CN100434356C - Method for producing metal fluoride materials - Google Patents
Method for producing metal fluoride materials Download PDFInfo
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- CN100434356C CN100434356C CNB2003801039776A CN200380103977A CN100434356C CN 100434356 C CN100434356 C CN 100434356C CN B2003801039776 A CNB2003801039776 A CN B2003801039776A CN 200380103977 A CN200380103977 A CN 200380103977A CN 100434356 C CN100434356 C CN 100434356C
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- hydrofluoric acid
- ferric
- iron trichloride
- anhydrous hydrofluoric
- fluorides
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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
The cross reference of related application
It is METHODFOR PRODUCING HIGH CATALYTIC ACTIVITY that this non-provisional application has required the title of application on October 28th, 2002, SUBMICRON, the US temporary patent application No.60/421 of METAL FLUORIDECATALYST MATER IALS, 716, the title of application was the non-temporary patent application No.10/662 of the U.S. of METHOD FOR PRODUCING METAL FLUORI EMATERIALS with on September 15th, 2003,991 right of priority, their disclosure all is hereby incorporated by reference.
Technical field
The application relates to as catalyzer or does the manufacturing of the metal fluoride of other any application.
Background technology
Those technician in this area can know, metal fluoride can be produced by metal or metallic compound (for example metal-salt) are mixed mutually with hydrofluoric acid in many cases.Wherein metallic compound is a metal chloride, reaction be following basically these:
MCl+HF→MF+HCl↑
MCl
2+2HF→MF
2+2HCl↑
MCl
3+3HF→MF
3+3HCl↑
MCl
4+4HF→MF
4+4HCl↑
Reaction between metal chloride and hydrofluoric acid can be absorbed heat.In the case, finish for reaction is proceeded to, reactant must absorb heat from their environment.When reaction is when heat absorption, observed heat delivery to the speed in the reactant big more and when reaction temperature high more, formed metal pentafluoride composition granule is more little.In general, the metal pentafluoride composition granule is more little, and the exposed surface area of the metal fluoride of per unit weight is big more.Consider that catalyzer is a tensio-active agent, usually demonstrate bigger catalytic activity and and proved this kind situation with the large surface area expectation of the per unit weight relevant than small-particle.
For the reaction between metal chloride and anhydrous hydrofluoric acid is the situation of heat release, and the reaction needed release of heat is finished to proceed to.In this case, conclusion given more than is estimated opposite with the thermopositive reaction situation.
The method of blending metal chloride and hydrofluoric acid has the result who how much changes, and this depends on employed metal chloride; Yet the general reaction of explanation has for example provided the particular case of making three ferric fluorides by blending iron trichloride and anhydrous hydrofluoric acid here.
The method of blending iron trichloride and anhydrous hydrofluoric acid causes that some incidents take place:
Iron trichloride dissolves and ionization in liquid anhydrous hydrofluoric acid;
The dissolving and the individual molecular of ionization iron trichloride exchange with first chlorine atom and from the fluorine atom in liquid, ionization, anhydrous hydrofluoric acid source, the individual molecular reaction product remains solubility and ion turns to FeFCl2 (dichloro ferric fluoride) in this case, have simultaneously the emitting of hydrogen chloride gas (under the normal atmosphere and be higher than under-84.9 ℃ the temperature).
Individual dissolving and ionization dichloro ferric fluoride exchange second and the 3rd chlorine atom and two fluorine atoms from liquid, ionization, anhydrous hydrofluoric acid source, in this case, formed three fluoridize iron molecule, and to be insoluble to liquid anhydrous hydrofluoric acid neutralization precipitation be the lime green solid, discharges additional hydrogen chloride gas simultaneously.
At present the practice of accepting is that liquid anhydrous hydrofluoric acid is added in the solid iron trichloride, when making three ferric fluorides, as at for example US patent No.4, describes in detail in 938,945, and its disclosure is all introduced for reference here.This method is because at US patent No.4, and the various reasons of enumerating in 938,945 are implemented.The additional reason that liquid anhydrous hydrofluoric acid is added in the solid iron trichloride is security.General acceptable is that reaction has the lower tendency that splashes, so this method is considered to than iron trichloride being added to the safer method of anhydrous hydrofluoric acid.Yet evidently, the aliquot iron trichloride of first weight is exposed to very limited amount anhydrous hydrofluoric acid (anhydrous hydrofluoric acid compares with the utmost point low weight of iron trichloride) in this method.Each follow-up aliquot iron trichloride also is exposed to the limited weight ratio of anhydrous hydrofluoric acid and iron trichloride, but adds final enough anhydrous hydrofluoric acids, till the optimum weight ratio that foundation is awared.Yet whole at this moment iron trichlorides is according to reacting than the much lower anhydrous hydrofluoric acid of optimum level and the weight ratio of iron trichloride.This one side of advocating this method can cause bigger primary granule, primary granule coalescent, long response time, incomplete reaction, low to the catalytic activity that does not have at all, and fluoridize the chemistry of iron product and the poor quality control for the physical property for formed three.
In addition, the way of accepting at present is to fluoridize in the iron process each composition of blending under barometric point three.In view of liquid anhydrous hydrofluoric acid is depressed in 19.8 ℃ (67.6) the following ebullient fact at standard atmosphere, the boiling point of anhydrous hydrofluoric acid has limited before reaction and the temperature that environment was elevated to of reactant in the process.Under the situation that does not have temperature-control device and/or equipment, the prior art manufacture method is tended to cool off when each composition is by blending, because the endothermic nature of reaction.Thereafter, in case reaction is finished, final product tends to be adjusted in envrionment temperature or under 19.8 ℃ of (67.6) (depressing the boiling point of anhydrous hydrofluoric acid at standard atmosphere), if the environment temperature is greater than 19.8 ℃ (67.6 °F).
After reaction was finished, at present the way of accepting was that three ferric fluoride products are immersed in and reach three to ten days in the liquid anhydrous hydrofluoric acid.The longer residence time (" pickling time ") generally causes reacting more completely, and then obtains three purer ferric fluoride products.
After the reaction times and the residence time, the way of accepting is by decantation and/or evaporation hydrofluoric acid solid three ferric fluoride products to be separated with the residue anhydrous hydrofluoric acid at present.Thereafter, three ferric fluoride products are dry stage by stage, are about 250 ℃ up to top temperature.In this case, can reckon with that the residual anhydrous hydrofluoric acid of any free and/or any free-water should drive away, stay anhydrous three ferric fluoride products.This product is then according to making it and the isolated mode of environment pack and avoid the absorption of moisture etc.
The present invention's general introduction
Use the method for prior art, in the three ferric fluoride processes of manufacturing or the observations that is obtained afterwards be as follows:
The anhydrous hydrofluoric acid temperature is high more, the maximum of (67.6) up to 19.8 ℃, and formed three ferric fluoride particles are more little.
The weight ratio of anhydrous hydrofluoric acid and iron trichloride is big more, reaches 60 to 1 weight ratio, and formed three ferric fluoride particles are more little.
Reaction product residence time in the anhydrous hydrofluoric acid environment, long more then reaction was complete more, and therefore formed three ferric fluoride products are purer.
In the process of anhydrous hydrofluoric acid being added in the iron trichloride, stir or stir and obtain three less ferric fluoride particles, shortened the necessary residence time of iron trichloride in anhydrous hydrofluoric acid obviously so that cause complete reaction, it produces more purified three ferric fluorides.
In submicron particle diameter scope, cause forming discrete, three ferric fluoride products of accumulative primary granule have not proved in some specific reaction and have demonstrated bigger catalytic effect, wherein PTFE and steel and aluminium react under envrionment temperature and barometric point.Referring to, for example, US patent No.5,877,128, its disclosure all is hereby incorporated by reference.Therefore, less submicron three ferric fluoride particles are considered to generally constitute better catalysate.
This special catalyst material must manifest following performance and technical parameter, when preparation is finished for predetermined the application.
This catalystic material must have and is not more than 0.50 micron individual particle.
Catalystic material must not assembled.Each particle must be disperse and must not adhere to each other particle.
Catalyst chemical must be at least 99.9% purity and lack spuious element and pollutent, comprising water.
This catalystic material must not demonstrate and be lower than 3.5 pH, when in softening water according to 1 gram material to the weight ratios of 10 gram softening waters when being made into slurry.
Catalystic material must have activity and can be as catalyzer, this can by this material under the test conditions of regulation, cause PTFE (
) and steel between the ability of chemical reaction determine.
A kind of material and another kind of material be the ability of blending or trend and the degree that is blended into equably, is called " solubleness " of a kind of predetermined substance in another kind of predetermined substance.Particularly importantly some metallic solid, solute, the solubleness of material in some liquid, solvent, material.Solid can be found for being to change to very large amount from very little for their solubleness separately in the particular fluid in the solubleness in the liquid.Yet, each situation when being dissolved in the liquid when solid, the dissolved solid has fully been lost its last material property such as granularity, crystalline structure, hardness etc. and has been existed with molecule or ionic condition thereafter, when solid keeps being dissolved in this liquid.Institute's dissolved molecule and/or ion in fact fully disperse and form true solution.
Method of the present invention comprises soluble metal source (" source metal ") compound (being metal-salt) is dissolved in the solvent that wherein metal source compound is dissolved fully and formed true solution (" solution ").Solution mixes up hill and dale with organic polymer then and forms polymers soln and/or stable colloidal suspension.For latter event, organic polymer embodies feature in having gellifying property, becomes mutually outside or disperse phase and be used to comprise and keep this solution in suspension.As definition, here the organic polymer of Shi Yonging constituted solution wherein dissolve in wherein a kind of material and/or organic polymer as there being disperse phase (solution) to be produced material by blending colloid therein; Yet organic polymer constitutes external phase and is used to produce the blending product of gel or viscosity.The product of blending is called " source metal polymkeric substance " here.In case preparation, the source metal polymkeric substance drop by drop is introduced in the anhydrous hydrofluoric acid, is equal to or less than corresponding molar 1/2nd of anhydrous hydrofluoric acid up to the molar stoichiometric ratio of source metal in the source metal polymkeric substance.
Source metal in the source metal polymkeric substance and anhydrous hydrofluoric acid will be when contacting immediate response, to react on molecule and/or ion concentration with them and form the metal fluoride reaction product because this is reflected at and takes place on molecule or the ion concentration, formed particle has submicron-scale.
In case source metal is reacted with anhydrous hydrofluoric acid and the metal component of source metal polymkeric substance has changed into metal fluoride, then metal fluoride can separate with the remainder of material.
If metal fluoride keeps solubility after reaction, metal fluoride can separate from polymer/solvent by the evaporation and/or the decomposition of polymer/solvent mixture.
Precipitate from solution and separate out if metal fluoride is insoluble to polymer/solvent mixture neutralization, then solid metal fluorochemical throw out can separate by the polymer/solvent decantation being come in the independent container of appropriate designs from liquid separation or it to wait by other usual way such as filtration.Solid metal fluorochemical product is dried to 100 ℃ then stage by stage slowly, till whole volatile matter (comprising water) have been purged, thereafter, temperature can be elevated to residual solvent evaporation and/or decomposition and metal fluoride and becomes and do not contain a certain temperature of polymer/solvent mixture fully.
Remaining polymer/solvent/anhydrous hydrofluoric acid material can be by using well-known method as distillation, and freezing, extraction is decomposed to wait and separated.
Some source metal materials is found to be insoluble in the whole actual solvent that uses in process of the present invention with whole their all cpds (being salt) forms.Other source metal material when changing into their all cpds, proves that only actually is dissolved in the aqueous alkaline solvent.
In the above almost unlikely the previous case that exemplifies, wherein the whole compounds of source metal proof is insoluble to all solvents, and method of the present invention belongs to the situation that solid phase and solvent belong to liquid phase in source metal and can not use.
For the above latter event of enumerating, the water-soluble metal source compound should be dissolved in the water of minimum quantity and formed solution then can with the blend of wetting ability organic polymer material, it (is sucrose that this material is selected from carbohydrate, starch, Mierocrystalline cellulose etc.), carbohydrate derivates, the wetting ability homopolymer, ethylene glycol polymer, the glycol ester polymkeric substance, ethylene glycol, 2-hydroxy ethylene-methyl acrylic ester, the hydroxyalkyl methacrylate class, vinylformic acid hydroxyalkyl acrylate class, acrylamide, N-vinylpyrrolidone copolymers class, urethane, polyurethane-acrylate, urethane-alkylmethacrylate polymer, protein for animal matter-gelatin, or the like.
Generally be found to be water miscible and be applicable to that the metal source compound of method of the present invention comprises metal chloride, carbonate, oxyhydroxide, Virahol thing, nitrate, acetate, epoxide, oxalate and their mixture.
Under situation of the present invention, the water-soluble metal source compound should be with minimum quantity formation solution soluble in water.Solution and wetting ability organic polymer material carry out blend according to the approrpiate wts ratio of one to one (1: 1) then, but under any circumstance have the wetting ability organic polymer material of q.s to make that belonging to source compound in GOLD FROM PLATING SOLUTION keeps dissolved state.Thereafter, this mixture of solution and wetting ability organic polymer material should with the anhydrous hydrofluoric acid blending.This blending is preferably by very lentamente, drop by drop being incorporated into solution in the anhydrous hydrofluoric acid in the reaction vessel of appropriate designs, until the molar stoichiometric ratio of source metal in the source metal polymkeric substance be equal to or less than anhydrous hydrofluoric acid corresponding molar 1/2nd till.In one embodiment, stoichiometric ratio is between corresponding molar 1/2nd and sixtieth of anhydrous hydrofluoric acid.
Although have in the metal source compound water soluble the fact, proof it is desirable to use some other solvents to replace water because the introducing of water can unavoidably cause the product of hydration, this is undesirable.
An object of the present invention is to produce discrete, the metal fluoride of accumulative submicron particle size particle form not.
An object of the present invention is to produce does not have impurity to be incorporated into metal fluoride in the product.
An object of the present invention is to produce chemical pure and mild physical form even metal fluorochemical.
An object of the present invention is to provide high purity, submicron that production is made up of list or polycomponent metal fluoride class, do not assemble, discrete general, the low cost method of chemical pure particulate.
An object of the present invention is to provide high purity, submicron that production is made up of list or polycomponent metal fluoride class, do not assemble, discrete chemical pure particulate technology, in this technology, do not need atmosphere highly-specialised, control.
The front has been listed feature of the present invention and technical superiority quite widely, so that following of the present invention being described in detail can be understood better.Supplementary features of the present invention and advantage are described below, and they have constituted the theme of claim of the present invention.Should be realized that disclosed notion and particular can be easily with the bases that makes improvements or be designed for other structure that realizes same purpose of the present invention.It should further be appreciated that these equivalent configurations do not depart from the scope of the invention that defines in claims.When considering when combining with accompanying drawing, the novel feature that is considered to characteristic of the present invention (simultaneously for its tissue and working method) will better be understood from following narration with other purpose and advantage.Yet, it will be appreciated that especially each accompanying drawing only is used for giving an example and purpose of narrating and the definition of not thinking various restrictions of the present invention.
The summary of accompanying drawing
Fig. 1 is the graphic representation of explanation in the vapour pressure and the relation between the temperature of anhydrous hydrofluoric acid.
Describe in detail
Though the metal fluoride useful as catalysts of producing in the disclosed here illustrative embodiment, the present invention is not limited to the production metal fluoride catalysts.On the contrary, metal fluoride produced according to the invention can be used for almost any application.
To have obtained several important conclusions, they have arranged several important requirements of improvement " prior art " method for the foregoing observation carried out of experiment repeatedly that is labeled as " prior art " method here, and they are listed below:
Higher temperature of reaction: improve the more small diameter particles that the temperature of reacting can cause obtaining three ferric fluoride products between iron trichloride and anhydrous hydrofluoric acid.Be used to realize that the mode of pyroreaction is as follows:
Under pressure, heat: by making by being lined with PTFE in fully or can under specified reaction vessel service temperature and pressure, withstanding the pressure resistant type reaction vessel that nickel, nickelalloy or other metal of harsh other polymkeric substance that contacts of anhydrous hydrofluoric acid constitute, the temperature of anhydrous hydrofluoric acid can be increased to this sour boiling point under the pressure rating of reaction vessel, but does not have hydrofluoric acid because the caused loss of evaporation.This reaction vessel logically needs to be equipped with pressure relieving valve, not only for security purpose with but also can escape for the hydrogen chloride gas that produces in reaction process.
Preheating: reactant, anhydrous hydrofluoric acid and iron trichloride before mixed, can carry out preheating.For example, anhydrous hydrofluoric acid can be preheating to that temperature that this sour vapour pressure equals the operating pressure of reaction vessel.Referring to, for example, shown in Figure 1 in the vapour pressure of anhydrous hydrofluoric acid and the relation between the temperature.Similarly, before iron trichloride and anhydrous hydrofluoric acid blending, iron trichloride is preheating to about 300 ℃.(note: iron trichloride has 306 ℃ fusing point and 319 ℃ boiling point; Yet it begins to decompose at its 306 ℃ of fusing points or a shade below its fusing point.)
Utilize the continuous heating of variety of way: can't help metal constitutes if reaction vessel is made of the polymkeric substance of PTFE or some other anti-anhydrous hydrofluoric acids, then it can heat by using micro-wave energy, but requires to be no more than by this heating operation the pressure rating of reaction vessel.It may be noted that importantly microwave heating can cause rising to the surface and causing serious danger at lower face formation vapour bubble and this vapour bubble of liquid anhydrous hydrofluoric acid.If this reaction vessel is made of metal, then it can pass through more common mode such as resistive heating, electrical induction heating, and flame or steam heat continuously.In addition, some heating and mixing can realize by reaction vessel is used the high-energy ultrasonic wave.
The high weight ratio of anhydrous hydrofluoric acid and iron trichloride: the high weight ratio (for example up to 60 to 1) of keeping anhydrous hydrofluoric acid and iron trichloride can obtain the smaller diameter particles of three ferric fluoride products, cause quicker and reaction more completely and obtain more approaching purified reaction product.The mode that is used for the high weight ratio of realization response thing is as follows:
The solid iron trichloride is added in the liquid anhydrous hydrofluoric acid: well-knownly be, the reaction between anhydrous hydrofluoric acid and iron trichloride takes place by debating other several steps, but entire reaction takes place at once.Reaction proceeds to the degree of finishing, form purer final product and will depend on the weight ratio of reactant and the amount of the residence time.In the intermittent type manufacture method, the weight ratio of anhydrous hydrofluoric acid and iron trichloride can maintain optimum value, if the solid iron trichloride is added in the liquid anhydrous hydrofluoric acid in the reaction vessel (sealing for safety) that has sealed, and make it possible to be easy to mix, keep-up pressure and make it possible to be heated to more than the atmospheric boiling point of anhydrous hydrofluoric acid.
For each aliquot solid three ferric fluoride that is added in the liquid anhydrous hydrofluoric acid, the weight ratio of this reactant is best, possible when using two kinds of reactants of fixed amount.This is that this reaction takes place at once and formed product three ferric fluorides will precipitate and drop to the bottom of reaction vessel because when the aliquot iron trichloride of each weight is introduced in the reaction vessel that contains anhydrous hydrofluoric acid.In this method, should consume the only anhydrous hydrofluoric acid of less share.Therefore, when being incorporated into the aliquot iron trichloride of next weight in the reaction vessel, it will be in accordance with the anhydrous hydrofluoric acid approximately identical with initial aliquot iron trichloride and the weight ratio of iron trichloride.Begin if this method is the initial weight ratio with 60 to 1 (anhydrous hydrofluoric acid and iron trichlorides), then last of ten aliquot iron trichlorides should be abideed by and be not less than 56 to 1 weight ratio.
The chemical reaction that takes place when iron trichloride mixes with anhydrous hydrofluoric acid provides below, and wherein the stoichiometry blending weight of each compound provides below each this compounds in reaction, and is as follows:
FeCl
3 + 3HF → FeF
3 + 3HCl↑
162.2031 60.0189 112.8402 109.3818
The iron trichloride that presupposes 1 mol or 162.2031 grams will carry out blending according to 60 (60) parts of anhydrous hydrofluoric acids than the weight ratio of one (1) part of iron trichloride with a certain amount of anhydrous hydrofluoric acid.The iron trichloride of first aliquot 1 mol or 162.2031 grams will be introduced in (by 60 to 1 weight ratios) in 9,732.1860 anhydrous hydrofluoric acids that restrain.This reaction will cause the consumption of the anhydrous hydrofluoric acid of 60.0189 grams, stay the unreacted anhydrous hydrofluoric acid of 9,672.1671 grams.
The iron trichloride of second aliquot 1 mol or 162.2031 grams is introduced in residue 9,672.1671 cause the reaction and the consumption of the anhydrous hydrofluoric acid of other 60.0189 grams in the anhydrous hydrofluoric acid of gram, stay the unreacted anhydrous hydrofluoric acid of 9,612.1482 grams.Blending ratio for the second aliquot interpolation should be anhydrous hydrofluoric acid and 59.63 to 1 of iron trichloride.
Similarly, be introduced at first ten aliquot 1 mol (for each aliquot) in the anhydrous hydrofluoric acid (" AHF ") of initial amount (9,672.1671 gram) or the iron trichloride (" FeCl of 162.2031 grams
3") the blending ratio be as follows:
| FeCl 3Aliquot No. | Remaining AHF gram number | AHF and FeCl 3Weight ratio |
| 0 | 9,732.1860 | 60.0000 than 1 |
| 1 | 9,672.1671 | 59.6300 than 1 |
| 2 | 9,612.1482 | 59.2600 than 1 |
| 3 | 9,552.1293 | 58.8899 than 1 |
| 4 | 9,492.1104 | 58.5199 than 1 |
| 5 | 9,432.0915 | 58.1499 than 1 |
| 6 | 9,372.0726 | 57.7799 than 1 |
| 7 | 9,312.0537 | 57.4098 than 1 |
| 8 | 9,252.0348 | 57.0398 than 1 |
| 9 | 9,192.0159 | 56.6698 than 1 |
| 10 | 9,131.9970 | 56.2998 than 1 |
After this ten step of imagination reaction process, the residue anhydrous hydrofluoric acid can be recovered and reuse.
Add the anhydrous hydrofluoric acid of phase weighing during the course: in case set up the optimum weight ratio of anhydrous hydrofluoric acid and iron trichloride significantly, recommendable is with optimum chemical calculated weight ratio anhydrous hydrofluoric acid to be added in the reaction vessel before next aliquot iron trichloride is added, and this depends on that certainly optimum weight is compared to the importance of concrete reaction.
The long residence time: the long residence time is unwanted.As what state previously, the reaction between iron trichloride and anhydrous hydrofluoric acid takes place at once.The mode of using the way of accepting at present to carry out reaction process can cause the needs to long residence time, finishes so that allow reaction proceed to.Can infer, the rising temperature of reaction, keep best anhydrous hydrofluoric acid and iron trichloride weight ratio and enough stirring and/or stir to cause complete reaction and producing the submicron of three ferric fluorides of catalytic activity, aggregated particles not, need not to allow reactant accept the residence time of length.
Stir or stir: stirring or stirring have been inferred is of value to method of the present invention.Stir and stir and can finish according to following manner:
Rotation: reaction vessel is interior in some way to be supported, and this mode allows reaction vessel to rotate on one or more planes in reaction process.
Ultrasonic wave: do not consider to constitute reaction container materials, the composition of reaction vessel uses the high-energy ultrasound source to stir.This ultrasonic wave also is used to the reaction vessel heating on than low degree.
Magnetic agitation equipment: this reaction vessel can stir by enough magnetic agitation equipment.
Common whipping device: reaction vessel can stir by means of the common whipping device (as the Lightening mixing tank) that adopts electric motor and one or more rotating paddles, and this equipment is introduced by pressurization filling gland (pressure packing gland).
Catalytic activity: based on above-mentioned observations, think if adopt and carry out above generalized recommendation, formed three ferric fluoride products not only by discrete, the accumulative submicron particles is not formed, and it also demonstrates the catalytic activity for test conditions described here.
The method of producing metal fluoride catalysts has been disclosed in the US temporary patent application No.60/421 of the title of application on October 28th, 2002 for " METHOD FOR PRODUCING HIGH CATALYTIC ACTIVITY; SUBMICRON; METAL FLUORIDE CATALYST MATERIALS ", 716, the title of application was the pendent US patent application No.10/662 of " PROCESS FOR THEPRODUCTION OF METAL FLUORIDE MATERIALS " with on September 15th, 2003, in 992, their disclosure all is hereby incorporated by reference.The invention provides to produce and have submicron particle size and have the another kind of method of the metal fluoride catalysts material of high catalytic activity.The present invention also provides preferable quality control inherently to have the consistent chemistry and the reaction product of physical property with providing.
The preferred embodiments of the invention discuss in more detail below.These methods can be used for producing the metal fluoride catalysts material that has submicron particle size and have high catalytic activity.These methods provide preferable quality control inherently to have the consistent chemistry and the reaction product of physical property (comparing with art methods) with providing.
Situation 1 (organic solvent):
Basically chemical pure FERRIC CHLORIDE ANHYDROUS is dissolved in one or more of one group of solvent, and this group is by water, alcohol, and ether, benzene, compositions such as acetone, iron trichloride dissolve in the solvent of this group.Although in the iron trichloride water soluble, water is not The suitable solvent for the present invention when final product is used as catalyzer, because formed final product is likely the hydrated form of required metal fluoride.The general discovery of the hydrated form of metal fluoride is not a catalytic activity.
The dissolving operation can under atmospheric pressure and at ambient temperature be carried out, but the hydration of this iron trichloride before must preventing very carefully in being dissolved in solvent.The iron trichloride of q.s should be dissolved into and use saturated this solvent of iron trichloride basically, should be borne in mind that wherein the subsequent operations and the reaction between source metal (iron trichloride) and anhydrous hydrofluoric acid of iron trichloride, solvent and mixture of polymers and anhydrous hydrofluoric acid blending should be absorbed heat.This reaction can cause the remarkable decline of temperature, if heat is not appended in the system with the speed that is enough to compensate the heat absorption in reaction.If allow the mixture of material or system cool off, possible is that iron trichloride is separated out from solution before reaction.This be because iron trichloride in solvent solubility with temperature and become and in general iron trichloride be less solubility at a lower temperature.
For that reason, the solubleness of iron trichloride in specific solvent should be in the minimum temperature of estimating to run in whole process (for example 0 ℃) test and measurement down.The solubleness of iron trichloride is determined, preferably should use at the very start as the X gram/solvent of every Y gram and the weight ratio of determined iron trichloride and solvent.
Iron trichloride/solvent solution then with the polymkeric substance blending.
This situation 1 time, methyl alcohol is to be dissolved in the methanol solvate as solvent with the iron trichloride of necessary amounts.
Thereafter, iron trichloride/methanol solution and polymkeric substance blending.This situation 1 time, polymkeric substance is a polyoxyethylene glycol.Enough polyoxyethylene glycol (for example Dow Chemical Grade 4500 polyoxyethylene glycol powder) are added in iron trichloride/carbinol mixture to dissolve fully and/or to seal iron trichloride/carbinol mixture.The blending of these compositions needs violent mixing, until the system of composition become transparent, evenly till and be stable.
Then, the above mixture of enumerating is added in the suitable vessel that contains anhydrous hydrofluoric acid.This interpolation lentamente, drop by drop carry out is equal to or less than corresponding molar 1/2nd of anhydrous hydrofluoric acid until the molar stoichiometric ratio of iron trichloride in mixture.The interpolation of mixture is attended by violent stirring in this step of situation 1.
In case iron trichloride reacts with anhydrous hydrofluoric acid and changes into three ferric fluorides, then three ferric fluorides can separate with the remainder of material.
Isolated three fluoridize iron material drying slowly stage by stage then, reach 100 ℃, till whole volatile matter (comprising any moisture that is comprised) has been displaced, temperature rises to 240 ℃ then, has reached the degree that evaporation of residual solvent and polymkeric substance and/or decomposition and this three ferric fluoride do not contain all solvents and/or polymkeric substance fully.
Finished product put into prevent in the container that three ferric fluorides from becoming hydration.
Formed anhydrous three ferric fluoride products are chemical pure basically and are revealed as and have about 0.2 micron mean particle size and about 150 meters
2The surface-area of/gram discrete, assemble, homogeneous granules.In addition, formed three ferric fluoride products are presented at the pH between 4.0 and 7.0, when the softening waters that restrain when three ferric fluorides and 10 of 1 gram mix and higher surface area cause much higher catalytic activity/per unit weight, and fluoridize the iron phase ratio by three of known other method manufacturing of major part.
Situation 2 (water solvent):
Basically the chemical pure catalyzer grade iron trichloride of 530 grams is dissolved in the distilled warm water of 100mL.With the Dow Chemical Grade 4500 polyoxyethylene glycol powder blending of this salts solution and 20 grams with till being stirred to mixture and becoming clear solution.
Then, the above mixture of enumerating is added in the container of the appropriate designs that contains anhydrous hydrofluoric acid.This interpolation lentamente, drop by drop carry out is equal to or less than corresponding molar 1/2nd of anhydrous hydrofluoric acid until the molar stoichiometric ratio of iron trichloride in mixture.The interpolation of mixture is attended by violent stirring in this step of situation 2.
In case iron trichloride reacts with anhydrous hydrofluoric acid and changes into three ferric fluorides, then three ferric fluorides can separate with the remainder of material.
Isolated three fluoridize iron material drying slowly stage by stage then, reach 100 ℃, till whole volatile matter (comprising any moisture that is comprised) has been displaced, temperature rises to 240 ℃ then, has reached the degree that evaporation of residual solvent and polymkeric substance and/or decomposition and this three ferric fluoride do not contain all solvents and/or polymkeric substance fully.
Finished product put into prevent in the container that three ferric fluorides from becoming hydration.
Formed anhydrous three ferric fluoride products are chemical pure basically and are revealed as and have about 0.2 micron mean particle size and about 150 meters
2The surface-area of/gram discrete, assemble, homogeneous granules.In addition, formed three ferric fluoride products are presented at the pH between 4.0 and 7.0, when the softening waters that restrain when three ferric fluorides and 10 of 1 gram mix and higher surface area cause much higher catalytic activity/per unit weight, and fluoridize the iron phase ratio by three of known other method manufacturing of major part.
Though the present invention and its advantage are described in detail, should be appreciated that various changes can be made under the prerequisite that does not break away from the scope of the invention that is defined by claims, replace and change.In addition, the application's scope is without wishing to be held to the process of describing in specification sheets, and machine is made the combination of incident, mode, the specific examples of method and step.Easily recognize from disclosure thing, exist at present or having given play to the substantially the same function of corresponding embodiment described here or realized substantially the same result's process, machine of exploitation later on, make, the combination of incident, mode, method or step can be used.Therefore, claims wish to comprise this class process in its scope, and machine is made the combination of incident, mode, method, or step.
Claims (22)
1. produce the method for the nano-scale particle size powder of 8 group 4 transition metal fluorochemicals, comprising:
The solution that will comprise at least a 8 group 4 transition metal cationic salts mixes with wetting ability organic polymer disperse phase;
Form 8 group 4 transition metal cationic salts/polymer gels and allow gel be exposed to anhydrous hydrofluoric acid and 8 group 4 transition metal cationic salts are changed into 8 group 4 transition metal positively charged ions and fluoridize thing salt;
After being exposed to anhydrous hydrofluoric acid, under the water and organic temperature that are enough to drive away in this gel, this gel of thermal treatment; With
Stay nano-scale particle size powder as 8 group 4 transition metal fluorochemicals of residue.
2. the method for claim 1, wherein wetting ability organic polymer disperse phase comprises and is selected from carbohydrate, carbohydrate derivates, from animal protein-gelatin deutero-protein, the wetting ability homopolymer, ethylene glycol polymer, the glycol ester polymkeric substance, ethylene glycol, 2-hydroxy ethylene-methyl acrylic ester, hydroxyalkyl methacrylate class, vinylformic acid hydroxyalkyl acrylate class, acrylamide and N-vinylpyrrolidone copolymers class, urethane, the organic materials in polyurethane-acrylate and the urethane-alkylmethacrylate polymer.
3. the process of claim 1 wherein thermal treatment under the temperature of gel in 22 ℃ of-240 ℃ of scopes.
4. the process of claim 1 wherein that at least a 8 group 4 transition metal cationic salts are selected from: muriate, carbonate, isopropoxide, nitrate, acetate, epoxide, and oxalate.
5. the process of claim 1 wherein that 8 group 4 transition metal fluorochemicals are catalyzer, this method further comprises:
Produce iron trichloride/solvent solution in the solvent by FERRIC CHLORIDE ANHYDROUS is dissolved in, form solution;
By iron trichloride/solvent solution and polymer blending are produced mixture, form 8 group 4 transition metal cationic salts/polymer gels;
Wherein allow gel expose and comprise the interpolation mixture in anhydrous hydrofluoric acid, thereby iron trichloride is changed into three ferric fluorides;
Separate three ferric fluorides; With
Dry three ferric fluorides.
6. the method for claim 5, wherein FERRIC CHLORIDE ANHYDROUS is chemical pure basically.
7. the method for claim 5, wherein solvent comprises alcohol, ether, one or more in benzene and the acetone.
8. the method for claim 5 is wherein dissolved the iron trichloride of q.s, so that saturated basically this solvent of iron trichloride.
9. the method for claim 5, wherein polymkeric substance is a polyoxyethylene glycol.
10. the method for claim 5 further comprises:
Mix this iron trichloride/solvent solution and polymkeric substance, become up to the composition of blending transparent, all even stable till.
11. the method for claim 5 is wherein added step and is further comprised stirring.
12. the method for claim 5 is wherein added step and is further comprised:
Mixture is added in the anhydrous hydrofluoric acid, between the molar stoichiometric ratio of iron trichloride in mixture is corresponding molar 1/2nd and sixtieth at anhydrous hydrofluoric acid.
13. the method for claim 5, wherein three ferric fluorides drying slowly stage by stage reaches 100 ℃, and till any moisture had been driven away, temperature rose to 240 ℃ then.
14. the method for claim 13, wherein any residual solvent and polymkeric substance at high temperature evaporate, thereby make three ferric fluorides remove solvent and/or polymkeric substance.
15. the method for claim 5 further comprises:
Exsiccant three ferric fluorides are put into prevent in the container that three ferric fluorides from becoming hydration.
16. the method for claim 5, wherein formed three ferric fluoride products are chemical pure basically and are revealed as and have about 0.2 micron mean particle size and about 150 meters
2The surface-area of/gram discrete, assemble, homogeneous granules.
17. the method for claim 5, wherein formed three ferric fluoride products are presented at the pH between 4.0 and 7.0, when three ferric fluorides of 1 gram mix with the softening water of 10 grams.
18. the process of claim 1 wherein that described 8 group 4 transition metal fluorochemicals are three ferric fluorides, described method further comprises:
By iron trichloride being dissolved in the distilled warm water, form solution;
By with solution and the blending of polyoxyethylene glycol powder, form 8 group 4 transition metal cationic salts/polymer gels;
Stir gel, up to gel become transparent till;
Gel is added in the anhydrous hydrofluoric acid, thereby make iron trichloride and anhydrous hydrofluoric acid reaction and change into three ferric fluorides;
Separate three ferric fluorides; With
Dry isolating three ferric fluorides.
19. the method for claim 18 is wherein drop by drop added mixture in the anhydrous hydrofluoric acid to, until the molar stoichiometric ratio of iron trichloride in mixture be equal to or less than anhydrous hydrofluoric acid corresponding molar 1/2nd till.
20. the method for claim 18 is wherein added step and is attended by stirring.
21. the method for claim 18, wherein isolated three fluoridize iron material drying slowly stage by stage, reach 100 ℃, be elevated to residual solvent and polymkeric substance evaporation and/or decompose up to whole volatile matter so that three ferric fluorides do not contain certain temperature of all solvents and/or polymkeric substance fully by the temperature of iron trichloride till displacing and wherein.
22. the method for claim 18 further comprises:
The exsiccant iron trichloride put into prevent in the container that three ferric fluorides from becoming hydration.
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 |
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| CN100434356C true CN100434356C (en) | 2008-11-19 |
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| CN 200380103978 Pending CN1714047A (en) | 2002-10-28 | 2003-10-27 | Process for the production of metal fluoride materials |
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| 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 |
| 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 |
| 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 |
| CN103996851A (en) * | 2014-05-16 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery positive pole active material |
| CN103996831B (en) * | 2014-05-16 | 2016-03-02 | 江苏华东锂电技术研究院有限公司 | The preparation method of anode active material of lithium ion battery |
| 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 |
Citations (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 |
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2003
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Patent Citations (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 |
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| CN1714047A (en) | 2005-12-28 |
| CN1714043A (en) | 2005-12-28 |
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