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WO1999066989A1 - Method for the treatment of waste - Google Patents

Method for the treatment of waste Download PDF

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Publication number
WO1999066989A1
WO1999066989A1 PCT/NL1999/000390 NL9900390W WO9966989A1 WO 1999066989 A1 WO1999066989 A1 WO 1999066989A1 NL 9900390 W NL9900390 W NL 9900390W WO 9966989 A1 WO9966989 A1 WO 9966989A1
Authority
WO
WIPO (PCT)
Prior art keywords
mono
waste
paste
phosphate
calcium hydroxide
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/NL1999/000390
Other languages
French (fr)
Inventor
Aldo Bennini
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.)
KIROR BV
Original Assignee
KIROR BV
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 KIROR BV filed Critical KIROR BV
Priority to AU46586/99A priority Critical patent/AU736283B2/en
Priority to PL99345201A priority patent/PL345201A1/en
Publication of WO1999066989A1 publication Critical patent/WO1999066989A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • 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
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • 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
    • A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
    • 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
    • A62D2101/24—Organic substances containing heavy 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
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • the present invention relates to a method for the treatment of waste contaminated with heavy metals and for rendering the latter inert. It is known that specific harmful and/or toxic materials which originate from various sources and which contain heavy metals, such as arsenic, cadmium, chromium, mercury, lead, selenium or tellurium, and which in a transfer test have the tendency to yield an eluate that does not comply with the acceptance limits that have been laid down, are stored in protected dumps for hazardous toxic waste.
  • heavy metals such as arsenic, cadmium, chromium, mercury, lead, selenium or tellurium
  • the interfering ions chlorides
  • the present invention is characterised in that the following steps are carried out: - determination of the acidity of the contaminated material, partial neutralisation of the material if the latter is acidic (pH between 0.5 and 3), the addition of a solution of orthophosphoric acid and an alkali metal salt thereof in water, forming a homogeneous paste from the mixture formed, - the addition of calcium oxide (CaO) and/or calcium hydroxide (Ca(OH) 2 ) to the paste, and allowing the paste to dry in the air.
  • steps are carried out: - determination of the acidity of the contaminated material, partial neutralisation of the material if the latter is acidic (pH between 0.5 and 3), the addition of a solution of orthophosphoric acid and an alkali metal salt thereof in water, forming a homogeneous paste from the mixture formed, - the addition of calcium oxide (CaO) and/or calcium hydroxide (Ca(OH) 2 ) to the paste, and allowing the paste to dry in the air.
  • CaO
  • the calcium hydroxide or the calcium oxide can be added in powder form in an amount of between 50 and 350 kg per tonne of waste to be rendered inert. Good results have been obtained with pulverulent calcium oxide or calcium hydroxide of the type that is suitable for building applications.
  • the concentrated aqueous solution of orthophosphoric acid and of the alkali metal salt thereof can be the commercially available "Fissa Met" solution for rendering inert, which contains orthophosphoric acid and mono-, di- and trisodium phosphate (NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 ), mono-, di- and tripotassium phosphate (KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 ), or mono-, di- and tricalcium phosphate (CaHPO , Ca(H 2 PO 4 ) 2 , Ca 3 (PO 4 ) 2 ), in the anhydrous form or in the form of the hydrate and which is used in an amount of between 5 and 150 litres per tonne of waste to be rendered inert.
  • “Fissa Met” solution for rendering inert which contains orthophosphoric acid and mono-, di- and trisodium phosphate (NaH 2 PO 4 , Na 2 HPO 4 , Na 3
  • the method according to the present invention is highly versatile and can be used on waste from various sources, such as metal slags, demolition debris or scrap, ash from incinerators or solid industrial and inorganic chemical waste material from towns, special installations, hospitals, industry and the like.
  • the method according to the invention for rendering waste inert was used on fly ash originating from the incineration of waste from a hospital. This material was placed in a mixer. Calcium hydroxide (slaked lime) in an amount of 90 kg per tonne waste was added by pneumatic means from suitable silos simultaneously with 50 litres of the "Fissa Met" solution for rendering inert, which is a concentrated aqueous solution of orthophosphoric acid and of the disodium hydrogen salt thereof (disodium monohydrogen phosphate (Na 2 F£PO )), which was added from another container, together with just enough water to guarantee intimate contact of the mixture. The mixture had to remain in a stirrable composition and was stirred for several minutes.
  • the wet mixture was placed on a suitable surface so that said mixture was able to dry completely, or said mixture was dried immediately in a stream of hot air (where heat recovery was possible).

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)

Abstract

The invention relates to a method for the treatment of waste contaminated with heavy metals. Said contaminants are rendered inert by carrying out the following steps: determination of the acidity of the contaminated material, partial neutralisation of the material if the latter is acid, the addition of a solution of orthophosphoric acid and an alkali metal salt thereof in water, forming a homogeneous paste from the mixture formed, the addition of calcium oxide (CaO) and/or calcium hydroxide (Ca(OH)2) to the paste, and allowing the paste to dry in the air. The material thus obtained is suitable for storage in accordance with local environmental legislation.

Description

Method for the treatment of waste
The present invention relates to a method for the treatment of waste contaminated with heavy metals and for rendering the latter inert. It is known that specific harmful and/or toxic materials which originate from various sources and which contain heavy metals, such as arsenic, cadmium, chromium, mercury, lead, selenium or tellurium, and which in a transfer test have the tendency to yield an eluate that does not comply with the acceptance limits that have been laid down, are stored in protected dumps for hazardous toxic waste. Numerous technologies are disclosed in the prior art with which metals can be immobilised in stable matrices, as a result of which they acquire chemically inert properties and as a result of which the transfer thereof can be prevented, so that this type of waste can be dumped under less stringent conditions (the transfer tests with these materials fall within the limits imposed by national and international legislation). Frequently these types of waste have a composition which requires large quantities of reagents, such as, for example, cement, to obtain an adequate degree of stabilisation, or for which expensive substances have to be used in combination with long periods of action. Other solidification techniques make use of additives such as slags, finely ground brick, grit and sand mixed with bentonite, as a result of which an excessive increase in the final weight and volume takes place, and moderate results are obtained in respect of restricting transfer of the metals.
To reduce the proportion of binder when rendering inert flue gas produced in the mining industry, the interfering ions (chlorides) are washed with water.
A number of the systems that have been used recently use aqueous solutions of chemical products which are particularly expensive, as a result of which inadequate data are known with regard to the physical and the physico-chemical conditions which are necessary for the various types of waste or with regard to the quantities which have to be used in order to achieve the desired result.
There is thus a need, in special cases, to be able to use a versatile method with which special pre-treatments are not necessary and with which inexpensive reagents available on a large scale can be used, which reagents can be added in limited quantities in order to minimise the increase in the weight finally to be dumped.
By means of the present invention it is possible to comply with the abovementioned requirements as well as to obtain a number of other advantages which will become clear below.
To this end the present invention is characterised in that the following steps are carried out: - determination of the acidity of the contaminated material, partial neutralisation of the material if the latter is acidic (pH between 0.5 and 3), the addition of a solution of orthophosphoric acid and an alkali metal salt thereof in water, forming a homogeneous paste from the mixture formed, - the addition of calcium oxide (CaO) and/or calcium hydroxide (Ca(OH)2) to the paste, and allowing the paste to dry in the air.
The calcium hydroxide or the calcium oxide can be added in powder form in an amount of between 50 and 350 kg per tonne of waste to be rendered inert. Good results have been obtained with pulverulent calcium oxide or calcium hydroxide of the type that is suitable for building applications.
The concentrated aqueous solution of orthophosphoric acid and of the alkali metal salt thereof can be the commercially available "Fissa Met" solution for rendering inert, which contains orthophosphoric acid and mono-, di- and trisodium phosphate (NaH2PO4, Na2HPO4, Na3PO4), mono-, di- and tripotassium phosphate (KH2PO4, K2HPO4, K3PO4), or mono-, di- and tricalcium phosphate (CaHPO , Ca(H2PO4)2, Ca3(PO4)2), in the anhydrous form or in the form of the hydrate and which is used in an amount of between 5 and 150 litres per tonne of waste to be rendered inert.
The method according to the present invention is highly versatile and can be used on waste from various sources, such as metal slags, demolition debris or scrap, ash from incinerators or solid industrial and inorganic chemical waste material from towns, special installations, hospitals, industry and the like.
A description of the general characteristics according to the present invention has been given above. The characteristics, advantages and the way in which the method has to be used will be better understood with reference to the appended example, which gives a detailed description of a specific embodiment. Example
The method according to the invention for rendering waste inert was used on fly ash originating from the incineration of waste from a hospital. This material was placed in a mixer. Calcium hydroxide (slaked lime) in an amount of 90 kg per tonne waste was added by pneumatic means from suitable silos simultaneously with 50 litres of the "Fissa Met" solution for rendering inert, which is a concentrated aqueous solution of orthophosphoric acid and of the disodium hydrogen salt thereof (disodium monohydrogen phosphate (Na2F£PO )), which was added from another container, together with just enough water to guarantee intimate contact of the mixture. The mixture had to remain in a stirrable composition and was stirred for several minutes.
At the end of this step the wet mixture was placed on a suitable surface so that said mixture was able to dry completely, or said mixture was dried immediately in a stream of hot air (where heat recovery was possible).
When the material obtained by the abovementioned treatment was subjected to a leaching test, it was found that the release of lead, cadmium, copper and selenium remained within the acceptable limits to enable the material to be dumped immediately without further treatment in a protected dump.
The initial original values of the metal concentrations in the eluate with a solution of 0.5M acetic acid before and after treatment are given for comparative purposes in appended Tables 1 and 2. "T.Q." in Table 2 gives the initial concentration of the heavy metals.
Table 1
Figure imgf000006_0001
Table 2
Figure imgf000007_0001

Claims

Claims
1. Method for the treatment of waste contaminated with heavy metals, characterised in that the following steps are carried out: - determination of the acidity of the contaminated material, partial neutralisation of the material if the latter is acidic, the addition of a solution of orthophosphoric acid and an alkali metal salt thereof in water, forming a homogeneous paste from the mixture formed, - the addition of calcium oxide (CaO) and/or calcium hydroxide (Ca(OH)2) to the paste, and allowing the paste to dry in the air.
2. Method according to Claim 1, characterised in that the contaminated material is stirred.
3. Method according to Claim 1 or 2, characterised in that between 50 kg and 350 kg pulverulent calcium oxide and/or calcium hydroxide is added per tonne of waste to be rendered inert.
4. Method according to one of the preceding claims, characterised in that the pulverulent calcium oxide or the calcium hydroxide is of the type that is suitable for building applications.
5. Method according to one of the preceding claims, characterised in that the solution of orthophosphoric acid and an alkali metal salt thereof contains mono-, di- and trisodium phosphate and/or mono-, di- and tripotassium phosphate and/or mono-, di- and tricalcium phosphate, in the anhydrous form or in the form of the hydrate.
6. Method according to Claim 5, characterised in that the mono-, di- and trisodium phosphate and/or mono-, di- and tripotassium phosphate and/or mono-, di- and tricalcium phosphate are used in an amount of between 5 1 and 150 1 per tonne of waste to be rendered inert.
PCT/NL1999/000390 1998-06-25 1999-06-24 Method for the treatment of waste Ceased WO1999066989A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU46586/99A AU736283B2 (en) 1998-06-25 1999-06-24 Method for the treatment of waste
PL99345201A PL345201A1 (en) 1998-06-25 1999-06-24 Method for the treatment of waste

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1009490 1998-06-25
NL1009490A NL1009490C8 (en) 1998-06-25 1998-06-25 PROCESS FOR TREATMENT OF WASTE.

Publications (1)

Publication Number Publication Date
WO1999066989A1 true WO1999066989A1 (en) 1999-12-29

Family

ID=19767373

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000390 Ceased WO1999066989A1 (en) 1998-06-25 1999-06-24 Method for the treatment of waste

Country Status (5)

Country Link
AU (1) AU736283B2 (en)
NL (1) NL1009490C8 (en)
PL (1) PL345201A1 (en)
RU (1) RU2203709C2 (en)
WO (1) WO1999066989A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10044326A1 (en) * 2000-09-07 2002-04-04 Grillo Werke Ag Reduction of the residual solubility of sulfuric acid sludge, and other residues containing lead, involves converting lead to phosphate at an alkaline pH adjusted with alkali without forming soluble phosphates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737356A (en) * 1985-11-18 1988-04-12 Wheelabrator Environmental Systems Inc. Immobilization of lead and cadmium in solid residues from the combustion of refuse using lime and phosphate
EP0568903A1 (en) * 1992-04-27 1993-11-10 SAMAG MASCHINENFABRIK SANGERSHAUSEN GmbH i.K. Process for treatment of materials containing heavy metals
DE4217133A1 (en) * 1992-05-23 1993-11-25 Asea Brown Boveri Minimising dust and slag to remove chloride, heavy metal(s) and salt(s) - by washing with organic acid, filtering and adding quicklime or slaked lime to solid to give hydraulic binder properties
GB2277515A (en) * 1993-03-15 1994-11-02 Sevenson Environmental Service Treating metal-bearing waste
WO1997031874A1 (en) * 1996-02-28 1997-09-04 Solvay (Societe Anonyme) Ash inerting method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3851832T2 (en) * 1988-03-31 1995-02-09 Wheelabrator Environment Syst Immobilization of lead and cadmium in waste incineration residues using lime and phosphate.
US5037479A (en) * 1990-04-20 1991-08-06 Rmt, Inc. Method for reduction of heavy metal leaching from hazardous waste under acidic and nonacidic conditions
GB9124353D0 (en) * 1991-11-15 1992-01-08 Albright & Wilson Immobilisation of metal contaminants from a liquid to a solid metal
DE4230223A1 (en) * 1992-09-10 1994-03-17 Hoechst Ag Process and plant for removing lead, cadmium and zinc from dusts
WO1996020049A1 (en) * 1994-12-28 1996-07-04 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Waste disposal material and method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737356A (en) * 1985-11-18 1988-04-12 Wheelabrator Environmental Systems Inc. Immobilization of lead and cadmium in solid residues from the combustion of refuse using lime and phosphate
EP0568903A1 (en) * 1992-04-27 1993-11-10 SAMAG MASCHINENFABRIK SANGERSHAUSEN GmbH i.K. Process for treatment of materials containing heavy metals
DE4217133A1 (en) * 1992-05-23 1993-11-25 Asea Brown Boveri Minimising dust and slag to remove chloride, heavy metal(s) and salt(s) - by washing with organic acid, filtering and adding quicklime or slaked lime to solid to give hydraulic binder properties
GB2277515A (en) * 1993-03-15 1994-11-02 Sevenson Environmental Service Treating metal-bearing waste
WO1997031874A1 (en) * 1996-02-28 1997-09-04 Solvay (Societe Anonyme) Ash inerting method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10044326A1 (en) * 2000-09-07 2002-04-04 Grillo Werke Ag Reduction of the residual solubility of sulfuric acid sludge, and other residues containing lead, involves converting lead to phosphate at an alkaline pH adjusted with alkali without forming soluble phosphates
DE10044326B4 (en) * 2000-09-07 2004-04-22 Grillo-Werke Ag Process for reducing the residual solubility of lead-containing sludges and other residues

Also Published As

Publication number Publication date
PL345201A1 (en) 2001-12-03
NL1009490C2 (en) 2000-01-04
RU2203709C2 (en) 2003-05-10
AU736283B2 (en) 2001-07-26
AU4658699A (en) 2000-01-10
NL1009490C8 (en) 2002-12-05

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