WO1995011865A1 - Materiaux ceramiques et leur procede de fabrication - Google Patents

Materiaux ceramiques et leur procede de fabrication Download PDF

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Publication number
WO1995011865A1
WO1995011865A1 PCT/GB1994/002352 GB9402352W WO9511865A1 WO 1995011865 A1 WO1995011865 A1 WO 1995011865A1 GB 9402352 W GB9402352 W GB 9402352W WO 9511865 A1 WO9511865 A1 WO 9511865A1
Authority
WO
WIPO (PCT)
Prior art keywords
ash
mixture
sewage sludge
ceramic
firing
Prior art date
Application number
PCT/GB1994/002352
Other languages
English (en)
Inventor
Michael Anderson
Glynn Skerratt
Colin Birchall
Original Assignee
British Technology Group Limited
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 British Technology Group Limited filed Critical British Technology Group Limited
Priority to AU79980/94A priority Critical patent/AU7998094A/en
Priority to GB9608781A priority patent/GB2297971B/en
Publication of WO1995011865A1 publication Critical patent/WO1995011865A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/027—Lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/135—Combustion residues, e.g. fly ash, incineration waste
    • C04B33/1355—Incineration residues
    • C04B33/1357—Sewage sludge ash or slag
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This invention relates to ceramic material and a method of manufacturing same, and is particularly concerned with ceramic articles, such as paving tiles, wall tiles and bricks, and also to a method of manufacturing such articles.
  • the treatment of waste water generally involves screening the sewage and then directing this to storage/settlement tanks where sewage sludge settles out. After any necessary thickening, the sewage sludge may be fed to filter presses, which form it into sludge cake.
  • GB-B-2061241 there is disclosed the non-conventional manufacture of bricks from a mixture containing pulverised fuel ash (P.F.A.) and clay, the manufacturing method including, in one embodiment, mixing with the P.F.A. and the clay, a predetermined quantity of fuel.
  • P.F.A. pulverised fuel ash
  • One form of a suitable low grade fuel mentioned is raw sewage sludge.
  • a method of manufacturing ceramic material comprising mixing together pulverised fuel ash (P.F.A.), sewage sludge ash and carbon containing material, and firing the mixture so that combustion gases from the combustible carbon containing material are trapped within the fired mixture.
  • ceramic material formed by firing a mixture of P.F.A., sewage sludge ash and combustible carbon containing material.
  • a method of manufacturing a ceramic article comprising mixing together pulverised fuel ash (P.F.A.) and sewage sludge ash, shaping the mixed material into the form of the ceramic article to be produced, and firing the shaped mixture to produce vitrification.
  • P.F.A. pulverised fuel ash
  • the mixture is shaped by pressing.
  • a ceramic article formed by firing a mixture of P.F.A. and sewage sludge ash in the shape of the article.
  • said ceramic article is a paving tile for use as flooring for concourses and walkways, and said tile may have a non-slip surface.
  • said article is a brick or a wall tile. It has been found by the inventors that finely milled sewage sludge clinker ash from multiple hearth incinerators or the fine ash from fluidised bed incinerators fuses over a similar temperature range to many brickmaking clays. However the ash has also been found to display unsatisfactory firing properties if used alone. Most seriously, it has been found to possess a narrow firing range and exhibit excessive shrinkage.
  • the inventors found that discs of sewage sludge ash intermixed with pulverised fuel ash (P.F.A.), when fired over the same temperature range, produced acceptable shrinkage, attractively coloured, durable products.
  • P.F.A. pulverised fuel ash
  • the glassy melt phase which develops during firing can encapsulate, and thus immobilise, the heavy metals present in the sewage sludge ash, thereby preventing their subsequent release, by leaching of the heavy metals, which may occur with standard leaching tests on the sewage sludge itself.
  • Influent sewage to sewage works comprises both domestic and industrial effluent as well as some infiltration water, and undergoes both physical settlement and biological oxidation during treatment, and produces two products.
  • liquid effluent is discharged to a watercourse or to the sea.
  • the composition of this sludge will depend upon the precise treatment processes and on the nature of the sewage being treated, particularly with respect to the input ratio of domestic to industrial sewage.
  • Table 1 shows a typical metal analysis of raw sewage sludge.
  • Raw sewage sludge is usually made up of approximately 2-8% dry solid matter and 92-98% water. Of this dry solid matter approximately 20- 35% is mineral, 65-80% organic and volatile matter, 3-5% nitrogen and 2-3% phosphates. Sewage sludge from some highly industrialised areas may well have much greater heavy metal concentrations.
  • DOMESTIC DOMESTIC/INDUSTRI ⁇ L
  • the firing of the mixture immobilises the metals, primarily the heavy metals, therein, and thus it is the metal concentration of the sludge, and the ash, that is of prime concern in relation to the present invention.
  • the phosphorus content may also be of interest, however, with regard to fluxing properties.
  • the sewage sludge Before the sewage sludge is incinerated, it is dewatered to decrease the water content from about 95% to approximately 70-75%. This increases the dry solids concentration and produces 'sludge cake'. This is then burnt and loses the organic matter present (approximately 75% of the mass of the sludge cake) leaving the mineral ash (approximately 25% of the mass).
  • the composition of the ash will clearly depend on the composition of the initial sludge. Table 2 shows some general data on an analysis of typical ash from sewage sludge with a relatively high metals level.
  • TYPICAI PUBI.ISHFP VALUES ASSOCIATED WITH THF ANALYSIS OF SFWAGF SLUDGE INCINFRATOR ASH
  • the main ceramic product will, at least initially, be a paving tile for use as flooring for concourses and walkways. This type of product was selected primarily to minimise any customer resistance to products with "sewage origin connotations", it being felt that this would be at a minimum with a product used for walking on, rather than, for example, a wall tile. Of course other ceramic articles, such as bricks, can be produced instead.
  • P.F.A. size classification of P.F.A.
  • a suitable batch-blending system is used.
  • One such system is in the form of a large capacity silo with air-jets inside. In use the jets create a convection action which blend the ash charged into the silo into a homogeneous mixture, which can then be used in the mixture to produce the tile or other ceramic article.
  • the P.F.A. which may or may not have been size classified, is mixed with the sewage sludge ash in correct proportions, along with an appropriate amount of binder material, e.g. clay, and water.
  • binder material e.g. clay
  • the mixture is then formed into the required shape by pressing, this being more suitable than extrusion or roller bat due to the non-plastic nature of the body.
  • the forming, drying (if applicable) and firing properties can be monitored and evaluated to determine the most suitable mix-design route to be followed.
  • Drying may or may not constitute a stage in the manufacturing process, depending on the method of firing. If the tiles are fired one-high in a slot kiln where they move forward on a conveyor, they could be taken straight off the production machine and dry in the early zone of the kiln as they are conveyed to the firing zone. If alternatively they are to be fired in a kiln which requires them to be stacked-up in piles, they would have to be dry to support the loading weight. Thus drying is an optional stage of production dependent on the firing method to be employed.
  • I.S.S.A. may be size classified before mixing it with the P.F.A. This is more likely to be the case with multiple hearth ash, which needs prior grinding to a powder before mixing with the P.F.A., than with fluidised - ash. This latter ash has individual ash particles which appear very friable and possibly prone to break-down during mixing with the P.F.A. Accordingly they may well break-down in the rough air-turbulence occurring inside an air classifier. However it is considered that the behaviour of I.S.S.A. is unlikely to be size-dependent in the way that P.F.A. is. Instead, any difference in melting behaviour will be dependent on composition variations, i.e.
  • This incineration also sinters together the non-combustible residue in the raw sewage into a 'char-like' form. In this condition it has only limited mechanical cohesion and is consequently still reasonably friable, but it is readily transportable and mixable in suitable tile/brickmaking equipment with the P.F.A. and binder.
  • the P.F.AVl.S.S.A. mixture ready for firing would be shaped, preferably in a hydraulic press.
  • the terms 'shape', 'shaping' and 'shaped' in relation to the mixture include in their respective scopes the extrusion and soft-mud making methods also used for making conventional bricks and tiles.
  • Physical tests on the product can include bulk density, shrinkage, strength, water absorption and textural character,its microstructure being examined by an optical microscope and a scanning electron microscope.
  • a study of the firing behaviour can involve dilatometry, Differential Thermal Analysis Thermo Gravimetric Analysis and thermal shock determination.
  • the product will be tested for compliance with any relevant British Standard, e.g. BS 1286: 1974, covering clay tiles.
  • a key area of product testing is in relation to the immobilisation within the ceramic product of the heavy metals contained in the sludge ash. As mentioned previously, these can leach from the ash itself but are encapsulated in the ceramic product. Chemical leaching studies can be carried out to determine the degree of heavy metal encapsulation, and thus the ability of the product to effect such immobilisation.
  • Tests can be based upon the EPA Extraction Procedure Toxicity Test and the EPA Toxicity Characteristics Leaching Procedure, and the DEV - S4 procedure for example.
  • the sewage sludge ash is preferably produced by using a fluidised bed incinerator, this giving an ash of fine quality. However the ash can also be produced by a multi-hearth incinerator.
  • the clinker produced can be reduced to a fine powder of the same size as that produced from a fluidised bed incinerator by milling. The firing of the mixture containing P.F.A.
  • a typical mixture ready for firing has the following percentage by-weight composition:
  • F.B.A. Furnace Bottom Ash
  • F.B.A. is composed of approximately 20% of ash which does not escape a power station boiler, but falls to the floor and is quenched with water into a mainly glassy slag.
  • the F.B.A. performs useful work as a 'grog' or filler in ceramic products that are of very fine particle composition, as it serves to open the body up for rapid oxidation.
  • a typical mixture incorporating F.B.A. could be as below, with the percentage by-weight being indicated: 12
  • Binders other than sodium silicate could be used, for example clay or starch, or possibly phosphoric acid, lignosulphonate etc.
  • the invention is also applicable to the production of ceramic material in the form of lightweight aggregate comprising P.F.A. and I.S.S.A.
  • the method of manufacture would be similar to that used in the Lytag (Registered Trade Mark) process where pelletised P.F.A. is 'flash-fired' into a lightweight ceramic aggregate. All the considerations mentioned above in relation to the production of a ceramic article can apply to the production of this aggregate, including sizing of ash. However the aggregate can probably be manufactured using P.F.A. which is subject to neither size classification nor batch- blending.
  • the pellets are formed by rolling and accretion, building up coating after coating of ash around a moist 'seed' pellet, and not pressed to a close dimension as with the ceramic article mixture, which requires the grading of the mixture to be consistent to produce products of invariable dimensions.
  • the P.F.AJI.S.S.A. mixture has a small quantity of pulverised coal or other combustible carbon containing material added to it. The mixture is then pelletised in the same way as for producing Lytag conveyed on a sinter-strand. Before they reach a gas firing hood their temperature is well below the combustion temperature of the carbon within them.
  • the aggregate pellet is 'bloated' by the generation of such combustion gases, produced from the coal or other carbon providing material in the mixture, which gases are trapped by the formation of a surface skin due to fusion, which causes the body to 'bloat' as the pressure of the combustion gases expands the 'plastic' enclosing skin, producing an open-textured or porous interior sealed within a semi-vitreous outer shell.
  • one component is P.F.A. and water, with the P.F.A. ideally containing up to 8% unburned carbon for the sintering process. Any diff ⁇ cie ⁇ cy can be corrected by adding the appropriate amount of pulversised coal/breeze at the mixing stage.
  • the P.F.AJI.S.S.A. 'Lytag-like' product would be made up of P.F.A. and I.S.S.A. in a 50:50 ratio, instead of P.F.A. alone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Environmental & Geological Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)

Abstract

Cette invention se rapporte à un procédé consistant à mélanger de la cendre de boues résiduaires incinérées (ISSA) avec de la cendre de combustible pulvérisée (PFA) afin d'obtenir un matériau brut approprié à la fabrication d'articles de construction tels que des briques, des tuiles ou des agrégats d'argile cuite expansée. Lors de l'incinération des boues résiduaires afin de réduire leur volume d'encombrement avant leur élimination, se pose le problème de la résistance à la destruction par combustion des métaux lourds normalement présents dans les boues brutes, ces métaux se retrouvant ensuite concentrés dans la cendre formée en tant que résidu de la combustion. Ceci est indésirable tant du point de vue de l'environnement que du point de vue de la santé. La présente invention résout ce problème en utilisant une technique destinée à piéger de telles substances toxiques à l'intérieur du produit brûlé, minimisant ainsi leur libération. En outre, puisque les métaux lourds sont piégés dans la masse de la brique, de la dalle ou de l'agrégat, ils ne se séparent pas par lessivage de la matrice de l'article de construction et par conséquent peuvent être utilisés dans une gamme plus large d'applications.
PCT/GB1994/002352 1993-10-26 1994-10-26 Materiaux ceramiques et leur procede de fabrication WO1995011865A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU79980/94A AU7998094A (en) 1993-10-26 1994-10-26 Ceramic materials and method of manufacturing such materials
GB9608781A GB2297971B (en) 1993-10-26 1994-10-26 Ceramic materials and method of manufacturing such materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9322067A GB9322067D0 (en) 1993-10-26 1993-10-26 Ceramic materials and method of manufacturing such materials
GB9322067.1 1993-10-26

Publications (1)

Publication Number Publication Date
WO1995011865A1 true WO1995011865A1 (fr) 1995-05-04

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AU (1) AU7998094A (fr)
GB (1) GB9322067D0 (fr)
WO (1) WO1995011865A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2020429B1 (en) * 2018-02-13 2019-08-20 Dukeron B V Process for preparing a ceramic article containing domestic sludge
WO2019160408A1 (fr) 2018-02-13 2019-08-22 Dukeron B.V. Procédé de préparation d'un article en céramique contenant des boues domestiques
IT201800004789A1 (it) * 2018-04-23 2019-10-23 Processo di lavorazione del gres porcellanato e manufatti
RU2753792C1 (ru) * 2020-12-07 2021-08-23 федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный энергетический университет имени В.И. Ленина" (ИГЭУ) Способ получения керамического материала

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600476A (en) * 1968-09-18 1971-08-17 Kanagawa Prefectural Governmen Method for manufacture of light weight aggregates
US4120735A (en) * 1974-10-25 1978-10-17 Gilbert Associates, Inc. Brick and method of making same
GB2061241A (en) * 1979-08-28 1981-05-13 Central Electr Generat Board Bricks containing pulverised fuel ash and their manufacture
US4624711A (en) * 1984-11-07 1986-11-25 Resource Technology, Inc. Light-weight aggregate
US4874153A (en) * 1985-10-24 1989-10-17 Fujimi Tile Co., Ltd. Process for producing ceramic products using the sludge obtained by sewage treatment
EP0430232A1 (fr) * 1989-11-30 1991-06-05 George C. Harrison Traitement de cendre et de papier
EP0566376A1 (fr) * 1992-04-15 1993-10-20 Kabushiki Kaisha Kobe Seiko Sho Procédé et dispositif pour frittage des cendres volantes de déchet municipaux cinérable
JPH06227853A (ja) * 1993-02-02 1994-08-16 Maruka Seito Kk 陶磁器用素地組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600476A (en) * 1968-09-18 1971-08-17 Kanagawa Prefectural Governmen Method for manufacture of light weight aggregates
US4120735A (en) * 1974-10-25 1978-10-17 Gilbert Associates, Inc. Brick and method of making same
GB2061241A (en) * 1979-08-28 1981-05-13 Central Electr Generat Board Bricks containing pulverised fuel ash and their manufacture
US4624711A (en) * 1984-11-07 1986-11-25 Resource Technology, Inc. Light-weight aggregate
US4874153A (en) * 1985-10-24 1989-10-17 Fujimi Tile Co., Ltd. Process for producing ceramic products using the sludge obtained by sewage treatment
EP0430232A1 (fr) * 1989-11-30 1991-06-05 George C. Harrison Traitement de cendre et de papier
EP0566376A1 (fr) * 1992-04-15 1993-10-20 Kabushiki Kaisha Kobe Seiko Sho Procédé et dispositif pour frittage des cendres volantes de déchet municipaux cinérable
JPH06227853A (ja) * 1993-02-02 1994-08-16 Maruka Seito Kk 陶磁器用素地組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9437, Derwent World Patents Index; Class D15, AN 94-299581 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2020429B1 (en) * 2018-02-13 2019-08-20 Dukeron B V Process for preparing a ceramic article containing domestic sludge
WO2019160408A1 (fr) 2018-02-13 2019-08-22 Dukeron B.V. Procédé de préparation d'un article en céramique contenant des boues domestiques
IT201800004789A1 (it) * 2018-04-23 2019-10-23 Processo di lavorazione del gres porcellanato e manufatti
WO2019207433A1 (fr) * 2018-04-23 2019-10-31 Saxa Grestone S.P.A. Processus de production de grès cérame et produits
CN112055620A (zh) * 2018-04-23 2020-12-08 萨克萨格雷斯通股份有限公司 陶瓷炻瓷生产方法和产品
RU2753792C1 (ru) * 2020-12-07 2021-08-23 федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный энергетический университет имени В.И. Ленина" (ИГЭУ) Способ получения керамического материала

Also Published As

Publication number Publication date
AU7998094A (en) 1995-05-22
GB9322067D0 (en) 1993-12-15

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