EP2900864A1

EP2900864A1 - Method and apparatus for manufacturing a material component, a material component and its use, an extender pigment product and a final product

Info

Publication number: EP2900864A1
Application number: EP13841588.0A
Authority: EP
Inventors: Taru PÄIVÄLÄINEN; Teuvo LEPPÄNEN; Matti Ristolainen; Meri Ventola; Nina PYKÄLÄINEN; Folke ÖRSÅ; Heiko Hilbert; Matti Lindeman
Original assignee: UPM Kymmene Oy
Current assignee: UPM Kymmene Oy
Priority date: 2012-09-25
Filing date: 2013-09-25
Publication date: 2015-08-05
Also published as: WO2014049206A1; EP2900864A4

Abstract

The invention relates to a method for manufacturing an extender pigment from ash, and an extender pigment and its use and an extender pigment product and a final product. According to the invention, method comprises forming the mate- rial component (4, 24) from ash (1,21).

Description

METHOD AND APPARATUS FOR MANUFACTURING A MATERIAL COMPONENT, A MATERIAL COMPONENT AND ITS USE, AN EXTENDER PIGMENT PRODUCT AND A FINAL PRODUCT FIELD OF THE INVENTION

The invention relates to a method for manu^¬ facturing a material component. Further, the invention relates to a material component, an extender pigment product and a final product. Further, the invention relates to a use of the material component. Further, the invention relates to an apparatus for manufacturing a material component.

BACKGROUND OF THE INVENTION

Known from prior art are different residue sludges in the paper, pulp and board manufacturing. Typically the sludges are waste, and they are inciner^¬ ated or are disposed. Also boiler ash generated in combustion of different sludges is usually waste pro- ducing disposal costs. Further, lime kiln ash generat^¬ ed in lime kiln is usually waste.

Known from WO 2007/025580 is the use of ash as an alkalizing agent. OBJECTIVE OF THE INVENTION

The objective of the invention is to disclose a new method for treating ash or ash type material to form a new type material component which can be uti^¬ lized. Further, the objective of the invention is to disclose a new method for utilizing ash as a raw mate^¬ rial .

SUMMARY OF THE INVENTION The method for manufacturing a material component according to the present invention is charac^¬ terized by what is presented in claim 1.

The method for manufacturing a material com- ponent from boiler ash according to the present invention is characterized by what is presented in claim 4.

The apparatus, such as also process, contain^¬ ing different devices for manufacturing a material component according to the present invention is char- acterized by what is presented in claim 18.

The material component according to the pre^¬ sent invention is characterized by what is presented in claim 27.

The use of the material component according to the present invention is characterized by what is presented in claim 28.

The final product according to the present invention is characterized by what is presented in claim 30.

The method for manufacturing an extender pig^¬ ment according to the present invention is characterized by what is presented in claim 31.

The extender pigment according to the present invention is characterized by what is presented in claim 41.

The use of the extender pigment according to the present invention is characterized by what is pre^¬ sented in claim 42.

The extender pigment product according to the present invention is characterized by what is present^¬ ed in claim 44.

The final product according to the present invention is characterized by what is presented in claim 45.

BRIEF DESCRIPTION OF THE FIGURES The accompanying figures, which are included to provide a further understanding of the invention and constitutes a part of this specification, illus^¬ trate some embodiments of the invention and together with the description help to explain the principles of the invention. In the figures:

Fig. 1 is a flow chart illustration of a method according to one embodiment of the present in^¬ vention,

Fig. 2 is a flow chart illustration of a method according to another embodiment of the present invention,

Fig. 3 is a flow chart illustration of a method according to another embodiment of the present invention,

Fig. 4 is a flow chart illustration of a method according to another embodiment of the present invention,

Fig. 5 is a flow chart illustration of a waste paper treatment,

Fig. 6 is a flow chart illustration of a method according to one embodiment of the present in^¬ vention,

Fig. 7 is a flow chart illustration of a method according to another embodiment of the present invention,

Fig. 8 is a flow chart illustration of a method according to another embodiment of the present invention, and

Fig. 9 is a flow chart illustration of a method according to another embodiment of the present invention .

DETAILED DESCRIPTION OF THE INVENTION In the method of the present invention a mate^¬ rial component 4, 24 is formed from ash 1, 21.

In this context, the material component 4, 24 can be formed from ash 1,21 which can contain one or more ash component. The ash and ash component can con^¬ tain any ash and/or ash type raw material. The ash can be coming from paper industry, paper mill, pulp mill, saw mill, plywood mill, waste paper treatment, dein- king process, waste water treatment, gasification and/or other suitable mill or process. The ash can be coming from boiler or lime kiln or gasification. The ash can be formed by incineration or combustion using any technique in any boiler. The ash can be produced in different incineration temperatures. The ash can be formed by using any suitable lime kiln technique in any lime kiln. The ash can be formed by using any suitable gasification technique in any gasification.

In one embodiment the ash is selected from the group containing boiler ash, lime kiln ash, residue from the gasification, such as char, and their combinations. Preferably, the ash may include 0 - 100 % by weight boiler ash, 0 - 100 % by weight lime kiln ash and/or 0 - 100 % by weight residue from the gasification. In one embodiment the ash includes boiler ash. In one embodi- ment the ash is boiler ash. The boiler ash can be formed in any boiler. In one embodiment the boiler ash contains fly ash and/or bottom ash. In one embodiment the boiler ash contains 0 - 100 % by weight fly ash and/or 0 - 100 % by weight bottom ash.

In one embodiment the boiler ash is formed from a sludge which contains reject or rejects from a waste paper treatment, such as from a deinking pro^¬ cess, recycled fiber production, a paper mill and/or a waste water treatment plant. The boiler ash can be formed from any sludge by incineration or combustion in any boiler. In this context, the sludge contains rejects, such as sludges, rejects and residues, from a waste paper treatment, such as from a deinking process, re^¬ cycled fiber production, a paper mill and/or a waste water treatment plant. In one embodiment the sludge contains at least rejects, such as sludges, rejects and residues, from a waste paper treatment, e.g. RCF sludge (recycled fiber sludge), deinking sludge and/or coarse screening rejects and/or possibly drum rejects. A typical waste paper treatment process is presented in figure 5. Further, the sludge may include rejects, such as sludges, rejects and residues, from a paper mill. Further, the sludge may include rejects, such as sludges, from a waste water treatment plant, e.g. pri- mary sludge and/or biosludge. Further, the sludge may include rejects, such as sludges, rejects and resi^¬ dues, from any paper and board industry process. Further, the sludge may also include sludges and rejects from other processes. In this context, RCF sludge means any RCF reject or any combination of different RCF rejects from recycled fiber plant, e.g. wood based recycled fibre production. In this context, deinking sludge means any sludge and reject which is separated in a deinking step from the recovered paper, board or related fiber based products. The deinking sludge may include coarse screening rejects and/or biosludge. The sludge may include minerals used in paper coating, filler and printing inks, and fibers, fines, sticky materials like starch, latex and adhesive, and other inorganic components and/or small amount of other com^¬ ponents, preferably other reject components. In one embodiment, the sludge is high solid sludge in which dry solid content can be about 50 - 70 %. Preferably, the sludge can be dewatered to form the high solid sludge. In one embodiment, the sludge may be treated in the dewatering, for example by means of a gravita^¬ tion table and/or disc filter and/or screw press or the like before the method of the present invention. The sludge can also be dried to higher, even 99 % con sistency prior to incineration. Furthermore, the mate^¬ rial that is combusted can consist solely of the inor- ganic fraction separated from the deinking sludge. Fi^¬ nally, additional fuels such as bark, wood, waste wood, adhesive laminate waste, adhesive material, re^¬ lease material, green liquor dregs, wood-based, fiber- based or plastic-based composite material, bags, ener- gy waste, peat, oil for instance and/or any raw mate^¬ rial which produces ash, can be mixed with the sludges and other residues listed here in order to enhance the incineration .

In one embodiment the ash is formed from bark, wood, waste wood, adhesive laminate waste, adhe^¬ sive material, release material, green liquor dregs, wood-based, fiber-based or plastic-based composite ma^¬ terial, bags, energy waste, peat, oil for instance and/or any raw material which produces ash. In one em- bodiment the ash is formed in any boiler.

In one embodiment the method comprises reduc^¬ ing particle size of the ash (1,21) in at least one stage. The particle size reduction can be carried out such as presented in this context.

In one embodiment the method comprises neu^¬ tralizing the ash (1,21) . The neutralizing can be made such as presented in this context.

In one embodiment a material component 4 is formed from boiler ash 1, wherein method comprises: reducing 2 particle size of the boiler ash 1 in at least one reduction stage and neutralizing 3 the boil^¬ er ash in a liquid composition in a neutralizing stage in order to form the material component.

Some method and apparatus embodiments of the present invention are presented in figures 1, 2, 3 and 4. Preferably the boiler ash such as defined above is used as a raw material. In this context, the boiler ash 1 contains one or more ash component. The boiler ash can be formed by incineration or combustion using any technique in any boiler. The boiler ash can be produced in different incineration temperatures. In one embodiment the boiler ash or its component is formed from a sludge such as defined above.

The boiler ash 1 is fed to the apparatus. Preferably the apparatus includes a feeding device for feeding the boiler ash 1 to the apparatus.

A technical effect of the present invention is that the boiler ash with high alkalinity, abrasive- ness and inappropriate particle size distribution can be utilized in a material component thanks to the treatment containing particle size reduction and neu^¬ tralization of the boiler ash.

A technical effect of the invention is that different boiler ash can be utilized to form a new product. An additional technical effect of the inven^¬ tion is that different rejects for example from a waste paper treatment and/or a paper mill and/or waste water treatment plant can be utilized in the incinera^¬ tion in order to produce the ash that is being uti- lized in the end products, e.g. in the ink composi^¬ tions. Then environmental load decreases.

In this context, particle size reduction 2 means any reduction of the material particle size, e.g. by mechanically. The particle size reduction may be selected from the group of pulverization, grinding, crushing, cutting, chopping, shearing, compressing, breaking up of a material, e.g. by braying or rubbing or by air, by sound wave or by ultrasound, to a de^¬ sired particle size or other suitable grinding method or their combinations. Preferably, in the particle size reduction it is important to produce ultrafine particles. The particle size reduction can be carried out by means of any suitable method. The particle size reduction can be carried out in one stage or in more than one stage. In one embodiment the particle size re^¬ duction stage 2 comprises a grinding device. In one em- bodiment the particle size reduction can be made in two stages so that the boiler ash is pre-ground by first de^¬ vice to produce fine particles and then is ground by second device to produce ultrafine particles. The parti^¬ cle size reduction containing more than one stage can comprise different devices. It is important that ul^¬ trafine particles are produced in at least the finish particle size reduction stage.

The particle size reduction 2 can be carried out by any suitable grinding method and devices, e.g. by dry grinding, such as by fluidized bed jet mill or dry agitating ball mill, or by wet grinding, such as by ball mill or pearl mill, or by any kind of other grinder, e.g. by abrasion resistant grinder, that can produce ultrafine particles. The grinding method can be select- ed from the group consisting of crushing-based grind^¬ ing, attrition-based grinding, abrasion-based grind^¬ ing, cutting-based grinding, blasting-based grinding, explosion-based grinding, wet grinding, dry grinding, grinding under pressure, other suitable grinding meth- od and their combinations. In one embodiment the grinding device used for grinding is selected from the group consisting of impact mill, air jet mill, sand mill, bead mill, pearl mill, ball mill, vibration mill, screw mill, extrusion device, other suitable de- vice and their combinations.

In the particle size reduction 2 the grinding additives can be used.

In one embodiment, classifiers can be used for obtaining a narrower particle size distribution after the particle size reduction stage. Any classifiers known per se may be used. In one embodiment the neutralizing 3 is made by C0₂. Either pure C0₂ or recovered waste C0₂ can be uti^¬ lized. In one embodiment the neutralizing 3 is made by an acid. Any suitable acid known per se, e.g. HC1, car- boxylic acid or lipid such as fatty acid, e.g stearic acid, oleic acid, myristic acid or caprylic acid or any other fatty acid or mixture of them, can be used in the neutralizing. In one embodiment the lipid is originated from side flows of the wood- or fiber processing indus- try. In one embodiment the fatty acid or fatty acid con^¬ taining compound is originated from side flows of the wood- or fiber processing industry. Preferably, the apparatus comprises at least one device for feeding acid or C0₂ into the boiler ash 1 before or during the neu- tralizing stage 3.

Preferably, the boiler ash 1 is mixed with a liquid 5 to form a liquid composition before the neu^¬ tralizing 3, before grinding 2 and neutralizing 3 or during the neutralizing 3. Preferably, the neutralizing is made in the liquid composition so that the ground boiler ash has been mixed with a liquid to form a liquid composition, and a liquid composition containing boiler ash is neutralized. If the wet grinding is used in the particle size reduction, so then the boiler ash is mixed with a liquid before the particle size reduc^¬ tion. In one embodiment the apparatus comprises at least one device for mixing the liquid 5 and the boiler ash 1 before or during the neutralizing stage 3.

In one embodiment the liquid is selected from the group water, acid, ink, paint or colour vehicle or one or several components of vehicles, and their combi^¬ nations. Vehicle is either ink, paint or color vehicle which can comprise several substances like water, var^¬ nish, oils and the like, and their different combina- tions. In one embodiment the liquid is selected from the group water, acid, solvent, varnish, oils, fatty ac^¬ ids and their combinations. Varnish can include mineral oil, tall oil, vegetable oil or their fractions, e.g. distillates, or their combination. In one embodiment oils or their fractions or distillates can be originated from industrial side streams. In one embodiment the boiler ash is mixed with acid and varnish to form a neutralized material component.

In one embodiment the liquid composition in^¬ cludes 10 - 50 w-%, preferably 10 - 20 w-%, more prefer^¬ able 12 - 18 w-%, boiler ash. Preferably, the neutraliz- ing 3 is carried out at 10 - 20 % concentration of the boiler ash.

In one embodiment the particle size of the boiler ash is reduced 2 and after that the boiler ash is neutralized 3. In one embodiment the particle size of the boiler ash is reduced 2 at two stages and after that the boiler ash is neutralized 3.

In one embodiment the boiler ash is neutral^¬ ized 3 and after that the particle size of the boiler ash is reduced 2.

In one embodiment the boiler ash is neutral^¬ ized in connection with the particle size reduction of the boiler ash, preferably at the same time and/or at the same process stage.

In one embodiment the particle size of the boiler ash is reduced 2 in at least two stages and the boiler ash is neutralized 3 between two particle size reduction stages.

If two particle size reduction stages are used so the first stage may be a dry-treating stage, i.e. a dry grinding stage, and the second stage may be a wet-treating stage, i.e. a wet grinding stage. In one embodiment the first stage may be a dry-treating stage, i.e. a dry grinding stage, and the second stage may be a dry-treating stage, i.e. a dry grinding stage. In one embodiment the first stage may be a wet- treating stage, i.e. a wet grinding stage, and the second stage may be a dry-treating stage, i.e. a dry grinding stage. In one embodiment the first stage may be a wet-treating stage, i.e. a wet grinding stage, and the second stage may be a wet-treating stage, i.e. a wet grinding stage.

In one embodiment, the neutralizing is made by

C0₂, wherein the boiler ash, the particle size of which is reduced or not reduced, is mixed with a liquid and after that the neutrilizing is carried out. If the particle size of the boiler ash is not reduced before the neutralization so the particle size reduction is made after the neutralization. The particle size re^¬ duction can also be made both before and after the neutralization .

In one embodiment, the neutralizing is made by an acid, wherein the boiler ash, the particle size of which is reduced or not reduced, is mixed with the acid and neutralized. The acid acts as a liquid in the liquid composition during the neutralizing. If the particle size of the boiler ash is not reduced before the neutralization so the particle size reduction is made after the neutralization. The particle size re^¬ duction can also be made both before and after the neutralization .

In one embodiment the boiler ash is first mixed with varnish and the particle size reduction is carried out for the ash-based mixture, and then the neutralization is carried out after the particle size reduction of said ash-based mixture.

In one embodiment the particle size reduction and the neutralization is made at the same stage.

After the neutralizing it is important that pH of the material component 4 is at neutral level, prefer^¬ ably about 6 - 8, more preferable about 6 - 7.5, after the neutralizing 3. Preferably, pH has to be about 6 - 7 for example in printing inks.

In one embodiment the material component 4 is in the form of slurry, dispersion, solution or the like. Alternatively the material component may be dry compo^¬ nent, e.g. in the form of fine pulver or powder.

Preferably, the material component has particle size which is in the size range of the ultrafine parti- cles. In one embodiment the particle size reduction is carried out so that the mean particle size of the ma^¬ terial component is under 10 ym, preferably between 0.1 - 8 μιη and more preferable between 0.1 - 5 ym, af^¬ ter the particle size reduction and the neutraliza- tion. In one embodiment the mean particle size of the material component is under 5 ym, preferably between 0.1 - 4 ym, more preferable between 0.1 - 3 ym and most preferable between 0.1 - 2 ym, after the particle size reduction and before the neutralization. In one embodiment the mean particle size of the material com^¬ ponent is measured by the Coulter-device. Alternative^¬ ly, the mean particle size can be measured by any oth^¬ er suitable device or method.

In one embodiment the apparatus comprises at least one drying device 6, preferably for drying the ma^¬ terial component.

In one embodiment the material component 4, e.g. material component slurry 8, is dried after the combination of the particle size reduction 2 and neu- tralization 3. In one embodiment the material compo^¬ nent is dried at temperatures between 90 - 120 ^°C, preferably between 100 - 110 ^°C, in order to form a dry cake. Preferably, the dried material component is then ground again into fine pulver.

In one embodiment the boiler ash 1 is dried after the neutralization 3 and before the particle size reduction 2 when the boiler ash is first neutralized 3 and after that the particle size of the boiler ash is reduced 2. In one embodiment dry grinding can be used in the particle size reduction. In one embodi^¬ ment wet grinding can be used in the particle size re^¬ duction. If the wet grinding is used so then the mate- rial component is preferably dried again after the particle size reduction and after that preferably re- ground .

The drying can be carried out by any suitable method or device. The drying can be made by means of drying device selected from the group: indirect dryer, direct dryer, paddle dryer, flash dryer, fluidized bed dryer, cyclone dryer, air dryer, air grinder, rotor mill, centrifugal mill, air turbulence mill, air tur- bulence dryer and other suitable dryers and other suitable mills, and their combinations. Preferably the drying is carried out by such air dryer or air grinder in which particles can be separated one from the oth^¬ er. Also other drying devices are possible. It is im- portant that drying temperature is selected so that the boiler ash or material component is not damaged.

In one embodiment the dried material compo^¬ nent can be re-ground, preferably after the drying. Preferably, the material component is re-ground in order to form fine pulver or powder. In one embodiment the ap^¬ paratus comprises at least one re-grinding device, pref^¬ erably for re-grinding the material component. The re- grinding can be made by any grinding device known per se. In one embodiment re-grinding can be made by some method or device presented previously in this applica^¬ tion, in connection with particle size reduction. In one embodiment a drying device can also act as a grinder. In one embodiment a grinder can act as a drying device. In one embodiment the drying and re- grinding may be made by the same device at one process step. The grinding additives may be used in the grind^¬ ing .

In one embodiment, classifiers can be used for obtaining a narrower particle size distribution after the re-grinding stage. Any classifiers known per se may be used. In one embodiment the drying and re-grinding can be made once or more than once.

Preferably, the material component has particle size which is in the size range of the ultrafine parti- cles after the drying and re-grinding. In one embodiment the mean particle size of the material component is under 10 μπι, preferably between 0.1 - 8 ym and more preferable between 0.1 - 5 μπι, after the drying and re- grinding .

In one embodiment the boiler ash or the mate^¬ rial component is treated, e.g. surface-treated. The treatment may be selected from the group containing dispersing, hydrogenation, acidifying, making the material component or its surface into hydrophobic, mix- ing of the material component or boiler ash with other agents, blackening of the material component and their combinations. In one embodiment the dispersing of the material component and making the material component into hydrophobic are carried out at the same stage.

In one embodiment the material component, e.g. its surface, is treated so that the material com^¬ ponent, e.g. its surface, becomes hydrophobic. This treatment can be made by means any method known per se and/or by means of any suitable agents, e.g. lipid, fatty acid, carboxylic acid, dispergation agents, hy^¬ drophobic agents or any other suitable agents. In one embodiment the material component is treated with fat^¬ ty acids. In one embodiment the material component be^¬ comes hydrophobic during the neutralization. If the neutralization is carried out by lipid, fatty acid or carboxylic acid then the surface of the material com^¬ ponent can be turned into hydrophobic during the neu^¬ tralization. In one embodiment the boiler ash is treated with fatty acids.

In one embodiment a material component 4 is formed from boiler ash 1 so that particle size of the boiler ash is reduced by dry grinding 2, the boiler ash 1 is mixed with a liquid 5 to form a liquid composition and the boiler ash is neutralized 3 in a liquid compo^¬ sition. In one embodiment the material component 4 is dried 6 and re-grinded 12 after the dry grinding and the neutralization. In one embodiment the material component 4 is turned into hydrophobic after the dry grinding and the neutralization. In one embodiment the material component 4 is dried 6 and re-grinded 12 af^¬ ter the dry grinding, neutralization and turning into hydrophobic. In one embodiment the material component 4 is dried 6 and re-grinded 12 after the dry grinding and the neutralization, and after that the material component is turned into hydrophobic.

In one embodiment a material component 4 is formed from boiler ash 1 so that the boiler ash 1 is mixed with a liquid 5 to form a liquid composition, particle size of the boiler ash is reduced by wet grind^¬ ing 2 and the boiler ash is neutralized 3. In one em^¬ bodiment the material component 4 is dried 6 and re- grinded 12 after the wet grinding and the neutraliza^¬ tion. In one embodiment the material component 4 is turned into hydrophobic after the wet grinding and the neutralization. In one embodiment the material compo^¬ nent 4 is dried 6 and re-grinded 12 after the wet grinding, neutralization and turning into hydrophobic. In one embodiment the material component 4 is dried 6 and re-grinded 12 after the wet grinding and the neu^¬ tralization, and after that the material component is turned into hydrophobic.

In one embodiment a material component 4 is formed from boiler ash 1 so that the boiler ash 1 is mixed with a liquid 5 to form a liquid composition, the boiler ash is neutralized 3 and particle size of the boiler ash is reduced by wet grinding 2. In one embod- iment the material component 4 is dried 6 and re- grinded 12 after the neutralization and the wet grind^¬ ing. In one embodiment the material component 4 is turned into hydrophobic after the neutralization and the wet grinding. In one embodiment the material com^¬ ponent 4 is dried 6 and re-grinded 12 after the neu^¬ tralization and wet grinding, and after that the mate- rial component 4 is turned into hydrophobic.

In one embodiment a material component 4 is formed from boiler ash 1 so that the boiler ash 1 is mixed with a liquid 5 to form a liquid composition, the boiler ash is neutralized 3, dried 6 and particle size of the dried boiler ash is reduced by grinding 2. In one embodiment the material component 4 is turned into hydrophobic after the neutralization, drying and grinding .

In one embodiment a material component 4 is formed from boiler ash 1 so that the boiler ash 1 is mixed with a liquid 5 to form a liquid composition, and after that the boiler ash is neutralized 3, turned in^¬ to hydrophobic and particle size of the boiler ash is reduced by wet grinding 2 at the same process stage. In one embodiment the material component 4 is dried 6 and re-grinded 12 after the neutralization, turning into hydrophobic and wet grinding.

In one embodiment a material component is formed from boiler ash so that particle size of the boiler ash is reduced by dry grinding in the first grinding stage, the boiler ash is mixed with a liquid to form a liquid composition, particle size of the boiler ash is reduced by wet grinding in the second grinding stage and the boiler ash is neutralized in a liquid composition. In one embodiment the material component is dried and re-grinded after the grinding stages and the neutralization. In one embodiment the material component is turned into hydrophobic after the grinding stages and the neutralization. In one em- bodiment the material component is dried and re- grinded after the grinding stages, neutralization and turning into hydrophobic. In one embodiment the mate- rial component is dried and re-grinded after the grinding stages and the neutralization, and after that the material component is turned into hydrophobic.

In one embodiment a material component is formed from boiler ash so that particle size of the boiler ash is reduced by dry grinding in the first grinding stage, the boiler ash is mixed with a liquid to form a liquid composition, the boiler ash is neutralized in a liquid composition and particle size of the boiler ash is reduced by wet grinding in the sec^¬ ond grinding stage. In one embodiment the material component is dried and re-grinded after the grinding stages and the neutralization. In one embodiment the material component is turned into hydrophobic after the grinding stages and the neutralization. In one embodiment the material component is dried and re- grinded after the grinding stages, neutralization and turning into hydrophobic. In one embodiment the mate^¬ rial component is dried and re-grinded after the grinding stages and the neutralization, and after that the material component is turned into hydrophobic.

The material component can be utilized as such. Alternatively, a mixture can be formed contain^¬ ing the material component and at least one other com- ponent, e.g. varnish, carbon black, fatty acids, pig^¬ ments separated directly from deinking sludge, fresh extender pigments and/or pitch oil and tar oil and their derivates that can be originated from industrial side streams. In one embodiment carbon black, varnish, pigments separated directly from deinking sludge and/or pitch oil is added into the material component to form a mixture and later a recycling based product. In one em^¬ bodiment the mixture includes the material component and varnish. In one embodiment the mixture includes the material component and carbon black. In one embod^¬ iment the mixture includes the material component, carbon black and varnish. In one embodiment the mix- ture includes the material component and the pitch oil. In one embodiment the mixture includes the mate^¬ rial component and the pigments separated directly from deinking sludge. In one embodiment the mixture includes the material component, carbon black and the pigments separated directly from deinking sludge. The mixture is utilized as such or in final products. The material component may be in the form of wet slurry, dry powder, dried and ground material, such as fine pulver or powder, or the like. The mixture may be in the form of wet slurry, dry powder, dried and ground material, such as fine pulver or powder, or the like.

In this context, the material component or the mixture can include one or more material component formed according to the method of the invention.

In one embodiment the material component formed only by grinding is mixed with carbon black, varnish, pigments separated directly from deinking sludge and/or pitch oil to form a mixture.

In one embodiment the apparatus comprises at least one second mixing stage 9 for forming a composi^¬ tion from the material component or the mixture which is in the form of wet slurry, dry powder, dried and ground material, such as fine pulver or powder, or the like.

In one embodiment the composition is re- ground by wet-grinding after the mixing. Said composition can be e.g. in the form of dispersion, slurry, solution or the like. The dispersing can be carried out by any suitable way, e.g. by mill, such as by three roll mill.

In one embodiment the material component or the mixture or the composition is mixed with other ink compounds to form an ink composition or a printing ink composition. Said ink composition can be in the form of dispersion, slurry, solution or the like. It is important in the printing that pH of the printing ink composition is neutral or slightly acidic. Therefore it is important to form a neutral or slightly acidic composition for the printing.

In one embodiment carbon black is added into the material component or the mixture or the composi^¬ tion. In a preferred embodiment carbon black is in the form of carbon black flush. Preferably, the carbon black is side product in energy or bioenergy production.

In one embodiment the carbon black is added into the material component to form a mixture, and the mixture is used in manufacturing a product. In one em^¬ bodiment the carbon black and the material component is combined in flush to form an ink raw material, paint material or any other colour material.

In one embodiment the carbon black is mixed with the boiler ash. In one embodiment the carbon black and the boiler ash are ground at same time, and then the neutralization is carried out after the grinding. If the carbon black and the boiler ash are ground at same time so pigment particles of the boiler ash or the material component may act as a grinding aid. Then the forming of carbon black agglomerates can be reduced. Further, more even print quality can be achieved in the printing. It is preferable to produce a flush which contains both carbon black as a colour pigment and boiler ash based material component as an extender in same flush.

In one embodiment the carbon black and var- nish is mixed with the boiler ash. In one embodiment the carbon black and the boiler ash and varnish are ground at same time, and then the neutralization is carried out after or during the grinding.

In one embodiment the pigments separated di- rectly from deinking sludge is mixed with the boiler ash. In one embodiment this composition combination are ground at same time, and then the neutralization is carried out after or during the grinding. In one embodiment the carbon black and pigments separated di^¬ rectly from deinking sludge is mixed with the boiler ash. In one embodiment this composition combination are ground at same time, and then the neutralization is carried out after or during the grinding. In one embodiment the carbon black and pigments separated di^¬ rectly from deinking sludge and varnish is mixed with the boiler ash. In one embodiment this composition combination are ground at same time, and then the neu^¬ tralization is carried out after or during the grinding .

In one embodiment the pitch oil is mixed with the boiler ash. In one embodiment the boiler ash and pitch oil are ground at same time, and then the neu^¬ tralization is carried out after or during the grinding .

Preferably, a material component can be used as a bio-based pigment agent, e.g. a colorant, as a filler and/or an extender in different purposes and in different final products. In this context, the final product includes the material component, preferably 1 to 100 w-%. In one embodiment the material component can be used in papers, composites, coating colors, printing inks, paints and other suitable products. Preferably, each product includes also other compo^¬ nents. In one embodiment the extender composition includes both the material component as extender and fresh extenders. Preferably, the material component can be used in connection with cyan, magenta and black colours and/or spot colours in final product applica^¬ tions. In black inks it may also include pigments sep^¬ arated directly from deinking sludge that have been ground after or during the separation of the pigments or together with boiler ash according to this invention. Extenders are used as additional pigments in printing inks. Normally fresh fillers, e.g. calcium carbonate or clay, which are ground to small enough particle size are used as extenders. The material com- ponent formed from the boiler ash can offer a cheaper and more ecological alternative to the fresh filler based extender pigments.

In one embodiment the material component used as extender has been treated so that it is hydropho- bic. In one embodiment the material component used as extender in the printing ink has been treated so that it is hydrophobic.

In one embodiment when using C0₂ for the neu^¬ tralization stage, the end product obtained from this process can, in addition to printing ink extender embodiments, be used also as fine filler in paper embod^¬ iments or as an extender in coating colors and paints. If acid is used for the neutralization stage, its presence in the final printing ink can improve the emulsifiability of the printing ink and thus render the size distribution of the ink drops more uniform which results more even print quality.

In one embodiment a material component is formed from boiler ash so that the particle size of the boiler ash is reduced in at least one stage. In one embodiment the neutralization of the boiler ash is carried out in connection with the particle size re^¬ duction of the boiler ash, preferably at the same time. In one embodiment the neutralization is made by means of the liquid in connection with the particle size reduction of the boiler ash, e.g. in wet- grinding. In one embodiment the neutralization is not made but the particle size of the boiler ash is re^¬ duced, e.g. by grinding, such as by dry-grinding and/or by wet-grinding, in one or more steps, without the neutralization. The particle size reduction can be carried out by any method or device disclosed in this application. The formed material component is used as an extender, e.g. in printing inks. In one embodiment the printing ink composition with neutral properties is obtained from the material component which has been reduced in at least one stage but not neutralized at separate neutralization stage. In one embodiment a neutral mixture or composition is formed from the ma^¬ terial component in connection with the mixing with other components.

The process according to the invention can be a continuous and/or batch process.

In the present invention, different boiler ashes can be utilized as secondary raw material for new high value products. Further, different sludges and rejects can be utilized via the forming boiler ash. The present invention provides products with good quality. The method of the present invention offers a possibility to prepare the products from the boiler ash cost-effectively. The present invention provides an industrially applicable, simple and affordable way of treating boiler ash and making the products from boiler ash.

A technical effect of the present invention is that boiler ash can be turned into material compo- nent product through particle size reduction and neu^¬ tralization, and then costs can be saved. An additional technical effect is that the material component of the present invention can replace fresh extenders and fillers and turn waste into product. Further, when the material component of the present invention is used in the printing ink compositions then even print quality is obtained.

The method according to the present invention is suitable for use in the manufacture of the differ- ent products from different boiler ashes and sludges that are first incinerated. The present invention brings both economical and ecological benefits. The material component is ecological. The material compo^¬ nent preserves environment on one hand by reducing landfilling of deinking rejects and on the other hand by replacing fresh filler based extenders with second- ary raw material based extenders. Furthermore, if waste C0₂ is utilized in the neutralization step, the product actually adsorbs this greenhouse gas and thus prevents it from entering the atmosphere.

In one embodiment the material component is the extender pigment 24, preferably for printing ink. The extender pigment is formed from ash 21.

Some method embodiments of the present inven^¬ tion are shown in figures 6, 7, 8 and 9.

In this context, the extender pigment 24 can be formed from ash 21 such as defined above.

In this context, the extender 24 can be formed from ash 21 which can be any ash and/or ash type raw material, such as defined above. The ash may include any ash and/or ash component and/or ash type component, for example combustion residue or gasifica^¬ tion residue or char. The ash can include one or more components. The extender pigment can be formed from one or more ashes or ash components. In one embodiment the extender pigment 24 is in the form of slurry, dis- persion, solution, flush, paste or the like. Alternatively the extender pigment may be dry component, e.g. in the form of fine pulver or powder. The extender pig^¬ ment can be used in any final product. In one embodi^¬ ment the extender pigment is used in the printing ink compositions.

In this context, the extender pigment product 26 can be formed from the extender pigment 24. The ex^¬ tender pigment product includes the extender pigment. The extender pigment product may include also other components, e.g. oil, such as mineral oil, tall oil or vegetable oil, fatty acid, additives, varnish, other printing ink component or components, other oil based component or components from refinery, paint or colour vehicle or one or several components of vehicles and/or their combinations. In one embodiment the extender pig^¬ ment product includes 1 - 100 % by weight extender pigment. In one embodiment the extender pigment prod^¬ uct is extender pigment. In one embodiment the extender pigment product is in the form of slurry, dispersion, solution, flush, paste, fine pulver or powder or the like. In one embodiment the extender pigment product is selected from the group containing extender varnish, extender base or the like.

In one embodiment the ash is selected from the group containing boiler ash, lime kiln ash, residue from the gasification, such as char, and their combinations.

A technical effect of the present invention is that the ash with high alkalinity, abrasiveness and inappropriate particle size distribution can be uti^¬ lized in an extender pigment thanks to the treatment of the present invention.

A technical effect of the invention is that different ashes can be utilized to form a new product. An additional technical effect of the invention is that different rejects for example from a waste paper treatment and/or a paper mill and/or waste water treatment plant can be utilized in the incineration in order to produce the ash that is being utilized in the end products, e.g. in the ink compositions. Then envi^¬ ronmental load decreases.

Preferably, the particle size of the ash is reduced. In one embodiment the ash is treated by reduc^¬ ing particle size of the ash in at least one stage. In one embodiment the ash is treated by grinding. In one embodiment the ash is ground. In one embodiment the ash is ground as such. In one embodiment the ash is ground in a separate grinding step. In one embodiment the ash is ground during other process step, such as during mixing. In this context, particle size reduction 22 means any reduction of the material particle size, e.g. by mechanically. The particle size reduction may be selected from the group of pulverization, grinding, crushing, cutting, chopping, shearing, compressing, breaking up of a material, e.g. by braying or rubbing or by air, by sound wave or by ultrasound, to a de^¬ sired particle size or other suitable grinding method or their combinations. Preferably, in the particle size reduction it is important to produce ultrafine particles. Preferably, abrasiveness of the ash can be reduced during the particle size reduction, such as during the grinding. The particle size reduction can be carried out by means of any suitable method. The parti- cle size reduction can be carried out in one stage or in more than one stage. In one embodiment the particle size reduction stage 22 comprises a grinding device. In one embodiment the particle size reduction can be made in two stages so that the ash is pre-ground by first device to produce fine particles and then is ground by second device to produce ultrafine particles. The particle size reduction containing more than one stage can comprise different devices. It is important that ultrafine parti^¬ cles are produced in at least the finish particle size reduction stage.

The particle size reduction 22 can be carried out by any suitable grinding method and devices, e.g. by dry grinding, such as by fluidized bed jet mill or dry agitating media mill, or by wet grinding, such as by ball mill or pearl mill, or ultra-fine grinding or by any kind of other grinder, e.g. by abrasion resistant grinder, that can produce ultrafine particles, or by their combination. In one embodiment ultra-fine dry grinding is used. The grinding method can be selected from the group consisting of crushing-based grinding, attrition-based grinding, abrasion-based grinding, cutting-based grinding, blasting-based grinding, ex- plosion-based grinding, wet grinding, dry grinding, grinding under pressure, other suitable grinding method and their combinations. In one embodiment the parti^¬ cle size reduction is carried out by three roll mill treating, such as three roll mill grinding. In one embodiment the grinding device used for grinding is se^¬ lected from the group consisting of impact mill, air jet mill, sand mill, bead mill, pearl mill, dry agitated pearl mill, ball mill, vibration mill, screw mill, three roll mill, extrusion device, other suita^¬ ble device and their combinations.

In the particle size reduction 22 the grinding additives can be used.

In one embodiment, classifiers can be used for obtaining a narrower particle size distribution after the particle size reduction stage. Any classifiers known per se may be used.

In one embodiment classifiers can be used for separating a coarse ash fraction from a fine ash frac- tion after the particle size reduction stage, such as after the grinding. In one embodiment the particle size of the coarse ash fraction is again reduced, and after that said fraction is mixed together with the fine ash fraction and is utilized in the process. In one embodi- ment classifiers can be used for separating a coarse ash fraction from a fine ash fraction before the the parti^¬ cle size reduction stage, such as before the grinding. The fine ash fraction is used as such and the particle size of the coarse ash fraction is reduced by grinding.

Preferably, the extender pigment has particle size which is in the size range of the ultrafine parti^¬ cles. In one embodiment the particle size reduction is carried out so that the mean particle size of the ex^¬ tender pigment is under 100 ym, more preferably under 50 ym. In one embodiment the mean particle size of the extender pigment is measured by the Coulter-device. Alternatively, the mean particle size can be measured by any other suitable device or method.

In one embodiment the ash is mixed with first component 28 in the first mixing step 23 and ground. The first component may be selected from the group contain^¬ ing oil, such as mineral oil, tall oil or vegetable oil, fatty acid, additives, grinding additive, other printing ink component or components, other oil based component or components from refinery and/or their combinations.

In one embodiment the extender pigment prod^¬ uct is formed by mixing ash with first component in the first mixing step and grinding the formed mixture.

In one embodiment the ash is treated by mixing with second component 31 in the second mixing step 25 in order to form an extender pigment 4 or extender pigment product 26. The second component may be selected from the group containing oil, such as mineral oil, tall oil or vegetable oil, fatty acid, additives, varnish, other printing ink component or components, other oil based component or components from refinery, paint or colour vehicle or one or several components of vehicles and/or their combinations. Vehicle is either ink, paint or col^¬ or vehicle which can comprise several substances like water, varnish, oils and the like, and their different combinations. Varnish can include mineral oil, tall oil, vegetable oil or their fractions, e.g. distillates, or their combination. In one embodiment oils or their fractions or distillates can be originated from industrial side streams. In one embodiment the ash is mixed with acid and varnish to form a neutralized extender pigment or extender pigment product.

In one embodiment the extender pigment prod^¬ uct is formed in the second mixing step.

In one embodiment the second mixing is a man- ufacturing step of the printing ink composition.

In one embodiment the particle size of the ash is reduced in connection with the second mixing, prefer- ably with the strong mixing, during the mixing. The ash may be used as such as extender pigment, e.g. in print^¬ ing ink, without treating in a separate particle size reduction step. Alternatively, the particle size of the ash may be reduced, for example by grinding, before or after the mixing step.

In one embodiment the ash is treated by neu^¬ tralizing and/hydrophobizing .

In one embodiment the ash is treated by neu- tralizing the ash. The neutralizing may be made in connection with the particle size reduction or the mixing, or at a separate neutralizing stage. In one embodiment the ash is neutralized in a liquid composi^¬ tion at a neutralizing stage. In one embodiment the neutralizing is made during the mixing of the ash with the other component or components. In one embodiment the neutralizing is made during the mixing of the ash with fatty acid or fatty acids.

In one embodiment the neutralization is car- ried out after the particle size reduction of ash. In one embodiment the neutralization is carried out be^¬ fore the particle size reduction of ash. In one embod^¬ iment the neutralization is carried out at the same time than the particle size reduction of ash.

In one embodiment the neutralizing is made with an acid. Any suitable acid known per se, e.g. fatty ac^¬ ids such as stearic acid, oleic acid, myristic acid or caprylic acid or any other fatty acid or mixture of them, can be used in the neutralizing. In one embodiment the fatty acid or fatty acid containing compound is originated from side flows of the wood- or fiber pro^¬ cessing industry.

In one embodiment the ash is hydrophobized. In the hydrophobizing the ash is treated so that the ex- tender pigment becomes hydrophobic. The hydrophobizing may be made in connection with the particle size re^¬ duction or the mixing, or at a separate hydrophobizing stage. In one embodiment the hydrophobizing is made during the mixing of the ash with the other component or components. In one embodiment the hydrophobizing is made during the mixing of the ash by means of fatty acid or fatty acids .

In one embodiment the hydrophobizing is carried out after the particle size reduction of the ash. In one embodiment the hydrophobizing is carried out before the particle size reduction of the ash. In one embodiment the hydrophobizing is carried out at the same time with the particle size reduction of the ash. In one embodiment the hydrophobizing is carried out after the particle size reduction of the ash and dur^¬ ing mixing the ash with other components.

In one embodiment the hydrophobizing is car^¬ ried out so that the ash is mixed with one or more printing ink components and/or fatty acids during the first mixing step 23 and after that the formed mixture is grinded.

In one embodiment the ash is treated with fat^¬ ty acid or fatty acids. Fatty acids can be used for hy^¬ drophobizing and/or neutralizing the surface of the ash wherein dispersibility of the ash improves with oils and other printing ink components. In one embodi- ment the ash is neutralized with fatty acids. In one em^¬ bodiment pH of the ash is adjusted with fatty acids. In one embodiment the ash is hydrophobized with fatty ac^¬ ids. Fatty acid may be in a solid form or fatty acid may be in a liquid form.

In one embodiment the extender pigment contains

0.1 - 50 % by weight fatty acids. The printing ink is manufactured so that the proportion of extender pigment to fatty acids is between 1000:1 and 1:300.

In one embodiment the ash or the extender pigment is surface-treated. The treatment may be se^¬ lected from the group containing dispersing, hydro- genation, acidifying, making the extender pigment or its surface into hydrophobic, mixing of the extender pigment or ash with other agents, blackening of the extender pigment and their combinations . In one embod^¬ iment the dispersing of the extender pigment and mak- ing the extender pigment into hydrophobic are carried out at the same stage.

In one embodiment the extender pigment, e.g. its surface, is treated so that the extender pigment, e.g. its surface, becomes hydrophobic. This treatment can be made by means of any method known per se and/or by means of any suitable agents, e.g. fatty acid, car- boxylic acid, dispersing agents, hydrophobizing agents or any other suitable agents. In one embodiment the extender pigment becomes hydrophobic during the neu- tralization. If the neutralization is carried out by carboxylic acid then the surface of the extender pig^¬ ment can be turned into hydrophobic during the neu^¬ tralization .

A final product 27 containing an extender pigment or an extender pigment product is formed. In one embodiment the final product is selected from the group containing printing ink composition, paint, e.g. lime wash or silicate paint, grinding paste, polishing wax and composites. In one embodiment the extender pigment or the extender pigment product is used as bulk pigment or filler pigment in paints. In one embodiment the extender pigment or the extender pigment product is used as a component in lime wash to produce colour without other pigments or together with other pig- ments. In one embodiment the extender pigment or the extender pigment product with suitable particle size is used in grinding pastes or polishing waxes. In one embodiment the extender pigment or the extender pigment product is used as an extender in the final product. For example the extender pigment is mixed with other printing ink components. The extender pigment obtained by the method of the invention may be used as a component in a final product, e.g. in a printing ink composition. In one embodiment the extender pigment is used as an extender pigment product. In one embodiment the extender pig^¬ ment can be utilized as such in the final product. In one embodiment carbon black, varnish, fatty acid, and/or other additive are added into the extender pig^¬ ment to form the extender pigment product, and the ex- tender pigment product is used as a component in a fi^¬ nal product.

In one embodiment the extender pigment product contains 1 - 100 % by weight the extender pigment ob^¬ tained by the method of the invention.

In one embodiment the final product contains 1

- 100 % by weight the extender pigment obtained by the method of the invention or the extender pigment prod^¬ uct of the invention.

In this context, the extender pigment or the extender pigment product can include one or more ex^¬ tender pigment formed according to the method of the invention .

In one embodiment at least one conventional extender, which is known per se, is added into the ex- tender pigment to form the extender pigment product. In this context, the conventional extender may be formed from virginal or fresh raw material or recy^¬ cling raw material. In one embodiment the extender pigment product contains the conventional extender 1 - 100 %. In one embodiment the extender pigment is mixed with carbon black, varnish, pigments separated directly from deinking sludge and/or pitch oil to form the extender pigment product.

In one embodiment carbon black, varnish, fatty acid and/or other additive are added into the extender pigment in order to form the extender pigment product which may be in the form of flush, paste or extender varnish, and the formed product is used, preferably as an extender, in a printing ink composition.

In one embodiment the extender pigment prod^¬ uct can be formed containing the extender pigment and at least one other component, e.g. varnish, carbon black, pigments separated directly from deinking sludge according to patent application FI20125993, ma^¬ terial component produced according to this present application, fresh extender pigments and/or pitch oil and tar oil and their derivates that can be originated from industrial side streams. In one embodiment carbon black, varnish, pigments separated directly from dein^¬ king sludge according to patent application FI20125993 or material component produced according to this pre- sent application and/or pitch oil is added into the ex^¬ tender pigment to form the extender pigment product and later a recycling based final product. In one embodi^¬ ment the extender pigment product includes the extend^¬ er pigment and varnish. In one embodiment the extender pigment product includes the extender pigment and car^¬ bon black. In one embodiment the extender pigment product includes the extender pigment, carbon black and varnish. In one embodiment the extender pigment product includes the extender pigment and the pitch oil. In one embodiment the extender pigment product includes the extender pigment and the pigments sepa^¬ rated directly from deinking sludge. In one embodiment the extender pigment product includes the extender pigment and pigments separated directly from deinking sludge according to patent application FI20125993 and/or material component produced according to this present application. In one embodiment the extender pigment product includes the extender pigment, carbon black and the pigments separated directly from dein- king sludge according to patent application FI20125993 and/or material component produced according to this present application. The extender pigment product is utilized as such or in final products. The extender pigment prod^¬ uct may be in the form of oil based slurry or dry pow^¬ der. In one embodiment the extender pigment product is in the form of dry powder. In one embodiment the ex^¬ tender pigment product consists of the extender pig^¬ ment and it is in the form of dry powder. In one embodiment the extender pigment product includes the ex^¬ tender pigment containing ash, and the extender pig- ment product is in the form of dry powder. In one em^¬ bodiment the extender pigment product includes the ex^¬ tender pigment containing ash and fatty acids, and the extender pigment product is in the form of dry powder. In one embodiment the extender pigment product con- tains the extender pigment and oil, e.g. mineral oil, tall oil, vegetable oil or the like. In one embodiment the extender pigment contains ash. In one embodiment the extender pigment contains ash and fatty acids . In one embodiment the extender pigment product is in the form of flush or paste containing the extender pigment and oil.

In one embodiment the extender pigment or the extender pigment product is post-ground, e.g. by wet- grinding, and/or dispersed after the mixing. The dis- persing can be carried out by any suitable way, e.g. by mill, such as by three roll mill.

In one embodiment the extender pigment is formed for printing ink from ash. The ash can be treated or used as such in order to form the extender pig- ment. In one embodiment the extender pigment is used, preferably as an extender, in a printing ink composition. If the ash is used as such so then the ash is mixed with other printing ink components to form printing ink composition. Preferably, the particle size of the ash is reduced during the mixing. Then the extender pigment, and also extender pigment product, is formed during the printing ink mixing. In one embodiment the extender pigment or the extender pigment product is mixed with other ink compounds to form an ink composition or a printing ink composition. Said ink composition can be in the form of dispersion, slurry, solution, flush, paste or the like .

In one embodiment fatty acid is added into the extender pigment or the extender pigment product. Fatty acids can be used for hydrophobizing and/or neu- tralizing the extender pigment. Preferably, fatty ac^¬ ids which are present for example in printing ink composition are able to hydrophobize and/or neutralize the extender pigment. Further, the extender pigment which has been mixed with printing ink components to form printing ink composition may be ground in the printing ink composition.

In one embodiment carbon black is added into the extender pigment or the extender pigment product. In a preferred embodiment carbon black is in the form of carbon black flush. Preferably, the carbon black is side product in energy or bioenergy production.

In one embodiment the carbon black is added into the extender pigment to form the extender pigment product, and the extender pigment product is used in manufacturing a final product. In one embodiment the carbon black and the extender pigment is combined in flush to form an ink raw material, paint material or any other colour material.

In one embodiment the carbon black is mixed with the ash. In one embodiment the carbon black and the ash are treated at same time. If the carbon black and the ash are ground at same time so pigment parti^¬ cles of the ash may act as a grinding aid. Then the forming of carbon black agglomerates can be reduced. Further, more even print quality can be achieved in the printing. It is preferable to produce a flush which contains both carbon black as a colour pigment and ash based extender pigment as an extender in same flush .

In one embodiment the carbon black and var^¬ nish is mixed with the ash. In one embodiment the car- bon black and the ash and varnish are treated, e.g. ground, at same time.

In one embodiment the pigments separated di^¬ rectly from deinking sludge according to patent appli^¬ cation FI20125993 and/or material component produced according to this present application is mixed with the ash. In one embodiment this composition combina^¬ tion is treated, e.g ground, at same time. In one em^¬ bodiment the carbon black and pigments separated di^¬ rectly from deinking sludge according to patent appli- cation FI20125993 and/or material component produced according to this present application is mixed with the ash. In one embodiment this composition combina^¬ tion is treated, e.g. ground, at same time. In one em^¬ bodiment the carbon black and pigments separated di- rectly from deinking sludge according to patent appli^¬ cation FI20125993 and/or material component produced according to this present application and varnish is mixed with the ash. In one embodiment this composition combination is treated, e.g. ground, at same time.

In one embodiment the pitch oil is mixed with the ash. In one embodiment the ash and pitch oil are treated, e.g ground at same time.

Preferably, an extender pigment can be used as a bio-based pigment agent, e.g. a colorant, as a filler and/or as an extender in different purposes and in different final products. In one embodiment the ex^¬ tender pigment can be used in papers, composites, coating colors, printing inks, paints and other suita^¬ ble products. Preferably, each final product includes also other components. In one embodiment the extender pigment product includes both the extender pigment of the invention and fresh extenders. Preferably, the ex- tender pigment can be used in connection with cyan, magenta and black colours and/or spot colours in final product applications. In black inks it may also in^¬ clude pigments separated directly from deinking sludge that have been ground after or during the separation of the pigments or together with ash according to this invention .

Extenders may be used as additional pigments in printing inks. Normally fresh fillers, e.g. calcium carbonate or clay, which are ground to small enough particle size are used as extenders. The extender pig^¬ ment formed from the ash can offer a cheaper and more ecological alternative to the fresh filler based ex^¬ tender pigments.

In one embodiment the extender pigment has been treated so that it is hydrophobic. In one embodi^¬ ment the extender pigment used as extender in the printing ink has been treated so that it is hydropho^¬ bic .

If fatty acid is used for the neutralizing and/or hydrophobizing, its presence in the final printing ink can improve the emulsifiability and dis- persibility of the printing ink. Furthermore, the hy- drophobized ash stays in the printing ink better com- pared to conventional extender without transferring to fountain solution.

In one embodiment an extender pigment 24 is formed from ash 21 so that the particle size of the ash is reduced in at least one stage 22. In one embod- iment the neutralization of the ash is carried out in connection with the particle size reduction 22 of the ash, preferably at the same time. In one embodiment the neutralization is made by means of suitable liquid in connection with the particle size reduction of the ash, e.g. in wet-grinding. In one embodiment the neu^¬ tralization is not made but the particle size of the ash is reduced, e.g. by grinding, such as by dry- grinding and/or by wet-grinding, in one or more steps, without the neutralization. The particle size reduc^¬ tion can be carried out by any method or device dis^¬ closed in this application. The formed extender pig- ment or extender pigment product is used as an extend^¬ er, e.g. in printing inks. In one embodiment the printing ink composition with neutral properties is obtained from the extender pigment of which particle size has been reduced in at least one stage but the extender pigment has not been neutralized at separate neutralization stage. In one embodiment a neutral mix^¬ ture or composition is formed from the extender pig^¬ ment in connection with the mixing with other components .

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with printing ink components 30, e.g. by means of three roll mill, in a printing ink mixing step 29. The ash 21 is used as such as the extender pigment.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed in the second mixing step 25 with other components by a strong mixing in a suitable device, e.g. in three roll mill. Simultaneously the particle size of the ash is reduced.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed in the second mixing step 25 with other components containg fatty acids by a strong mixing in a suitable device, e.g. in three roll mill. Simultaneously the particle size of the ash is reduced and the ash is neutralized and turned into hydrophobic thanks to fatty acids.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed in the second mixing step 5 with fatty acids by a strong mix^¬ ing in a suitable device, e.g. in three roll mill, and after that they are mixed with printing ink components 30 in the printing ink mixing step 29. Simultaneously the particle size of the ash is reduced and the ash is neutralized and turned into hydrophobic thanks to fat^¬ ty acids .

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed in the second mixing step 25 with fatty acids and mineral oil by a strong mixing in a suitable device, e.g. in three roll mill, and after that they are mixed with printing ink components 30 in the printing ink mixing step 29. Simultaneously the particle size of the ash is reduced and the ash is neutralized and turned into hydrophobic thanks to fatty acids .

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed in the second mixing step 25 with mineral oil by a strong mixing in a suitable device, e.g. in three roll mill, and after that they are mixed with printing ink compo^¬ nents 30 in the printing ink mixing step 29. Simulta- neously the particle size of the ash is reduced.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is ground in the grinding step 22. After the grinding 22 the extender pigment 24 is mixed with printing ink components 30 in the printing ink mixing step 29. In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is ground by ultra-fine dry-grinding 22.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with printing ink components in the first mixing step 23 and after that they are ground in the grinding step 22.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with min- eral oil in the first mixing step 23 and after that they are ground in the grinding step 22. The formed mixture is mixed with printing ink components 30 in the printing ink mixing step 29.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with addi- tives in the first mixing step 23 and after that they are ground in the grinding step 22. The formed mixture is mixed with printing ink components 30 in the print^¬ ing ink mixing step 29.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with fatty acids in the first mixing step 23 and after that they are ground in the grinding step 22. In one embodiment dry-grinding, preferably ultra-fine dry-grinding, is used. The formed mixture is mixed with printing ink components 30 and/or oil in the printing ink mixing step 29. Simultaneously the the extender pigment is neutralized and turned into hydrophobic thanks to fat^¬ ty acids .

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with fatty acids and mineral oil in the first mixing step 23 and after that they are ground in the grinding step 22. The formed mixture is mixed with printing ink compo^¬ nents 30 in the printing ink mixing step 29. Simulta- neously the the extender pigment is neutralized and turned into hydrophobic thanks to fatty acids.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with fatty acids 28 in the first mixing step 23 and after that the mixture including ash and fatty acids is ground in the grinding step 22. After the grinding 22 the extender pigment 24 is mixed with printing ink components 30 in the printing ink mixing step 29. Simulta^¬ neously the extender pigment is neutralized and turned into hydrophobic thanks to fatty acids.

In one embodiment an extender pigment 24 is formed from ash 21 so that the ash is mixed with fatty acids 28 in the first mixing step 23 and after that the mixture including ash and fatty acids is ground in the grinding step 22. The extender pigment is mixed with mineral oil 31 in the second mixing step 25 in order to form an extender pigment product 26. After the second mixing 25 the extender pigment product 26 is mixed with printing ink components 30 in the print^¬ ing ink mixing step 29. Simultaneously the extender pigment product is neutralized and turned into hydro- phobic thanks to fatty acids.

In the present invention, different ashes can be utilized as secondary raw material for new high value products. Further, different sludges and rejects can be utilized via the forming ash. The present in^¬ vention provides products with good quality. The meth^¬ od of the present invention offers a possibility to prepare the products from the ash cost-effectively. The present invention provides an industrially appli^¬ cable, simple and affordable way of treating ash and making the products from ash. The ash can be utilized economically and ecologically.

A technical effect of the present invention is that ash can be turned into extender pigment prod^¬ uct, and then costs can be saved. An additional tech^¬ nical effect is that the extender pigment of the pre^¬ sent invention can replace fresh extenders and fillers and turn waste into product.

The method according to the present invention is suitable for use in the manufacture of the differ^¬ ent products from different ashes and sludges that are first incinerated. The present invention brings both economical and ecological benefits. The extender pig- ment is ecological. The extender pigment preserves en^¬ vironment on one hand by reducing landfilling of dein- king rejects, lime kiln ash and gasification rejects and on the other hand by replacing fresh filler based extenders with secondary raw material based extenders.

EXAMPLES

The invention is described in more detail by the following examples with reference to accompanying figures 1 to 4 and 6 to 9.

Example 1

In this example, which is shown in figure 1, a material component is formed from a boiler ash 1 originated from incineration of a sludge comprising deinking sludge.

The boiler ash 1 is fed to the apparatus, and the boiler ash is treated so that particle size of the boiler ash is reduced by dry grinding in a particle size reduction stage 2 and the boiler ash 1 is neu^¬ tralized in a neutralizing stage 3 to form a material component 4. A liquid 5 is added into the boiler ash before the neutralizing stage 3.

Example 2

In this example, which is shown in figure 2, a material component is formed from a boiler ash 1 originated from incineration of a sludge comprising deinking sludge.

The boiler ash 1 is fed to the apparatus, and the boiler ash is treated so that the boiler ash 1 is neutralized in a neutralizing stage 3 and particle size of the boiler ash is reduced by wet grinding in a particle size reduction stage 2 to form a material component 4. A liquid 5 is added into the boiler ash before the neutralizing stage 3. Example 3 In these tests a material component was formed separately from two boiler ashes, ash A and ash B, originated from deinking sludge. This process is shown in figure 3.

The ash, ash A or ash B, 1 was first ground in a grinding stage 2 with a fluidized bed opposed jet mill, and then mixed with water 5 to form a liquid composition with about 15 % concentration and neutral- ized in a neutralizing stage 3 by introducing C0₂ to the ash slurry until pH of the slurry remained at about 7. Grinding pressure was about 10 bar and clas^¬ sifier speed was about 22 000 rpm. After the neutral^¬ izing stage 3, an excess of water 7 was removed 16 from material component slurry 8 to provide dry con^¬ tent of the material component over 20 %. The specific surface area of the material components were 38.94 m²/g (ash B) and 62.9 m²/g (ash A) . The mean particle sizes of the material components measured by Coulter- device were 5.66 ym (ash B) and 4.323 ym (ash A) .

The neutralized material component 4 was mixed with other printing ink compounds 10 in a mixing stage 9 to form a printing ink composition 11. Laboratory scale printing experiments were carried out with the Prtifbau device. Even print quality was obtained with both A and B ash based extenders. ISO brightnesses of the produced extenders were surpris^¬ ingly high, 74.8 % and 82.4 %.

In the tests it was observed that good and even print quality was obtained with the material com^¬ ponent containing printing ink. Further, it was observed that the material component can be used as the extender in connection with black inks, cyan inks and/or magenta inks thanks to good optical properties. Further, it was observed that the material component has high specific surface area. Example 4

In these tests a material component was formed separately from two boiler ashes, ashes A and B, originated from deinking sludge. This process is based on figure 4.

The ashes 1 was first ground in a dry grind^¬ ing stage 2 with an ultrafine grinder by means of typ^¬ ical grinding additive and then mixed with water 5 to form a liquid composition with about 15 % concentra^¬ tion, and neutralized in a neutralizing stage 3 by in^¬ troducing C0₂ to the ash slurry until pH of the slurry remained at about 7. The neutralized material compo^¬ nent 8 was dried in a drying stage 6 at temperature about 105 °C to form a dry cake. The cake 13 was re- ground in a re-grinding stage 12 to form pulverized material component 14 which was mixed with other printing ink compounds 10 in a mixing stage 9 to form a printing ink composition 11. Laboratory scale print- ing experiments were carried out with the Prtifbau de^¬ vice .

The specific surface area of the material components were 33.53 m²/g (ash B) and between 33.56 - 69.01 m²/g (ash A) . The mean particle size of the ma- terial components measured by Coulter-device were 3.648 ym (ash B) and between 4.211 - 4.461 ym (ash A) .

In the tests it was observed that good and even print quality was obtained with the material com^¬ ponent containing printing ink. Even print quality was obtained with both A and B ash based extenders. Fur^¬ ther, it was observed that the material component can be used as the extender in connection with black inks, cyan inks and/or magenta inks thanks to good optical properties. Further, it was observed that the material component has high specific surface area. In the tests it was observed that the print^¬ ing inks containing the material component had even lower mottling tendency than the inks containing fresh extender .

A particle size and dispersibility are im^¬ portant for the material component formed in the pro^¬ cess according to the invention. Preferably, the mate^¬ rial component of the invention is used to replace ex^¬ pensive pigments and extenders.

Example 5

In this example, which is shown in figure 6, an extender pigment 24 is formed from a boiler ash 21 originated from incineration of a sludge comprising deinking sludge. The ash 21 is used as such as the ex^¬ tender pigment. The ash 21 is fed to a printing ink mixing step 29 in which the ash is mixed with printing ink components 30 by means of three roll mill. During the printing ink mixing the ash is grinded by the three roll mill wherein an extender pigment is formed. The printing ink components may contain fatty acids. A final product 27 including printing ink components and extender pigment is formed in the printing ink mixing 29.

Example 6

In this example, which is shown in figure 7, an extender pigment 24 is formed from a boiler ash 21 originated from incineration of a sludge comprising deinking sludge. The ash is ground in the grinding step 22 which may be ultra-fine dry-grinding. After the grinding 22 the extender pigment 24 is mixed with with printing ink components 30 in the printing ink mixing step 29. The printing ink components may con- tain fatty acids. A final product 27 including print^¬ ing ink components and extender pigment is formed in the printing ink mixing 29. Alternatively, an extender pigment 24 can be used as an extender pigment product 26 before the printing ink mixing 29. Example 7

In this example, which is shown in figure 8, an extender pigment 24 is formed from a boiler ash 21 originated from incineration of a sludge comprising deinking sludge. The ash is mixed with fatty acids 28 in the first mixing step 23 and after that the mixture including ash and fatty acids is ground in the grind^¬ ing step 22 which may be ultra-fine dry-grinding in order to form the hydrophobic extender pigment 24. The extender pigment is in the form of hydrophobic powder. After the grinding 22 the extender pigment 24 is mixed with with printing ink components 30 in the printing ink mixing step 29. The printing ink components may contain additional fatty acids. A final product 27 in^¬ cluding printing ink components and extender pigment is formed in the printing ink mixing 29. Alternative^¬ ly, an extender pigment 24 can be used as an extender pigment product 26 before the printing ink mixing 29.

Example 8

In this example, which is shown in figure 9, an extender pigment 24 is formed from a boiler ash 21 originated from incineration of a sludge comprising deinking sludge. The ash is mixed with fatty acids 28 in the first mixing step 23 and after that the mixture including ash and fatty acids is ground in the grind^¬ ing step 22 which may be ultra-fine dry-grinding in order to form the hydrophobic extender pigment 24. The extender pigment is mixed with mineral oil 31 in the second mixing step 25 in order to form an extender pigment product 26. The extender pigment product 26 may be in the form of flush or paste. Preferably, the extender pigment product has good flow properties and viscosity properties. After the second mixing 25 the extender pigment product 26 is mixed with with print^¬ ing ink components 30 in the printing ink mixing step 29. The printing ink components may contain additional fatty acids. A final product 27 including printing ink components and extender pigment product is formed in the printing ink mixing 29. Alternatively, an extender pigment product 26 can be utilized separately. Example 9

In the test made by example 8, the ash was mixed with about 1 % of fatty acid. The mixture was dry-ground with a ball mill. A hydrophobic powder was obtained that was mixed with mineral oil. Even with 60 % ash consistency, an ash-oil paste with good flow and viscosity properties was obtained.

Example 10

In this example, an extender pigment was formed from a boiler ash originated from incineration of a sludge comprising deinking sludge.

The ash was ground with a dry agitating media mill to 1.824 ym mean particle size (Coulter) . 1 % of grinding additive was used in the dry grinding. In- stead of fresh extender pigments the ground ash powder was mixed with other printing ink compounds and the laboratory printing experiments were carried out with the Prtifbau device. The laboratory results indicate that most of the ground ash stays in the printing ink without transferring to the fountain solution. Furthermore, even print quality was obtained with the printing ink containing the ground ash as extender pigment . In the tests it was observed that the extend^¬ er pigment of the invention can be used to replace ex- pensive fresh raw material based and/or conventional pigments and extenders.

The material components according to the pre- sent invention are suitable in different embodiments to be used in different products. The method according to the present invention is suitable in different em^¬ bodiments to be used for manufacturing the most dif^¬ ferent kinds of material components.

The invention is not limited merely to the example referred to above; instead many variations are possible within the scope of the inventive idea de^¬ fined by the claims.

Claims

1. A method for manufacturing a material compo^¬ nent, wherein the material component (4,24) is formed from ash (1, 21) .

2. The method according to claim 1, wherein the method comprises reducing particle size of the ash (1,21) in at least one stage.

3. The method according to claim 1 or 2, wherein the method comprises neutralizing the ash

(1,21) .

4. The method according to claim 1, wherein method comprises

- forming the material component from boiler ash;

- reducing (2) particle size of the boiler ash (1) in at least one stage; and

- neutralizing (3) the boiler ash (1) in a liquid composition.

5. The method according to claim 4, wherein the neutralizing (3) is made by C0₂.

6. The method according to claim 4 or 5, wherein the neutralizing (3) is made by an acid.

7. The method according to any one of claims 4 to 6, wherein the boiler ash (1) is mixed with a liquid (5) to form a liquid composition and the neutralizing (3) is made in the liquid composition.

8. The method according to any one of claims 4 to 7, wherein the particle size of the boiler ash (1) is reduced (2) and after that the boiler ash is neu- tralized (3) .

9. The method according to any one of claims 4 to 8, wherein the boiler ash (1) is neutralized (3) and after that the particle size of the boiler ash is re^¬ duced (2 ) .

10. The method according to any one of claims

4 to 9, wherein the particle size reduction (2) is car- ried out by a method selected from the group containing dry grinding and wet grinding and their combinations.

11. The method according to any one of claims 4 to 10, wherein the liquid (5) is selected from the group containing ink, paint or colour vehicle and their components, water, acid, solvent, varnish, oils, fatty acids and their combinations.

12. The method according to any one of claims 4 to 11, wherein the material component (4) is dried af- ter the particle size reduction (2) and neutralization (3) .

13. The method according to claim 12, wherein the material component (4) is re-ground after the dry^¬ ing .

14. The method according to any one of claims

4 to 13, wherein the material component (4) is treated so that the material component becomes hydrophobic.

15. The method according to any one of claims 4 to 14, wherein the material component (4) is treated by fatty acids so that the material component becomes hydrophobic .

16. The method according to any one of claims 4 to 15, wherein the particle size reduction (2) is carried out so that the mean particle size of the ma- terial component (4) is under 10 ym.

17. The method according to any one of claims 4 to 16, wherein carbon black, varnish, pigments separated directly from deinking sludge and/or pitch oil is added into the material component (4) .

18. An apparatus for manufacturing a material component from boiler ash, wherein the apparatus includes

- a feeding device for feeding the boiler ash (1) to the apparatus ,

- at least one particle size reduction stage (2) for reducing particle size of the boiler ash, and - a neutralizing stage (3) for neutralizing the boiler ash in a liquid composition.

19. The apparatus according to claim 18, where^¬ in the particle size reduction stage (2) comprises a grinding device.

20. The apparatus according to claim 18 or 19, wherein the apparatus comprises at least one device for feeding acid or C0₂ into the boiler ash (1) before or during the neutralizing stage (3) .

21. The apparatus according to any one of claims 18 to 20, wherein the apparatus comprises at least one device for mixing a liquid (5) and the boiler ash (1) before or during the neutralizing stage (3) .

22. The apparatus according to any one of claims 18 to 21, wherein the particle size reduction stage (2) is arranged before the neutralizing stage (3) .

23. The apparatus according to any one of claims 18 to 22, wherein the neutralizing stage (3) is arranged before the particle size reduction stage (2) .

24. The apparatus according to any one of claims 18 to 23, wherein the apparatus comprises at least one drying device (6) .

25. The apparatus according to any one of claims 18 to 24, wherein the apparatus comprises at least one re-grinding device.

26. The apparatus according to any one of claims 18 to 25, wherein the apparatus comprises at least one mixing device (9) for forming a composition.

27. The material component, which is formed from a boiler ash (1) and the boiler ash (1) has been treated by reducing particle size of the boiler ash in at least one stage, and by neutralizing in a liquid composition .

28. A use of the material component obtained by the method of any one of claims 4 to 17, wherein the material component is used as a bio-based pigment agent, as a filler and/or as an extender in a final product .

29. The use according to claim 28, wherein the material component is used in papers, composites, coating colors, printing inks, paints and other prod^¬ ucts .

30. A final product, wherein the final prod^¬ uct contains a material component obtained by the method of any one of claims 4 to 17, and the material component is a filler and/or an extender in the final product .

31. The method according to claim 1, wherein

- the material component is the extender pigment (24) which is formed from ash (21) .

32. The method according to claim 31, wherein the ash (21) is treated by reducing (22) particle size of the ash in at least one stage.

33. The method according to claim 31 or 32, wherein the particle size reduction (22) is carried out by a method selected from the group containing grinding, dry grinding, wet grinding, ultra-fine grinding and their combinations.

34. The method according to any one of claims 31 to 33, wherein the particle size reduction (22) is carried out by three roll mill treating.

35. The method according to any one of claims 31 to 34, wherein the ash (21) is mixed (23) with first component (28) and ground (22) .

36. The method according to any one of claims 31 to 35, wherein the ash (21) is treated by mixing (25) with second component (31) .

37. The method according to any one of claims 31 to 36, wherein the ash (21) is treated by neutralizing the ash.

38. The method according to any one of claims

31 to 37, wherein the ash (21) is hydrophobized.

39. The method according to any one of claims 31 to 38, wherein the ash (21) is treated with fatty ac^¬ ids .

40. The method according to any one of claims 31 to 39, wherein the ash (21) is selected from the group containing boiler ash, lime kiln ash, residue from the gasification and their combinations.

41. An extender pigment for printing ink, wherein the extender pigment (24) is formed from ash (21) .

42. A use of the extender pigment obtained by the method of any one of claims 31 to 40, wherein the extender pigment (24) is used as an extender pigment product (26) in a printing ink composition (27) .

43. The use of the extender pigment according to claim 41, wherein carbon black, varnish, fatty acid, and/or other additive are added into the extender pig^¬ ment (24) to form the extender pigment product (26) .

44. An extender pigment product, wherein the extender pigment product (26) contains 1 - 100 % by weight the extender pigment obtained by the method of any one of claims 31 to 40.

45. A final product, wherein the final prod^¬ uct (27) contains an extender pigment (24) obtained by the method of any one of claims 31 to 40.

46. The final product according to claim 45, wherein the final product (27) is selected from the group containing printing ink composition, paint, grinding paste, polishing wax and composites.

47. The final product according to claim 45 or 46, wherein the extender pigment (24) is used as an extender in the final product (27) .