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AU2005218055A1 - Niobium compound - Google Patents

Niobium compound Download PDF

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Publication number
AU2005218055A1
AU2005218055A1 AU2005218055A AU2005218055A AU2005218055A1 AU 2005218055 A1 AU2005218055 A1 AU 2005218055A1 AU 2005218055 A AU2005218055 A AU 2005218055A AU 2005218055 A AU2005218055 A AU 2005218055A AU 2005218055 A1 AU2005218055 A1 AU 2005218055A1
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batch
shipment
lot
compound
formulation
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AU2005218055A
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HC Starck GmbH
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HC Starck GmbH
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Priority to AU2005218055A priority Critical patent/AU2005218055A1/en
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Abandoned legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S):: H. C. Starck GmbH ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys Level 10, 10 Barrack Street, Sydney, New South Wales, Australia, 2000 INVENTION TITLE: Niobium compound The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5102
I
Niobinm coMoun The present invention relates to a novel niobium compound, a process for its preparation and formulations comprising said niobium compound.
Niobiumn compounds are, amongst other applications, suitable to be used as dopanta for ccrtain catalysts or ferites.
00 I this application, the catalyst carrier or active species will be mixed with the dopant and oaloined tn in a subsequent process step. The calcination usually takes place under conditions where the niobiumn compound is converted to pure niobium pentoxide. Such applications encompass, but are not limited to, ethane hydrogenolysis, dehydrogenation of hydrocarbons, solid acid catalysis in polycondensation, or ammnoxidation. Such catalysts in which niobiumn compounds are used are in particular catalysts to convert butane to acrylonitrile in the presence of ammonia and oxygen, conversion of butane to acrolain in the presence of oxygen (oxidation), oxidative dehydrogenation of alkanes, like conversion of propane to propene. Such applications are, for example, disclosed in Chemical Reviews 1999, 3603 3624, which is enclosed by referenice for all useful purposes.
Mixing with the niobium compound often takes place in at aq~ueous solution, suspension or emulsion.
For such applications it is important that the niobium compound exhibits excellent water solubility, yields pure niobium pentoxide with no impurities from complexing agents or counterions when calcined under appropriate onditions and has a high content of niobium in weight percent, so with addition of small amounts of' the niobium compound an aqucous solution having a suitable high niobium concentration can be prepared.
Limar at al. in Russlatn Journal of Inorganic Chemistry, Vol. 9 No. 10, October 1964, pages 1288.
1291, disclose the niobium oxalate complexes Naf[Nb(O)(C20 4 )2AHz()] 4 H,70 as well as 4 x H20O. These complexes, howover, do not fully satisfy the conditions as set out above. With sodium as countercation, sodium impurities will remain in the niobium pentoxide, after calcination, The ammonium complex is 3-old negatively charged resulting in lower niobitum content, Coordination with three oxalate ions has the same effect of lowering the niobium content in percent by weight. Additionally, the water solubility of merely 20 1; Nb I and g Nb 1, respectively, needs to be significantly improved, It was an object of the invention to provide a niobium compound exhibiting excellent water solubility (greater than 30 g Nb/I), which yields niobium pentoxide with a purity of at least 99%, consequently comprising up to 1% impurities from cnpiexing agents or counteions when -2calcined under appropriate conditions, and has a high content of niobiumn (greater than 22 percent by weight) in weight percent. This problem. is solved by the niobium, compound anumniuin(bleaquo oxobisoxalato)niobate
(NH
4 )ENb(O)(C 2 0 4 )2(H2O)a), and the corresponding tihydrate, ammonium- (bisaquo oxobisoxalato)fliobatbtrihydrat* @lH 4 )[Nb(O)(CZO4 WH2O)zJ 3 I-1,0, of formula 1.
00
NH
4 0 Af0
~OH
2 3 H 2 0 0
OH
2 5(1 The compound according to the invenltionl yields niobium pentoxide with a purity of 99% and not more than 1% of impurities from cornplexlng agents or coumterfonis when calcined under appropriate conditons. Preferably, the compound has a purity of at least 99.9 in particular at least 99.99 Figure 1 shows the three-dimensionlal structure of the compound according to the invention as determined by X-ray structure analysis. The numbers show the respoctive bond lengths in Angstr6ml.
The compound according to the invention exhibits excellent water solubility of 52 g Nb/i (grams niobium per litre) at 20"C and a maximum solubility of 114.8 S Nb/I at a temperature of 501C in compar'isonf to the prior ant compo unds with solubilities as set out above.
The compound according to the invention baa a niobium content of 24.3 weight percent, while the prior art compound (NHI4stNb(O)(C2O4),] has a niobium content of merely 21.8 weight percent of niobium. The high percentage of niobium in the material is economically advantageous because all other elements in the complex like nitrogen and carboni will be removed during calcination, Othier counterions than anmonium. are usually unsuitable, since other counterions such as alkaline Ions will either cause impurities on calcination while amm~onium does evaporate as gaseous ammonila, or such cations hasve a higher molcular weight than ammufonium ions thus causing a lower weight percentage of niobium, The present invention also relates to a process for making the compound according to the invention.
rior art compounds were made by dissolving niobium hydroxide and ammnoniumn oxalate in water and, in a subsequent step, either reducing the volumec by subsequent reduction of water or addition of acetone in order to reduce the solubility of the niobiumn compound, which in both cases does precipitate, The niobium concentration is about 2 mmml Nb/i (mole niobium per litro).
00 (71In contrast thereto, in the process according to the present invention niobiumn hydroxide and oxalic acid are dissolved in water and gaseous ammonia is passed through. The ammonia dissolves and neutralizes the oxalic acid, which causes warming to about 35 0 C to about 50 0 C, Preferably about 4O*C to about 450(7, in order to speed up the reaction it is also possible to heat up the reaction mixture to not more tbin 80 0 C, preferubly less than 700C, and more specifically about 60 0
C.
The sequence of the addition is preferably niobium hydroxide, oxalic acid and airmonia. The eduots are usually added into water during agitation, The addition of the educts may be carried out at once, although addition in portions is preferred, in particular if larger amounts of the compound according to the invention are to be produced.
The molar ratio of niobiumn to oxalic acid is 1, 2.8, whereas the calculation is based on the molecular weight of oxalic acid including crystal water.
The concentration of Niobium must be less than about 2 mol Nb/I, preferably fromn about 1.4 mol Nb/i to about 1.9 mol Nb/i, in particular from about 1.5 reol Nb/i to about 1.7 mnol Nb/I, miore specifically about 1.6 rmol Nb/i or less.
An aqueous armmonia solution may be used instead of gaSSOUB ammonia, provided the niobium conoentration is at a suitable level as act out above.
Preferably, an aqueous solution comprising 25% by weigt of ammonlia is used for the process according to the invention.
The pH-value of the reaction mixture is less than about 3.5, more specifically the pH-value of the reaction mixture is from about I to about 3, particularly from about 1 to about 2.
The amount of the anronia added is suitable to achieve this pH value and can easily calculated by the artisan.
After the addition of ammonia has finished, the reaction mixture is allowed to cool to a temperatture of about 2S*C or less, in particular to from I 0 0 C to 23C or from 159C to 22 0 C, or ffrm 18 0 C to 0
C.
Depending on the amount of reaction mixture active cooling is required to achieve cooling in a reasonable time, that is, cooling to the desired temperature in 24 hours or less. The active cooling may be carried out by any suitable means known to the artisan, like external cooling of the reaction 00 container or by means of airculation of a coolant through a huAt exchanger which is placed inside the reaction container.
Preferably, the cooling from 40"C to 20"C takes place within 4 hours, The average cooling rate throughout the tooling time is in the range of from about 3 6 C/hour to about 1 OOG/hour, preferably from about 4 0 C/hour to about 8 0 C/hour, in particular about 5 0 C/hour.
The reaction product does precipitate during cooling, is filtered off fro the reaction mixture and subsequently dried at a temperature of less than about 80*C, preferably less than about 75"C, in particular at about 701C Dlrying may take place in air, in an Inert gas such as argon or nitr~ogen or under reduced pressure. in the presence of either air or an inert gas.
Further purification may be achieved by additional recrystallizatioii, Preferably, said ryTOIdYHizatiOn is oarried out using water as solvent. The drying step as set out above can be carried out in the same way to aohieve removal of the water.
It was surprisingly found that a reaction product with higher niobium content was prepared.
although the niobiumn concentration. in the reaction mixture is lower than in the processes according to the prior art. For this reason, the process according to the present invention is also more economical as less energy is consumed, no organic solvents are involved and a higher niobiumn content of the resulting compound can be achieved, The present invention also relates to formulations conmprisilij the compounds according to the present invention, eamoniutn(bisaquo oxiobisoxalatOniobate (Nfl 4 )[Nb(O)(C 2 ,04 2
(U
2 01.M In the most simple case the formulation according to the invention comprises arnmonilun(bisaquo oxobisoxalato)niobate (N11)[Nb(O)(C%00 2 (HaO) 2 and water, Such a formulation may be a saturated aqueous solution of the compound in water or may be an aqueous slurry, but may contain additional ingredients such as adjuvant3, like emulgators or antinicrobia, like fungricidcs, herbicides or bactericides. IPreflarably, the formulation comprisus oxalic acid and/or ammnonium oxalate. More preferably, the oxalic acid and/or ammonium oxaluto is present in an amount of between 5% by weight to 10% by weight, more preferably between 7% by weight and 9% by weight, mnore specifically 80% by weight. The weight percentages describe the amount of oxalic acid and ammnoniutn oxalate each.
The compound may be irritating to the skin or respiratory organs of humans or might affect the health and well-being of humans or have disadvantageous effects to plants, animanls or the environment. For these reasons it is preferred if the compound accordin~g to the invention is 0 ~provided in a form less prone to raise dust and thus exposing the surrounding with the compound 00 in an uncontrolled mnn~er. Additionally, providing the compound according to the invention in a N ~defined amount provider, for easy gravimetric or volumnetric metering.
0 ~Such solutions or slurries are suitable for volumectric metering, For gravimetric metering, which ia used oven more often and for which exposition and dusting is not only to be avoided during actual metering the material, but also during weighing, it is preferred to put a defined amount of the compound according to the invention into a container which is being destroyed when used, e.g. a bag, More specifically, the formulation according to the invention also includes a defined amount of the compound according to the invention being inside a bag. Preferably, this bag is soluble in the reaction medium the niobium compound according to the invention is used for producing catalysts or ferrite.. Most preferably, the bag is a water soluble polymer, like the bags described in international Patent Applications WO 98451 85, WO 9737903 and US patent US-B-5666785, as well as "Verpackungs.Rundschau", November 19p97, page 40, which are incorporated by rofrevnca for all useful purposes.
It is particularly preferred that, although the bag dissolves when put into water, the inner side is equipped to be water resistant, In this way, an aqueous solution or slurry can be put into a water soluble bag and put Into an aqueous reaction medium, 71w present invention thus also relates to a formulation comprising a container made of a soluble polymeric film comprising the compound according to the invention, its solution or its slurry. In a preferred emnbodiment, the polymeric film is a film comprising polyvitsyl alcohol. In another preferred embodinient, the formuzlation is a slurry or 4 powder of the niobium ompound according to the invention inside a closed bag comprising a film of polyvinyl alcohol.
In another embodiment, the formulation is a solid nioblum. compound according to the invention inside a olosod bag comprising a film of polyvinyl alcohol.
Becmuse the process according to the present invention is more economical, less cnergy consuming, no organic solVentS arTc involved and a higher niobium. content of the resulting -6.
compound can be achieved, the present invention atlso is a contribution to the protection of the environment.
The invention thus also relates to a promes for protecting the environment comprising the preparation of niobium compounds by a process consuming a reduced amount of energy, not involving organjo solvents, In a preferred embodiment, this process does as well provide compounds having increased niobiumn content.
00 c-I The invention also relates to a method for creating a product specification for a batch, Wo, or tn shipment of a chemical material, preferably a compound according to the invention, comprising specifying at least one property value for said batch, lot, or shipmnent. Thu property value may be a property value either specffc for the chemical compound, like chemical formula, molecular weight, weight percentage of a certain element, melting point, boiling point or the like, or a property value specific to the lot, batch or shipment, like purity, a batch number or lot number, a list of ingredients of the formulation, grain size, shape of the particles, particle size distribution or the like, In particular, such method compriles the step of specifying at least one property value per lot, batch or shipment; archiving the property values of said lots, batches or shipments in connection with infonti~on identifying th e lot, batch or shipment, selecting at least one property value of at least one lot, batch or shipment 1 putting together the product specification by arranging the at least one property value of the identified said lot, batch or shipmont in connection with information identifying the lot, batch or shipment and creatinig the product specification by displaying the at least one property valuc together with informati on identifying the lot, batch or shipment.
Displaying within the meaning of this invention may be creating a paper copy of the product specification by, for example, printing by a computer printout or conventional printing, but also involves displaying the product specification on a computer screen, The display can be effected by a comnputer program having access to the archive of at least one property value in connection with information identifying the lot, batch or shipment, or by means of an internet webpage displayed in a web browser.
In a Aurther embodiment, the method for crating a product specification is a method Wherein the property value is included on a product specification sheet, purchaso order, invoice, contract, waiver to a contract, or combinations thereof for the batch, lot, or shipment of a compound.
Preferably, the compound is at compound according to the invention, or a different niobium.
compound, in particular a tiobium oxalate complex.
in yet another embodiment of the invention the method for creating a product speoifioation, is a method wherein said specifying comprises determining at least one property value for said batch, lot, or shipment of particulate material. Determining comprises measuring or analyzing said batchi, lot, or shipment by conventional measuring methods and thus determining either a property value speoific for the lot batch or shipment, or being speoific for the chemical compound. If the property value to be determined is a property Value specific to the chemical compound, the determining stop 00 does also encompass accessing the prope"t value specific to the chemical compound in a directory comprising such property values. The directory may be available in physical form in a library or in the form of an electronic database. In the latter cone, said deterrmining can be carried out by meas of a computer program.
In a further embodiment of the invention, the method for creatiog a product specification is a method wherein said specifying comprises characterizing the batch, lot, or shipment of particulate material by at least one interfacial potential value, In a fuirther embodiment of the invenition, the method for creating a product specification further comprites the step of specifying at least one morphological value like surface area, particle size, structure, porosity, or combinations thereof, to said batch, lot, or shipment of particulate material.
The present invcntion also relates to a method of doing business with a customer comprising using a product specification that includes at property value to request a certain batch, lot, or shipment and/or to provide a certain batch, lot, or shipmrent of chemical material.
Suchi a process involves the steps of providing a product specification, preferably a product spocification as set out above, to the custome r, ;he customer ulhoosing at least one property value of at least one lot, batch or shipment suitable for his purposes, identifying the lot, batoll or shipment providing at chemical miaterial suitable for the customners purposes, selcting said lot batch or shipment and placing an order for said selected lot, batch or shipment.
Additionally, the method mnay further comprise thte step providing the ordered lot, batch or shipment to said customer having selectod the lot, batch or shipment.
The present invention also extends to a method for improving identification of a grad;, type, or brand of chemical material comprising the 6tep of updating an existirg product description for the grade, type, or brand of particulate material by adding at least one property value.
The present invention also extends to a method for creating a product specification, a method for improving identification of a grade, type, or brand of chemnical material as set out above or a method of doing business with a customner ooznpri~iftg using a product specification, wherein said product description is in a catalog=w, Web site, brorhure, chemical miaterial literature, advcrtleement label, or combinations th&.of.
00 Example I' M ~Niobium hydroxide (241 kg, niobium content: 23,6 was added to 30L of water under stirring.
Oxalic acid (225 Wg and aqueous ammonia (3 3 1, 25 u/9 by weight NH 3 were added subsequently, 5 Additioti of anmmonia caused the solution to heat up to 40 0 C. The solution was stirred overnight 00 and thien cooled to 231 C, causing the desired niobium oxAlate complex to precipitate out of the solution. The precipitate was filtered off and dried for about 20 h at 700C, yielding 213 kg of the ovudc arnmonium niobium oxalato complex. Recrystallization from water yielded the pure
[NH
4 )[Nb(O)(C2O4)2(HO)aJ 3 HO complex.
Example 2: Niobium hydroxide (254 kS, niobium content: was added to 34L of water under stirring.
Oxalic acid (238,4 kg) and aqueous aLmonia (37 1, 25 by weigh NH-I,) were added subsequmtly. After addition of animonit the solution was heated up to 61 0 C and stirred for 9 hours at this temperature. Afterwards the solution wasn cooled to 24TC, causing the desired niobiumn oxalate complex to precipitate out of the solution. The precipitate was filtered off and dried for about 24 hi at 78TC, yielding 204 kg of the crude ammonium niobium oxalate complex.
Recrystallizatn~i ftotn water yielded the pure I(N 1 4 ]Nb(O)(C 2 0 4 2 H)2]*3H30 complex, The niobium, content of the niobiura hydroxide is dependent on the water content of the batah used, Throughout this specification and the claims which follow, unless the context requires otherwise the word "comprise", or variations such as "comprises" or 'comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference to any prior art in this specification is not, and should not be taken as an acknowledgment or any form of suggestion that, that prior art forms part of the common general knowledg e o f Austral Ia.

Claims (22)

1. A niobium compound smmonium(biSuqlo aobisoxalato)niobato (NH 4 )[NbO)( 2 0JA(HO2 and hydrates thereof.
2. A process for the preparation of the compoamd according to claim 1, comprising the staps of: 0C) dissolving niobium hydroxide and oxalic acid in water; adding ammonia cooling the reaction mixture.
3. Process according to claim 2, wherein the riobium concentration in the reaction mixture Is loe than about 2gNbfl.
4. Process according to claiim 2 or 3, wherein the reaction mixture has a temnporature of about 0 C to about 809C. Process according to any of claims 2 to 4, wherein the reactioni mixture is cooled to a temperature of about 25 0 C or legs.
6. Process according to any of claims 2 to 5, wherein the addition of ammonia is carried out by addition of aqueous ammonia or passing gaseous aznrnonia through the reaction mixture. 7, Process according to any of claims 2 to 6, wherein the process fuirther comprises a filtration step.
8. Process according to claim 7, wherein the process further comprises a drying step.
9. Process according to claim 8, wherein the drying step is curried out at a tempcrature of less than about A formulation comprising a compound of formula 1 together with at least one fwnther ingredient selected from the group conaitting of water, adjuvant, emulgator, antimicrobial, a watesolubic bag, a watersoluble polymer, polyvinyl alcohol, oxalic Soid, amrntiutn oxalate,
11-~ A formulation according to claim 10, the formulation couprising a saturated iuion. of the compound of formnala I in water or an aqueous slurry thereof. -11.
12. A formulation according to claim 10, wherein the fornulation comprisos a defned amount of the compound according to claim 1 in a bag.
13. A formulation according to claim 12, wherein the bag is a bag soluble in water or a. reaction medium.
14. A formulation according to claim 10, said formulation omnprising a container made of a 00 soluble polymnerio film comprising the compound according to claim 1, its solution or its slurry. A formulation acrording to any of claims 10 to 14, the polymeric film comprising N polyvinyl alcohol.
16. A formulation according to any of claims 14 to 15, sai4 formulation being a solid compoand according to claim 1 inside a closed bag compri sing, a film of polyvinyl alcohol
17. The use of a compound according to claim I or formulations thereof for the preparation of catalysts or ferrites. 18, A method for creating at product spcification for a batch, Ic;,or shipment of a compound is accordinig to claim 1, comprising specifying at least one property value for said batch lot, or shipment.
19. A method of doing business with a customer comprising using a product specification that includes a property value to request a certain batch, lot or shipment and/or to provide a certan batch, lot, or shipment of particulate matcrial.
20. The method of claim 18 or 19, wherein the property valuz is included on a product specification sheat, purchase order, invoice, contract, waiver to a contract, or combinlationsi thereof for the batch, lot, or shipment of a compound according to claim 1.
21. The method of claim 18 to 19, wherein said specifying comprises determining at least one property value for said batch, lot, or shipment of particulate material,
22. The method of claim 21, wherein said determining comprises measuring or anlyzing said batch, )ot, or shipnmt.
23. The method of claim 18 to 19, wherein said specif~ing comprises characturiliflg the batch, lot, or shipment of particulate material by at least one interfacial potential value. .12-
24. Tho method of claim 18 or 19, tuther comprising the step of specifying at least one morphological value like surface area, pinrticle size, structure, porosity, or combinations thereof~, to said batch, lot, or shipment of particulate triaterial. A method for improving identification of a grade, type, or brand of' partioulate matcrial comnpisins the step of updating an existing product description for the grade, type, or brand of partliulate material by adding at leout one property value. 00
26. The mnethod of claimn 18, 19 or 25, wherein said product description is in a catalogue, web site, brochure, particulate material literature, advertisemeont, label, or combinations thereof. CK1 27. Niobiumn compounds, and methods/processes for preparing the smsbtnilya hereinibefore described including with reference to the Examples.
28. Methods involving niobium compounds substantially as hereinibefore described with 1 5 reference to the description and/or Examples.
29. The steps, features, compositions and compounds disclosed herein or referred to or indicated in the specification and/or claims of this application, individually or collectively, and any and all combinations of any two or more of said steps or features. DATED this 30"' day of September, 2005 H.C. Starck GmbH By their patent attorneys DAVIES COLLISON CAVE
AU2005218055A 2005-09-30 2005-09-30 Niobium compound Abandoned AU2005218055A1 (en)

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