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WO1988008407A1 - Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede - Google Patents

Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede Download PDF

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Publication number
WO1988008407A1
WO1988008407A1 PCT/US1987/000999 US8700999W WO8808407A1 WO 1988008407 A1 WO1988008407 A1 WO 1988008407A1 US 8700999 W US8700999 W US 8700999W WO 8808407 A1 WO8808407 A1 WO 8808407A1
Authority
WO
WIPO (PCT)
Prior art keywords
accordance
reaction
mineral
kaolin
clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1987/000999
Other languages
English (en)
Inventor
Weyman H. Dunaway
Jorge E. Salinas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ECC America Inc
Original Assignee
ECC America Inc
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 ECC America Inc filed Critical ECC America Inc
Priority to PCT/US1987/000999 priority Critical patent/WO1988008407A1/fr
Priority to DE19873790946 priority patent/DE3790946T1/de
Priority to JP62502875A priority patent/JPH01503056A/ja
Priority to BR8707720A priority patent/BR8707720A/pt
Publication of WO1988008407A1 publication Critical patent/WO1988008407A1/fr
Priority to GB8828801A priority patent/GB2210609B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • This invention relates generally to silicates and siliceous compositions, including siliceous minerals, such as aluminosilicates and the like, and more specifically relates to a method for chlorinating materials of this type in order to produce intermediates having new and unusual properties enabling subsequent functionalization thereof.
  • Clays are generally fine grained, earthy material made up of minerals which are essentially hydrous aluminosilicates. Numerous processes have been utilized for recovering aluminum from clays, which involve a chlorination step, and which are conducted at relatively very high temperatures. These processes generally produce aluminum chloride, which is further reacted to ultimate ⁇ ly produce the desired aluminum.
  • British Patent Specification No. 894,383 teaches subjecting a kaolin clay to shock heating and thereafter to bleaching of same by treatment with chlorine gas at 700 'to 900°C.
  • Nordberg, U.S. Patent No. 2,141,444 discloses the use of carbon and chlorine in the course of removing iron from high. alumina materials, including kaolin, kyanite, bauxite, diaspore, and the like, by heating the materials in the pres- ence of the said components at temperatures of 900 to 1150°C.
  • U.S. Patent No. 3,615,359 teaches a process for producing aluminum involving conversion of alumina under reducing conditions in the presence of carbon with manganese chloride to form aluminum trichloride and manganese, the reac ⁇ tion taking place in a first reaction zone the temperature of which is about 190°C at the inlet and 1400°C at the outlet of the zone, and then reacting the latter at a temperature of up to about 1400°C, to reduce the aluminum trichloride -to aluminum, by reacting the manganese with the said aluminum trichloride.
  • Willhoft U.S. Patent No. 4,073,872 discloses a process for recovering aluminum values from aluminum contain ⁇ ing minerals such as bauxite and aluminosilicates, including kaolinite and the like.
  • the aluminum containing mineral, together with carbon, is chlorinated to recover aluminum chloride.
  • the process involves heating an intimate mixture of an aluminum- containing mineral and a solid carbonizable organic material, so as to carbonize the organic material, and chlorinating the solid residue from the carbonization step.
  • the temperature of reaction may be up to 1500°C, but is preferably slightly lower than the carbonization temperature, for example, in the range of 500°C to 800°C. yndham et al, U.S. Patent No.
  • 4,082,233 describes a method for carbo-chlorinating clay to produce aluminum chloride and silicon chloride.
  • the clay is initially calcined with a solid carbonaceous reductant to. form a reaction mass.
  • Carbo- chlorination, in the presence of a sulphur-containing member, is conducted at temperatures within the range of from about 400°C to about 1000°C.
  • Wyndham et al U.S. Patent No. 4,083,927, relates to further improvements for carbo-chlorination of clays which have previously been calcined.
  • the reaction mixture during - carbo-chlorination is in the temperature range of 600 °C to 950°C, using dry chlorine to which is added about .3% to 2.5% by volume of boron chloride.
  • Martin et al U.S. Patent No. 4,096,234, discloses the production of aluminum chloride from clay by chlorinating the clay through contact with a mixture consisting of a chlorinating agent, a reducing agent, an alkaline metal com ⁇ pound catalyst and silicon chloride.
  • the chlorination process is carried out in a fluidized bed at a temperature of 550 °C to 650°C.
  • Wyndham et al U.S. Patent No. 4,139,602 relates to the preferential chlorination of alumina over silica in kaolin- itic ores to produce aluminum chloride.
  • the process utilizes carbo-chlorination; the kaolin clay is initially dried, com in- uted , and calcined in the temperature ranging from 500°C to 1000°C.
  • the carbo-chlorination is effected in the temperature range of from 600°C to 1000°C.
  • Dell, U.S. Patent No. 4,244,935 discloses a method for chlorinating particles of a substance containing metal and oxygen, utilizing a coking step carried out in a tempera- ture range of 450 to 650°C, followed by a heating step carried out between 700° to 1100°C.
  • Reynolds et al U.S. Patent No. 4,288,414, discloses a process for recovering aluminum from clays associated with coal or bauxite containing iron, siliceous material and titanium, comprising chlorinating the material at temperatures of from about 650°C to 900°C, in an oxidizing atmosphere in the presence of added oxygen; and then chlorinating the residue from the said step with chlorine at a temperature of from about 600°C to 850°C, in a reducing atmosphere of carbon monoxide.
  • Dunn, U.S. Patent No. 4,355,007 discloses a two stage process for chlorinating aluminum value-containing materials such as bauxite, clay, etc.
  • the material is dehydrated, and then chlorinated in the presence of chlorine and carbon at a tempera ⁇ ture of below about 1200°K (temperature of about 1100° ⁇ is typical) ; oxygen is introduced, and thereafter the non-gaseous product is chlorinated in the presence of chlorine and carbon at a temperature above about 1300°K.
  • kaolin clays are described, the surfaces of which are modified with organofunctional silanes.
  • a typical such agent e.g. is a methacryloxypropyltrimethoxy silane.
  • the kaolin clays so modified are advantageously used as fillers for natural and synthetic rubbers and the like.
  • modified products can serve as in ermedi- ates for synthesis of new pigments, which are useful as fillers for polymers, elastomers and resins. This result obtains oecause the silanes used to modify the kaolin clays are di- or polyfunctional, and only one functional group, the silane, is attached to the clay, leaving the remaining reactive groups to react further.
  • the said reaction is conducted at temperatures above the boiling point of said SiCl (56°C) and below about 300°C, and preferably in the range of from about 60°C to 150°C. These temperatures are such as to be below that at which the starting materials are so chemically or physically altered as to lose ' their basic properties. For example, in the instance of a hydrous kaolin clay, these temperatures are below those at which substantial volatilization, dehydroxyla- tion, and/or changes in the crystalline structure will occur. Accordingly, when such a hydrous clay is treated by the inven ⁇ tion, it is not altered to a calcined kaolin; hence its low abrasion properties are in no way detrimentally affected by the present method.
  • the said reaction may be conducted in any apparatus wherein intimate contact between the particulate material and the gaseous reactants is possible.
  • These include mechanical mixers, such as high shear mixers.
  • the reaction can be conducted in a fluidized bed reactor with the gaseous components passing upwardly through a suitable diffuser plate, and into a fluidized bed of the particulate material being treated.
  • a dry inert gas such as nitrogen or argon, which is warmed prior to intermixing, can be used as a carrier for the SiCl4. Typical reaction times are from about 1 minute (or less) to about 15 minutes.
  • the quantity of SiCl4 used in the reaction will vary in accordance with the surface area characteristics and the available reaction sites in the starting-material.
  • the quantity of SiCl4 is preferably such as to provide from about 1 to 5 milliequiva- lents of chlorine per 100 grams of the starting material.
  • Various clay minerals may be treated by the method of the invention. Thus, for example, clays of the halloysite, illite, kaolinite, montmorillonite, and polygorskite groups, can be readily treated by the present invention.
  • the intermediates prepared by use of the present process are highly reactive, and will decompose by hydrolysis if substantial moisture is present. For such reason, once the said intermediates are prepared, and until they are used, they must be maintained in a substantially dry state, which is preferably accomplished by maintaining such intermediates under a dry inert blanket, i.e. a dry inert gas atmosphere — such as nitrogen.
  • a dry inert blanket i.e. a dry inert gas atmosphere — such as nitrogen.
  • the functionalization of the- chlorinated intermediates can be achieved by various methods, such as contacting same under suitab-le reaction conditions with compounds having active organic groups, such as organo-metallic compounds.
  • the reaction can be carried out with the functionalizing reactant in the gaseous phase, in the liquid phase, or in a system containing inert organic solvents. These reactions can be effected by various techniques, for example in many instances by simple mixing of the intermediates with the reactants.
  • the reaction takes place in three different ways:
  • the stable chlorinated intermediate thus undergoes nucleophilic substitution when reacted with functional com- pounds , for example metallic alkyls , such as aluminum alkyls .
  • functional com- pounds for example metallic alkyls , such as aluminum alkyls .
  • the bond energy of the silicon-chlorine bond is higher than the energy of the silicon-carbon bond , the halide bond will react with the organic residue of the x_rgano-metallic reactant to form a silicon-carbon bond .
  • the silicon-chlorine bond is a more polar bond , allowing nucleophilic attack on the silicon or electrophilic attack on the chlorine , thus making it very reactive and susceptible to attack .
  • the silicon-carbon bond is not a very polar bond , thus a very* stable bond , and it is preferred in the reaction.
  • Silicon tetrachloride was bubbled through a clean dry Dudley bubbler , and passed via a Te flon ® tubing into the blender jar .
  • the bubbler was maintained in a water bath at
  • the sa id silicon tetrachlor ide was introduced in accom ⁇ paniment of argon as a carrier, while the blender was operating .
  • a different pre-measured quan ⁇ tity of SiCl4 was used , as wa s appropriate to yield a desired number of chlorine milliequivalents for the quantity of the particular sample.
  • the quantity of silicon tetrachlor ide varied between .2 and 2 ml .
  • the vapors from the sil icon tetra ⁇ chloride were exuded into the argon atmosphere , with the blender then being run for an additional period .
  • the resulting clay samples were transferred still under argon , and tested for chloride content via a specific ion meter .
  • Air-float kaolin 10.8 1.87
  • the air float clay sample (1) from the preceding Example was thereupon subjected to functional ization by being processed under argon. Specifically, 50 grams of the sample resulting from processing in accordance with Example I of the 15 air float sample, were placed in a clean, dry blender container.
  • An aluminum alkyl specifically tri-N-butyl-aluminum in the quantity of 1.5 ml, was added to the said sample. Mixing was continued for 5 minutes. Then the sample was dried in an. ' oven and subjected to testing.
  • the resultant functionalized product was found to have markedly different properties than the starting kaolin clay.
  • the functionalized product, along with the untreated kaolin clay starting material were subjected to evaluation by a wetout test.
  • This wetout test consists of placing a known volume of water in a beaker, then pouring a known weight of the sample on top of the water in the beaker with no agitation of any type, and measuring the time it takes for the clay to drop below the surface of the water.
  • the said product was hydrophobic in nature. While it took only 15 seconds for the starting material to wetout, the functionalized material required 113 seconds to drop below the water surface.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Procédé de chloruration d'une composition de départ de minerais d'argile pour produire des intermédiaires rßctifs de chlorure, le procédé consistant à faire réagir cette composition sous une forme particulaire essentiellement sèche avec du SiCl4 pour activer la surface de ladite composition, formant ainsi l'intermédiaire de chlorure réactif, cette réaction se produisant à des températures inférieures à 300°C environ. Les composés obtenus sont des intermédiaires hautement réactifs qui peuvent ensuite être fonctionnaliser par réaction avec un large groupe de dérivés organiques.
PCT/US1987/000999 1987-04-28 1987-04-28 Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede Ceased WO1988008407A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/US1987/000999 WO1988008407A1 (fr) 1987-04-28 1987-04-28 Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede
DE19873790946 DE3790946T1 (de) 1987-04-28 1987-04-28 Verfahren zur oberflaechenbehandlung von tonmineralien und nach dem verfahren hergestellte reaktionsfaehige zwischenprodukte
JP62502875A JPH01503056A (ja) 1987-04-28 1987-04-28 クレーミネラルの表面処理方法及び該方法により生産される反応性中間体
BR8707720A BR8707720A (pt) 1987-04-28 1987-04-28 Processo para clorar uma composicao de partida de mineral de argila,intermediario contendo cloro quimicamente reativo e produto
GB8828801A GB2210609B (en) 1987-04-28 1988-12-09 Process for surface treating clay minerals and reactive intermediates produced by said process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1987/000999 WO1988008407A1 (fr) 1987-04-28 1987-04-28 Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede

Publications (1)

Publication Number Publication Date
WO1988008407A1 true WO1988008407A1 (fr) 1988-11-03

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PCT/US1987/000999 Ceased WO1988008407A1 (fr) 1987-04-28 1987-04-28 Procede de traitement en surface de minerais a base d'argile, et intermediaires reactifs produits par ce procede

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JP (1) JPH01503056A (fr)
BR (1) BR8707720A (fr)
DE (1) DE3790946T1 (fr)
GB (1) GB2210609B (fr)
WO (1) WO1988008407A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227675A (en) * 1963-05-01 1966-01-04 Huber Corp J M Silane-treated clay reinforced resin compositions
US4083927A (en) * 1976-11-02 1978-04-11 Toth Aluminum Corporation Controlled carbo-chlorination of kaolinitic ores
US4096234A (en) * 1977-03-23 1978-06-20 Aluminum Company Of America Production of anhydrous aluminum chloride from clay using catalyst and recycling of silicon chloride
US4120937A (en) * 1977-10-25 1978-10-17 Blount David H Process for the production of halosilicon acids and organic silicon acid compounds and resinous products
US4213943A (en) * 1978-12-22 1980-07-22 Aluminum Company Of America Production of aluminum chloride from clay using staged reactors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227675A (en) * 1963-05-01 1966-01-04 Huber Corp J M Silane-treated clay reinforced resin compositions
US4083927A (en) * 1976-11-02 1978-04-11 Toth Aluminum Corporation Controlled carbo-chlorination of kaolinitic ores
US4096234A (en) * 1977-03-23 1978-06-20 Aluminum Company Of America Production of anhydrous aluminum chloride from clay using catalyst and recycling of silicon chloride
US4120937A (en) * 1977-10-25 1978-10-17 Blount David H Process for the production of halosilicon acids and organic silicon acid compounds and resinous products
US4213943A (en) * 1978-12-22 1980-07-22 Aluminum Company Of America Production of aluminum chloride from clay using staged reactors

Also Published As

Publication number Publication date
GB8828801D0 (en) 1989-02-15
BR8707720A (pt) 1989-10-17
GB2210609B (en) 1991-05-15
GB2210609A (en) 1989-06-14
JPH01503056A (ja) 1989-10-19
DE3790946T1 (de) 1989-05-03

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