JPH01503056A - Clay mineral surface treatment method and reactive intermediate produced by the method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Clay mineral surface treatment method and applicable Reactive intermediates produced by lyu food staff The present invention generally relates to silicates and silicon containing siliceous minerals such as aluminosilicates, etc. ! Novel and extraordinary inventions regarding the composition and more particularly its subsequent functionalization. for the chlorination of substances of this type to produce intermediates with specific properties. Regarding the method.

Silicates, silicates, for the purpose of producing chlorides for various industrial and other uses. For a long time, basic minerals have been treated with halides, especially those containing gaseous chlorine. For example, clays are generally composed of minerals that are essentially hydrated aluminosilicates. It is a fine particle-like ball-like substance formed from neral. Contains a chlorination step and is relatively non-containing. Many processes for the recovery of aluminum from clay are carried out at constantly high temperatures. has been used. These processes typically produce aluminum chloride, which This is further reacted to finally produce the desired aluminum.

In other cases, high-temperature reactions of silicates or siliceous materials or minerals with chlorine may cause optical damage. The present invention has been utilized for the production of hydroxide-free silica for lath. Other related prior art techniques are as follows.

No. 3,236,606 to Moore et al., a gaseous compound containing hot chlorine A reaction in which a substance is present in the presence of fuel and air and whose temperature is on the order of 600 to 1200'C It is used to bleach the clay inside the vessel.

British Patent Specification No. 894.383 discloses impact heating of kaolin clay and then It teaches bleaching by chlorine treatment at 700°C to 900°C.

Nordbelb's U.S. Patent No. 2.141.444 covers kaolin, kaolinite, From high alumina-containing materials such as bauxite and diaspore, the material is Iron is removed by heating in the presence of carbon and chlorine at a temperature of 1150°C. discloses the use of said carbon and chlorine in the process of

Hall U.S. Pat. No. 1.405.115 discloses aluminum chloride and sulfur dioxide. by bringing alumina, sulfur and chlorine into contact at a sufficient temperature to produce teaches the production of aluminum chloride.

Hall U.S. Pat. No. 1.422.568 discloses that chlorine and sulfur vapors are present in a heating chamber. consisting of maintaining an atmosphere of and injecting a powdered aluminum compound into it A method for producing aluminum chloride is taught.

Toth U.S. Pat. No. 3,615,359 describes a reduction process in which carbon and manganese chloride are present. Aluminum trichloride and manganese formation by conversion of alumina under conditions The reaction temperature is 190℃ at the inlet and 190℃ at the outlet. takes place in a first reaction zone at 1400° C. and then converts the manganese into the trisalt. By reacting with aluminum chloride, aluminum trichloride can be heated to about 1400℃. The aluminum trichloride is reduced to aluminum by reaction at a temperature of .

Wilhot, US Pat. It is a valuable product derived from aluminum-containing minerals such as xite and aluminosilicate. Discloses a process for recovering aluminum. The aluminum-containing aluminum Neral is chlorinated together with carbon and alumina chloride↓ is recovered. the process Adds a sufficient mixture of aluminum-containing minerals and solid carbonizable organic matter. heating to carbonize the organic matter and chlorinate the solid residue from the carbonization step. The reaction temperature can be up to 1500℃, but the carbonization temperature Preferably, the temperature is slightly lower, for example in the range of 500°C to 800°C.

U.S. Pat. No. 4,082,233 to Windham et al. This article describes a method for producing aluminum chloride and silicon chloride. The The ray is first calcined with a solid carbonaceous reducing agent to form a reactant. of sulfur-containing substances Carbochlorination in the presence of temperatures in the range of about 400°C to about 1000°C It will be carried out at the same time.

U.S. Pat. No. 4,083,927 to Windham et al. This invention relates to further improvements in carbochlorination. capo chlorine - reaction mixture is in the temperature range of 600°C to 950°C; Dry chlorine to which about 0.3 to 2.5 volume percent boron chloride is added is used.

U.S. Pat. No. 4,096,234 to Martin et al. uses clay as a chlorinating agent and as a reducing agent. , chlorinated by contact with a mixture consisting of an alkali metal compound catalyst and silicon chloride. It is disclosed that aluminum chloride is produced from the clay by . The chlorination process is carried out in a fluidized bed at a temperature of 550°C to 650°C.

U.S. Pat. No. 4,139,602 to Windham et al. Regarding the production of aluminum chloride by preferentially chlorinating alumina over lyca. It is something to do. The process utilizes carbochlorination, Kaolin clay is first dried, crushed, and heated within a temperature range of 500℃ to 1000℃. Fire. The carbochlorine silane is heated within a temperature range of 600°C to 1000°C. Implemented.

Martin U.S. Pat. No. 4,213.943 discloses that a two-step chlorination process Produce aluminum chloride from clay containing aluminum oxide and silicon oxide The method is disclosed.

Dell's U.S. Patent No. 4,244,935 describes The coking step carried out is used to remove particles of metal and oxygen-containing substances. chlorination, followed by a heating step carried out between 700°C and 1000°C The method is disclosed.

US Pat. No. 4,288,414 to Reynolds et al. Chlorinate the siliceous material at a temperature of about 650°C to 900°C in an oxidizing atmosphere, then from the previous step in a carbon monoxide reducing atmosphere at a temperature of about 600°C to 850°C. chlorinating the residue with chlorine, containing iron, said siliceous material and titanium. process for recovering aluminum from clay associated with coal or bauxite is disclosed.

Dunn's U.S. Patent No. 4,355,007 describes the A two-step process for chlorinating aluminum-containing materials is disclosed.

The material is dehydrated and then heated to a temperature of less than about 1200° (temperatures of about 1100° are typical). Chlorination is carried out in the presence of chlorine and carbon (typically), oxygen is introduced, and then the non-gas The product is chlorinated in the presence of chlorine and carbon at temperatures above about 1300°K.

Dunn Jr. U.S. Patents 4.355.008 and 4.363,789 is the process by which aluminum is removed from substances containing valuable aluminum through chlorination. Dunn Jr.'s US specialty in that the production route involves chlorination. It is similar to No. 4,355.007.

In the case of kaolin clay, combining these aluminosilicates with organic substances It has long been known that products with novel properties and uses can be formulated by . However, any useful developments in this direction may occur at the mineral/organic interface. tend to be limited due to the lack of available covalent bonds. In the past, this Difficulties arise when processing various materials such as titanates, organosilicates, aluminozirconates etc. Partially solved by surface modification of the kaolinite through the use of camping agents. It has been decided.

Thus, for example, Papalos U.S. Pat. No. 3,227,675, whose surface Kaolin clays modified with organofunctional silanes are described. This typical Such a reagent is, for example, methacryloxypropyltrimethoxysilane. This way Kaolin clay modified by sea urchin can be conveniently used as a filler in natural and synthetic rubbers, etc. used. In this patent, products modified in this way are defined as polymers, medium for the synthesis of novel pigments useful as fillers for lastomers and resins. It has also been pointed out that it can function as an interstitial body. This result indicates that the above-mentioned modification of kaolin If the silane used is di- or poly-functional, only one functional Because the group binds to the clay and leaves other reactive groups for further reaction , can be obtained.

Other references of this type include Ianniselli U.S. Pat. No. 3,290.165 and and Iannicelli U.S. Pat. No. 3,567.680.

However, aluminosilicates such as kaolin clay due to the use of organosilanes modification is a complex and expensive process. Among other things, the value of the organosilane itself Furthermore, regardless of the specific organosilane utilized, the resulting products are Furthermore, it has limited ability to carry out functionalization.

In accordance with what has been said, it is an object of the present invention to The surface of clay minerals to form reactive chloride intermediates that markedly enable To provide a relatively simple, inexpensive and effective process that enables the activation of will be recognized as such.

Another object of the invention is to convert reactive siliceous materials, such as clay minerals, into gaseous 3iC. jn to activate its surface, thereby forming a reactive chloride intermediate. The object of the present invention is to provide a method for forming kaolin loops, montmorillonite, Objects containing multiple types of clays such as groups, illite groups, etc. It can be performed on a very wide range of substances such as

Supervising the live performance! According to the invention, the foregoing objectives and others that will become apparent from the following description of the specification The purpose of is to react a substantially dry particulate composition with a gaseous S i C j a activating its surface, thereby forming a reactive chloride intermediate. and at temperatures that would otherwise substantially alter the starting materials. Creme materials such as kaolin and bentonite are used to carry out the above reaction at lower temperatures. This is accomplished by chlorinating neral to produce a highly reactive intermediate.

The reaction is carried out at a temperature above the boiling point (56°C) of the 5iCja (below about 300°C, preferably Preferably, the temperature is about 60°C to 150°C. These temperatures indicate that the starting material below the temperature at which they change chemically or physically and lose their basic properties For example, in the case of hydrous kaolin clay, these temperatures are The temperature is below that at which oxidation, dehydration, and/or changes in crystal structure occur. Therefore Even if such hydrated clay is treated according to the present invention, it will not change into calcined kaolin. and therefore its low abrasion properties are not adversely affected by the finishing process.

The reaction can be carried out in any apparatus that allows intimate contact between the particulate matter and the gaseous reactants. It can be done with These include mechanical mixers such as high shear mixers, as well as The reaction is carried out by passing the gaseous components upward through a suitable diffusion plate. It can be carried out in a fluidized bed reactor in which the particulate matter to be treated is introduced into the fluidized bed. Wear. Before mixing, heat a dry inert gas such as nitrogen or argon to SiCj! a Can be used as a middle rear. Typical reaction time is about 1 minute (or less) It takes about 15 minutes from

The amount of SiCIIa used in the reaction depends on the surface area characteristics of the starting materials and the amount used. For example, in the case of kaolin clay, the 5i The amount of Cja can provide about 1 to 5 milliequivalents of chlorine per 100 g of the starting material. Preferably, however, at least all uses in the starting materials are -0 and -H groups up to the appropriate stoichiometric amount to completely react with the -0 and -H groups. 5iCja can also be reacted.

A variety of clay minerals can be treated with the method of the present invention. Therefore, for example, halo Isite, illite, kaolinite, montmorillonite and polygorskitog Loop clays can be easily treated according to the present invention.

The intermediates prepared by use of this method are highly reactive and require the presence of substantial amounts of moisture. It decomposes by hydrolysis. For this reason, once the said intermediate has been prepared, and until it is used, they must be kept substantially dry. This is usually a dry inert blanket, i.e. a dry inert blanket such as nitrogen. Preferably achieved by keeping such intermediates under an active gas atmosphere .

Functionalization of the chlorinated intermediate renders it as an organometallic compound under suitable reaction conditions. This can be achieved by a variety of methods, such as contacting compounds with active groups such as can be done. The reaction can be carried out in the gas phase, in the liquid phase or in a system containing an inert solvent. It can be carried out together with the above-mentioned functionalization reagents in These reactions are often , by various techniques such as simply mixing the intermediate with the reagent. It can be carried out.

A large number of groups such as alkyl, allyl, aryl, mercapto, amine, etc. These intermediates can be used to functionalize them.

Although applicants do not wish to be bound by any particular hypothesis, the possible reactions of the present invention is as follows.

Starting materials used in the practice of this invention, such as kaolin clay, etc. It has oxide and hydroxyl groups, i.e., 10 and -0H groups, present in the surface layer. Tetrachloride Silicon therefore reacts with these silicates to form very stable 5i-O3i (siloxanes). ) form a bond. The reaction occurs in three different routes.

1) = 5i-Ql + C1-3i-C1s = H3i-0-5iCh + HCI All these reactions are very strong intermediates and active organic groups. surface chlorination that can react with compounds containing Generates silicon.

The stable chlorinated intermediate is a functional compound such as an aluminum alkyl. A silicon-chlorine bond which undergoes nuclear substitution when reacted with a metal alkyl such as energy is greater than that of silicon-carbon bonds, but halide bonds are Reacts with organic residues of genus reactants to form silicon-carbon bonds. The silicon-chlorine bond is a more polar bond, resulting in a nuclear attack on silicon or an electrophilic attack on chlorine. , thereby making it highly reactive and vulnerable to attack. Said Silicon-carbon bonds are not very polar bonds and are therefore very stable bonds. , it is preferred in the above reaction.

childish i″■ The invention is illustrated by a series of examples, which are merely examples of the practice of the invention. It should not be thought of as limiting.

Five ridges In this example, five different 50 g samples were prepared using silicon tetrachloride according to the present invention. reacted with the raw material. The samples each contained 88% by weight of the +11 particles with 2 mics. air-floated kaolin with a particle size distribution that is less than the romometer ESD The B, E, and T surface areas of this sample were 10.8 trr/g.

(2) It exhibits high light scattering properties and can be used especially as a filler and as a coating pigment. Gygia is a calcined kaolin clay product with relatively fine particle size that is also used in The Alf of Anglo-American Craze Corporation in Atlanta ATEX® products.

+31 100.5 n? /g of B, E, T, surface area of Georgia. tonite.

(4) Relatively fine coarse cocoa that is simply kneaded and degrissed without further classification Linkley, the material produced was 86% by weight less than 2 micrometers, 79 % by weight is 1 micrometer and 23.5 td/g B, E, T, surface It had a product. +51 As coarse clay, 90% by weight of the initial particles are 2 mil. is a kaolin clay with a particle size distribution below the chromium ESD; A fine fraction of less than 1 micrometer ESD of 95% by weight fractions and coarse fractions. B of 24.5rrr/g.

A fine fraction with a surface area of E, T was used in this example.

It contained.

Each of the above five types of samples was initially placed in an oven at 150°C for 30 minutes to 1 hour. Dry for a while. The sample was then preheated to 100°C and its temperature was compared in the container. Transferred to a Waring blender vessel where it was kept relatively constant. Purge this container with argon. to ensure that the atmosphere was an inert blanket of argon.

Blow silicon tetrachloride through a clean, dry Dadri bubbler and use a Teflon (registered Trademark) tube into the Prendager.

The blender was kept in a 65°C water bath. While operating the blender, Silicon tetrachloride was introduced with argon as a carrier. About each sample , predetermined different amounts of 5iC14 were added to the chlorine concentration for a particular sample amount. It was used as appropriate to give the desired number of equivalents. The amount of silicon tetrachloride is 0. It was varied between 2 and 2-1. The vapor from the silicon tetrachloride is in the argon atmosphere. The blender was run for an additional period of time. The resulting cresa Transfer the sample still under argon and use a specifin ion meter to determine the chlorine content. The amount was tested.

The samples mentioned above have the following milliequivalents (M, E) per 100 g of sample.

It was found to have a chlorine content expressed as Q,).

U-Top The air float clay sample (1) from the previous example was then treated under argon. It was functionalized by In particular, according to Example 1 of said air float sample. Place 50 g of the sample resulting from the above treatment into a clean and dry blender container. I made him put it there. Aluminum alkyl, especially tri-N-butyl-alkyl in an amount of 1.5 ml Minium was added to the sample. Mixing was continued for 5 minutes, then the sample was dried in an oven and tested.

The resulting functionalized product has significantly different properties than the starting kaolin clay. It was found that it has. In particular, with the untreated kaolin clay starting material The functionalized product was evaluated by a wettability test. This wettability test Place a known amount of water in a beaker, then place a known amount of saline on top of the water in the beaker. Pour the sample without any type of agitation and let the clay rise to the surface of the water. It consists of measuring the time it takes for the object to sink to the bottom. After undergoing such a wettability test, When analyzed, the product was found to be hydrophobic in nature. Said The starting material required only 15 seconds to wet, whereas the functionalized material It took 113 seconds to sink below the ice surface. Furthermore, even after 48 hours, the new substance The main part remains in the E turbid state as separated particles, while the starting material is about 3 Complete sedimentation occurred within 5 minutes. Furthermore, the product wets in hexane in less than 10 seconds. In contrast, ordinary kaolin clay showed extreme organophilicity like hexane. Unaari! Shows little or no tendency to wetting by solvents.

Although the invention has been described with respect to specific embodiments thereof, variations thereof may still be contemplated by the present teachings. It is the view of this disclosure that numerous variations are possible to those skilled in the art, such as within the scope of As may be understood from this point, the invention should therefore be broadly construed and hereby It is to be limited only by the scope and spirit of the appended claims.

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Claims (19)

[Claims] 1. The clay mineral starting composition, which is substantially dry and particulate, is dissolved in gaseous SiCl. 4 to activate the surface of the composition, thereby forming reactive chloride intermediates. wherein said reaction is carried out at a temperature below about 300°C. chlorinating the clay mineral starting composition to produce the reactive chloride intermediate; method for. 2. The process of claim 1, wherein said reaction is carried out at a temperature of about 56°C to 300°C. vinegar. 3. Claim 1, wherein said process is carried out at a temperature in the range of about 60° to 150°C. process. 4. Claim 1, wherein the SiCl4 is mixed with a dry inert gas carrier. Method described. 5. Claim 1: The reaction is carried out in an apparatus for contacting particulate solids with gas. The method described in. 6. The method according to claim 1, wherein the substance comprises an aluminosilicate. Law. 7. The method according to claim 1, wherein the mineral comprises kaolin. . 8. Claim 1, wherein the mineral comprises montmorillonite. How to put it on. 9. 9. The method of claim 8, wherein the material comprises bentonite. . 10. Claim 3, wherein the mineral comprises an aluminosilicate. How to put it on. 11. The method according to claim 3, wherein the mineral comprises kaolin. Law. 12. Claim 3, wherein the mineral comprises montmorillonite. Method described. 13. Claim 3, wherein the mineral comprises bentonite. the method of. 14. Claim 1 further comprising functionalizing said intermediate with active organic groups. How to put it on. 15. Claim 3 further comprising functionalizing said intermediate with active organic groups. How to put it on. 16. A clay mineral whose surface has been activated by reaction with gaseous SiCl4 chemically reactive chlorine capable of functionalization with reactive organic groups comprising Containing intermediates. 17. 17. The product of claim 16, wherein the clay mineral is kaolin. 18. The clay mineral according to claim 16, wherein the clay mineral is montmorillonite. A product. 19. 19. The product of claim 18, wherein the clay mineral is bentonite. .