Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/34—Other details of the shaped fuels, e.g. briquettes
  • C10L5/36—Shape
  • C10L5/361—Briquettes

Definitions

• the presently claimed invention relates to a briquette comprising coal fines and a binder composition comprising at least one homo- or copolymer of (meth)acrylic acid (i) and at least one alkyl(meth)acrylate-styrene-copolymer (ii), a method for manufacturing said briquette and the use of a binder composition for the agglomeration of coal fines.
• coal fines are obtained in addition to lumps of coal. Further processing of said coal fines is possible, e.g. by using floatation processes.
• the thus obtained coal fines con- centrate is briquetted and the obtained tailings which still contain a considerable amount of coal fines are discarded onto a mining waste tip.
• the whole coal fines fraction is dumped onto a mining waste heap without any further processing.
• Such a coal fines may comprise more than 20 wt.-% of unburnable minerals rendering the coal fines as such inopportune to use as fuel.
• coal fines on mining waste tips lead to significant amounts of escaping coal dust which is undesirable and maybe in the future or already is prohibited by law in some countries.
• existing mining waste heap have to be closed and the coal fines removed.
• direct combustion of coal fines having high ash content is not possible, such coal fines can be combusted in a plant provided that the coal fines are present as briquettes.
• briquettes of course are much easier to transport compared to coal fines.
• the combustion can take place where needed.
• the briquettes need to be stable during transport and in particular resistant to damage by dropping from a certain height as transport from one vessel to another frequently occurs, e.g. when the pellets are moved from a train to a ship or the like.
• the briquettes break during transport or the surface is abraded due to friction undesired small particles are formed and even coal fines may be formed causing environmental contamination and, in case the worst comes to the worst, even dust explosions.
• the object of the presently claimed invention is to provide briquettes comprising coal fines and a binder composition which show a good mechanical stability and strength, whereby the mechanical stability and strength is developed at relatively low temperatures without the need to heat the binder composition.
• briquettes that comprise coal fines and a binder composition comprising at least one homo- or copolymer of (meth)acrylic acid (i) and at least one al- kyl(meth)acrylate-styrene-copolymer (ii).
• a binder composition comprising at least one homo- or copolymer of (meth)acrylic acid (i) and at least one al- kyl(meth)acrylate-styrene-copolymer (ii).
• the presently claimed invention is directed to a briquette comprising
• briquette denotes a compressed block of any shape including spheres, rectangles, squares, rods, broken strips and broken sheets.
• coal fines denotes the entirety of solid inorganic components comprising coal particles and ash particles.
• coal particles denotes particles consisting substantially, i.e. > 85 wt.-%, of carbon.
• ash particles denotes particles of non-coal minerals including silica, clay and pyrite.
• the coal particles make up at least 50 wt.-%, more preferably at least 60 wt.-% and most preferably at least 70 wt.-%, based on the total weight of the coal fines.
• the coal fines may further comprise ash particles.
• a low ash particle content e.g. 10 wt.-% or less, preferably 5 wt.-% or less, based on the total weight of the coal fines is preferable, the coal fines may comprise up to 40 wt.-% of ash particles determined according to standard gravimetric methods.
• the inventive pellets can still be utilized in a power plant, a coal lique- faction (Fischer-Tropsch/Sasol process) plant at such a high ash particle content.
• the ash particle content is up to 25 wt.-%, based on the total weight of the coal fines.
• Coal fines with high ash particle content include waste coal, run-of-mine coal and freshly mined coal.
• the coal fines comprise at least 50 wt.-% coal particles having a particle diameter of less than 1 mm determined according to DIN 66165, more preferably comprise at least 75 wt.-% coal particles having a particle diameter of less than 1 mm and most preferably consist of coal particles having a particle diameter of less than 1 mm.
• the coal fines comprise at least 50 wt.-% coal particles having a par- tide diameter of less than 500 ⁇ determined according to DIN 66165, more preferably comprise at least 75 wt.-% coal particles having a particle diameter of less than 500 ⁇ and most preferably consist of coal particles having a particle diameter of less than 500 ⁇ .
• the coal fines comprise at least 50 wt.-% coal particles having a particle diameter of less than 300 ⁇ determined according to DIN 66165, more preferably comprise at least 75 wt.-% coal particles having a particle diameter of less than 300 ⁇ and most preferably consist of coal particles having a particle diameter of less than 300 ⁇ .
• the coal fines comprise at least 50 wt.-% particles passing Tyler Mesh 16 sieve (1 mm sieve opening), more preferably comprise at least 75 wt.-% particles passing Tyler Mesh 16 sieve (1 mm sieve opening) and most preferably consist of particles passing Tyler Mesh 16 sieve (1 mm sieve opening).
• the coal fines comprise at least 50 wt.-% particles pass- ing Tyler Mesh 32 sieve (500 ⁇ sieve opening), more preferably comprise at least 75 wt.-% particles passing Tyler Mesh 32 sieve (500 ⁇ sieve opening) and most preferably consist of particles passing Tyler Mesh 32 sieve (500 ⁇ sieve opening).
• the coal fines comprise at least 50 wt.-% particles passing Tyler Mesh 48 sieve (300 ⁇ sieve opening), more preferably comprise at least 75 wt.-% particles passing Tyler Mesh 48 sieve (300 ⁇ sieve opening) and most preferably consist of particles passing Tyler Mesh 48 sieve (300 ⁇ sieve opening).
• the at least one homo- or copolymer of (meth)acrylic acid (i) is not an al- kyl(meth)acrylate-styrene-copolymer (ii).
• the at least one homo- or copolymer of (meth)acrylic acid (i) is selected from the group consisting of homopolymers of acrylic acid, optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• homopolymers of methacrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• copolymers of acrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts, and at least one nonionic monomer;
• copolymers of methacrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts, and at least one nonionic monomer.
• nonionic monomer is a monomer which is electrically neutral.
• nonionic monomers are selected from the group consisting of methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylamide, methac- rylamide, N-methylacrylamide, N-isopropylacrylamide, N-tert-butyl acrylamide, N-methylo- lacrylamide, N, N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(2-hydroxypro- pyl)methacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-N- methylacetamide, poly(ethylene glycol)(meth)acrylate, poly(ethylene glycol) monomethyl ether mono(meth)acrylate, N-vinyl-2-pyrrolidone,
• nonionic monomers are selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N-tert-butyl acrylamide, N-methylolacrylamide, methacrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
• the homo- or copolymers of (meth)acrylic acid (i) are selected from the group consisting of homopolymers of acrylic acid, optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• homopolymers of methacrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• copolymers of acrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts, and at least one nonionic monomer selected from the group consisting of acryla- mide, methacrylamide, N-isopropylacrylamide, N-tert-butyl acrylamide, N-methylolacrylamide, methacrylate, ethyl acrylate, propyl acrylate and butyl acrylate; and
• copolymers of methacrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts, and at least one nonionic monomer selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N-tert-butyl acrylamide, N-methylolacrylamide, methacrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
• the homo- or copolymers of (meth)acrylic acid (i) are selected from the group consisting of homopolymers of acrylic acid, optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• homopolymers of methacrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts;
• copolymers of acrylic acid optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts, and acrylamide;
• the at least one homo- or copolymer of (meth)acrylic acid (i) is comprising a copolymer of acrylic acid and acrylamide.
• the at least one homo- or copolymer of (meth)acrylic acid (i) is comprising a copolymer of acrylic acid and acrylamide.
• the at least one homo- or copolymer of (meth)acrylic acid (i) is comprising a copolymer of acrylic acid and acrylamide.
• (meth)acrylic acid (i) consists of a copolymer of acrylic acid and acrylamide.
• a copolymer of acrylic acid and acrylamide is available as Alcotac® CB6 of BASF.
• the at least one homo- or copolymer of (meth)acrylic acid (i) is comprising for exam- pie a polymer of acrylic acid, in particular polyacrylic acid.
• the at least one homo- or copolymer of (meth)acrylic acid (i) consists of polyacrylic acid.
• the at least one homo- or copolymer of (meth)acrylic acid (i) has a weight average molecular weight of ⁇ 1 000 to ⁇ 5 000 000 g/mol, more preferably in the range of ⁇ 10 000 to ⁇ 500 000 g/mol, determined according analysis via gel permeation chromatography.
• the at least one copolymer of (meth)acrylic acid (i) is derived from a mixture comprising > 50 wt.-%, more preferably ⁇ 70 wt.-%, even more preferably ⁇ 80 wt.-%, most preferably > 90 wt.-%, methacrylic acid and/or acrylic acid, each optionally in form of its alkali metal salts, alkaline metal salts and ammonium salts.
• the remainder of the copolymers of (meth)acrylic acid (i) is derived from at least at least one nonionic monomer as defined above.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is different to the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is derived from a mixture comprising
• At least one monomer A selected from the group consisting of esters of acrylic acid or methacrylic acid with n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, octanol, decanol, dodecanol and stearyl alcohol
• the mixture comprises > 20 to ⁇ 90 wt.-%, more preferably ⁇ 40 to ⁇ 80 wt.-%, most preferably ⁇ 50 to ⁇ 70 wt.-%, of at least one monomer A, based on the total weight of the mixture.
• the mixture comprises ⁇ 10 to ⁇ 80 wt.-%, more preferably > 20 to ⁇ 60 wt.-%, most preferably ⁇ 30 to ⁇ 50 wt.-%, of at least one monomer B, based on the total weight of the mixture.
• the at least one monomer A is selected from the group consisting of esters of acrylic acid or methacrylic acid with n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert- butanol, pentanol, hexanol, 2-ethylhexanol, octanol, decanol, dodecanol or stearyl alcohol or mixtures thereof, more preferably with n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, octanol, decanol, dodecanol or stearyl alcohol or mixtures thereof and most preferably with n-butanol, isobutanol, sec-butanol or tert-butano ⁇ .
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) may also be derived from a mixture comprising other monomers in an amount of up to 10 wt.-%, preferably 5 wt.-% based on the total weight of the mixture.
• these other monomers are preferably selected from vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl ethyl ether, ethylene, propylene, butadiene, isoprene, N-vinylpyrrolidone, vinylsulfonic acid and alkali metal salts thereof, acrylamidopropanesulfonic acid and alkali metal salts thereof, sulfonated styrene and alkali metal salts thereof, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, N-alkyl- and N-hydroxyalkylamides of ethylenically unsaturated C3 -C6 - mono- or dicarboxylic acids, diesters of dihydric alcohols of ethylenically unsaturated C
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) may also be present as a mixture of two or more alkyl(meth)acrylate-styrene-copolymers (ii) according to the invention. Usually not more than three alkyl(meth)acrylate-styrene-copolymers (ii) are present, preferably only one al- kyl(meth)acrylate-styrene-copolymer (ii) is present.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is comprising a butyl acrylate - styrene copolymer.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) consists of a butyl acrylate - styrene copolymer.
• a butyl acrylate - styrene copolymer is available as Acronal® S 728 of BASF.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is formu- lated in a ready to use formulation together with preferably the at least one homo- or copolymer of (meth)acrylic acid (i) which is not an alkyl(meth)acrylate-styrene-copolymer (ii).
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is comprising a butyl acrylate - styrene copolymer which is formulated in a formulation which is comprising for example a copolymer of acrylic acid and acrylamide as the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is comprising a butyl acrylate - styrene copolymer which is formulated in a formulation which is comprising for example a polymer of acrylic acid, in particular polyacrylic acid, as the at least one homo- or copolymer of (meth)acrylic acid (i).
• a formulation comprising butylacry- late styrene copolymer and a polymer of acrylic acid in water is available as Alcotac® CBF60 from BASF.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) has a weight average molecular weight of > 1 000 to ⁇ 2 000 000 g/mol, more preferably in the range of > 1 000 to ⁇ 1 000 000 g/mol, even more preferably in the range of ⁇ 1 000 to ⁇ 500 000 g/mol, determined according to gel permeation chromatography measurement.
• the binder composition comprises at least one cross-linking agent (iii) selected from the group consisting of polymers having at least one functional group which is selected from the group comprising hydroxy, primary, secondary and tertiary amine, epoxy and aldehyde and pol- yvalent metal complexes.
• the cross-linking can also be effected by the addition of alkali.
• the polyvalent metal in the polyvalent metal complex is selected from the group con- sisting of calcium, magnesium, zinc, barium, aluminum, zirconium, nickel, iron, cadmium, strontium, bismuth, beryllium, cobalt, lead, copper and antimony.
• the ligand for forming the polyvalent metal complex is selected from the group consisting of carbonic acid ion, acetic acid ion, oxalic acid ion, malic acid ion, hydroxyacetic acid ion, tartaric acid ion, acrylic acid ion, lactic acid ion, formic acid ion, salicylic acid ion, benzoic acid ion, gluconic acid ion, glutamic acid ion, glycine, alanine, ammonia, morpholine, ethylene diamine, dimethylaminoethanol, di- ethylaminoethanol, monethanolamine, diethanolamine and triethanolamine.
• the polymers having at least one functional group which is selected from the group comprising hydroxy, primary, secondary and tertiary amine, epoxy and aldehyde comprise, as a rule, the substances known to the person skilled in the art, generally used for aminoplasts or phenol- formaldehyde resins and usually referred to as curing agents, such as ammonium sulfate or am- monium nitrate or inorganic or organic acids, for example sulfuric acid, formic acid, or acid- regenerating substances, such as aluminum chloride, aluminum sulfate, in each case in the customary, small amounts, for example in the range from 0.1 % by weight to 10% by weight, based on the total amount of cross-linking agent (iii).
• curing agents such as ammonium sulfate or am- monium nitrate or inorganic or organic acids, for example sulfuric acid, formic acid, or acid- regenerating substances, such as aluminum chloride, aluminum sulfate, in each case in
• Phenol-formaldehyde resins are known to the person skilled in the art, cf. for example Kunststoff-Handbuch, 2nd edition, Hanser 1988, volume 10 "Du- roplaste", pages 12 to 40.
• the binder composition further comprises at least one cross-linking agent (iii), whereas the cross-linking agent (iii) preferably is comprising a phenol formaldehyde resin.
• phenol formaldehyde resins are available from BASF as Alcotac® CBX60 or from Resichem as Reslink® GTC 50.
• aminoplast resin is understood as meaning polycondensates of compounds having at least one carbamide group optionally partly substituted by organic radicals (the carbamide group is also referred to as carboxamide group) and an aldehyde, preferably formaldehyde.
• Preferred aminoplast resins are polycondensates of compounds having at least one carbamide group, also partly substituted by organic radicals, and formaldehyde.
• aminoplast resins are urea-formaldehyde resins (UF resins), melamine- formaldehyde resins (MF resins) or melamine-containing urea-formaldehyde resins (MUF res- ins).
• UF resins urea-formaldehyde resins
• MF resins melamine- formaldehyde resins
• MAF res- ins melamine-containing urea-formaldehyde resins
• Very particularly preferred aminoplast resins are urea-formaldehyde resins, for example Kaurit® glue types from BASF SE.
• Further very preferred aminoplast resins are polycondensates of compounds having at least one amino group, also partly substituted by organic radicals, and aldehyde, in which the molar ratio of aldehyde to amino group optionally partly substituted by organic radicals is in the range from 0.3 to 1.0, preferably from 0.3 to 0.60, particularly preferably from 0.3 to 0.45, very particularly preferably from 0.30 to 0.40.
• aminoplast resins are polycondensates of compounds having at least one amino group -Nhb and formaldehyde, in which the molar ratio of formaldehyde to -Nhb group is in the range from 0.3 to 1.0, preferably from 0.3 to 0.60, particularly preferably from 0.3 to 0.45, very particularly preferably from 0.30 to 0.40.
• aminoplast resins are urea-formaldehyde resins (UF resins), melamine- formaldehyde resins (MF resins) or melamine-containing urea-formaldehyde resins (MUF res- ins), in which the molar ratio of formaldehyde to -Nhb group is in the range from 0.3 to 1 .0, preferably from 0.3 to 0.60, particularly preferably from 0.3 to 0.45, very particularly preferably from 0.30 to 0.40.
• UF resins urea-formaldehyde resins
• MF resins melamine- formaldehyde resins
• MAF res- ins melamine-containing urea-formaldehyde resins
• aminoplast resins are urea-formaldehyde resins (UF resins) in which the molar ratio of formaldehyde to -Nhb group is in the range from 0.3 to 1.0, preferably from 0.3 to 0.60, particularly preferably from 0.3 to 0.45, very particularly preferably from 0.30 to 0.40.
• UF resins urea-formaldehyde resins
• Said aminoplast resins are usually used in liquid form, generally suspended in a liquid suspending medium, preferably in aqueous suspension, but can also be used as a solid.
• the solids content of the aminoplast resin suspensions is usually from 25 to 90% by weight, preferably from 50 to 70% by weight.
• the aminoplast resins are prepared by known processes (cf. abovementioned Ullmann literature "Aminoplaste” and “Amino Resins”, and abovementioned literature Dunky et al.) by reacting the compounds containing carbamide groups, preferably urea and/or melamine, with the aldehydes, preferably formaldehyde, in the desired molar ratios of carbamide group to aldehyde, preferably in water as a solvent.
• the desired molar ratio of aldehyde, preferably formaldehyde, to amino group optionally partly substituted by organic radicals can also be established by addition of monomers carrying -Nhb groups to formaldehyde-richer prepared, preferably commercial, aminoplast resins.
• Monomers carrying Nhb groups are preferably urea or melamine, particularly preferably urea.
• the resin constituents of the cross-linking agent (iii) can be used by themselves, i.e. for exam- pie aminoplast resin as the sole resin constituent of the cross-linking agent (iii) or PF resin as the sole constituent of the cross-linking agent (iii).
• the resin constituents of the cross-linking agent (iii) can, however, also be used as a combination of two or more resin constituents of the cross-linking agent (iii).
• the binder composition further comprises additives that have an advantageous effect on the overall characteristics of the briquette or the process for manufacturing briquettes. Suitable additives include defoaming agents, water-repellent agents, surfactants and coalescing solvents.
• the defoaming agents that are suitable for the inventively used binder composition can be those commonly used in the art.
• examples of defoaming agents that are suitable for the inventively used binder composition include, but are not limited to, polyol defoamers, polyether defoamers, mineral oil defoamers, silicone defoamers, or mixtures thereof.
• the defoamers can be used in an amount of ⁇ 0.01 wt.-% to ⁇ 1.0 wt.- %, based on the total weight of the binder composition.
• surfactants that are suitable for the presently claimed invention include, but are not limited to, anionic surfactants, nonionic surfactants, cationic surfactants and combinations thereof.
• anionic surfactants that are suitable for the presently claimed invention include, but are not limited to: alkylsulfates, alkylsulfonates, alkylbenzenesulfonat.es, alkyl poly- oxyethylene ether sulfates, alkylpolyoxyethylene-propylene ether sulfates, sodium fatty alcohol succinic acid mono ester sulfonates, disodium fatty alcohol polyoxyethylene ether, sul- fosuccinates, disodium fatty alcohol polyoxyethylene-propylene ether sulfosuccinates, al- kylpolyoxyethylene phosphates, alkylpolyoxyethylene-propylene phosphates, and alkali metal salts and ammonium salts of fatty acids.
• nonionic surfactants that are suitable for the presently claimed invention include, but are not limited to: linear or branched alkyl alcohol polyoxyethylene ethers, linear or branched alkyl alcohol polyoxyethylene-propylene ethers, fatty acid polyoxyethylene monoesters, fatty acid polyoxyethylene-propylene mo- noesters.
• the EO (ethylene oxide) numbers of polyoxyethylene section in nonionic surfactants determine the HLB value of the nonionic surfactants, and the HLB value of the nonionic surfactants is typically in the range of about 20 to 40.
• water-repellent agents that are suitable for the presently claimed invention include, but are not limited to, sodium oleates or organosilicon compounds such as alkoxysilanes.
• coalescing solvents that are suitable for the presently claimed invention include, but are not limited to, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
• the binder composition comprises
• defoaming agents water-repellent agents, surfactants and coalescing solvents.
• the binder composition comprises
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is different to the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one homo- or copolymers of (meth)acrylic acid (i) is not an alkyl(meth)acrylate-styrene-co- polymer (ii).
• (meth)acrylic acid (i) to the amount of the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is within the range of 1 :25 to 25:1 , more preferably within the range of 1 :10 to 10:1 , even more preferably within the range of 1 :5 to 5:1 and most preferably within the range of 1 :1 to 5:1.
• the at least one homo- or copolymer of (meth)acrylic acid (i) is present in an amount of ⁇ 0.05 to ⁇ 1.0 wt.-%, more preferably in an amount of ⁇ 0.1 to ⁇ 0.8 wt.-%, most preferably in an amount of ⁇ 0.1 to ⁇ 0.5 wt.-%, based on the total weight of the briquette.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is present in an amount of ⁇ 0.05 to ⁇ 1.0 wt.-%, more preferably in an amount of ⁇ 0.05 to ⁇ 0.5 wt.-%, most preferably in an amount of ⁇ 0.05 to ⁇ 0.3 wt.-%, based on the total weight of the briquette.
• the presently claimed invention is directed to a briquette comprising
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is different to the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one homo- or copolymers of (meth)acrylic acid (i) is not an alkyl(meth)acrylate-styrene-copolymer (ii).
• the longitudinal direction of extension is preferably the maximum extension of the briquette.
• the transversal direction of extension is preferably the maximum extension of the briquette orthogonal (perpendicular) to the longitudinal direction of extension.
• the longitudinal direction of extension is longer than the transversal direc- tion of extension.
• the briquette of the presently claimed invention has a longitudinal axis being substantially longer than its transversal axis it exhibits an oblong shape.
• the length of the briquette corresponds to the longitudinal direction of extension of the briquette
• the height corresponds to the maximum ex- tension of the briquette orthogonal to the length
• the width corresponds to the transversal direction of extension orthogonal to the length and orthogonal to the width (Cartesian space).
• the length of the briquette is in the range of ⁇ 1 to ⁇ 10 cm, more preferably in the range of ⁇ 2 to ⁇ 8 cm, most preferably in the range of ⁇ 2 to ⁇ 4 cm.
• the height of the briquette is in the range of ⁇ 0.5 to ⁇ 6 cm, more preferably in the range of ⁇ 1 to ⁇ 5 cm, most preferably in the range of ⁇ 1 to ⁇ 2 cm.
• the width of the briquette is in the range of ⁇ 1 to ⁇ 10 cm, more preferably in the range of ⁇ 2 to ⁇ 8 cm, most preferably in the range of ⁇ 2 to ⁇ 4 cm.
• the presently claimed invention is directed to a process for manufacturing a briquette as defined above comprising the steps of
• a) mixing coal fines and a binder composition comprising (i) at least one homo- or copolymer of (meth)acrylic acid and (ii) at least one alkyl(meth)acrylate-styrene-copolymer to obtain a mixture;
• step b) forming the mixture obtained according to step a) into a block;
• step c) drying the block obtained according to step b) to obtain a briquette.
• step a) the coal fines and the binder composition are thoroughly mixed, e.g. in an Eirich mixer, for at least 1 and up to 30 minutes and then transported, e.g. by using a conveyor belt, to a briquetting apparatus wherein the briquettes are formed.
• the coal fines in step a) have a water content in the range of ⁇ 5 wt.-% to ⁇ 20 wt.-%, more preferably in the range of ⁇ 5 wt.-% to ⁇ 15 wt.-%, based on the total weight of the coal fines, determined according to standard gravimetric techniques, e.g. determination of water content via ASTM D2216-10.
• step b) the mixture obtained according to step a) is fed to a briquetting apparatus and formed into a block.
• the briquetting apparatus is preferably a briquetting apparatus that included briquetting rollers.
• the mixture is fed to the briquetting rollers.
• the rollers compress the mixture.
• One or more of the rollers preferably has pockets formed therein which pockets assist in defining the shape of the briquettes.
• the rollers also apply an amount of shear to the mixture as it passes through the briquetting apparatus.
• step c) the block is dried for a period of ⁇ 12 to ⁇ 48 h, more preferably for a period of ⁇ 18 to ⁇ 36 h.
• the curing temperature is preferably in the range of ⁇ 10 to ⁇ 45 °C, more preferably in the range of ⁇ 15 to ⁇ 35 °C.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is different to the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one homo- or copolymers of (meth)acrylic acid (i) is not an alkyl(meth)acrylate-styrene-co- polymer (ii).
• the presently claimed invention is directed to the use of a binder combination, as defined above, for the agglomeration of coal fines.
• the presently claimed invention is directed to the use of a binder combination comprising (i) at least one homo- or copolymer of (meth)acrylic acid, as defined above, and (ii) at least one alkyl(meth)acrylate-styrene-copolymer, as defined above, for the agglomeration of coal fines.
• the at least one alkyl(meth)acrylate-styrene-copolymer (ii) is different to the at least one homo- or copolymer of (meth)acrylic acid (i).
• the at least one homo- or copolymers of (meth)acrylic acid (i) is not an alkyl(meth)acrylate-styrene-copolymer (ii).
• Figure 1 describes in particular the cumulative % passing as a function of actual size with regard to for example coal fines.
• the size of coal fines according to figure 1 is in particular suitable for a briquette formation in presence of a binder composition comprising at least one homo- or copolymer of (meth)acrylic acid (i), which is not a alkyl(meth)acrylate-styrene-copolymer (ii) and at least one alkyl(meth)acrylate-styrene-copolymer (ii).
• the coal fines according to figure 1 can be used in a method for manufacturing said briquette.
• the binder composition according to the present invention can for example be used for the agglomeration of coal fines according to figure 1. Examples
• Coal fines are supplied by a coal mine.
• the particle size distribution was determined using Tyler Mesh 16 sieve (1 mm sieve opening).
• Fig. 1 shows the cumulative particle size distribution of the coal fines.
• Binder composition 1 comprising Acronal® S728 (available from BASF SE, butyl acrylate - sty- rene copolymer) and Alcotac® CB 6 (available from BASF SE, copolymer of acrylic acid and acryl amide) in water.
• Binder composition 2 comprising Acronal® S728 (available from BASF SE, butyl acrylate - sty- rene copolymer) and Alcotac® CB 6 (available from BASF SE, copolymer of acrylic acid and acryl amide) and Reslink® GTC 50 (available from Resichem, India, a phenol-formaldehyde resin) in water.
• Acronal® S728 available from BASF SE, butyl acrylate - sty- rene copolymer
• Alcotac® CB 6 available from BASF SE, copolymer of acrylic acid and acryl amide
• Reslink® GTC 50 available from Resichem, India, a phenol-formaldehyde resin
• Binder composition 3 comprising polyvinyl alcohol in water.
• Binder composition 4 comprising a formulation of butylacrylate styrene copolymer and a polymer of acrylic acid in water (available as Alcotac® CBF60 from BASF).
• Binder composition 5 comprising a formulation of butylacrylate styrene copolymer and a poly- mer of acrylic acid in water (available as Alcotac® CBF60 from BASF) combined with a phenol formaldehyde resin (available as Alcotac® CBX60 from BASF).
• the binder composition 1 was mixed with coal fines. The mixture was thoroughly mixed. The mixture was transferred to a briquetting roller and briquettes were formed.
• binder composition 5 instead of binder composition 1 .
• the dosage of binder composition in the examples 3, 4 and 5 were as follows:
• Example 3 (comparative): 0.5 wt%
• Example 5 the binder composition additionally is comprising a crosslinker in a dosage of 0.05% (liquid).
• the strength of the briquettes was tested in a drop test.
• the drop test the briquette was continuously dropped from a height of 2 meters onto a concrete surface until it completely shatters.
• the drop test was carried out to test the green strength of the briquette, whereby the briquette was in the green state and had undergone no form of curing.
• Besides the cured strength of the briquettes was tested, whereby the briquette was allowed to cure at room temperature for a period of 24 hours after formation of the briquette.
• the strength of the briquettes was tested in a compressive strength. In the compression strength test, 20 briquettes were individually compressed to break in pieces and data recorded per KgF (kilogram-force).
• the compression test was carried out to test the green compression strength (Day 0) of the briquette, whereby the briquette was in the green state and had undergone no form of curing. Besides the cured strength (Day 2) of the briquettes was tested, whereby the briquette was allowed to cure at room temperature for a period of 48 hours after formation of the briquette. The strength of the briquettes was tested in a tumbling test.
• tumbling test 20 briquettes were put in a tumbling drum, rotating at 60 rpm for 10 minutes to observe the amount (% of briquettes) of fines generated from the briquettes in the tumbling drum.
• the tumbling test was carried out on the green briquettes (Day 0) of the briquette production, whereby the briquette were in the green state and had undergone no form of curing.
• Day 2 the cured tumbled briquettes (Day 2) of the briquettes were tested, whereby the briquette were allowed to cure at room temperature for a period of 48 hours after formation of the briquette.
• Table 1 reflects the number of drops of the briquette until the briquette was shattered.
• Table 2 reflects the number of drops of the briquette until the briquette was shattered.
• examples 4 and 5 in table 2 demonstrate that the inventively claimed binder composition leads to the formation of briquettes having a strength that is equal to or better than the strength of briquettes that were formed by using polyvinyl alcohol (comparative example 3).
• the presence of for example a phenol formaldehyde resin in the binder composition surprisingly shows better results with regard to cured strength test in comparison to example 3.
• Table 3 reflects the average compression strength of the briquette in Day 0 for green and in Day 2 for cured briquettes.
• Table 4 reflects the tumble test strength of the briquette in Day 0 for green and in Day 2 for cured briquettes. The lower the amount of fines generated, the better the briquettes.

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• 2016
  • 2016-05-25 EP EP16728242.5A patent/EP3303526A1/en not_active Withdrawn
  • 2016-05-25 AU AU2016269064A patent/AU2016269064B2/en not_active Expired - Fee Related
  • 2016-05-25 CN CN201680030102.5A patent/CN107660230A/zh active Pending
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• 2017
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