Patent Application
20190352189
The invention relates to a process for producing metal oxides by means of spray pyrolysis.
Spray pyrolysis and flame spray pyrolysis are established processes for producing simple metal oxides right through to complex mixed metal oxides. In spray pyrolysis, metal compounds in the form of fine droplets are introduced into a high-temperature zone where they are oxidized and/or hydrolysed to give metal oxides. A special form of this process is that of flame spray pyrolysis, in which the droplets are supplied to a flame which is formed by ignition of a fuel gas and an oxygen-containing gas.
Numerous reaction parameters are available to the person skilled in the art in order to vary the physicochemical properties of the metal oxides produced. For instance, temperature, concentration of the metal compound, residence time and velocity of the reaction mixture influence the structure of the metal oxides.
Thus, erroneous settings often result in incomplete conversion of the input material, for instance by inclusion of the input material in the actually desired oxide.
EP-A-2944611 describes a process for producing a mixed oxide of composition LixLa3Zr2AlyO8.5+0.5x+1.5y where 6≤x≤7, 0.2≤y≤0.5 having a garnet structure. An essential process step is flame spray pyrolysis where a solution containing the compounds of lithium, lanthanum, aluminium and zirconium is atomized into fine droplets and brought to reaction in a flame. The obtained product has the desired composition. However, the desired high crystallinity can only be achieved by an additional heat treatment step.
The situation is similar for the production of lithium-containing mixed oxides. EP-A-3026019 discloses a mixed oxide powder of composition Li1+x(NiaCobMnc)BdO2, where 0<x≤0.2; 0<a≤1; 0≤b≤1; 0≤c≤1, 0≤d≤0.2. Flame spray pyrolysis does not result in the desired high crystallinity in this process either.
The problem addressed by the present invention is accordingly that of providing a process for producing metal oxides by flame spray pyrolysis which provides parameters which make it possible to specifically adjust the properties of the metal oxide to be produced. This includes for example complete conversion of the input materials or adjustment of the crystallinity of the metal oxides.
The invention provides a process for producing a metal oxide powder by flame spray pyrolysis where
In the context of the present invention the term “internal” or “internals” is always to be understood as meaning double-walled internals. A reaction space and an internal are generally tubular. The internal is installed in the reaction space such that its outer wall is in contact with the inner wall of the reaction space. The internal is closed at top and bottom. If a plurality of internals are present these may be identical or different in terms of length or diameter for example. The successive internals may conduct identical or different gases. It is likewise possible for individual internals not to conduct gases.
The process according to the invention is preferably implemented such that an internal comprises four slots. When the internal is taken to be tubular then in cross section the four slots are preferably arranged such that one slot is located in each quadrant. This is shown in
Usually, the length of a slot is 50-100 mm, the width thereof is 0.5-3 mm and the slot length/slot width ratio is 10:1-200:1.
The angle α of a slot to the vertical is preferably 15°≤α≤60° and particularly preferably 25°≤α≤40°.
The process as claimed in claims 1 to 5, characterized in that the angle β which describes the angle between the section axis of the slot to the circle perpendicular of the centre is preferably 30°≤β≤60° and particularly preferably 40°≤β≤50°.
A further feature with which the flame may be varied is the ratio of the diameter of the reaction space to the total slot area. This ratio is preferably 15:1-200:1 and particularly preferably 25:1-50:1.
The gas supplied via the slot in an internal may be a fuel gas. Examples of fuel gases are hydrogen, methane, ethane, natural gas and/or carbon monoxide. It is particularly preferable to employ hydrogen. A fuel gas is employed in particular for embodiments where a high crystallinity of the metal oxides to be produced is desired, for example for mixed lithium oxides for use in lithium ion batteries.
The gas supplied via the slot in an internal may be an oxygen-containing gas. This is generally air or oxygen-enriched air. An oxygen-containing gas is employed in particular for embodiments where for example a high BET surface area of the metal oxide to be produced is desired.
The fuel gas or oxygen-containing gas supplied via a slot in an internal is generally the same and as used for ignition of the flame in the reaction space. The total amount of oxygen is chosen such that, taken over all internals, it is sufficient at least for complete conversion of the fuel gas and the metal compounds.
Furthermore, inert gases such as nitrogen or reactive vapours such as water vapour may also be supplied via a slot in an internal.
In the process according to the invention the solution is introduced into the reaction space in the form of an aerosol. The fine droplets of the aerosol preferably have an average droplet size of 1-120 μm, particularly preferably of 30-100 μm. The droplets are typically produced using single- or multi-material nozzles. To increase the solubility of the metal compounds and to attain a suitable viscosity for atomization of the solution the solution may be heated.
Suitable solvents include water, alkanes, alkanecarboxylic acids and/or alcohols. Preference is given to using aqueous solutions, wherein an aqueous solution is to be understood as meaning a solution in which water is the main constituent of a solvent mixture or in which water alone is the solvent. The concentration of the employed solutions is not particularly limited. If only one solution containing all mixed oxide components is present, the concentration is generally 1 to 50 wt %, preferably 3 to 30 wt %, particularly preferably 5-20 wt %, in each case based on the sum of the oxides.
The metal compounds may be inorganic metal compounds, such as nitrates, chlorides, bromides, or organic metal compounds, such as alkoxides or carboxylates. The alkoxides employed may preferably be ethoxides, n-propoxides, isopropoxides, n-butoxides and/or tert-butoxides. The carboxylates used may be the compounds based on acetic acid, propionic acid, butanoic acid, hexanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, 2-ethylhexanoic acid, valeric acid, capric acid and/or lauric acid.
The metal component is preferably selected from the group consisting of Ag, Al, Au, B, Ba, Ca, Cd, Ce, Co, Cr, Cu, Dy, Fe, Ga, Ge, Hf, In, La, Li, Mg, Mn, Mo, Nb, Ni, Pd, Rh, Ru, Sc, Si, Sm, Sn, Sr, Ta, Ti, V, Y, Yb and Zn. In the context of the invention silica and boron are to be regarded as metals.
In a particular embodiment the solution contains Zn, Ti or Ca as the metal of the metal compound.
In a further particular embodiment the solution contains Li, La and Zr as the metal of the metal compound. In addition to these the solution may further contain Al, Au, Ba, Ca, Ce, Dy, Ga, Ge, Hf, Mg, La, Nb, Sc, Si, Sm, Sn, Sr, Ta, Ti, V, Yb or Zn.
In a further particular embodiment the solution contains Li and Ni as the metal of the metal compound. In addition to these the solution may further contain Co and Mn.
On account of the rotating flame the average residence time of the particles in the flame is lengthened. The rotational movement causes the flame itself to become narrower but also substantially longer compared to a flame burning in a reaction space without internals. The process according to the invention is preferably implemented such that gas supplied via a slot in an internal lengthens the average residence time of the reaction mixture in the reaction space by at least a factor of 1.2, particularly preferably 1.2-5, compared to a reaction space comprising none of these internals.
It is likewise possible to influence the rotation of the flame via the gas entry velocity from a slot in an internal into the reaction space. The gas entry velocity is preferably at least 10 Nm/s, particularly preferably 10-50 Nm/s.
In the comparative examples the cylindrical reaction space comprises no internals.
In the inventive examples the reaction space 3 comprises successive tubular internals, internal I-III, of 50 cm in length respectively. These are affixed in the reaction space. The internals comprise four slots having a length of 10 cm and a width of 0.15 cm. The arrangement of the slots is as shown in
The ratio of the diameter of the reaction space to the total slot area is 31.4:1.
Solution Employed:
Calcium octoate solution, Octa-Soligen Calcium 10, a mixture of calcium salts of C6-C19-fatty acids and naphtha (petroleum), OMG Borchers, containing 10 wt % of calcium.
2.5 kg/h of the solution are atomized into the tubular reaction space with 3.5 Nm3/h of atomization air by means of a two-material nozzle.
The reaction space comprises no internals.
The flame is formed by the reaction of 5 Nm3/h of hydrogen, 13 Nm3/h of primary air and 15 Nm3/h of secondary air. Further reaction parameters are reported in the table.
The obtained powder has a BET surface area according to DIN ISO 9277 of 20 m2/g.
As per example 1 but via internal 115 Nm3/h of air are introduced into the reaction space.
The obtained powder has a BET surface area of 38 m2/g.
Zinc octoate solution, Octa-Soligen Zink 29, a mixture of zinc salts of C6-C19-fatty acids and naphtha (petroleum), TIB, containing 29 wt % of zinc.
1.5 kg/h of the solution are atomized into the tubular reaction space with atomization air (4 Nm3/h) by means of a two-material nozzle. The reaction space comprises no internals.
The flame is formed by the reaction of 5 Nm3/h of hydrogen and 24 Nm3/h of primary air. Further reaction parameters are reported in the table
The obtained powder has a BET surface area according to DIN ISO 9277 of 11 m2/g.
As per example 1 but via
internal I 20 Nm3/h of air and 1 Nm3/h of water vapour
internal II 10 Nm3/h of air and 1 Nm3/h of water vapour and
internal III 10 Nm3/h of air
are introduced into the reaction space.
The obtained powder has a BET surface area of 70 m2/g.
Solution used: 5.21 wt % of lithium nitrate, 15.66% wt % of lanthanum nitrate, 10.35 wt % of zirconium nitrate, wt % of aluminium nitrate, remainder water. The concentration based on the oxide Li6.27La3Zr2Al0.24O12 is 10.26 wt %.
8 kg/h of the solution are atomized into the tubular reaction space with an atomization gas consisting of 15 Nm3/h of air and 0.05 kg of ammonia gas/Nm3 of air by means of a two-material nozzle.
The reaction space comprises no internals.
The flame is formed by the reaction of 13 Nm3/h of hydrogen, 75 Nm3/h of primary air and 25 Nm3/h of secondary air. Further reaction parameters are reported in the table.
The mixed oxide powder has a composition of Li6.27La3Zr2Al0.24O12. The BET surface area is 5 m2/g.
As per example 5 but via internal I and internal II 3 Nm3/h respectively of hydrogen are introduced into the reaction space.
The mixed oxide powder has a composition of Li6.27La3Zr2Al0.24O12. The BET surface area is <1 m2/g.
As per example 5 but via internal II 20 Nm3/h of air and via internal III 30 Nm3/h of air are introduced into the reaction space.
The mixed oxide powder has a composition of Li6.27La3Zr2Al0.24O12. The BET surface area is 20 m2/g.
Employed solution consisting of 13.3 wt % of lithium nitrate, 3.8 wt % of nickel(II) nitrate, 15.6 wt % of manganese(II) nitrate, 3.7 wt % of cobalt(II) nitrate and 0.05 wt % of boric acid, remainder water. Sum of metal is 8.6wt %.
10 kg/h of the solution are atomized into the tubular reaction space with an atomization gas consisting of 15 Nm3/h of air and 1.5 kg of ammonia gas/Nm3 of air by means of a two-material nozzle.
The reaction space comprises no internals.
The flame is formed by the reaction of 13.9 Nm3/h of hydrogen and 45 Nm3/h of primary air. Further reaction parameters are reported in the table.
The mixed oxide powder has the composition Li1.2(Ni0.13Co0.125Mn0.54B0.05)O2. The BET surface area is 14 m2/g, the crystallite diameter dXRD=750 nm.
As per example 7 but via internal I 40 Nm3/h of air and via internal II 10 Nm3/h of air are introduced into the reaction space.
The mixed oxide powder has the composition Li1.2(Ni0.13Co0.125Mn0.54B0.05)O2. The BET surface area is 5 m2/g, the crystallite diameter dXRD=5500 nm.
Examples 1 and 2 show how the BET surface areas of a metal oxide powder may be increased by means of the process according to the invention compared to a process comprising no internals in the reaction space.
Examples 3 show that by means of the process according to the invention the BET surface area of the metal oxide powder may be both reduced (example 3.2) and increased (example 3.3) in each case compared to a process comprising no internals in the reaction space. The method oxide powder from example 3.2 also exhibits a high crystallinity.
Examples 4 show how the crystallinity of a metal oxide powder may be increased by means of the process according to the invention compared to a process comprising no internals in the reaction space.
Key to Table:
| Number | Date | Country | Kind |
|---|---|---|---|
| 17150660.3 | Jan 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/083749 | 12/20/2017 | WO | 00 |
