

Country Status (2)

Country Link
AU (1) AU622372B2 (fr)
WO (1) WO1990012753A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0670174A1 (fr) * 1994-03-04 1995-09-06 Hideo Hayakawa Méthode et dispositif pour traiter des gaz résiduaires
WO2010078727A1 (fr) * 2009-01-12 2010-07-15 马士科技有限公司 Procédé pour retirer des composants toxiques et des gaz à effet de serre de fumées

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US825057A (en) * 1903-10-10 1906-07-03 Woolsey Mca Johnson Method of making sulfuric acid.
US3836630A (en) * 1971-03-29 1974-09-17 Chiyoda Chem Eng Construct Co Method for treatment of gas containing sulfur dioxide
US3944401A (en) * 1973-05-08 1976-03-16 Metallgesellschaft Aktiengesellschaft Process for the removal of gaseous impurities from the exhaust gases of a contact-process plant for the production of sulfuric acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US825057A (en) * 1903-10-10 1906-07-03 Woolsey Mca Johnson Method of making sulfuric acid.
US3836630A (en) * 1971-03-29 1974-09-17 Chiyoda Chem Eng Construct Co Method for treatment of gas containing sulfur dioxide
US3944401A (en) * 1973-05-08 1976-03-16 Metallgesellschaft Aktiengesellschaft Process for the removal of gaseous impurities from the exhaust gases of a contact-process plant for the production of sulfuric acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0422066A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0670174A1 (fr) * 1994-03-04 1995-09-06 Hideo Hayakawa Méthode et dispositif pour traiter des gaz résiduaires
WO2010078727A1 (fr) * 2009-01-12 2010-07-15 马士科技有限公司 Procédé pour retirer des composants toxiques et des gaz à effet de serre de fumées

Also Published As

Publication number Publication date
AU3847289A (en) 1990-11-16
AU622372B2 (en) 1992-04-02

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