WO2007085559A1 - Méthode de traitement d'une boue pierreuse - Google Patents

Méthode de traitement d'une boue pierreuse Download PDF

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Publication number
WO2007085559A1
WO2007085559A1 PCT/EP2007/050477 EP2007050477W WO2007085559A1 WO 2007085559 A1 WO2007085559 A1 WO 2007085559A1 EP 2007050477 W EP2007050477 W EP 2007050477W WO 2007085559 A1 WO2007085559 A1 WO 2007085559A1
Authority
WO
WIPO (PCT)
Prior art keywords
value
wet sludge
sludge
oxidising agent
adjusted
Prior art date
Application number
PCT/EP2007/050477
Other languages
English (en)
Inventor
Michael Salzmann
Michel Buser
Original Assignee
Ciba Holding Inc.
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 Ciba Holding Inc. filed Critical Ciba Holding Inc.
Publication of WO2007085559A1 publication Critical patent/WO2007085559A1/fr

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Classifications

    • 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
    • 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
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • 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
    • A62D2101/26—Organic substances containing nitrogen or phosphorus
    • 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
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

Definitions

  • the present invention relates to a method of eliminating NCV and Cr(VI) from stone sludge obtained from washing natural stone and concrete.
  • MSP material separation plant
  • NCV nitrite
  • the tunnel wall is lined with sprayed concrete. Residues of concrete consequently get into the material removed from the excavations.
  • the concrete contains hexavalent chromium (Cr(VI)).
  • NO 2 " and Cr(VI) pass into the water circulation system and into the sludge particles, which are not suitable for further use. The result of this is that NO 2 " and Cr(VI) are also present in the dry-pressed sludge, which needs to be sent for disposal at a landfill site.
  • a treatment for reduction with FeSO 4 is proposed for the detoxification of Cr(VI)-containing stone sludge, for example, in US 5 304 710.
  • Limits are set worldwide for the storage of waste at landfill sites. If the pressed sludge is to be stored at an inert material landfill site, for example, in Switzerland, the concentration of NO 2 " in the eluate must not exceed the value of 0.1 mg/l. The limit for Cr(VI) in the eluate for storage at an inert material landfill site is 0.01 mg/l. Such limits are often exceeded in the pressed sludge. The sludge therefore cannot be stored at an inert material landfill site but needs to be disposed of at a separate landfill site (bioreactor landfill site). Storage at such a landfill site is associated with considerable effort expenditure and appreciable costs. There is accordingly a need for a method by which the sludge produced can be so treated that, at most, extremely small traces of NO 2 " and Cr(VI) are still present after treatment, but are in any event below the legally prescribed limits.
  • reaction unit that is provided with means of ensuring thorough mixing and in which treatment with specific chemicals can be carried out. It is unimportant whether that reaction unit is designed for batchwise or for continuous operation. It is merely necessary to ensure that thorough mixing that is as uniform as possible is achieved, for example by means of a stirring device. Suitable means and measures are known to the person skilled in the art.
  • the present invention relates to a method of eliminating NO 2 " and Cr(VI) in wet sludge obtained from washing natural stone and concrete, which comprises the steps of a) adjusting the pH value to less than pH 4 using an inorganic acid and allowing reaction to take place; b) adding an oxidising agent and allowing the mixture to react; c) adjusting the pH value to from pH 6 to 12; and d) separating the solid phase from the liquid phase.
  • the concentrations of NO 2 " prior to treatment are in the range from 0.1 to 1000 mg/l and those of Cr(VI) from 0.01 mg/l to 10 mg/l. It is, however, also possible, using the present method, to treat and eliminate concentrations departing from those ranges.
  • the wet sludge originates from the excavated stone material from tunnel construction.
  • the wet sludge has a dry substance content of from 1 to 65 percent by weight, preferably from 10 to 60 and especially from 30 to 50 percent by weight.
  • wet sludge should still be readily pumpable and stirrable. If necessary, additional water may be added in order to ensure improved processability.
  • the wet sludge Prior to treatment, the wet sludge in many cases has a pH value of from 3 to 14, preferably from 6 to14 and especially from 10 to 13.
  • step a) The nature of the inorganic acid that is added in step a) is not important per se.
  • the addition of H 2 SO 4 , HCI, HI, HCIO 4 , HBr, HNO 3 or H 2 SO 3 has proved advantageous. Special preference is given to the use of H 2 SO 4 .
  • the amount of acid added is, in principle, governed by the initial pH of the wet sludge and the desired pH that is to be set. Normally, from 0.05 mol H + to 0.7 mol H + needs to be added per kg of wet sludge.
  • the acid may be added in one or more batches or continuously over a specific period of time.
  • the addition can be carried out, for example, for from 1 minute up to 1 hour, with preference being given to a range of from 5 to 15 minutes.
  • the pH value is preferably adjusted to from 1 to 3, especially to pH 2.
  • reaction time in step a) may vary within wide limits. Typically, it is from 5 minutes to 2 hours, with preference being given to from 5 to 30 minutes.
  • the temperature in reaction step a) may vary within a wide range, for example from 5 to 95°C; it is preferably about ambient temperature, for example from 10°C to 30°C. During the reaction, heat may be evolved, resulting in an increase in temperature.
  • the external pressure is not in itself important for the reaction, but the procedure is preferably carried out at the prevailing normal pressure. - A -
  • the oxidising agent used is, for example, NH 2 SO 3 H, H 2 O 2 , NaOCI, an oxide of chlorine (CI x Oy), KMnO 4 , Na 2 CO 3 x3H 2 O, NaBO 2 (OH) 2 , HOCI, NaO 2 , BaO 2 , O 3 , NO x or 1O 3 H.
  • the oxidising agent used is preferably NH 2 SO 3 H or H 2 O 2 , especially H 2 O 2 .
  • the amount of oxidising agent that needs to be used depends largely on the amount of of NO 2 " and of other oxidisable substances that may be present in the wet sludge, as well as on the chosen oxidising agent.
  • the oxidising agent is added, for example, in an amount of from 0.01 mol/kg of dry substance to 0.5 mol/kg of dry substance, preferably from 0.1 to 0.5 mol/kg of dry substance.
  • the oxidising agent may likewise be added in one or more batches or continuously over a specific period of time.
  • the addition can be carried out, for example, for from 1 minute up to 1 hour, with preference being given to a range of from 5 to 15 minutes.
  • reaction time in step b) may likewise vary within wide limits. Typically, it is from 5 minutes to 2 hours, with preference being given to from 5 minutes to 30 minutes.
  • step c) the pH value is adjusted using, for example, NaOH, Ca(OH) 2 , CaO, Ba(OH) 2 , BaO, NH 3 , CaCO 3 , Na 2 CO 3 , MgCO 3 or Na 3 PO 4 .
  • the pH is adjusted using NaOH, CaO Or Ca(OH) 2 .
  • the addition may in this instance, too, be carried out in one or more batches or continuously over a specific period of time.
  • the addition can be carried out, for example, for from 1 minute up to 1 hour, with preference being given to a range of from 5 to 15 minutes.
  • the pH value in step c) may be adjusted to a value of from pH 6 to 12.
  • it is adjusted to a value of from 6 to 8, especially from 6 to 7.
  • the separation of the solid phase from the liquid phase can be carried out using any known means.
  • Examples are filters, presses, suction filters or pressure suction filters. Such means are known to the person skilled in the art and are widely used in material separation.
  • all of the process steps a) to d) are carried out at a temperature of from 10°C to 50°C and under normal pressure conditions.
  • wet sludge from a Swiss tunnel-construction project is used.
  • the wet sludge is pumped into a container having a stirring device: wet sludge 375 kg dry substance 40% pH 12.2
  • Step a 1 1.5 kg of H 2 SO 4 (96%) are added to the reaction mass over a period of 10 minutes with continuous stirring. pH after addition: 2.
  • Step b
  • the wet sludge specimen is dewatered by means of filtration.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)

Abstract

La présente invention concerne une méthode d'élimination de NO2 et de Cr(VI) d'une boue pierreuse obtenue par rinçage de pierre naturelle et de béton, résultant par exemple d’une excavation lors de la construction d'un tunnel.
PCT/EP2007/050477 2006-01-27 2007-01-18 Méthode de traitement d'une boue pierreuse WO2007085559A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06100967.6 2006-01-27
EP06100967 2006-01-27

Publications (1)

Publication Number Publication Date
WO2007085559A1 true WO2007085559A1 (fr) 2007-08-02

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ID=36084180

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/050477 WO2007085559A1 (fr) 2006-01-27 2007-01-18 Méthode de traitement d'une boue pierreuse

Country Status (1)

Country Link
WO (1) WO2007085559A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115810A1 (fr) * 2009-04-09 2010-10-14 Wieland Dental + Technik Gmbh & Co. Kg Procédé de traitement de déchets à teneur en nitrite
CN111229815A (zh) * 2020-02-13 2020-06-05 华南理工大学 一种修复铬污染场地土壤的方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5235449A (en) * 1975-09-16 1977-03-18 Giken Kogyo Kk Disposal method for industrial waste containing compound chromium
US4260491A (en) * 1978-11-15 1981-04-07 Amchem Products, Inc. Chrome removal waste treatment process
US5304710A (en) * 1993-02-18 1994-04-19 Envar Services, Inc. Method of detoxification and stabilization of soils contaminated with chromium ore waste
DE4319974A1 (de) * 1993-06-14 1994-12-15 Lfu Labor Fuer Umweltanalytik Verfahren zur Verringerung der Schadstoffgefährlichkeit von Cr(VI)-kontaminierten festen und flüssigen Abfallstoffen
US5415848A (en) * 1993-06-24 1995-05-16 General Electric Company Method for removal of hexavalent chromium from a solution
EP0716892A1 (fr) * 1994-12-14 1996-06-19 ÖKOZENT Gesellschaft für Ökologieberatung Gesellschaft m.b.H. Procédé pour le traitement de déchets
EP0829276A1 (fr) * 1996-09-12 1998-03-18 Revatech S.A. Procédé de solidification de résidus d'épuration des fumées d'incinérateurs d'ordures ménagères et de déchets industriels
US5967965A (en) * 1997-08-29 1999-10-19 Envirem Method for treating soil contaminated with heavy metals
WO2001053204A1 (fr) * 2000-01-19 2001-07-26 Ari Pekka Syynimaa Procede de traitement de composes de chrome hexavalent dans des eaux usees provenant de traitements de metaux

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5235449A (en) * 1975-09-16 1977-03-18 Giken Kogyo Kk Disposal method for industrial waste containing compound chromium
US4260491A (en) * 1978-11-15 1981-04-07 Amchem Products, Inc. Chrome removal waste treatment process
US5304710A (en) * 1993-02-18 1994-04-19 Envar Services, Inc. Method of detoxification and stabilization of soils contaminated with chromium ore waste
DE4319974A1 (de) * 1993-06-14 1994-12-15 Lfu Labor Fuer Umweltanalytik Verfahren zur Verringerung der Schadstoffgefährlichkeit von Cr(VI)-kontaminierten festen und flüssigen Abfallstoffen
US5415848A (en) * 1993-06-24 1995-05-16 General Electric Company Method for removal of hexavalent chromium from a solution
EP0716892A1 (fr) * 1994-12-14 1996-06-19 ÖKOZENT Gesellschaft für Ökologieberatung Gesellschaft m.b.H. Procédé pour le traitement de déchets
EP0829276A1 (fr) * 1996-09-12 1998-03-18 Revatech S.A. Procédé de solidification de résidus d'épuration des fumées d'incinérateurs d'ordures ménagères et de déchets industriels
US5967965A (en) * 1997-08-29 1999-10-19 Envirem Method for treating soil contaminated with heavy metals
WO2001053204A1 (fr) * 2000-01-19 2001-07-26 Ari Pekka Syynimaa Procede de traitement de composes de chrome hexavalent dans des eaux usees provenant de traitements de metaux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 001, no. 093 (M - 032) 26 August 1977 (1977-08-26) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115810A1 (fr) * 2009-04-09 2010-10-14 Wieland Dental + Technik Gmbh & Co. Kg Procédé de traitement de déchets à teneur en nitrite
CN111229815A (zh) * 2020-02-13 2020-06-05 华南理工大学 一种修复铬污染场地土壤的方法

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