WO2001008833A1 - Systeme de durcissement a basse temperature - Google Patents

Systeme de durcissement a basse temperature Download PDF

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Publication number
WO2001008833A1
WO2001008833A1 PCT/GB2000/002884 GB0002884W WO0108833A1 WO 2001008833 A1 WO2001008833 A1 WO 2001008833A1 GB 0002884 W GB0002884 W GB 0002884W WO 0108833 A1 WO0108833 A1 WO 0108833A1
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WO
WIPO (PCT)
Prior art keywords
aggregate
composition
binder
binder composition
accelerator
Prior art date
Application number
PCT/GB2000/002884
Other languages
English (en)
Inventor
Paul Harry Jones
Original Assignee
Bitrez Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bitrez Ltd filed Critical Bitrez Ltd
Priority to AU62986/00A priority Critical patent/AU6298600A/en
Publication of WO2001008833A1 publication Critical patent/WO2001008833A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols

Definitions

  • the present invention relates to hexamine free phenolic binder compositions suitable for producing refractory shaped products, two and three part systems for preparing the compositions, the process for the preparation thereof, refractory aggregate compositions including the binder, the process for the preparation thereof, the method for manufacturing the shaped products and the use thereof in refractory applications.
  • phenolic resins systems are very effective and conventional formulations generally comprise of resole resins or novolak resins as binder, either used individually or in combination.
  • Novolak resins are thermoplastic and they can cure through reaction with resoles at elevated temperature, however it has been customary to incorporate an additional cross-linking agent - almost exclusively hexamethylenetetramine (hexamine).
  • Hexamine provides a source of methylene bridges and nitrogen, promoting cross-linking and enhanced reactivity.
  • the nitrogen may be liberated in the form of ammonia and other amines.
  • These decomposition products are considered problematical and potentially hazardous with their reduction considered advantageous.
  • hexamine free systems have been developed by alteration of the Phenol/Formaldehyde P/F ratio - increasing the formaldehyde level in the resole to partially or completely compensate for the absent hexamine. Absence of the hexamine and its catalytic influence necessitates higher cure temperatures in order to achieve desirable performance levels.
  • the cure rate can be promoted such that comparable performance can be achieved without hexamine, utilising cure temperatures more normally associated with hexamine containing systems.
  • a binder composition for mixing with a refractory aggregate and subsequently producing refractory shapes comprising the a novolak resin and/or a resole resin and an accelerator.
  • the composition comprises a phenolic novolak resin and/or a phenolic resole resin, and an accelerator.
  • the binder composition may comprise an optional solvent, and optional further additives known to those skilled in the art.
  • the system enables cure to be achieved at temperatures in the 100 - 150°C range. It is a particular advantage that the strength of the final cured and coked product of the present invention is equivalent or greater than the standard hexamine free systems subjected to cure temperatures in excess of 200°C.
  • the present invention has the advantage of being free from hexamine whilst capable of being cured at modest temperature and maintaining equivalent or improved properties after curing and coking. More preferably the binder composition comprises by % weight composition
  • the binder composition comprises by % weight :
  • the components of the binder composition are suitably as follows.
  • Novolak resins are commercially available and are obtained by the reaction of a phenol and an aldehyde in a strongly acidic pH region.
  • Suitable catalysts include the strong mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid as well as organic acid catalysts such as oxalic acid, para-toluenesulfonic acid, and inorganic salts such as zinc acetate, or zinc borate.
  • the phenol is preferably phenol itself, but a portion of the phenol can be substituted with cresols, xylenols, alkyl substituted phenols such as ethyl phenol, propyl phenol and mixtures thereof.
  • the aldehyde is preferably formaldehyde, but other aldehydes such as acetaldehyde, benzaldehyde and furfural can also be used to partially or totally replace the formaldehyde.
  • the reaction of the aldehyde and phenol is carried out at the molar ratio of 1 mole of the phenol to about 0.40 to about 0.85 moles of the aldehyde.
  • phenolic novolaks do not harden upon heating, but remain soluble and fusible unless a hardener (curing agent) is present.
  • the novolaks employed in this invention are generally solids such as in the form of a flake, powder, etc.
  • the molecular weight of the novolak will vary from about 500 to 12,000, preferably 2,000 to 8,000 depending on their intended use.
  • Resole resins are commercially available and are obtained by the reaction of a phenol and an aldehyde in an alkaline pH region.
  • Alkaline reaction conditions can be established by use of any of the wide variety of alkaline catalysts, organic and inorganic, known to those skilled in the art.
  • the alkaline catalyst promotes the reaction of the formaldehyde with phenol to form a phenol-formaldehyde resole resin.
  • the phenol is preferably phenol itself, but a portion of the phenol can be substituted with cresols, xylenols, alkyl substituted phenols such as ethyl phenol, propyl phenol and mixtures thereof.
  • the aldehyde is preferably formaldehyde, but other aldehydes such as acetaldehyde, benzaldehyde and furfural can also be used to partially or totally replace the formaldehyde.
  • the reaction of the aldehyde and phenol is carried out at the molar ratio of 1 mole of the phenol to about 1.8 to about 2.85 moles of the aldehyde, more preferably about 2.1 to about 2.4.
  • Phenolic resoles will harden with application of heat or catalysis.
  • the resoles employed in this invention are generally liquids.
  • the accelerator used in this invention is preferably an activated phenolic species added in monomeric or oligomeric state - preferably monomeric.
  • the activated species may be solid or liquid but is preferably solid and may be added to either component, resole or novolac or independantly. It is preferably added to the novolak for ease of use.
  • Activated phenolic species are known to those skilled in the art and include monohydroxy or polyhydroxy species such as di and trihydroxy. Preferred species include the mono hydroxy species phenol and dihydroxy species 1,3-dihydroxy-benzene (resorcinol) of which more preferred is resorcinol.
  • resorcinol 1,3-dihydroxy-benzene
  • the quantity of accelerator can vary and offer a broad range of reactivities and ultimate performance.
  • Solvents are commonly employed to aid wetting and viscosity reduction and many additives are potentially employed for coupling purposes and other functions known to those skilled in the art.
  • composition is prepared by mixing prior to use, and may be mixed and stored for subsequent use or mixed in situ.
  • a two part binder system for mixing in situ to provide a binder composition as hereinbefore defined, comprising in a first part a novolak or resole resin and in the second part the accelerator.
  • the system comprises in the first part a resole resin and in the second part a novolak resin and the accelerator.
  • a curable refractory aggregate composition comprising a binder composition as hereinbefore defined in admixture with a refractory aggregate.
  • the binder is included at a level of between 2 and 10% by weight, preferably between 3 and 6% by weight.
  • the aggregate forms the balance of the mixture.
  • the present invention employs conventional refractory aggregates known to be used in the manufacture of refractory shapes.
  • Preferred aggregates include quartz, silica, magnesia, alumina, zirconia, or chrome ore, e.g., chromite sand, and mixtures thereof employed with the binder of the present invention.
  • composition is prepared by mixing prior to use, and may be mixed and stored for subsequent use or mixed in situ.
  • a three part refractory aggregate system comprising a two part binder system as hereinbefore defined and in a third part a refractory aggregate.
  • a method of manufacturing cured refractory shapes comprising admixing a binder composition and aggregate as hereinbefore defined and curing at a temperature in the region of 100 - 200C, preferably 100 - 150C, for example 140C.
  • the resin solution, i.e., binder, of the present invention is used as follows.
  • the binder comprises the novolak resin and/or the resole resin and the accelerator - the accelerator may be conveniently added to the novolac as a two part system prior to incorporation of the resole.
  • Binder composition (A) is mixed with aggregate component (B) such that Component (A) comprises between 2 and 10% although preferably between 2 and 5% of the total mixed composition.
  • the method includes the further steps of pressing the mixed refractory composition to produce shapes. Optimum performance during refractory service necessitates curing the resin prior to coking.
  • the method includes the further steps of providing the shapes on a heat resistant support such as a pallet and curing at elevated temperatures as hereinbefore defined. The elevated temperature also drives off organic volatiles from the shapes.
  • the aggregate is prepared using multiple part systems as hereinbefore defined.
  • the binder system is sent by its manufacturer to a customer. The customer mixes the binder components and aggregate, and then shapes the mixture into bricks. The shaped bricks are placed on heat resistant pallets and cured whereby they are able to retain their shape. The bricks are either then coked, or preferably are then assembled for use in refractory applications at elevated temperatures whereby they are subsequently coked in service.
  • Curing is suitably at a temperature in the region of 100 - 200C, preferably 100 - 150 C, coking is suitably at a temperature in the region of lOOOC.
  • the present invention achieves comparable or improved performance with process temperatures in the region of 100 - 150°C unlike conventional hexamine free systems which require temperatures of in excess of 200°C to achieve the desired performance levels.
  • the method is suited for use with wooden heat resistant pallets by virtue of the lower cure temperatures employed with the process of the invention, or pallets not withstanding temperatures in excess of 200C, significantly reducing the cost and wastage in manufacture.
  • a refractory shape as hereinbefore defined.
  • refractory bricks are used in industrial applications for the manufacture of steel and the like.
  • Refractory shapes of the present invention in the form of bricks are suited for the manufacture of a refractory mould into which molten steel is poured at elevated temperature which serves to coke new refractory during cooling of the steel to form a product.
  • they may be used to line ladles and the like for transferring molten steel in production, and for any other structures required to move molten metals.
  • a preferred shape for this application is a convex brick having a domed base.
  • Phenolic Novolak resin 41 %
  • Phenolic Resole resin 59 %
  • System 4 comprises standard system containing no accelerator and utilising conventional resole/novolac resins in the 41/59% ratio.
  • the binder was added at 3.28% of the formulated refractory mix in all cases - ie; 3.28% Mixed binder 96.72% Aggregate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne: une composition liante à mélanger avec un agrégat, qui permet de former des produits de forme donnée, et qui comprend une novolaque et/ou une résine résol, et un accélérateur; une composition à base d'agrégats comprenant la composition liante; un procédé de fabrication de formes d'agrégat durci; les formes réfractaires ainsi obtenues et leur utilisation, de préférence, pour la production d'acier.
PCT/GB2000/002884 1999-07-31 2000-07-31 Systeme de durcissement a basse temperature WO2001008833A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62986/00A AU6298600A (en) 1999-07-31 2000-07-31 Low temperature cure system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9917899.8A GB9917899D0 (en) 1999-07-31 1999-07-31 Low temperature cure system
GB9917899.8 1999-07-31

Publications (1)

Publication Number Publication Date
WO2001008833A1 true WO2001008833A1 (fr) 2001-02-08

Family

ID=10858218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/002884 WO2001008833A1 (fr) 1999-07-31 2000-07-31 Systeme de durcissement a basse temperature

Country Status (3)

Country Link
AU (1) AU6298600A (fr)
GB (1) GB9917899D0 (fr)
WO (1) WO2001008833A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094590A (en) * 1965-12-03 1967-12-13 Borden Chemical Company Uk Ltd Improvements in or relating to nitrogen-free resin-coated granular refractory materials
US4089837A (en) * 1977-03-07 1978-05-16 Manley Bros. Of Indiana, Inc. Shell molding process and composition
EP0009519A1 (fr) * 1978-10-09 1980-04-16 Hoechst Aktiengesellschaft Application des liants résineuses dans la préparation de produits abrasifs, ainsi que produits abrasifs obtenus
US4426484A (en) * 1980-10-21 1984-01-17 Sumitomo Durez Company, Ltd. Method for accelerating cure of resole type phenolic resins
US4644022A (en) * 1985-11-27 1987-02-17 Acme Resin Corporation Cold-setting compositions for foundry sand cores and molds
JPH07188515A (ja) * 1993-12-27 1995-07-25 Sumitomo Bakelite Co Ltd 半導体封止用樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094590A (en) * 1965-12-03 1967-12-13 Borden Chemical Company Uk Ltd Improvements in or relating to nitrogen-free resin-coated granular refractory materials
US4089837A (en) * 1977-03-07 1978-05-16 Manley Bros. Of Indiana, Inc. Shell molding process and composition
EP0009519A1 (fr) * 1978-10-09 1980-04-16 Hoechst Aktiengesellschaft Application des liants résineuses dans la préparation de produits abrasifs, ainsi que produits abrasifs obtenus
US4426484A (en) * 1980-10-21 1984-01-17 Sumitomo Durez Company, Ltd. Method for accelerating cure of resole type phenolic resins
US4644022A (en) * 1985-11-27 1987-02-17 Acme Resin Corporation Cold-setting compositions for foundry sand cores and molds
JPH07188515A (ja) * 1993-12-27 1995-07-25 Sumitomo Bakelite Co Ltd 半導体封止用樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 10 30 November 1995 (1995-11-30) *

Also Published As

Publication number Publication date
AU6298600A (en) 2001-02-19
GB9917899D0 (en) 1999-09-29

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