WO2003095118A1 - Procedes de traitement de disulfure de carbone - Google Patents

Procedes de traitement de disulfure de carbone Download PDF

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Publication number
WO2003095118A1
WO2003095118A1 PCT/GB2003/002012 GB0302012W WO03095118A1 WO 2003095118 A1 WO2003095118 A1 WO 2003095118A1 GB 0302012 W GB0302012 W GB 0302012W WO 03095118 A1 WO03095118 A1 WO 03095118A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron
substance
carbon disulfide
contaminated
reactive
Prior art date
Application number
PCT/GB2003/002012
Other languages
English (en)
Inventor
Robert M. Kalin
Philip Myles
Original Assignee
The Queen's University Of Belfast
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
Application filed by The Queen's University Of Belfast filed Critical The Queen's University Of Belfast
Priority to AU2003233892A priority Critical patent/AU2003233892A1/en
Publication of WO2003095118A1 publication Critical patent/WO2003095118A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate

Definitions

  • the present invention relates to methods of carbon disulfide treatment.
  • Carbon disulfide is a toxic, highly flammable volatile liquid. It affects the nervous system, liver and heart as well as causing birth defects. Carbon disulfide evaporates at room temperature; the vapour easily explodes in air and burns to produce hydrogen sulfide, a poisonous gas.
  • Carbon disulfide is used in many applications, such as agricultural fumigants, the production of rubber chemicals and as the feedstock for carbon tetrachloride production.
  • the most important industrial use has been in the manufacture of viscose rayon and cellophane.
  • the large-scale use and production of carbon disulfide combined with a lack of awareness of the environmental and health implications, has left a legacy of sites with carbon disulfide contaminated soil and groundwater.
  • the US Environmental Protection Agency's (EPA) "National -Priorities List" (NPL) of the most serious hazardous waste sites in the USA has identified carbon disulfide as the contaminant of concern in at least 200 of the 1430 current or former NPL sites.
  • US Pat. 6,283,675 describes the in-situ chemical oxidation of carbon disulfide contaminated soil to produce sulfates.
  • the reference does not address remediation of carbon disulfide contaminated soil by chemical reduction or the addition of iron.
  • the reference relates to carbon disulfide contaminated soil and not groundwater.
  • US Pat 6,287,472 describes the treatment of groundwater contaminated with chlorinated organics by passing it through a permeable body of iron particles. However, it only relates to the treatment of groundwater and not contaminated soil. Also, it does not include carbon disulfide; it only claims to treat "organic compounds”.
  • the substance can be contacted with the iron either directly or indirectly.
  • Such contacting includes passing the substance through a permeable body of iron.
  • Iron generally zero-valent iron, destroys carbon disulfide by a chemical redox reaction.
  • the present invention is suitable for use with any substance contaminated with carbon disulfide.
  • This includes contaminated solids such as soil, liquids such as groundwater, and gases or vapour phase contaminants.
  • the iron may be in any suitable form e.g. iron filings or granules such as ⁇ granular iron' which is a " well known product generally having a granular diameter of about l-5mm, generally 3-4mm. Generally, it is preferred to provide the iron in a form having a large surface area.
  • One embodiment of the present invention includes the addition of one or more supplementary agents to enhance the iron - carbon disulfide reaction such as bicarbonate, peroxide or sodium hydroxide.
  • the contacting of the iron and contaminated substance can be carried out either in-situ or ex- situ.
  • In-situ methods include mechanical agitation of the substance, such as soil, whilst adding, e.g. in the form of injecting, iron additives such as granular iron, e.g. soil mixing or jet grouting.
  • In- situ methods also include the use of reactive zones such as Permeable Reactive Barriers (PRBs) .
  • PRBs Permeable Reactive Barriers
  • PRBs include an in-situ barrier of reactive material which allows groundwater to pass through it.
  • the reactive material in the barrier traps harmful chemicals in the groundwater or changes such chemicals to less harmful substances.
  • a common method to construct a PRB is by digging a trench in the path of the polluted groundwater. The trench is filled with reactive material; often sand is mixed with the reactive material to increase the permeability of the reactive barrier compared to the 1 surrounding soil and thus allow the groundwater to
  • Ex-situ methods include surface treatment cells into
  • a material-hardening substance such as 2 bentonite and/or cement could be admixed with the 3 other reactants so as to increase the geotechnical 4 properties of the contaminated substance.
  • Materials 5 such as bentonite increase the impenetrability of an 6 admixed substance such as soil, thereby decreasing 7 the rate of flow of any fluid therethrough, and so 8 increasing the contact time of the fluid with the 9 iron.
  • the testing was carried out at room temperature 23°C and the duration of the testing was 4 days (100 hours) .
  • 40 ml glass vials with PTFE septa were used as the reaction vessel.
  • the headspace to aqueous phase ratio was 3:1 to allow the sampling of the headspace.
  • the batch experiment vials were filled with 5g zero valent iron and 10 ml of carbon disulfide solution.
  • the zero-valent iron fillings were obtained from the University of Tuebingen, Germany.
  • FIGS. 1 and 2 show the concentration (actual and log) of carbon disulfide plotted versus time.
  • the carbon disulfide and iron mixture degrades within the first 90 hours with a half-life of 11 hours.
  • the test consisted of 60 samples prepared in 20ml glass vials.
  • the simulated groundwater consisted of organic free water spiked with 100 mg/L of Carbon disulfide (CS2) .
  • Three types of samples were prepared: blank vials, containing only simulated groundwater and two sets of reaction vials, each containing 5 grams of commercially available sources of zero valent iron and simulated groundwater. The mass of iron to volume solution ratio was lg: 3.7mL.
  • the simulated groundwater was prepared in a 5L gas tight Teflon lined plastic bag with Lurelock fittings. Carbon disulfide was first dissolved in methanol and then injected into the water filled bag leaving no headspace. The bag was shaken for 1 hour before the filling of the vials.
  • the vials were filled using Teflon tubing and a peristaltic pump, leaving no headspace, then sealed immediately with Teflon septa and aluminium crimp caps .
  • sample vials with no iron were filled at regular intervals to determine the initial value of carbon disulfide.
  • the test vials were then placed on a rotating disc operated at eight complete revolutions per hour.
  • Carbon disulfide analysis was performed using headspace extraction with a gas chromatograph mass spectrometer (GC-MS) .
  • the method detection limit for carbon disulfide was 10 ⁇ g/L.
  • Attached Figure 3 shows the concentration in parts per million (ppm) of carbon disulfide versus time in hours.
  • the decline in the control concentrations of the experiment is due to sorption of carbon disulfide onto the Teflon septa, after about two days this stabilises at a concentration approximately 70ppm.
  • the vials containing iron show a gradual decline with a half life estimated to be between 18 to 30 hours) within 80 hours.
  • the present invention provides a simple but effective method of treatment to remediate substances such as soil and groundwater contaminated with carbon disulfide.
  • the degradation of carbon disulfide by iron occurs due to a redox reaction.
  • the end products of the carbon disulfide and iron reaction are iron sulfates and sulfides.
  • Iron sulfide is a precipitate, and is in fact a naturally occurring compound, which is safe' compared with carbon disulfide.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Soil Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé de remédiement d'une substance contaminée par du disulfure de carbone consistant à mettre en contact la substance avec du fer. La dégradation du disulfure de carbone par le fer est engendrée par une réaction d'oxydoréduction et résulte en l'obtention de sulfates et de sulfures de fer. La mise en contact du fer et de la substance contaminée peut être effectuée in-situ ou ex-situ. Des procédés in-situ consistent à utiliser des zones réactives telles que des barrières perméables réactives (BPR). L'invention concerne également un procédé de traitement simple mais efficace permettant d'effectuer un remédiement de substances, telles que des eaux usées et l'eau souterraine, contaminées par du disulfure de carbone.
PCT/GB2003/002012 2002-05-10 2003-05-12 Procedes de traitement de disulfure de carbone WO2003095118A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003233892A AU2003233892A1 (en) 2002-05-10 2003-05-12 Methods of carbon disulfide treatment

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0210684.7 2002-05-10
GBGB0210684.7A GB0210684D0 (en) 2002-05-10 2002-05-10 Methods of carbon disulfide treatment

Publications (1)

Publication Number Publication Date
WO2003095118A1 true WO2003095118A1 (fr) 2003-11-20

Family

ID=9936391

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/002012 WO2003095118A1 (fr) 2002-05-10 2003-05-12 Procedes de traitement de disulfure de carbone

Country Status (3)

Country Link
AU (1) AU2003233892A1 (fr)
GB (1) GB0210684D0 (fr)
WO (1) WO2003095118A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8656997B2 (en) 2008-04-14 2014-02-25 Shell Oil Company Systems and methods for producing oil and/or gas
US8869891B2 (en) 2007-11-19 2014-10-28 Shell Oil Company Systems and methods for producing oil and/or gas
US9057257B2 (en) 2007-11-19 2015-06-16 Shell Oil Company Producing oil and/or gas with emulsion comprising miscible solvent
CN113697932A (zh) * 2021-09-15 2021-11-26 同济大学 一种原位削减雨天溢流污染的缓释净化装置及其方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113371810A (zh) * 2021-06-29 2021-09-10 轻工业环境保护研究所 一种膨润土负载硫化纳米铁修复剂的制备方法及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB164183A (en) * 1920-03-24 1921-06-09 Charles Claude Carpenter An improvement in the purification of coal gas and like gases
US4937058A (en) * 1980-04-23 1990-06-26 Rhone-Poulenc Industries Catalytic oxidation of sulfur compounds
DE19530593A1 (de) * 1995-08-21 1997-02-27 Bildungs Und Ingenieurgesellsc Verfahren zur Sanierung schadstoffbelasteter Deponien mit überstehendem Wasser und Mittel zur Durchführung des Verfahrens
DE10000269A1 (de) * 1999-01-08 2000-07-13 Franz Dietrich Oeste Reaktivierbare faserhaltige Wasserfilter
US6283675B1 (en) * 1999-05-28 2001-09-04 Crompton Corporation Method for oxidative destruction of carbon disulfide in soil
US6287472B1 (en) * 1995-10-18 2001-09-11 University Of Waterloo Method for treating contaminated water

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB164183A (en) * 1920-03-24 1921-06-09 Charles Claude Carpenter An improvement in the purification of coal gas and like gases
US4937058A (en) * 1980-04-23 1990-06-26 Rhone-Poulenc Industries Catalytic oxidation of sulfur compounds
DE19530593A1 (de) * 1995-08-21 1997-02-27 Bildungs Und Ingenieurgesellsc Verfahren zur Sanierung schadstoffbelasteter Deponien mit überstehendem Wasser und Mittel zur Durchführung des Verfahrens
US6287472B1 (en) * 1995-10-18 2001-09-11 University Of Waterloo Method for treating contaminated water
DE10000269A1 (de) * 1999-01-08 2000-07-13 Franz Dietrich Oeste Reaktivierbare faserhaltige Wasserfilter
US6283675B1 (en) * 1999-05-28 2001-09-04 Crompton Corporation Method for oxidative destruction of carbon disulfide in soil

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8869891B2 (en) 2007-11-19 2014-10-28 Shell Oil Company Systems and methods for producing oil and/or gas
US9057257B2 (en) 2007-11-19 2015-06-16 Shell Oil Company Producing oil and/or gas with emulsion comprising miscible solvent
US8656997B2 (en) 2008-04-14 2014-02-25 Shell Oil Company Systems and methods for producing oil and/or gas
CN113697932A (zh) * 2021-09-15 2021-11-26 同济大学 一种原位削减雨天溢流污染的缓释净化装置及其方法

Also Published As

Publication number Publication date
AU2003233892A1 (en) 2003-11-11
GB0210684D0 (en) 2002-06-19

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