EP3645465A1 - A method and an apparatus for processing an industrial side stream material - Google Patents

A method and an apparatus for processing an industrial side stream material

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Publication number
EP3645465A1
EP3645465A1 EP18752175.2A EP18752175A EP3645465A1 EP 3645465 A1 EP3645465 A1 EP 3645465A1 EP 18752175 A EP18752175 A EP 18752175A EP 3645465 A1 EP3645465 A1 EP 3645465A1
Authority
EP
European Patent Office
Prior art keywords
side stream
industrial side
stream material
calcium
industrial
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.)
Pending
Application number
EP18752175.2A
Other languages
German (de)
French (fr)
Inventor
Harri Hiltunen
Henri ÄRLING
Miikka SAARINEN
Riikka Silmu
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.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene Oy
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 UPM Kymmene Oy filed Critical UPM Kymmene Oy
Publication of EP3645465A1 publication Critical patent/EP3645465A1/en
Pending legal-status Critical Current

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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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • 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
    • C04B18/04—Waste materials; Refuse
    • 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
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/005—Lime, magnesia or dolomite obtained from an industrial by-product
    • 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
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • 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
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • C04B2/12—Preheating, burning calcining or cooling in shaft or vertical furnaces
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
    • F27B7/14—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • 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
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • This application relates to a method and an apparatus for processing an industrial side stream material. Further, this application relates to a product and a use of the product.
  • the objective is to disclose a new type of method and apparatus for processing industrial side streams. Another objective is to disclose a new method and apparatus for utilizing industrial side streams. Another objective is to form a product for excavating, road building or plant arrangement.
  • the apparatus for processing an industrial side stream material is characterized by what is presented in claim 13.
  • the modified industrial side stream material is characterized by what is presented in claim 16.
  • Fig. 1 is a flow chart illustration of an embodiment of the method and apparatus for processing an industrial side stream material
  • Fig. 2 is a flow chart illustration of another embodiment of the method and apparatus for processing an industrial side stream material
  • Fig. 3 is a flow chart illustration of another embodiment of the method and apparatus for processing an industrial side stream material.
  • the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature for modifying the industrial side stream material, the industrial side stream material (1) is treated in a treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying and in which the industrial side stream material is moved during the treatment, and the modified industrial side stream material (3) is formed.
  • the apparatus for processing an industrial side stream material (1) comprises at least one treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and in which the industrial side stream material is moved during the treatment and in which the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature, and at least one feeding device for supplying the industrial side stream material (1) into the treating oven (2 ) .
  • FIG. 1 One embodiment of the method and apparatus is shown in Fig 1.
  • FIG. 2 Another embodiments of the method and apparatus are shown in Figs 2 - 3.
  • the industrial side stream material (1) means any industrial side stream or industrial waste stream, e.g. side stream of the forest or energy industry.
  • the industrial side stream material (1) may comprise one or more industrial side stream components, e.g. side stream components of the forest or energy industry.
  • at least one of the industrial side stream components may comprise calcium.
  • the industrial side stream component does not comprise, at least essentially, calcium.
  • the industrial side stream component may comprise at least one of Al, Si, S or any combinations thereof.
  • the industrial side stream component comprises at least calcium and at least one of Al, Si, S or any combinations thereof. Ca, Al, Si or S may be in the form of any compound.
  • the industrial side stream component is selected from the group comprising an ash based material, calcium based material, green liquor dregs, lime mud, desulphurisation gypsum and their combinations.
  • the industrial side stream material can also comprise other components.
  • the industrial side stream material (1) comprises at least an ash based material.
  • the ash based material comprises at least fly ash, ash based side stream or ash based residue, e.g. electrostatic precipitator ash of lime kiln.
  • the ash based material further comprises at least another component.
  • the ash based material comprises calcium.
  • the fly ash is obtainable from a combustion of forest industry material or from a combustion of biomass, e.g. in a forest industry or bio power plant.
  • the fly ash is formed by combusting material selected from the group comprising wood based material, bark based material, forest felling residue, recycling material, plant based biomass, de-inked pulp, de-inking residue, waste water treatment sludge, peat and their combinations.
  • the fly ash is a wood based ash.
  • the fly ash is an ash from a deinking plant, and the ash may comprise preferably calcium.
  • moisture content of the ash based material is less than 40 %, such as 0 - 40 % (w/w) based on the total weight of the ash based material.
  • the ash based material (1) comprises calcium. Calcium may be in the form of any calcium compound, e.g. lime, CaC0 3 , in the ash based material (1) . In one embodiment, Ca content of the ash based material (1) is 5 - 35 % (w/w) based on the total dry weight of the ash based material.
  • the industrial side stream material (1) comprises at least a calcium based material which comprises calcium.
  • the calcium based material may be any material or composition which comprises calcium or calcium compound, e.g. from a forest or energy industry.
  • the calcium based material is formed from an industrial waste, residue or side stream.
  • the calcium based material is calcium containing waste stream, e.g. green liquor dregs or lime mud.
  • the calcium based material is selected from the group comprising lime fraction of the pulp manufacture, green liquor dregs, lime mud based deposit, rejected lime, lime kiln ESP ash (electrostatic precipitator ash of lime kiln) , desulphurisation gypsum and their combinations.
  • the calcium based material is a composition comprising calcium compound, such as recycling calcium compound.
  • moisture content of the calcium based material is less than 60 %, such as 0 - 60 % (w/w) based on the total weight of the calcium based material.
  • Calcium may be in the form of any calcium compound, e.g. lime, CaC0 3 or CaS0 4 , in the calcium based material.
  • Ca content of the calcium based material is 30 - 80 % (w/w) based on the total dry weight of the calcium based material.
  • the industrial side stream material (1) comprises at least said ash based material and calcium based material.
  • the industrial side stream material (1) is pre-treated, e.g. by grinding, screening, crushing, mixing and/or other homogenization method.
  • an addition (4) of the calcium based material is supplied to the industrial side stream material (1) or into the treating oven (2) .
  • the addition (4) of the calcium based material is added by mixing.
  • the addition (4) of the calcium based material is added into the treating oven (2) .
  • the calcium based material is added before the treating oven (2) .
  • a material mixture (5) which comprises calcium and comprises at least two material components is added to the industrial side stream material (1) or into the treating oven (2) .
  • the material mixture (5) which comprises at least one of calcium based material, green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added to the industrial side stream material (1) or into the treating oven (2) .
  • the material mixture (5) which comprises at least calcium based material is added to the industrial side stream material (1) or into the treating oven (2) .
  • the material mixture (5) which comprises at least one of green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added to the industrial side stream material (1) or into the treating oven (2) .
  • the material mixture (5) is added by mixing.
  • the material mixture is added into the treating oven (2) .
  • the material mixture is added before the treating oven (2) .
  • an additive may be added to improve the properties of the modified ash based material (3) .
  • the additive is added to the industrial side stream material (1) or into the treating oven (2) .
  • a feed of the treating oven (2) comprises the industrial side stream material (1) 1 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the ash based material 0 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the calcium based material 0 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the calcium based material of 1 - 99 % (w/w) based on the total dry weight of the total material is added to the industrial side stream material (1) .
  • the feed of the treating oven (2) comprises the industrial side stream material (1), which comprises the ash based material and/or calcium based material, about 100 % (w/w) based on the total dry weight of the feed.
  • the feed of the treating oven (2) comprises the ash based material 30 - 70 ⁇ 6 , in one embodiment 40 - 60 %, and the calcium based material 30 - 70 %, in one embodiment 40 - 60 %, (w/w) based on the total dry weight of the feed.
  • the feed of the treating oven (2) comprises the ash based material about 70 % and the calcium based material about 30 % (w/w) based on the total dry weight of the feed.
  • calcium content, determined as CaO, is 25 - 70 ⁇ 6 , in one embodiment 30 - 65 %, (w/w) based on the total dry weight of the material, in the industrial side stream material (1) or in the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) .
  • the industrial side stream (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) comprises Al, Si and/or S.
  • Al content of the industrial side stream material (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) , determined as A1 2 0 3 is 3 - 25 %, in one embodiment 5 - 15 % (w/w) based on the total dry weight of the material.
  • S content of the industrial side stream material (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5), determined as S0 3 is 1 - 15 %, in one embodiment 2 - 10 % (w/w) based on the total dry weight of the material.
  • the industrial side stream material (1) or the mixture of the industrial side stream material and the addition (4) or material mixture (5) comprises at least Ca and at least one of Al, Si and S in order to increase reactivity of the modified industrial side stream material (3) , and then sufficient hardening can be produced into the product.
  • the treating oven (2) may be any oven, kiln or furnace which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying the industrial side stream material
  • the treating oven (2) is selected from the group comprising a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven and their combinations.
  • the lime kiln, lime sludge reburning kiln or cement kiln is used as the treating oven.
  • the treating oven is selected from the group comprising a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven and their combinations.
  • the lime kiln, lime sludge reburning kiln or cement kiln is used as the treating oven.
  • the treating oven is selected from the group comprising a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven and their combinations.
  • the drum comprises a horizontal drum.
  • the drum is arranged into an inclined position in the treating oven.
  • the industrial side stream material can be moved during the treatment.
  • the process temperature is
  • the industrial side stream material (1) is dried during the treatment in the treating oven (2) .
  • water is evaporated in the treating oven (2) .
  • the residence time is 1.5 - 3.5, in one embodiment 1.75 - 2.5 hours, in one embodiment 2.0 - 2.5 hours, in one embodiment 2.0 - 3.0 hours, at the process temperature.
  • the industrial side stream material (1) is treated in presence of at least aluminum (Al) . In one embodiment, the industrial side stream material (1) is treated in presence of at least silicon (Si) . In one embodiment, the industrial side stream material (1) is treated in presence of at least sulphur (S) . In one embodiment, the industrial side stream material (1) is treated in presence of at least calcium and at least one of Al, Si, S or any combinations thereof in the treating oven (2) .
  • the industrial side stream material (1) is activated during the treatment in the treating oven (2) for increasing the reactivity of the material.
  • calcium is in the form of calcium oxide in the modified industrial side stream (3) .
  • calcium compound, such as CaC0 3 in the industrial side stream material (1), e.g. the ash based material and calcium based material, is calcined and share of amorphous structure is increased for forming the modified industrial side stream material (3), for example in the lime kiln.
  • the modified industrial side stream material (3) is post-treated after the treating in a treating oven (2) .
  • the modified industrial side stream material (3) is ground, pulverized or powdered.
  • the method is carried out as a continuous process. In one embodiment, the method is carried out as a batch process.
  • the modified industrial side stream material (3) is formed by the method and apparatus according to one or more embodiments described in this specification .
  • the modified industrial side stream material (3) comprises at least calcium.
  • calcium content of the modified industrial side stream material (3) determined as CaO, is 25 - 98 %, in one embodiment, 28 - 70 %, in one embodiment 30 - 65 % and in one embodiment 35 - 60 %, (w/w) based on the total dry weight of the modified industrial side stream material.
  • the modified industrial side stream material (3) comprises at least one of Al, Si, S and any combinations thereof.
  • Al content of the modified industrial side stream material (3) determined as A1 2 0 3 , is 3 - 25 %, in one embodiment 4 - 15 %, (w/w) based on the total dry weight of the modified industrial side stream material.
  • S content of the modified industrial side stream material (3) is 1 - 15 ⁇ 6 , in one embodiment 2 - 14 %, (w/w) based on the total dry weight of the modified industrial side stream material.
  • Si content of the modified industrial side stream material (3) is 2 - 35 %, in one embodiment 10 - 30 %, (w/w) based on the total dry weight of the modified industrial side stream material.
  • the modified industrial side stream material (3) and/or the product may be used as a raw material in a soil stabilization or subgrade stabilization, e.g. by means of a mass stabilization, deep stabilization, pillar stabilization, spray stabilization and/or sandwich stabilization, as a raw material in a fertilizer, earth construction material, earth-moving material, road building material, plant arrangement material or landscaping material, as a replacement or partial replacement for cement, or as a makeup lime in kraft pulp production, or in any combinations thereof.
  • at least a part of the cement can be replaced by means of the modified industrial side stream material or the product when the modified industrial side stream material has sufficient hardening.
  • the modified industrial side stream material (3) which is homogeneous material and has improved hardening can be produced.
  • the method and the apparatus provide the modified industrial side stream material which can be used as a replacement material for the cement.
  • the modified industrial side stream material is not used only as a filler in the cement or other material.
  • the method and apparatus provide an industrially applicable, simple and affordable way to treat various industrial side stream and waste materials.
  • the method or apparatus is easy and simple to realize as a production process.
  • the method and apparatus are suitable for use in connection with the manufacture of the different soil stabilization products from different waste and residue materials.
  • an industrial side stream material (1) is processed according to a process of Fig. 1.
  • the apparatus comprises at least one treating oven (2) and at least one feeding device for supplying the industrial side stream material (1) which comprises one or more components into the treating oven (2) .
  • the treating oven is selected such that the treating oven can be used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and that the industrial side stream material can be moved during the treatment in the treating oven.
  • the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3 hours at the process temperature .
  • the industrial side stream material (1) comprises component or components which may be selected from the group comprising an ash based material, calcium based material, green liquor dregs, lime mud, desulphurisation gypsum and their combinations.
  • the ash based material may comprise at least fly ash, ash based side stream or ash based residue or any combinations thereof.
  • the calcium based material may be selected from the group comprising lime fraction of the pulp manufacture, green liquor dregs, lime mud based deposit, rejected lime, lime kiln ESP ash (electrostatic precipitator ash of lime kiln) , desulphurisation gypsum and any combinations thereof.
  • the industrial side stream material (1) may be pre-treated, e.g. by grinding. An additive may be added to improve the properties of the modified ash based material (3) .
  • the treating oven (2) may be a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven or any combinations thereof.
  • the treating oven (2) comprises a horizontal drum, and the drum is preferably arranged into an inclined position in the treating oven.
  • the industrial side stream material (1) is treated in presence of at least calcium, and preferably at least one of Al, Si, S or any combinations thereof, in the treating oven (2) .
  • the industrial side stream material (1) is activated during the treatment for increasing the reactivity of the material. Further, the industrial side stream material (1) is dried during the treatment in the treating oven (2) .
  • the modified industrial side stream material (3) is post-treated, e.g. by grinding, after the treating in a treating oven (2) .
  • the modified industrial side stream material (3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material. Further, the modified industrial side stream material (3) may comprise at least one of Al, Si, S and any combinations thereof if the starting material comprises these agents. The modified industrial side stream material (3) may be used as a replacement or partial replacement for cement.
  • an industrial side stream material (1) is processed according to a process of Fig. 2 or Fig. 3.
  • the apparatus comprises at least one treating oven (2) and at least one feeding device for supplying the industrial side stream material (1) which comprises one or more components into the treating oven (2) .
  • the treating oven is selected such that the treating oven can be used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and that the industrial side stream material can be moved during the treatment in the treating oven.
  • the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3 hours at the process temperature .
  • the industrial side stream material (1) comprises component or components according to Example 1.
  • the industrial side stream material (1) may be pre-treated, e.g. by grinding.
  • An additive may be added to improve the properties of the modified ash based material (3) .
  • the treating oven (2) may be a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven or any combinations thereof.
  • the treating oven (2) comprises a horizontal drum, and the drum is preferably arranged into an inclined position in the treating oven.
  • an addition (4) of the calcium based material is supplied into the treating oven (2) .
  • an addition (4) may be supplied to the industrial side stream material ( 1 ) .
  • the material mixture (5) which comprises at least one of calcium based material, green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added into the treating oven
  • the material mixture (5) is added to the industrial side stream material (1) .
  • the industrial side stream material (1) is treated in presence of at least calcium, and preferably at least one of Al, Si, S or any combinations thereof, in the treating oven (2) .
  • the industrial side stream material (1) is activated during the treatment for increasing the reactivity of the material. Further, the industrial side stream material (1) is dried during the treatment in the treating oven (2) .
  • the modified industrial side stream material (3) is post-treated, e.g. by grinding, after the treating in a treating oven (2) .
  • modified industrial side stream material (3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material. Further, the modified industrial side stream material (3) may comprise at least one of Al, Si, S and any combinations thereof if the starting material comprises these agents. The modified industrial side stream material (3) may be used as a replacement or partial replacement for cement.
  • an industrial side stream material (1) was processed according to a process of Fig. 2 and Example 2.
  • the treating oven (2) was a lime kiln which comprises a horizontal drum and the industrial side stream material (1) was a fly ash.
  • Table 1 shows results of analyses of the fly ash.
  • the process temperature was between 950 - 1050 °C such that the temperature was 950 °C in the first trial, 950 - 1000 °C in the second trial and 1050 °C in the third trial.
  • the residence time was 3 hours at the process temperature.
  • Ca, Al, Si and S contents of the feed component were determined as CaO, A1 2 0 3 , Si0 2 and S0 3 , and these contents were based on the total dry weight of the component. Results are EDX normalized.
  • a modified industrial side stream was formed by activating the fly ash with the green liquor dregs in the lime kiln.
  • Ca, Al, Si and S contents of the modified industrial side stream material (3) were determined as CaO, A1 2 0 3 , Si0 2 and S0 3 , and these contents were based on the total dry weight of the modified industrial side stream material.
  • Results of Table 2 and free CaO in Table 3 are EDX normalized.
  • modified industrial side stream material (3) can be used to replace cement, for example in a soil stabilization, subgrade stabilization, earth construction material or earth-moving material.
  • a modified industrial side stream material was formed from industrial side stream materials by means of mill scale trials.
  • the starting materials i.e. industrial side stream materials, were green liquor dregs from kraft pulp mill recovery cycle, flue gas desulphurization gypsum, steel slag and biomass based fly ash comprising ash from bark, saw dust, forest residues, stump fuel and/or recycled fuel.
  • Samples 1 and 2 included 40 w-% green liquor dregs, 29 w-% biomass based fly ash, 21 w-% steel slag and 10 w-% flue gas desulphurization gypsum.
  • Samples 3 and 4 included 24 w-% green liquor dregs, 25 w-% biomass based fly ash, 37 w-% steel slag and 14 w-% flue gas desulphurization gypsum.
  • the trials were carried out in a rotating kiln in which a reaction time was about 3 hours and an average burning temperature was 1000 - 1250 °C.
  • the average burning temperature was 1000 - 1100 °C.
  • the average burning temperature was about 1100 °C.
  • the average burning temperature was 1200 - 1250 °C.
  • Blaine was determined after grinding with ball mill by SFS-EN 196-6.
  • Strength means compressive strength determined by SFS-EN 196-1.
  • the alkalinity modulus (CaO - 0.7Ti02) / ( (1.87Si02 + 0.73(A12O3 - 0.64Fe2O3) + 1.40Fe2O3)) defines an amount of free Ca when relevant Ca containing clinker phases have been formed.
  • the method and apparatus presented herein are suitable in different embodiments to be used in different processes to modify various industrial side streams. Further, the method and apparatus are suitable in different embodiments to be used for producing the most different kinds of products from different raw materials.

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Abstract

L'invention concerne un procédé et un appareil pour traiter un matériau de flux latéral industriel (1), le matériau de flux latéral industriel (1) est traité en présence de calcium à une température de traitement de 850 à 1400 °C et avec un temps de séjour d'environ 1,5 à 3 heures à la température de traitement pour modifier le matériau de flux latéral industriel. Le matériau de flux latéral industriel (1) est traité dans un four de traitement (2) qui est utilisé pour fournir une température de traitement élevée suffisante et un temps de séjour prolongé suffisant pour la modification et dans lequel le flux latéral industriel se déplace pendant le traitement, et le matériau de flux latéral industriel modifié (3) est formé. De plus, l'invention concerne un produit et une utilisation du produit.A method and apparatus for processing an industrial side flux material (1), the industrial side flux material (1) is treated in the presence of calcium at a process temperature of 850 to 1400 ° C and with a residence time of about 1.5 to 3 hours at the processing temperature to modify the industrial side flow material. The industrial side flow material (1) is treated in a treatment furnace (2) which is used to provide a sufficient high processing temperature and a sufficient residence time for the modification and wherein the industrial side flow moves during the treatment, and the modified industrial side flux material (3) is formed. In addition, the invention relates to a product and a use of the product.

Description

A METHOD AND AN APPARATUS FOR PROCESSING AN INDUSTRIAL SIDE STREAM MATERIAL
FIELD
This application relates to a method and an apparatus for processing an industrial side stream material. Further, this application relates to a product and a use of the product.
BACKGROUND
It is known that several industrial side and waste streams are generated in various industrial processes. For instance, fly ash, green liquor dregs, desulphurisation gypsum or the like are produced in a forest industry or an energy industry. These industrial side streams are difficult to utilize as a raw material or as a product. The ash produced by combustion of various materials may be used in fertilizer or soil conditioning applications.
OBJECTIVE
The objective is to disclose a new type of method and apparatus for processing industrial side streams. Another objective is to disclose a new method and apparatus for utilizing industrial side streams. Another objective is to form a product for excavating, road building or plant arrangement.
SUMMARY
The method for processing an industrial side stream material is characterized by what is presented in claim 1.
The apparatus for processing an industrial side stream material is characterized by what is presented in claim 13. The modified industrial side stream material is characterized by what is presented in claim 16.
The product is characterized by what is presented in claim 19.
The use of the modified industrial side stream material is characterized by what is presented in claim 20.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the method and apparatus and constitute a part of this specification, illustrate some embodiments of the method and apparatus and together with the description help to explain the principles. In the drawings:
Fig. 1 is a flow chart illustration of an embodiment of the method and apparatus for processing an industrial side stream material,
Fig. 2 is a flow chart illustration of another embodiment of the method and apparatus for processing an industrial side stream material, and
Fig. 3 is a flow chart illustration of another embodiment of the method and apparatus for processing an industrial side stream material.
DETAILED DESCRIPTION
In a method for processing an industrial side stream material (1), the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature for modifying the industrial side stream material, the industrial side stream material (1) is treated in a treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying and in which the industrial side stream material is moved during the treatment, and the modified industrial side stream material (3) is formed.
The apparatus for processing an industrial side stream material (1) comprises at least one treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and in which the industrial side stream material is moved during the treatment and in which the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature, and at least one feeding device for supplying the industrial side stream material (1) into the treating oven (2 ) .
One embodiment of the method and apparatus is shown in Fig 1. Another embodiments of the method and apparatus are shown in Figs 2 - 3.
In this context, the industrial side stream material (1) means any industrial side stream or industrial waste stream, e.g. side stream of the forest or energy industry. The industrial side stream material (1) may comprise one or more industrial side stream components, e.g. side stream components of the forest or energy industry. In one embodiment, at least one of the industrial side stream components may comprise calcium. Alternatively the industrial side stream component does not comprise, at least essentially, calcium. In one embodiment, the industrial side stream component may comprise at least one of Al, Si, S or any combinations thereof. In one embodiment, the industrial side stream component comprises at least calcium and at least one of Al, Si, S or any combinations thereof. Ca, Al, Si or S may be in the form of any compound. Preferably, Ca, Al, Si and S increase hardening in the modified industrial side stream material and/or in the product. In one embodiment, the industrial side stream component is selected from the group comprising an ash based material, calcium based material, green liquor dregs, lime mud, desulphurisation gypsum and their combinations. The industrial side stream material can also comprise other components.
In one embodiment, the industrial side stream material (1) comprises at least an ash based material. In one embodiment, the ash based material comprises at least fly ash, ash based side stream or ash based residue, e.g. electrostatic precipitator ash of lime kiln. In one embodiment, the ash based material further comprises at least another component. In one embodiment, the ash based material comprises calcium.
Preferably, the fly ash is obtainable from a combustion of forest industry material or from a combustion of biomass, e.g. in a forest industry or bio power plant. In one embodiment, the fly ash is formed by combusting material selected from the group comprising wood based material, bark based material, forest felling residue, recycling material, plant based biomass, de-inked pulp, de-inking residue, waste water treatment sludge, peat and their combinations. In one embodiment, the fly ash is a wood based ash. In one embodiment, the fly ash is an ash from a deinking plant, and the ash may comprise preferably calcium.
In one embodiment, moisture content of the ash based material is less than 40 %, such as 0 - 40 % (w/w) based on the total weight of the ash based material. In one embodiment, the ash based material (1) comprises calcium. Calcium may be in the form of any calcium compound, e.g. lime, CaC03, in the ash based material (1) . In one embodiment, Ca content of the ash based material (1) is 5 - 35 % (w/w) based on the total dry weight of the ash based material.
In one embodiment, the industrial side stream material (1) comprises at least a calcium based material which comprises calcium. The calcium based material may be any material or composition which comprises calcium or calcium compound, e.g. from a forest or energy industry. In one embodiment, the calcium based material is formed from an industrial waste, residue or side stream. In one embodiment, the calcium based material is calcium containing waste stream, e.g. green liquor dregs or lime mud. In one embodiment, the calcium based material is selected from the group comprising lime fraction of the pulp manufacture, green liquor dregs, lime mud based deposit, rejected lime, lime kiln ESP ash (electrostatic precipitator ash of lime kiln) , desulphurisation gypsum and their combinations. In one embodiment, the calcium based material is a composition comprising calcium compound, such as recycling calcium compound. In one embodiment, moisture content of the calcium based material is less than 60 %, such as 0 - 60 % (w/w) based on the total weight of the calcium based material. Calcium may be in the form of any calcium compound, e.g. lime, CaC03 or CaS04, in the calcium based material. In one embodiment, Ca content of the calcium based material is 30 - 80 % (w/w) based on the total dry weight of the calcium based material.
In one embodiment, the industrial side stream material (1) comprises at least said ash based material and calcium based material.
In one embodiment, the industrial side stream material (1) is pre-treated, e.g. by grinding, screening, crushing, mixing and/or other homogenization method.
In one embodiment, an addition (4) of the calcium based material is supplied to the industrial side stream material (1) or into the treating oven (2) . In one embodiment, the addition (4) of the calcium based material is added by mixing. In one embodiment, the addition (4) of the calcium based material is added into the treating oven (2) . In one embodiment, the calcium based material is added before the treating oven (2) .
In one embodiment, a material mixture (5) which comprises calcium and comprises at least two material components is added to the industrial side stream material (1) or into the treating oven (2) . In one embodiment, the material mixture (5) which comprises at least one of calcium based material, green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added to the industrial side stream material (1) or into the treating oven (2) . In one embodiment, the material mixture (5) which comprises at least calcium based material is added to the industrial side stream material (1) or into the treating oven (2) . In one embodiment, the material mixture (5) which comprises at least one of green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added to the industrial side stream material (1) or into the treating oven (2) . In one embodiment, the material mixture (5) is added by mixing. In one embodiment, the material mixture is added into the treating oven (2) . In one embodiment, the material mixture is added before the treating oven (2) .
In one embodiment, an additive may be added to improve the properties of the modified ash based material (3) . In one embodiment, the additive is added to the industrial side stream material (1) or into the treating oven (2) .
In one embodiment, a feed of the treating oven (2) comprises the industrial side stream material (1) 1 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the ash based material 0 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the calcium based material 0 - 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the calcium based material of 1 - 99 % (w/w) based on the total dry weight of the total material is added to the industrial side stream material (1) . In one embodiment, the feed of the treating oven (2) comprises the industrial side stream material (1), which comprises the ash based material and/or calcium based material, about 100 % (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the ash based material 30 - 70 ~6 , in one embodiment 40 - 60 %, and the calcium based material 30 - 70 %, in one embodiment 40 - 60 %, (w/w) based on the total dry weight of the feed. In one embodiment, the feed of the treating oven (2) comprises the ash based material about 70 % and the calcium based material about 30 % (w/w) based on the total dry weight of the feed. In one embodiment, calcium content, determined as CaO, is 25 - 70 ~6 , in one embodiment 30 - 65 %, (w/w) based on the total dry weight of the material, in the industrial side stream material (1) or in the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) . Further, in one embodiment, the industrial side stream (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) comprises Al, Si and/or S. In one embodiment, Al content of the industrial side stream material (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) , determined as A1203, is 3 - 25 %, in one embodiment 5 - 15 % (w/w) based on the total dry weight of the material. In one embodiment, S content of the industrial side stream material (1) or the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5), determined as S03, is 1 - 15 %, in one embodiment 2 - 10 % (w/w) based on the total dry weight of the material. Preferably, the industrial side stream material (1) or the mixture of the industrial side stream material and the addition (4) or material mixture (5) comprises at least Ca and at least one of Al, Si and S in order to increase reactivity of the modified industrial side stream material (3) , and then sufficient hardening can be produced into the product.
The treating oven (2) may be any oven, kiln or furnace which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying the industrial side stream material
(1) . In one embodiment, the treating oven (2) is selected from the group comprising a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven and their combinations. In one embodiment, the lime kiln, lime sludge reburning kiln or cement kiln is used as the treating oven. In one embodiment, the treating oven
(2) comprises a horizontal drum. In one embodiment, the drum is arranged into an inclined position in the treating oven. In the drum the industrial side stream material can be moved during the treatment.
In one embodiment, the process temperature is
870 - 1300 °C, in one embodiment 900 - 1200 °C and in one embodiment 950 - 1150 °C. In one embodiment, the industrial side stream material (1) is dried during the treatment in the treating oven (2) . In one embodiment, water is evaporated in the treating oven (2) . In one embodiment, the residence time is 1.5 - 3.5, in one embodiment 1.75 - 2.5 hours, in one embodiment 2.0 - 2.5 hours, in one embodiment 2.0 - 3.0 hours, at the process temperature.
In one embodiment, the industrial side stream material (1) is treated in presence of at least aluminum (Al) . In one embodiment, the industrial side stream material (1) is treated in presence of at least silicon (Si) . In one embodiment, the industrial side stream material (1) is treated in presence of at least sulphur (S) . In one embodiment, the industrial side stream material (1) is treated in presence of at least calcium and at least one of Al, Si, S or any combinations thereof in the treating oven (2) .
In one embodiment, the industrial side stream material (1) is activated during the treatment in the treating oven (2) for increasing the reactivity of the material. In one embodiment, calcium is in the form of calcium oxide in the modified industrial side stream (3) . In one embodiment, calcium compound, such as CaC03, in the industrial side stream material (1), e.g. the ash based material and calcium based material, is calcined and share of amorphous structure is increased for forming the modified industrial side stream material (3), for example in the lime kiln.
In one embodiment, the modified industrial side stream material (3) is post-treated after the treating in a treating oven (2) . In one embodiment, the modified industrial side stream material (3) is ground, pulverized or powdered. In one embodiment, the method is carried out as a continuous process. In one embodiment, the method is carried out as a batch process.
The modified industrial side stream material (3) is formed by the method and apparatus according to one or more embodiments described in this specification .
Preferably, the modified industrial side stream material (3) comprises at least calcium. In one embodiment, calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 %, in one embodiment, 28 - 70 %, in one embodiment 30 - 65 % and in one embodiment 35 - 60 %, (w/w) based on the total dry weight of the modified industrial side stream material. Further, in one embodiment, the modified industrial side stream material (3) comprises at least one of Al, Si, S and any combinations thereof. In one embodiment, Al content of the modified industrial side stream material (3) , determined as A1203, is 3 - 25 %, in one embodiment 4 - 15 %, (w/w) based on the total dry weight of the modified industrial side stream material. In one embodiment, S content of the modified industrial side stream material (3) , determined as S03, is 1 - 15 ~6 , in one embodiment 2 - 14 %, (w/w) based on the total dry weight of the modified industrial side stream material. In one embodiment, Si content of the modified industrial side stream material (3) , determined as Si02, is 2 - 35 %, in one embodiment 10 - 30 %, (w/w) based on the total dry weight of the modified industrial side stream material.
Further, the product which comprises the modified industrial side stream material (3) according to one or more embodiments described in this specification is disclosed. The modified industrial side stream material (3) and/or the product may be used as a raw material in a soil stabilization or subgrade stabilization, e.g. by means of a mass stabilization, deep stabilization, pillar stabilization, spray stabilization and/or sandwich stabilization, as a raw material in a fertilizer, earth construction material, earth-moving material, road building material, plant arrangement material or landscaping material, as a replacement or partial replacement for cement, or as a makeup lime in kraft pulp production, or in any combinations thereof. Preferably, at least a part of the cement can be replaced by means of the modified industrial side stream material or the product when the modified industrial side stream material has sufficient hardening.
By means of the method and apparatus the modified industrial side stream material (3) which is homogeneous material and has improved hardening can be produced. The method and the apparatus provide the modified industrial side stream material which can be used as a replacement material for the cement. Preferably, the modified industrial side stream material is not used only as a filler in the cement or other material.
By means of the method and apparatus various side stream and waste materials can be recirculated and reutilized in several products. Also wet or moist industrial side stream materials can be used.
The method and apparatus provide an industrially applicable, simple and affordable way to treat various industrial side stream and waste materials. The method or apparatus is easy and simple to realize as a production process. The method and apparatus are suitable for use in connection with the manufacture of the different soil stabilization products from different waste and residue materials.
EXAMPLES
Some embodiments of the method and apparatus are described in more detail by the following examples with reference to accompanying drawings.
Example 1
In this example, an industrial side stream material (1) is processed according to a process of Fig. 1.
The apparatus comprises at least one treating oven (2) and at least one feeding device for supplying the industrial side stream material (1) which comprises one or more components into the treating oven (2) . The treating oven is selected such that the treating oven can be used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and that the industrial side stream material can be moved during the treatment in the treating oven. In the treating oven the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3 hours at the process temperature .
The industrial side stream material (1) comprises component or components which may be selected from the group comprising an ash based material, calcium based material, green liquor dregs, lime mud, desulphurisation gypsum and their combinations. The ash based material may comprise at least fly ash, ash based side stream or ash based residue or any combinations thereof. The calcium based material may be selected from the group comprising lime fraction of the pulp manufacture, green liquor dregs, lime mud based deposit, rejected lime, lime kiln ESP ash (electrostatic precipitator ash of lime kiln) , desulphurisation gypsum and any combinations thereof. The industrial side stream material (1) may be pre-treated, e.g. by grinding. An additive may be added to improve the properties of the modified ash based material (3) .
The treating oven (2) may be a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven or any combinations thereof. The treating oven (2) comprises a horizontal drum, and the drum is preferably arranged into an inclined position in the treating oven.
The industrial side stream material (1) is treated in presence of at least calcium, and preferably at least one of Al, Si, S or any combinations thereof, in the treating oven (2) . The industrial side stream material (1) is activated during the treatment for increasing the reactivity of the material. Further, the industrial side stream material (1) is dried during the treatment in the treating oven (2) . The modified industrial side stream material (3) is post-treated, e.g. by grinding, after the treating in a treating oven (2) .
The modified industrial side stream material (3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material. Further, the modified industrial side stream material (3) may comprise at least one of Al, Si, S and any combinations thereof if the starting material comprises these agents. The modified industrial side stream material (3) may be used as a replacement or partial replacement for cement.
Example 2
In this example, an industrial side stream material (1) is processed according to a process of Fig. 2 or Fig. 3.
The apparatus comprises at least one treating oven (2) and at least one feeding device for supplying the industrial side stream material (1) which comprises one or more components into the treating oven (2) . The treating oven is selected such that the treating oven can be used to provide a sufficient high process temperature and sufficient long residence time for modifying the industrial side stream material (1) and that the industrial side stream material can be moved during the treatment in the treating oven. In the treating oven the industrial side stream material (1) is treated in presence of at least calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3 hours at the process temperature .
The industrial side stream material (1) comprises component or components according to Example 1. The industrial side stream material (1) may be pre- treated, e.g. by grinding. An additive may be added to improve the properties of the modified ash based material (3) .
The treating oven (2) may be a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven or any combinations thereof. The treating oven (2) comprises a horizontal drum, and the drum is preferably arranged into an inclined position in the treating oven.
According to the process of Fig. 2, an addition (4) of the calcium based material is supplied into the treating oven (2) . Alternatively, an addition (4) may be supplied to the industrial side stream material ( 1 ) .
According to the process of Fig. 3, the material mixture (5) which comprises at least one of calcium based material, green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added into the treating oven
(2) . Alternatively, the material mixture (5) is added to the industrial side stream material (1) .
The industrial side stream material (1) is treated in presence of at least calcium, and preferably at least one of Al, Si, S or any combinations thereof, in the treating oven (2) . The industrial side stream material (1) is activated during the treatment for increasing the reactivity of the material. Further, the industrial side stream material (1) is dried during the treatment in the treating oven (2) . The modified industrial side stream material (3) is post-treated, e.g. by grinding, after the treating in a treating oven (2) .
The modified industrial side stream material
(3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material. Further, the modified industrial side stream material (3) may comprise at least one of Al, Si, S and any combinations thereof if the starting material comprises these agents. The modified industrial side stream material (3) may be used as a replacement or partial replacement for cement. Example 3
In this example, an industrial side stream material (1) was processed according to a process of Fig. 2 and Example 2.
In this example, the treating oven (2) was a lime kiln which comprises a horizontal drum and the industrial side stream material (1) was a fly ash. Table 1 shows results of analyses of the fly ash. The process temperature was between 950 - 1050 °C such that the temperature was 950 °C in the first trial, 950 - 1000 °C in the second trial and 1050 °C in the third trial. The residence time was 3 hours at the process temperature.
An addition (4) of the calcium based material was supplied into the treating oven (2) . The calcium based material was green liquor dregs. Results of the analyses of the green liquor dregs are also shown in Table 1.
In the second trial, a sulphure containing agent was added into the fly ash. The sulphure containing agent was a residual gypsum, i.e. desulphurisation gypsum. Results of the analyses of the desulphurisation gypsum are also shown in Table 1. Table 1
Ca, Al, Si and S contents of the feed component were determined as CaO, A1203, Si02 and S03, and these contents were based on the total dry weight of the component. Results are EDX normalized.
A modified industrial side stream was formed by activating the fly ash with the green liquor dregs in the lime kiln. In the first trial, fly ash of 55 %
(w/w) and green liquor dregs of 45 % (w/w) were supplied into the lime kiln. In the second trial, fly ash of 49.5 % (w/w), green liquor dregs of 40.5 %
(w/w) and desulphurisation gypsum of 10 % (w/w) were supplied into the lime kiln. In the third trial, fly ash of 45 % (w/w) and green liquor dregs of 55 % (w/w) were supplied into the lime kiln. These amounts were based on the total dry weight of the feed.
Results of the analyses of the modified industrial side stream material are shown in Table 2 and Table 3.
Table 2
Trial samp1e CaO A1203 Si02 so3
% (w/w) % (w/w) % (w/w) % (w/w)
Trial 1 , samp1e 1 47.3 8.4 20.5 5.5
Trial 1 , samp1e 2 50.2 7.8 21.2 3.5
Trial 2 , samp1e 1 51.3 5.1 14.2 14.7
Trial 2 , samp1e 2 49.4 4.9 13.7 14.9
Trial 2 , samp1e 3 48.0 5.6 16.8 13.0
Trial 2 , samp1e 4 48.2 6.1 17.2 12.1
Trial 3, sample 1 44.9 7.3 21.2 8.3
Trial 3, sample 2 47.6 6.9 22.8 3.5
Trial 3, sample 3 57.4 6.1 16.1 3.8
Trial 3, sample 4 48.2 6.3 25.1 2.4 Table 3
Ca, Al, Si and S contents of the modified industrial side stream material (3) were determined as CaO, A1203, Si02 and S03, and these contents were based on the total dry weight of the modified industrial side stream material. Results of Table 2 and free CaO in Table 3 are EDX normalized.
Strength tests were carried out by means of
EN196-1, and strength in trials 1 and 2 was 2 MPa after 14 days and strength in trial 3 was 9 MPa after 14 days. Collecting samples of the trials were formed such that the product of the trial was ground by means of Desintegrator DESI 15/16 C, 75 Hz. After that the strength, 14 days (14 d) , was determined from the formed samples.
Heat of hydration was determined by means of EN 196-8. An amount of water was determined by means of EN 196-3.
It was observed that good strength of the modified industrial side stream material (3) can be achieved after 14 days. Further, it was observed that the modified industrial side stream material (3) can be used to replace cement, for example in a soil stabilization, subgrade stabilization, earth construction material or earth-moving material.
Example 4
In this example, a modified industrial side stream material was formed from industrial side stream materials by means of mill scale trials.
The starting materials, i.e. industrial side stream materials, were green liquor dregs from kraft pulp mill recovery cycle, flue gas desulphurization gypsum, steel slag and biomass based fly ash comprising ash from bark, saw dust, forest residues, stump fuel and/or recycled fuel. Samples 1 and 2 included 40 w-% green liquor dregs, 29 w-% biomass based fly ash, 21 w-% steel slag and 10 w-% flue gas desulphurization gypsum. Samples 3 and 4 included 24 w-% green liquor dregs, 25 w-% biomass based fly ash, 37 w-% steel slag and 14 w-% flue gas desulphurization gypsum.
The trials were carried out in a rotating kiln in which a reaction time was about 3 hours and an average burning temperature was 1000 - 1250 °C. In the trial of samples 1 and 4, the average burning temperature was 1000 - 1100 °C. In the trial of sample 2, the average burning temperature was about 1100 °C. In the trial of sample 3, the average burning temperature was 1200 - 1250 °C.
Results of the analyses of the modified industrial side stream material are shown in Table 4 and Table 5. Table 4
CaO, Si02, A1203, S03 and Fe203 have been analyzed means of XRF (SFS-EN 196-1) .
Table 5
Blaine was determined after grinding with ball mill by SFS-EN 196-6. Strength means compressive strength determined by SFS-EN 196-1.
It was observed that good strength of the modified industrial side stream material can be achieved, especially in samples 1 and 4. Further, it was observed that samples 2 and 3 had lower alkalinity modulus than samples 1 and 4, and thus the strength of samples 2 and 3 are lower. The alkalinity modulus, (CaO - 0.7Ti02) / ( (1.87Si02 + 0.73(A12O3 - 0.64Fe2O3) + 1.40Fe2O3)) defines an amount of free Ca when relevant Ca containing clinker phases have been formed.
The method and apparatus presented herein are suitable in different embodiments to be used in different processes to modify various industrial side streams. Further, the method and apparatus are suitable in different embodiments to be used for producing the most different kinds of products from different raw materials.
It is obvious to a person skilled in the art that with the advancement of technology, the basic idea of the method and apparatus may be implemented in various ways. The method and apparatus and their embodiments are thus not limited to the examples described above; instead they may vary within the scope of the claims. The embodiments described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined together to form a further embodiment of the method and apparatus .

Claims

1. A method for processing an industrial side stream material (1), wherein the method comprises
- treating the industrial side stream material (1) in presence of calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature for modifying the industrial side stream material,
- treating the industrial side stream material (1) in a treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying and in which the industrial side stream material is moved during the treatment, and
- forming the modified industrial side stream material (3) .
2. The method according to claim 1, wherein the industrial side stream material (1) comprises one or more industrial side stream components.
3. The method according to claim 1 or 2, wherein at least one of the industrial side stream components comprises calcium.
4. The method according to any one of claims 1 to 3, wherein the industrial side stream component comprises at least one of Al, Si, S or any combinations thereof.
5. The method according to any one of claims 1 to 4, wherein the industrial side stream component is selected from the group comprising an ash based material, calcium based material, green liquor dregs, lime mud, desulphurisation gypsum and their combinations .
6. The method according to any one of claims 1 to 5, wherein the industrial side stream material (1) comprises at least an ash based material which comprises at least fly ash, ash based side stream, ash based residue or any combinations thereof.
7. The method according to any one of claims 1 to 6, wherein the industrial side stream material (1) comprises at least the calcium based material which is selected from the group comprising lime fraction of the pulp manufacture, green liquor dregs, lime mud based deposit, rejected lime, lime kiln ESP ash (electrostatic precipitator ash of lime kiln) , desulphurisation gypsum and any combinations thereof.
8. The method according to any one of claims 1 to 7, wherein an addition (4) of the calcium based material is supplied to the industrial side stream material (1) or into the treating oven (2) .
9. The method according to any one of claims 1 to 8, wherein the material mixture (5) which comprises at least one of calcium based material, green liquor dregs, desulphurisation gypsum, lime mud, fly ash and any combinations thereof is added to the industrial side stream material (1) or into the treating oven (2) .
10. The method according to any one of claims 1 to 9, wherein calcium content, determined as CaO, is 25 - 70 % (w/w) , based on the total dry weight of the material, in the industrial side stream material (1) or in the mixture of the industrial side stream material (1) and the addition (4) or material mixture (5) .
11. The method according to any one of claims 1 to 10, wherein the industrial side stream material
(1) is treated in presence of at least calcium and at least one of Al, Si, S or any combinations thereof in the treating oven (2) .
12. The method according to any one of claims 1 to 11, wherein the industrial side stream material
(1) is activated during the treatment in the treating oven (2) for increasing the reactivity of the material .
13. An apparatus for processing an industrial side stream material (1), wherein the apparatus comprises
- at least one treating oven (2) which is used to provide a sufficient high process temperature and sufficient long residence time for the modifying the industrial side stream material (1) and in which the industrial side stream material is moved during the treatment and in which the industrial side stream material (1) is treated in presence of calcium at a process temperature of 850 - 1400 °C and with a residence time of about 1.5 - 3.0 hours at the process temperature, and,
- at least one feeding device for supplying the industrial side stream material (1) into the treating oven (2) .
14. The apparatus according to claim 13, wherein the treating oven (2) is selected from the group comprising a lime kiln, lime sludge reburning kiln, cement kiln, chamber oven, chamber furnace, heat treatment oven and their combinations.
15. The apparatus according to claim 13 or 14, wherein the treating oven (2) comprises a horizontal drum.
16. The modified industrial side stream material (3) obtainable by the method according to any one of claims 1 - 12, wherein the modified industrial side stream material (3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material.
17. The modified industrial side stream material according to claim 16, wherein the modified industrial side stream material (3) comprises at least one of Al, Si, S and any combinations thereof.
18. A product comprising the modified industrial side stream material (3) according to claim 16 or 17, wherein the modified industrial side stream material (3) comprises at least calcium, and calcium content of the modified industrial side stream material (3) , determined as CaO, is 25 - 98 % (w/w) based on the total dry weight of the modified industrial side stream material.
19. A use of the modified industrial side stream material (3) obtainable by the method according to any one of claims 1 - 12, wherein the modified industrial side stream material (3) is used as a raw material in a soil stabilization or subgrade stabilization, as a raw material in a fertilizer, earth construction material, earth-moving material, road building material, plant arrangement material or landscaping material, as a replacement or partial replacement for cement, or as a makeup lime in kraft pulp production, or in any combinations thereof.
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