CN1714043A - Method for producing metal fluoride materials - Google Patents
Method for producing metal fluoride materials Download PDFInfo
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- CN1714043A CN1714043A CN 200380103977 CN200380103977A CN1714043A CN 1714043 A CN1714043 A CN 1714043A CN 200380103977 CN200380103977 CN 200380103977 CN 200380103977 A CN200380103977 A CN 200380103977A CN 1714043 A CN1714043 A CN 1714043A
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Abstract
A process for the production of metal fluorides comprising introducing a predetermined weight of anhydrous hydrofluoric acid into a reaction vessel and initiate a mixing action, preheating a predetermined weight of anhydrous metal to a predetermined reaction temperature, introducing aliquots of the anhydrous metal into the reaction vessel at intervals until the entire predetermined weight of the anhydrous metal has been added, removing excess anhydrous hydrofluoric acid from the reaction vessel, and remove a metal fluoride resultant product from the reaction vessel.
Description
Cross Reference to Related Applications
This non-provisional application claims priority from US provisional patent application No.60/421,716 entitled METHOD OR PRODUCING HIGH CATALYTIC ACTIVITY, SUBMICRON, METAL FLUORIDATALYST MATERIALS, filed on 28.10.2002, and US non-provisional patent application No.10/662,991 entitled METHOD FOR PRODUCING METAL FLUORIDEMATERIALS, filed on 15.9.2003, the disclosures of which are incorporated herein by reference in their entireties.
Technical Field
This application relates to the manufacture of metal fluorides for use as catalysts or for any other application.
Background
Those skilled in the art will appreciate that in many cases metal fluorides can be produced by mixing a metal or metal compound (e.g., a metal salt) with hydrofluoric acid. Wherein the metal compound is a metal chloride, the reaction is substantially as follows:
the reaction between the metal chloride and hydrofluoric acid may be endothermic. In this case, the reactants must absorb heat from their environment in order for the reaction to proceed to completion. When the reaction is endothermic, it has been observed that the greater the rate of heat transfer into the reactants and the higher the temperature at which the reaction occurs, the smaller the metal fluoride particles formed. In general, the smaller the metal fluoride particles, the greater the exposed surface area per unit weight of metal fluoride. Considering that the catalyst is a surfactant, the larger surface area per unit weight normally associated with smaller particles is expected to show greater catalytic activity, and this has been shown to be the case.
For the case where the reaction between the metal chloride and anhydrous hydrofluoric acid is exothermic, the reaction requires the release of heat to proceed to completion. In this case, the conclusions given above are expected to be contrary to the exothermic reaction case.
The process of blending the metal chloride and hydrofluoric acid has somewhat varying consequences depending on the metal chloride used; however, to illustrate the general reaction, a specific case of producing iron trifluoride by blending ferric trichloride and anhydrous hydrofluoric acid is given here.
The process of blending ferric trichloride and anhydrous hydrofluoric acid causes several events to occur:
dissolving ferric trichloride in liquid anhydrous hydrofluoric acid and ionizing;
dissolving and ionizing individual molecules of ferric trichloride exchanged the first chlorine atom with a fluorine atom from a liquid, ionized, anhydrous hydrofluoric acid source, in which case the individual molecule reaction product remained soluble and ionized to FeFCl2 (iron dichlorofluoride) with evolution of hydrogen chloride gas (at one atmosphere of pressure and at temperatures above-84.9 ℃).
The individual dissolved and ionized iron dichlorofluoride exchanges the second and third chlorine atoms with two fluorine atoms from a liquid, ionized, anhydrous hydrofluoric acid source, in which case the iron trifluoride molecules formed are insoluble in liquid anhydrous hydrofluoric acid and precipitate as lime green solids, with additional hydrogen chloride gas being released.
It is currently accepted practice to add liquid anhydrous hydrofluoric acid to solid ferric trichloride, the disclosure of which is incorporated herein by reference in its entirety when making ferric trifluoride, as described in detail in, for example, US patent No.4,938,945. This method is carried out for various reasons listed in US patent No.4,938,945. An additional reason for adding liquid anhydrous hydrofluoric acid to solid ferric trichloride is safety. It is generally accepted that the reaction has a lower tendency to splash, and therefore this method is considered to be a safer method than adding ferric trichloride to anhydrous hydrofluoric acid. However, it is quite apparent in this process that the first weight aliquot of ferric trichloride is exposed to a very limited amount of anhydrous hydrofluoric acid (a very low weight ratio of anhydrous hydrofluoric acid to ferric trichloride). Each subsequent aliquot of ferric trichloride was also exposed to a finite weight ratio of anhydrous hydrofluoric acid to ferric trichloride, but eventually sufficient anhydrous hydrofluoric acid was added until the perceived optimal weight ratio was established. However, at this point all of the ferric trichloride reacted at a much lower than optimal level of anhydrous hydrofluoric acid to ferric trichloride weight ratio. This aspect of the process is claimed to result in larger primary particles, agglomeration of the primary particles, slow reaction times, incomplete reactions, low to no catalytic activity at all, and poor quality control with respect to the chemical and physical properties of the iron trifluoride product formed.
Furthermore, it is currently accepted practice to blend the ingredients at atmospheric pressure during the iron trifluoride manufacturing process. In view of the fact that liquid anhydrous hydrofluoric acid boils at 19.8 ℃ (67.6 ° F) at standard atmospheric pressure, the boiling point of anhydrous hydrofluoric acid limits the temperature to which the environment of the reactants can be raised before and during the reaction. Without temperature control devices and/or equipment, prior art manufacturing processes tend to cool while the ingredients are being blended because of the endothermic nature of the reaction. Thereafter, once the reaction is complete, the final product tends to adjust to ambient temperature or at 19.8 ℃ (67.6 ° F) (boiling point of anhydrous hydrofluoric acid at standard atmospheric pressure) if ambient temperature is greater than 19.8 ℃ (67.6 ° F).
After the reaction is complete, it is currently accepted practice to immerse the ferric trifluoride product in liquid anhydrous hydrofluoric acid for three to ten days. Longer residence times ("acid wash times") generally result in a more complete reaction, and thus a purer iron trifluoride product.
After the reaction time and residence time, it is currently accepted practice to separate the solid ferric trifluoride product from the remaining anhydrous hydrofluoric acid by decanting and/or evaporating the hydrofluoric acid. Thereafter, the ferric trifluoride product was dried in stages until the maximum temperature was about 250 ℃. In such a case, it is anticipated that any free residual anhydrous hydrofluoric acid and/or any free water should be driven off, leaving an anhydrous ferric trifluoride product. The product is then packaged in a manner that isolates it from the environment and avoids absorption of moisture and the like.
Summary of the invention
The observations obtained during or after the manufacture of iron trifluoride using the prior art method are as follows:
the higher the anhydrous hydrofluoric acid temperature, up to the highest value of 19.8 deg.C (67.6 deg.F), the smaller the iron trifluoride particles formed.
The larger the weight ratio of anhydrous hydrofluoric acid to ferric trichloride, the smaller the iron trifluoride particles formed, reaching a weight ratio of 60 to 1.
The longer the reaction product is in an anhydrous hydrofluoric acid environment, the more complete the reaction and hence the purer the iron trifluoride product formed.
Stirring or agitation during the addition of anhydrous hydrofluoric acid to ferric trichloride to provide smaller ferric trifluoride particles apparently shortens the necessary residence time of ferric trichloride in anhydrous hydrofluoric acid to cause complete reaction, which produces purer ferric trifluoride.
The ferric trifluoride product, which results in the formation of discrete, unagglomerated primary particles in the submicron size range, has been shown to exhibit greater catalytic effectiveness in certain specific reactions in which PTFE is reacted with steel and aluminum at ambient temperature and atmospheric pressure. See, for example, US patent No.5,877,128, the disclosure of which is incorporated herein by reference in its entirety. Thus, smaller submicron ferric trifluoride particles are generally believed to constitute a better catalytic product.
This particular catalyst material must exhibit the following properties and technical parameters when prepared for the intended application.
The catalyst material must have individual particles no greater than 0.50 microns.
The catalyst material must not agglomerate. Each particle must be discrete and must not adhere to every other particle.
The catalyst chemistry must be at least 99.9% pure and devoid of stray elements and contaminants, including water.
The catalyst material must not exhibit a pH below 3.5 when slurried in demineralized water at a weight ratio of 1 gram of material to 10 grams of demineralized water.
The catalyst material must be active to be able to act as a catalyst, as determined by the ability of the material to cause a chemical reaction between PTFE (TEFLON) and steel under the specified test conditions.
The ability or tendency of one substance to blend uniformly with another substance, and the extent to which it is blended, is referred to as the "solubility" of a particular substance in another particular substance. Of particular importance is the solubility of certain metal-containing solids, solutes, materials in certain liquids, solvents, materials. The solubility of solids in liquids can be found to vary from very small to very large amounts for their respective solubilities in a particular liquid. However, for each case when a solid is dissolved in a liquid, the dissolved solid completely loses its former material properties such as particle size, crystal structure, hardness, etc., and thereafter exists in a molecular or ionic state as the solid remains dissolved in the liquid. The dissolved molecules and/or ions are virtually completely dispersed to form a true solution.
The process of the present invention comprises dissolving a soluble metal source ("metal source") compound (i.e., metal salt) in a solvent, wherein the metal source compound is completely dissolved to form a true solution ("solution"). The solution is then thoroughly mixed with the organic polymer to form a polymer solution and/or a stable colloidal suspension. In the latter case, the organic polymer, which is characterized by having gelling properties, becomes an external or dispersed phase and serves to contain and maintain the solution in suspension. By way of definition, an organic polymer as used herein constitutes a substance in which a solution is soluble and/or an organic polymer serves as a colloid-producing substance in which a dispersed phase (solution) is blended; however, organic polymers constitute the continuous phase and are used to produce gelatinous or viscous blended products. The blended product is referred to herein as a "metal source polymer". Once prepared, the metal source polymer is introduced into the anhydrous hydrofluoric acid drop by drop until the stoichiometric ratio of moles of metal source within the metal source polymer is equal to or less than one-half of the relevant moles of anhydrous hydrofluoric acid.
The metal source and anhydrous hydrofluoric acid within the metal source polymer will react immediately upon contact and they will react at the molecular and/or ionic level to form metal fluoride reaction products because the reaction occurs at the molecular or ionic level, with the resulting particles having submicron dimensions.
Once the metal source has reacted with the anhydrous hydrofluoric acid and the metal component of the metal source polymer has been converted to a metal fluoride, the metal fluoride can be separated from the remainder of the material.
If the metal fluoride remains soluble after the reaction, the metal fluoride may be separated from the polymer/solvent by evaporation and/or decomposition of the polymer/solvent mixture.
If the metal fluoride is not soluble in the polymer/solvent mixture and precipitates out of solution, the solid metal fluoride precipitate can be separated from the liquid by decanting the polymer/solvent into a separate vessel of suitable design or it can be separated by other conventional methods such as filtration and the like. The solid metal fluoride product is then slowly dried in stages to 100 ℃ until all volatile materials (including water) have been driven off, after which the temperature may be raised to a temperature at which the remaining solvent evaporates and/or decomposes and the metal fluoride becomes completely free of the polymer/solvent mixture.
The remaining polymer/solvent/anhydrous hydrofluoric acid material may be isolated by using well known methods such as distillation, freezing, extraction, decomposition, and the like.
Certain metal source materials are found to be insoluble in all of the actual solvents used in the process of the present invention in all of their various compound (i.e., salt) forms. Other metal source materials, when converted to their various compounds, proved to be practically soluble only in aqueous alkaline solvents.
In the former case, which is almost impossible as exemplified above, in which all compounds of the metal source prove to be insoluble in all solvents, the process of the present invention is not applicable in the case where the metal source belongs to the solid phase and the solvent belongs to the liquid phase.
In the latter case, as exemplified above, the solution in which the water-soluble metal source compound should be dissolved in a minimum amount of water and neutralized may be blended with a hydrophilic organic polymer material selected from the group consisting of carbohydrates (i.e., sucrose, starch, cellulose, etc.), carbohydrate derivatives, hydrophilic homopolymers, ethylene glycol polymers, ethylene glycol ester polymers, ethylene glycol, 2-hydroxyethylene-methacrylates, hydroxyalkyl acrylates, acrylamides, copolymers of N-vinylpyrrolidone, polyurethanes, polyurethane-acrylates, polyurethane-methacrylate copolymers, animal-derived protein-gelatin, and the like.
Metal source compounds that are generally found to be water soluble and suitable for use in the methods of the present invention include metal chlorides, carbonates, hydroxides, isopropoxides, nitrates, acetates, epoxides, oxalates, and mixtures thereof.
In the case of the present invention, the water-soluble metal source compound should be dissolved in water to form a solution in a minimum amount. The solution is then blended with the hydrophilic organic polymeric substance in a suitable one-to-one (1: 1) weight ratio, but in any event there is a sufficient amount of the hydrophilic organic polymeric substance to maintain the metal source compound in solution. Thereafter, this mixture of solution and hydrophilic organic polymeric substance should be blended with anhydrous hydrofluoric acid. This blending is preferably carried out by introducing the solution very slowly, drop by drop, into anhydrous hydrofluoric acid in a suitably designed reaction vessel until the stoichiometric ratio of moles of metal source within the metal source polymer is equal to or less than one-half of the relevant moles of anhydrous hydrofluoric acid. In one embodiment, the stoichiometric ratio is between one-half and one sixty times the relative moles of anhydrous hydrofluoric acid.
Despite the fact that metal source compounds are soluble in water, it has proven desirable to use some other solvent in place of water, since the introduction of water can inevitably lead to hydrated products, which is undesirable.
It is an object of the present invention to produce metal fluorides in the form of discrete, unagglomerated submicron-sized particles.
It is an object of the present invention to produce metal fluorides that have no impurities introduced into the product.
It is an object of the present invention to produce metal fluorides that are chemically pure and physically homogeneous.
It is an object of the present invention to provide a versatile, low cost method for producing high purity, submicron, unagglomerated, discrete, chemically pure particles comprised of single or multi-component metal fluorides.
It is an object of the present invention to provide a process for producing high purity, submicron, unagglomerated, discrete chemically pure particles comprised of single or multi-component metal fluorides that does not require a highly specialized, controlled atmosphere in the process.
The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized that such equivalent constructions do not depart from the scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.
Brief description of the drawings
Fig. 1 is a graph illustrating the relationship between the vapor pressure and the temperature of anhydrous hydrofluoric acid.
Detailed Description
Although the metal fluorides produced in the exemplary embodiments disclosed herein may be used as catalysts, the present invention is not limited to producing metal fluoride catalysts. In contrast, the metal fluorides produced according to the present invention can be used in almost any application.
The observations previously described, carried out on repeated experiments, here labelled as "prior art" methods, have led to several important conclusions that govern several important requirements for improving the "prior art" method, which are listed below:
higher reaction temperature: increasing the temperature at which the reaction between ferric trichloride and anhydrous hydrofluoric acid is carried out results in smaller diameter particles of ferric trifluoride product being obtained. The means for achieving the high temperature reaction are as follows:
heating under pressure: by making a pressure-resistant reaction vessel comprised of nickel, nickel alloys, or other metals that are completely lined with PTFE or other polymers that can withstand the harsh contact of anhydrous hydrofluoric acid at the rated reaction vessel operating temperature and pressure, the temperature of the anhydrous hydrofluoric acid can be raised to the boiling point of the acid at the pressure rating of the reaction vessel, but without the loss of hydrofluoric acid due to evaporation. The reaction vessel is logically required to be equipped with a pressure relief valve, both for safety purposes and for the hydrogen chloride gas produced during the reaction to be able to escape.
Preheating: the reactants, anhydrous hydrofluoric acid and ferric chloride, may be preheated before being mixed. For example, anhydrous hydrofluoric acid can be preheated to a temperature at which the vapor pressure of the acid is equal to the operating pressure of the reaction vessel. See, for example, the relationship between vapor pressure and temperature of anhydrous hydrofluoric acid shown in fig. 1. Similarly, the ferric trichloride was preheated to about 300 ℃ prior to its admixture with anhydrous hydrofluoric acid. (Note: ferric trichloride has a melting point of 306 ℃ and a boiling point of 319 ℃ however, it begins to decompose at or slightly below its melting point of 306 ℃.)
Continuous heating using various means: if the reaction vessel is composed of PTFE or some other anhydrous hydrofluoric acid resistant polymer but not metal, it can be heated by using microwave energy, but it is desirable that the pressure rating of the reaction vessel be not exceeded by this heating operation. It is important to note that microwave heating can result in vapor bubbles forming below the surface of the liquid anhydrous hydrofluoric acid and rising to the surface causing a serious safety hazard. If the reaction vessel is constructed of metal, it may be heated continuously by more conventional means such as resistance heating, electric induction heating, flame or steam. In addition, some heating and mixing may be achieved by applying high energy ultrasound to the reaction vessel.
The weight ratio of the anhydrous hydrofluoric acid to the ferric trichloride is as follows: maintaining a high weight ratio of anhydrous hydrofluoric acid to ferric trichloride (e.g., up to 60 to 1) results in smaller diameter particles of ferric trifluoride product, resulting in a faster and more complete reaction, and a more nearly pure reaction product. The means for achieving a high weight ratio of reactants are as follows:
adding solid ferric trichloride into liquid anhydrous hydrofluoric acid: it is well known that the reaction between anhydrous hydrofluoric acid and ferric chloride occurs in several steps, which are distinguishable, but the entire reaction occurs at once. The extent to which the reaction proceeds to completion to form a purer final product will depend on the weight ratios of the reactants and the amount of residence time. In the batch-type production method, the weight ratio of anhydrous hydrofluoric acid to ferric trichloride can be maintained at an optimum value, and if solid ferric trichloride is added to liquid anhydrous hydrofluoric acid in a closed reaction vessel (closed for safety), the mixture can be easily mixed, the pressure can be maintained, and the anhydrous hydrofluoric acid can be heated to a boiling point at atmospheric pressure or higher.
For each aliquot of solid ferric trifluoride added to liquid anhydrous hydrofluoric acid, the weight ratio of the reactants is most favorable, possible when fixed amounts of the two reactants are used. This is because when each weight aliquot of ferric trichloride is introduced into the reaction vessel containing anhydrous hydrofluoric acid, the reaction takes place immediately and the product ferric trifluoride formed will precipitate and fall to the bottom of the reaction vessel. In this process, only a small fraction of anhydrous hydrofluoric acid should be consumed. Thus, when the next weight aliquot of ferric trichloride is introduced into the reaction vessel, it will follow about the same weight ratio of anhydrous hydrofluoric acid to ferric trichloride as the initial aliquot of ferric trichloride. If the process is started with an initial weight ratio of 60 to 1 (anhydrous hydrofluoric acid to ferric trichloride), the last of the ten aliquots of ferric trichloride should follow a weight ratio of no less than 56 to 1.
The chemical reaction that occurs when ferric trichloride is mixed with anhydrous hydrofluoric acid is given below, where the stoichiometric combined weight of the compounds in the reaction is given below each such compound, as follows:
162.2031 60.0189 112.8402 109.3818
it is presupposed that 1 mole or 162.2031 grams of ferric trichloride will be admixed with an amount of anhydrous hydrofluoric acid in a weight ratio of sixty (60) parts anhydrous hydrofluoric acid to one (1) part ferric trichloride. A first aliquot of 1 mole or 162.2031 grams of ferric chloride will be introduced into 9,732.1860 grams of anhydrous hydrofluoric acid (in a 60 to 1 weight ratio). This reaction will result in the consumption of 60.0189 grams of anhydrous hydrofluoric acid, leaving 9,672.1671 grams of unreacted anhydrous hydrofluoric acid.
The second aliquot of 1 mole or 162.2031 grams of ferric chloride was introduced into the remaining 9,672.1671 grams of anhydrous hydrofluoric acid to cause the reaction and consumption of an additional 60.0189 grams of anhydrous hydrofluoric acid, leaving 9,612.1482 grams of unreacted anhydrous hydrofluoric acid. The blending ratio for the second aliquot addition should be 59.63 to 1 for anhydrous hydrofluoric acid to ferric chloride.
Similarly, anhydrous hydrofluoric acid ("AHF") was introduced in an initial amount (9,672.1671 grams)Of the first ten aliquots of 1 molar (for each aliquot) or 162.2031 grams of iron trichloride ("FeCl3") are as follows:
| FeCl3aliquot No. | AHF g remaining | AHF and FeCl3Weight ratio of |
| 0 | 9,732.1860 | 60.0000 to 1 |
| 1 | 9,672.1671 | 59.6300 to 1 |
| 2 | 9,612.1482 | 59.2600 to 1 |
| 3 | 9,552.1293 | 58.8899 to 1 |
| 4 | 9,492.1104 | 58.5199 to 1 |
| 5 | 9,432.0915 | 58.1499 to 1 |
| 6 | 9,372.0726 | 57.7799 to 1 |
| 7 | 9,312.0537 | 57.4098 to 1 |
| 8 | 9,252.0348 | 57.0398 to 1 |
| 9 | 9,192.0159 | 56.6698 to 1 |
| 10 | 9,131.9970 | 56.2998 to 1 |
After this hypothetical ten-step reaction process, the remaining anhydrous hydrofluoric acid can be recovered and reused.
The process was charged with phase weighed anhydrous hydrofluoric acid: once the optimal weight ratio of anhydrous hydrofluoric acid to ferric chloride is clearly established, it may be recommended that anhydrous hydrofluoric acid be added to the reaction vessel in the optimal stoichiometric weight ratio before the next aliquot of ferric chloride is added, depending of course on the importance of the optimal weight ratio for the particular reaction.
Long residence time: long residence times are not required. As stated previously, the reaction between ferric trichloride and anhydrous hydrofluoric acid occurs immediately. The manner in which the reaction process is carried out using currently accepted practice results in the need for long residence times in order to allow the reaction to proceed to completion. It is concluded that increasing the reaction temperature, maintaining the optimum weight ratio of anhydrous hydrofluoric acid to ferric chloride, and sufficient agitation and/or stirring will result in complete reaction to produce submicron, unagglomerated particles of catalytically active ferric trifluoride without subjecting the reactants to long residence times.
Stirring or agitating: stirring or agitation has been inferred to be beneficial in the process of the present invention. Stirring and agitation may be accomplished in the following manner:
rotating: the reaction vessels are supported in a manner that allows the reaction vessels to rotate in one or more planes during the reaction.
Ultrasonic wave: regardless of the materials comprising the reaction vessel, the components of the reaction vessel are agitated using a high energy ultrasonic source. The ultrasound is also used to a lesser extent for heating the reaction vessel.
Magnetic stirring equipment: the reaction vessel can be stirred with a magnetic stirring device.
Ordinary stirring equipment: the reaction vessel can be stirred by means of a common stirring device (such as a lighting mixer) employing an electric motor and one or more rotating blades, which is introduced through a pressure packing gland.
Catalytic activity: based on the above observations, it is believed that if the recommendations outlined above are employed and implemented, the resulting ferric trifluoride product not only consists of discrete, unagglomerated submicron particles, but it also exhibits catalytic activity for the experimental conditions described herein.
Processes FOR PRODUCING METAL FLUORIDE catalysts have been disclosed in US provisional patent application No.60/421,716 entitled "Metal FOR catalyst HIGH CATALYTIC ACTIVITY, SUBMICRON, METAL FLUORIDE CATALYST MATERIALS", filed on day 10, month 28, 2002, and pending US patent application No.10/662,992 entitled "PROCESS FOR METAL FLUORIDE MATERIALS", filed on day 9, month 15, 2003, the disclosures OF which are incorporated herein by reference in their entirety. The present invention provides another method for producing metal fluoride catalyst materials having submicron particle size and high catalytic activity. The present invention also provides inherently better quality control and provides reaction products with consistent chemical and physical properties.
Preferred embodiments of the present invention are discussed in more detail below. These processes are useful for producing metal fluoride catalyst materials having submicron particle size and high catalytic activity. These processes provide inherently better quality control and provide reaction products with consistent chemical and physical properties (compared to prior art processes).
Case 1 (organic solvent):
substantially chemically pure anhydrous ferric chloride is dissolved in one or more of a group of solvents in which ferric chloride is soluble, the group consisting of water, alcohols, ethers, benzene, acetone, and the like. Although ferric chloride is soluble in water, water is not a suitable solvent for the present invention when the final product is used as a catalyst, since the final product formed is likely to be the hydrated form of the desired metal fluoride. Hydrated forms of metal fluorides are generally found to be not catalytically active.
The dissolution operation can be carried out at atmospheric pressure and at ambient temperature, but great care must be taken to prevent hydration of the ferric trichloride prior to dissolution in the solvent. A sufficient amount of ferric trichloride should be dissolved to substantially saturate the solvent with ferric trichloride, keeping in mind that the subsequent operations in which the mixture of ferric trichloride, solvent and polymer is admixed with anhydrous hydrofluoric acid and the reaction between the metal source (ferric trichloride) and anhydrous hydrofluoric acid should be endothermic. This reaction can result in a significant drop in temperature if heat is not added to the system at a rate sufficient to compensate for the endotherm in the reaction. If the mixture or system of materials is allowed to cool, it is possible that ferric trichloride precipitates from solution prior to the reaction. This is because the solubility of ferric trichloride in a solvent varies with temperature and in general ferric trichloride is less soluble at lower temperatures.
For this reason, the solubility of ferric trichloride in a particular solvent should be tested and measured at the lowest temperature expected to be encountered throughout the process (e.g., 0 ℃). The solubility of the ferric trichloride is determined and preferably as X grams per Y grams of solvent and the determined weight ratio of ferric trichloride to solvent should be used initially.
The ferric chloride/solvent solution is then blended with the polymer.
In this case 1, methanol is used as the solvent and the necessary amount of ferric trichloride is dissolved in the methanol solvent.
Thereafter, a ferric chloride/methanol solution was blended with the polymer. In this case 1, the polymer is polyethylene glycol. Sufficient polyethylene glycol (e.g., Dow Chemical Grade 4500 polyethylene glycol powder) is added to the ferric trichloride/methanol mixture to completely dissolve and/or encapsulate the ferric trichloride/methanol mixture. Blending of these ingredients requires vigorous mixing until the system of ingredients becomes clear, homogeneous and stable.
Next, the above-listed mixture is added to a suitable container containing anhydrous hydrofluoric acid. This addition is carried out slowly, drop by drop, until the stoichiometric ratio of the moles of iron trichloride in the mixture is equal to or lower than half the relative moles of anhydrous hydrofluoric acid. The addition of the mixture in this step of case 1 is accompanied by vigorous stirring.
Once the ferric trichloride has reacted with anhydrous hydrofluoric acid and has been converted to ferric trifluoride, the ferric trifluoride can be separated from the remainder of the material.
The separated ferric trifluoride material is then dried slowly in stages to 100 ℃ until all volatile matter (including any moisture contained) has been driven off, and then the temperature is raised to 240 ℃ to the point that the remaining solvent and polymer evaporate and/or decompose and the ferric trifluoride is completely free of all solvent and/or polymer.
The finished product is placed in a vessel to prevent the ferric trifluoride from becoming hydrated.
The anhydrous ferric trifluoride product formed is substantially chemically pure and appears to have an average particle size of about 0.2 microns and about 150 meters2Discrete, unaggregated, uniform particles per gram of surface area. Furthermore, the iron trifluoride product formed exhibits a pH between 4.0 and 7.0, when 1 gram of iron trifluoride is mixed with 10 grams of demineralized water, and the higher surface area results in a much higher catalytic activity per unit weight compared to iron trifluoride produced by most known other processes.
Case 2 (water solvent):
530 grams of substantially chemically pure catalyst grade ferric trichloride was dissolved in 100mL of distilled warm water. This salt solution was blended with 20 grams of Dow Chemical Grade 4500 polyethylene glycol powder and stirred until the mixture became a clear solution.
The above-listed mixture is then added to a suitably designed vessel containing anhydrous hydrofluoric acid. This addition is carried out slowly, drop by drop, until the stoichiometric ratio of the moles of iron trichloride in the mixture is equal to or lower than half the relative moles of anhydrous hydrofluoric acid. The addition of the mixture in this step of case 2 is accompanied by vigorous stirring.
Once the ferric trichloride has reacted with anhydrous hydrofluoric acid and has been converted to ferric trifluoride, the ferric trifluoride can be separated from the remainder of the material.
The separated ferric trifluoride material is then dried slowly in stages to 100 ℃ until all volatile matter (including any moisture contained) has been driven off, and then the temperature is raised to 240 ℃ to the point that the remaining solvent and polymer evaporate and/or decompose and the ferric trifluoride is completely free of all solvent and/or polymer.
The finished product is placed in a vessel to prevent the ferric trifluoride from becoming hydrated.
The anhydrous ferric trifluoride product formed is substantially chemically pure and appears to have an average particle size of about 0.2 microns and about 150 meters2Discrete, unaggregated, uniform particles per gram of surface area. In addition, the iron trifluoride product formed exhibits a pH of between 4.0 and 7.0,when 1 gram of ferric trifluoride is mixed with 10 grams of demineralized water, and the higher surface area results in much higher catalytic activity per unit weight compared to ferric trifluoride made by most known other processes.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one will readily appreciate from the disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.
Claims (24)
1. A method for producing a nano-sized powder of metal fluoride comprising:
mixing a continuous phase comprising at least one metal cation salt with a hydrogenated or organic polymer dispersed phase;
forming a metal cation salt/polymer gel and exposing the gel to anhydrous hydrofluoric acid to convert the metal cation salt to a metal cation fluoride salt;
heat treating the gel after having been exposed to anhydrous hydrofluoric acid at a temperature sufficient to drive off water and organics within the gel; and
leaving a nano-sized powder of the metal fluoride as a residue.
2. The method of claim 1, wherein the hydrophilic organic polymer dispersed phase comprises an organic material selected from the group consisting of carbohydrates, derivatives, polymers, and proteins derived from animal protein-gelatin.
3. The method of claim 1, wherein the gel is heat treated at a temperature in the range of 22 ℃ to 240 ℃.
4. The method of claim 1, wherein the at least one metal cation salt is selected from the group consisting of: chlorides, carbonates, isopropoxides, nitrates, acetates, epoxides, and oxalates.
5. The method of claim 1, wherein the metal cation is at least one metal selected from groups 1A, 2A, 3A, 4A, 5A, 6A, 1B, 2B, 3B, 4B, 5B, 6B, 7B, and 8 of the periodic table of elements.
6. The method of claim 2 wherein the hydrophilic polymer is a hydrophilic homopolymer or copolymer selected from the group consisting of ethylene oxide, 2-hydroxyethylene methacrylate, hydroxyalkyl acrylate, acrylamide and N-vinyl pyrrolidone.
7. A method of producing a catalyst comprising:
dissolving anhydrous ferric trichloride in a solvent to generate a ferric trichloride/solvent solution;
blending the ferric trichloride/solvent solution with the polymer to produce a mixture;
adding the mixture to anhydrous hydrofluoric acid to convert the ferric trichloride to ferric trifluoride;
separating ferric trifluoride; and
drying the ferric trifluoride.
8. The process of claim 7, wherein the anhydrous ferric chloride is substantially chemically pure.
9. The method of claim 7, wherein the solvent comprises one or more of an alcohol, methanol, ether, benzene, and acetone.
10. The process of claim 7, wherein a sufficient amount of ferric trichloride is dissolved so that the ferric trichloride substantially saturates the solvent.
11. The method of claim 7, wherein the polymer is polyethylene glycol.
12. The method of claim 7, further comprising:
the ferric chloride/solvent solution and polymer are mixed until the blended ingredients become clear, homogeneous and stable.
13. The method of claim 7, wherein the adding step further comprises stirring.
14. The method of claim 7, wherein the adding step further comprises:
the mixture is added to anhydrous hydrofluoric acid until the stoichiometric ratio of moles of ferric trichloride within the mixture is between one-half and one sixteenth of the associated moles of anhydrous hydrofluoric acid.
15. The process of claim 7 wherein the ferric trifluoride is dried slowly in stages to 100 ℃ until any water has been driven off, then the temperature is raised to 240 ℃.
16. The process of claim 15 wherein any remaining solvent and polymer are evaporated at elevated temperature to remove the solvent and/or polymer from the iron trifluoride.
17. The method of claim 7, further comprising:
the dry ferric trifluoride is placed in a vessel to prevent the ferric trifluoride from becoming hydrated.
18. The process of claim 7 wherein the anhydrous ferric trifluoride product formed is substantially chemically pure and appears to have an average particle size of about 0.2 microns and about 150 meters2Discrete, unaggregated, uniform particles per gram of surface area.
19. The process of claim 7 wherein the iron trifluoride product formed exhibits a pH of between 4.0 and 7.0 when 1 gram of iron trifluoride is mixed with 10 grams of demineralized water.
20. A method of producing a catalyst comprising:
dissolving ferric trichloride in distilled warm water to form a salt solution;
blending the salt solution with polyethylene glycol powder to form a mixture;
stirring the mixture until the mixture becomes a clear solution;
adding the mixture to anhydrous hydrofluoric acid, thereby reacting and converting ferric trichloride with the anhydrous hydrofluoric acid into ferric trifluoride;
separating ferric trifluoride; and
drying the separated ferric trifluoride.
21. The method of claim 20, wherein the mixture is added to the anhydrous hydrofluoric acid, drop by drop, until the stoichiometric ratio of moles of ferric trichloride within the mixture is equal to or less than one-half of the associated moles of anhydrous hydrofluoric acid.
22. The method of claim 20, wherein the step of adding is accompanied by stirring.
23. The process of claim 20 wherein the separated ferric trifluoride material is slowly dried in stages to 100 ℃ until all volatile materials have been driven off, and wherein the temperature of the ferric trichloride is raised to a temperature at which the remaining solvent and polymer evaporate and/or decompose so that the ferric trifluoride is completely free of all solvent and/or polymer.
24. The method of claim 20, further comprising:
the dry ferric trichloride was placed in a container to prevent the ferric trifluoride from becoming hydrated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42171602P | 2002-10-28 | 2002-10-28 | |
| US60/421,716 | 2002-10-28 | ||
| US10/662,961 | 2003-09-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1714043A true CN1714043A (en) | 2005-12-28 |
| CN100434356C CN100434356C (en) | 2008-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380103978 Pending CN1714047A (en) | 2002-10-28 | 2003-10-27 | Process for the production of metal fluoride materials |
| CNB2003801039776A Expired - Fee Related CN100434356C (en) | 2002-10-28 | 2003-10-27 | Method for producing metal fluoride materials |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380103978 Pending CN1714047A (en) | 2002-10-28 | 2003-10-27 | Process for the production of metal fluoride materials |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826616A (en) * | 2012-09-13 | 2012-12-19 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| CN103708565A (en) * | 2014-01-06 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103771534A (en) * | 2014-02-26 | 2014-05-07 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| WO2015172626A1 (en) * | 2014-05-16 | 2015-11-19 | 江苏华东锂电技术研究院有限公司 | Method for preparing active material for positive electrode of lithium-ion battery |
| WO2015172625A1 (en) * | 2014-05-16 | 2015-11-19 | 江苏华东锂电技术研究院有限公司 | Method for preparing active material for positive electrode of lithium-ion battery |
| CN109081383A (en) * | 2018-07-10 | 2018-12-25 | 扬州大学 | The preparation method of transition metal fluorides |
| CN110407219A (en) * | 2019-08-23 | 2019-11-05 | 福建新汉唐非金属材料有限公司 | A kind of preparation process improving kaolin whiteness |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4938945A (en) * | 1988-10-18 | 1990-07-03 | Pennwalt Corporation | High purity anhydrous FeF3 and process for its manufacture |
| US5698483A (en) * | 1995-03-17 | 1997-12-16 | Institute Of Gas Technology | Process for preparing nanosized powder |
-
2003
- 2003-10-27 CN CN 200380103978 patent/CN1714047A/en active Pending
- 2003-10-27 CN CNB2003801039776A patent/CN100434356C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826616A (en) * | 2012-09-13 | 2012-12-19 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| CN102826616B (en) * | 2012-09-13 | 2014-05-28 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| CN103708565A (en) * | 2014-01-06 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103708565B (en) * | 2014-01-06 | 2015-06-03 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103771534A (en) * | 2014-02-26 | 2014-05-07 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| CN103771534B (en) * | 2014-02-26 | 2015-06-03 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| WO2015172626A1 (en) * | 2014-05-16 | 2015-11-19 | 江苏华东锂电技术研究院有限公司 | Method for preparing active material for positive electrode of lithium-ion battery |
| WO2015172625A1 (en) * | 2014-05-16 | 2015-11-19 | 江苏华东锂电技术研究院有限公司 | Method for preparing active material for positive electrode of lithium-ion battery |
| CN109081383A (en) * | 2018-07-10 | 2018-12-25 | 扬州大学 | The preparation method of transition metal fluorides |
| CN109081383B (en) * | 2018-07-10 | 2023-08-25 | 扬州大学 | Process for preparing transition metal fluorides |
| CN110407219A (en) * | 2019-08-23 | 2019-11-05 | 福建新汉唐非金属材料有限公司 | A kind of preparation process improving kaolin whiteness |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1714047A (en) | 2005-12-28 |
| CN100434356C (en) | 2008-11-19 |
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