Compositions: coating or plastic – Coating or plastic compositions – Bituminous material or tarry residue
Reexamination Certificate
2001-08-01
2004-06-15
Brunsman, David (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Bituminous material or tarry residue
Reexamination Certificate
active
06749678
ABSTRACT:
This is a 371 filing of PCT/EP00/00734.
FIELD OF THE INVENTION
The present invention relates to solid-state compositions comprising solid particles and a hydrocarbonaceous binder. Further, the present invention relates to a process for preparing such composition, to the use of such composition in construction, to a construction element containing such composition, and to a construction containing such construction elements.
BACKGROUND OF THE INVENTION
It is known to mix carbon particles such as petroleum coke, carbon black or anthracite coal with binder materials such as coal tar pitch and petroleum pitch, forming these mixtures by molding or extrusion and baking the mixtures in furnaces at temperatures from 800-1400° C. (Kirk-Othmer Encyclopedia of Chemical Technology 3
rd
edition, volume 4, page 557).
U.S. Pat. No. 4,961,837 describes a specific petroleum pitch for binding carbon black to manufacture electrodes for the aluminium and steel industries, which petroleum pitch has been obtained by pre-heating a feedstock, feeding the pre-heated feedstock to a soaker so as to promote condensation and polymerisation, and separating off a petroleum tar pitch of a quality suitable for use as a binder in the manufacture of electrodes.
The teaching of both documents is limited to the use of these binders with carbon particles.
U.S. Pat. No. 5,759,250 describes the use of a very hard bitumen binder for road bed foundations. The bitumen preferably is a blend of bitumen obtained from a hard base produced by direct distillation and having a penetrability from 15 to 25 and a heavy fraction obtained by distillation of crude petroleum or of products obtained by a process such as catalytic or thermal cracking. It is stated that these bitumen binders can only be used in road bed foundation layers because they do not have sufficient adherence properties and asphalt prepared from it does not present a closed, smooth surface without holes and roughness. Further, it is described that these foundation layers must be covered by a top layer to ensure good thermal protection.
Surprisingly, we have now found binders which can be hard while having good adhesion properties.
Japanese laid open patent application No. 61-89215 describes a method for selectively separating high molecular weight polycyclic aromatic polymer from residual oil produced by thermal cracking of naphtha. The polymer is described to be suitable as an auxiliary material for moulding sand to overcome the disadvantages of existing quartz powder.
The best model of the bonding action in moulding sand is that of a wedge-and-block bond at the interface of the particles. The bonding action is not that of a glue or adhesive causing the particles to adhere to each other (Kirk-Othmer Encyclopedia of Chemical Technology 3
rd
edition, volume 6, page 213). Therefore, the flexural strength of a moulding sand approaches 0 N/mm
2
. The compositions according to the present invention differ from moulding sands in that the compositions according to the present invention have a flexural strength of at least 0.5 N/mm
2
.
SUMMARY OF THE INVENTION
The solid-state compositions according to the present invention have a flexural strength of at least 0.5 N/mm
2
and comprise from 70 to 99% by weight of solid particles and from 30 to 1% by weight of a hydrocarbonaceous binder, which binder contains (i) from 15 to 95% by weight, based on total binder, of asphaltenes, which asphaltenes contain at least 60% aromatic carbon, and (ii) from 5 to 85% by weight, based on total binder, of further hydrocarbons, with the proviso that the solid particles are not solely carbon particles.
The amounts of solid particles and hydrocarbonaceous binder are based on amount of total composition.
Hydrocarbonaceous binders according to the present invention, are generally considered waste products. They are usually thought unsuitable for any attractive application other than as anode binder material or as part of fuel oil.
Surprisingly, compositions according to the present invention were observed to have good flexural strength. Further, compositions according to the present invention were observed to retain their flexural strength relatively well after exposure to water optionally containing salt and/or acid.
It was further found that compositions according to the present invention could be made harder by keeping them at elevated temperature either by a dedicated heat treatment or by keeping them at elevated temperature during manufacture and/or hot storage. Furthermore, it was found that this increased the flexural strength of compositions.
The flexural strength is measured according to NEN 7014, “Nederlands Normalisatie Instituut”, 2
nd
edition, August, 1974.
The amount of asphaltenes in the hydrocarbonaceous binder is determined according IP 143/96.
The percentage of aromatic carbon atoms present in the asphaltenes is measured by separating off the asphaltenes in the binder as described in IP 143/96, dissolving a sample of the asphaltenes in carbon disulphide or chloroform and assessing the percentage of aromatic carbon by H and
13
CNMR.
The present invention further relates to a process for preparing a composition according to the present invention, which process comprises mixing from 70 to 99% by weight of solid particles and from 30 to 1% by weight of molten hydrocarbonaceous binder and allowing the resulting mixture to solidify, which binder contains (i) from 15 to 95% by weight, based on total binder, of asphaltenes, which asphaltenes contain at least 60% aromatic carbon, and (ii) from 5 to 85% by weight, based on total binder, of further hydrocarbons, with the proviso that the solid particles are not solely carbon particles.
The present invention further relates to the use of a composition according to the invention in construction, to a construction element containing such composition and to a construction containing such construction elements.
DETAILED DESCRIPTION OF THE INVENTION
The solid-state composition according to the present invention comprises hydrocarbonaceous binder which contains from 15 to 95% by weight, based on total binder, of asphaltenes as determined according IP 143/96. The asphaltenes comprise hydrogen, carbon and optionally other atoms. Specifically, the asphaltenes can contain up to 15% by weight of atoms other than hydrogen and carbon, more specifically sulphur, nitrogen and oxygen, preferably at most 12% by weight, most preferably at most 10% by weight, based on asphaltenes.
The hydrocarbonaceous binder comprises from 5 to 85% by weight of further hydrocarbons. The further hydrocarbons are compounds other than asphaltenes as determined according IP 143/96. The further hydrocarbons comprise hydrogen, carbon and optionally other atoms. Generally, the further hydrocarbons can contain up to 15% by weight of atoms other than hydrogen and carbon, more specifically sulphur, nitrogen and oxygen, preferably at most 12% by weight, most preferably at most 10% by weight, based on further hydrocarbons.
Preferably, the binder contains at least 20% by weight of asphaltenes, based on total binder. More preferably, the hydrocarbonaceous binder contains at least 25% by weight of asphaltenes. The amount of asphaltenes is up to 95% by weight, preferably up to 70% by weight, more preferably up to 60% by weight, more preferably up to 50% by weight, more preferably up to 45% by weight, most preferably at most 40% by weight. The remainder of the hydrocarbonaceous binder is further hydrocarbons.
The hydrocarbonaceous binder does not solely consist of carbon as produced after full carbonization, e.g. by heat treating of a coal tar or thermally cracked residual fraction.
Coal tar pitch differs from the present hydrocarbonaceous binder in that coal tar pitch contains a limited amount of asphaltenes. The amount of asphaltenes in coal tar pitch typically is less than 10% by weight. Furthermore, coal tar pitch contains substantial amounts of hazardous polyaromatic compounds containing 4 or 5 aromatic rings. The binder of the present invention will generally contain a very li
Brunsman David
Shell Oil Company
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