WO2020234075A1 - Process for performing endothermic reactions, and reaction vessel suitable therefore - Google Patents
Process for performing endothermic reactions, and reaction vessel suitable therefore Download PDFInfo
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- WO2020234075A1 WO2020234075A1 PCT/EP2020/063287 EP2020063287W WO2020234075A1 WO 2020234075 A1 WO2020234075 A1 WO 2020234075A1 EP 2020063287 W EP2020063287 W EP 2020063287W WO 2020234075 A1 WO2020234075 A1 WO 2020234075A1
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- Prior art keywords
- rotary drum
- wall
- drum reactor
- reactor
- process according
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Classifications
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- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
- B01J6/002—Calcining using rotating drums
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
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- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/28—Moving reactors, e.g. rotary drums
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- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
- B01J3/048—Multiwall, strip or filament wound vessels
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0218—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of ceramic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0236—Metal based
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0277—Metal based
- B01J2219/0286—Steel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0879—Solid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/187—Details relating to the spatial orientation of the reactor inclined at an angle to the horizontal or to the vertical plane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
Definitions
- the present invention is directed towards a process for performing an endothermic reaction in a rotary drum reactor at a temperature in the range of from 300 to 1500°C, said process comprising the step of introducing at least one particulate material into said rotary drum reactor and moving it through the rotary drum reactor with a flow of a gas, wherein said rotary drum reactor contains the following elements:
- a key element of the reaction technology is the reactor.
- An example of reactor for performing endothermic reactions at high temperature is the rotary kiln technology.
- Rotary kilns such as those used for cement productions can cope with highly corrosive materials.
- the reaction good is exposed directly to hot gas stemming from the com bustion of gas, oil, pulverized petroleum coke or pulverized coal, and to radiation.
- the hot gas comprises CO2 that does not impose any quality restrictions to the reaction good.
- the tube that forms the body of said kiln is therefore protected from the corrosive reaction good with ceram ics.
- inventive process is a continuous process.
- the inventive process is performed at a temperature in the range of from 300 to 1500°C, preferred are 400 to 1100°C and even more preferred are 500 to 900°C.
- the temperature in this context refers to the highest temperature as measured in a distance of 1 cm to the inner wall.
- the contemplated reaction is endothermic, for example a de-hydration or carbon dioxide re moval or a combination of at least one of the foregoing and the introduction of lithium, for exam ple the lithiation reaction of a precursor of a cathode active material.
- Suitable endothermic reactions are the dehydration of inorganic oxyhydrox- ides and hydroxides in the formation of catalysts, e.g., copper oxide based catalysts, alumina based catalysts, and zeolite-based catalysts.
- catalysts e.g., copper oxide based catalysts, alumina based catalysts, and zeolite-based catalysts.
- carrier-based reactions such as, but not limited to carbonaceous granule carrier-based reactions, for example carbona ceous granule carrier-based hydrogen cyanide synthesis from methane and ammonia, CO syn thesis according to the Boudouard reaction, iron-containing shaped body-based reactions such as, but not limited to dehydrogenation of alkanes to olefins, e.g., propylene from propane or butadiene from butane or n-butane, and aldehyde synthesis from alkanols.
- carbonaceous granule carrier-based reactions for example carbona ceous granule carrier-based hydrogen cyanide synthesis from methane and ammonia
- iron-containing shaped body-based reactions such as, but not limited to dehydrogenation of alkanes to olefins, e.g., propylene from propane or butadiene from butane or n-butane
- Rotary drum reactors in the con text of the present invention are vessels that rotate along a longitudinal axis that may be hori zontal or tilted by 0.1 to 15 degrees and that have a length to diameter ratio in the range of from 0.1 to 20, preferably from 0.5 to 20.
- rotary drum reactors may have a length in the range of from 1 to 20 meters, preferably 4 to 10 meters.
- top and bottom phase of rotary drum reactors are preferably spherical.
- rotary drum reactors in the context of the present invention are cylindrically shaped, preferably as right cylinders.
- the rotary drum reactor is operated with 0.01 to 20 rounds per minute, preferred are 1 to 10 rounds per minute, and, in each case, continuously or in intervals.
- operation in an interval mode it is possible, for example, to stop the rotation after one to 5 rounds for one to 60 minutes, and then to again perform 1 to 5 rounds and again stop for 1 to 60 minutes, and so forth. More details are described further down below.
- the inventive process comprises the step of introducing a particulate solid into the rotary drum reactor and moving it through said rotary drum reactor with a flow of gas.
- the flow of gas may be co-current or preferably counter-current.
- the gas flow comprises air that is co- currently or counter-currently with respect to the particulate solids.
- the particular solid may serve as a carrier, a catalyst, as seed or as reacting good.
- two different particulate solids are introduced into the rotary drum reactor.
- Said particulate solid may have an average diameter (d50) in the range of from 1 pm to 1 mm, preferably 2 pm to 100 pm.
- Said particulate solid may have an irregular shape but in a preferred embodiment, said particulate solid has a regular shape, for example spheroidal or even spheri cal.
- the aspect ratio may be in the range of from 1 and 10, preferably from 1 to 3.
- said par ticulate solid preferably has an average particle diameter (d50) in the range of from 2 to 20 pm and even more preferably from 3 to 15 pm.
- a lithium source for example LiOH, U 2 CO 3 , U 2 O, UNO 3
- anhydrous or as hydrate if applicable, for example as Li OH H 2
- a precursor for example a mixed hydroxide or mixed oxyhydroxide or mixed oxide or mixed carbonate of transition metals, especially of nickel and at least one metal selected from manganese and cobalt.
- Further metals may be present in the precursor such as, but not limited to Mg, Ca, Al, Ba, B, Ti, Zr, Nb, Ta, W, Mo, and Y.
- the stoichiome try of the transition metals in the precursor corresponds to the stoichiometry of the transition metals in the targeted cathode active material.
- two different particulate solids are introduced simultaneously into said rotary drum reactor, one being selected from an inorganic lithium compound selected from U 2 O, LiOH and U 2 CO 3 , anhydrous or as hydrate, if applicable, and the other being selected from a mixed oxide, mixed carbonate, mixed hydroxide or mixed oxyhydroxide of nickel and at least one transition metal selected from cobalt and manganese and containing, optionally, at least one further metal selected from Mg, Ca, Al, Ba, B, Ti, Zr, Nb, W, Mo, and Y.
- the metal part of mixed oxide, mixed carbonate, mixed hydroxide or mixed oxyhydroxide of nickel and at least one transition metal selected from cobalt and manganese corresponds to general formula (I) NialVTbMric (I) where the variables are each defined as follows:
- the average residence time of the particulate solid is in the range of from 10 minutes to 12 hours, preferably 1 to 6 hours.
- the aver age residence time refers to the average residence time of the particulate material in the rotary drum reactor.
- the particulate solid is introduced into the rotary drum reactor at ambient temperature.
- the par ticulate solid is introduced into the rotary drum reactor at a temperature of from 100°C to 300°C.
- said particulate solid is moved through the rotary drum reactor with a co-current flow of gas.
- said flow of gas and said particulate solid are moved through the rotary drum reactor counter- currently.
- the co-current flow has the disadvantage that, in case of electrode active materials for lithium ion batteries, the almost finished cathode active material is in contact with gas com parably rich in humidity and carbon dioxide. This disadvantage is avoided if flow of gas and mo tion of particulate solid are counter-current.
- the gas temperature at the inlet to the reactor is in the range of from 10°C to 800°C, preferably from 20°C to 400°C
- the average superficial velocity of the gas is in the range of from 0.005 m/s to 1 m/s, preferably 0.05 m/s to 0.2 m/s. With a higher superficial gas velocity, dust evolution may exceed a tolerable level.
- the gas may be inert or oxidizing or a reactant, such as in the case of alkanols in the case of aldehyde formation.
- an electrode active material is made the gas is oxidizing, for example pure oxygen, oxygen-enriched air or air, oxygen-enriched air and air being preferred.
- An example of oxygen-enriched air is a mixture of 1 :0.5 by volume to 1 :5 by volume air : oxygen, determined at ambient conditions.
- the inventive process is performed at ambient pressure or ⁇ 50 mbar, preferably ambient pressure up to 20 mbar above ambient pressure.
- the filling level of said rotary drum reactor is in the range of from 5 to 70%, preferred are 20 to 65%.
- the filling level is determined under neglecting the voids between particles of particulate solid.
- the rotary drum reactor contains the following elements:
- (A) a double-wall steel drum, hereinafter also referred to as steel drum (A) or element (A), wherein the space of the outer and the inner wall is evacuated,
- heating system (B) with an electrical heating system attached to the inner wall, hereinafter also referred to as heating system (B) or element (B),
- layer (D) and, optionally, a corrosion protection layer attached to the electric heating system hereinafter also referred to as layer (D) or element (D).
- Element (A) is a double-wall steel drum.
- the dis tance between the outer and the inner wall is in the range of from 1 to 20 cm, preferably 5 to 10 cm, determined at ambient temperature. The distance is an average value.
- Each wall may have a thickness in the range of from 5 to 30 mm, preferred between 7 and 20 mm.
- the inner and the outer wall may have the same or different thicknesses.
- the outer wall is 1.5 to 3 times thicker than the inner wall.
- Outer and inner wall may be kept apart by spacers.
- spacers may have a round or polygo nal shape.
- the length of the spacers may be in the range of from 10 to 100 mm, preferred are 20 to 70 mm.
- both outer and inner wall are from stainless steel.
- the space between outer and inner wall is evacuated.“Evacuated” in the context of the present invention shall not be restricted to vacuum but also include a reduced pressure, that the pres sure in this space is in the range of from 1 to 100 mbar.
- the residual gas may be selected from nitrogen or noble gasses such as argon. However, the residual gas may be selected from air or oxygen and thereby cause a passivation of the hot surface of the inner wall of the drum.
- the space between outer and inner wall may be empty or contain loose elements.
- the space between outer and inner wall contains rock wool or porous stone.
- the rotary drum reactor further comprises a heating system (B).
- the heating system (B) is elec tric and attached to the inner wall of the rotary drum reactor, and it may be selected from heat ing selected from resistance heating, inductive heating, and micro-wave heating.
- the heating system (B) covers the inner surface of the inner wall of the drum to the extent of 70 to 100% of the inner surface of the inner wall.
- the heating system (B) is attached to the inner wall through bolts or screws.
- the heating system (B) is drum shaped and has the same outer diameter as the inner diameter of the inner drum, upon heating and thermal expansion, the heating system is pressed to the wall of the drum due to the thermal expansion.
- the region of rotary drum reactors that is exposed to the heating system is the reaction zone of such rotary drum reactor.
- a corrosion protection layer (D) is attached to the heating system (B).
- Said layer (D) may be made from a ceramic matrix composite or an alloy selected from steels and nickel-based alloys and cobalt refractory alloys, or a metal selected from tungsten, molybdenum, iron, and nickel.
- a ceramic matrix composite contains ceramic fibers, and it additionally comprises a ceramic matrix material.
- the fibers are in an ordered or non-ordered orientation, for example 0 90° layup or randomly criss-cross.
- Ceramic fibers and ceramic matrix material may have identical or different chemical compositions.
- ceramic matrix compo sites comprise fibers embedded in ceramic oxide or non-oxide matrices. The bonding forces between the fibers and the matrix are comparatively low.
- Oxide matrix materials such as alumi num oxide are preferably in particulate form.
- Ceramic fibers and ceramic matrix materials may each be selected from oxide and non-oxide ceramics. Examples of non-oxide ceramics are carbides and borides and nitrides.
- non-oxide ceramics are silicon carbide, silicon boride, silicon nitride, silicon-boron- nitride, hereinafter also referred to as SiBN, silicon carbon nitride, hereinafter also referred to as SiCN, and in particular combinations from SiC and Si3N4.
- oxide ceramics here inafter also referred to as oxide-based ceramics.
- Oxide ceramics are oxides of at least one ele ment selected from Be, Mg, Ca, Sr, Ba, rare earth metals, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Ga, Si, Ge, Sn, Re, Ru, Os, Ir, In, Y, and mixtures of at least two of the foregoing.
- Oxide-based ceramics may be selected from doped ceramics, wherein one main component is doped with up to 1 molar % components other than the main component, and from reinforced ceramics, wherein one component is the main component, for example at least 50 molar %, and one or more further components - reinforcing components - are present in ranges from 1.1 to 25 molar %.
- Further examples are titanates and silicates. Titanates and sili cates each may have a stoichiometric composition.
- titanates is aluminum titanate.
- silicates is magnesi um silicate.
- reinforced ceramics are reinforced alumina and reinforced zirconia. They may con tain two or more different reinforcement oxides and may thus be referred to as binary or ternary mixtures.
- the following binary and ternary mixtures are preferred: aluminum oxide reinforced with 1.1 to 25% by weight of one of the following: cerium oxide Ce0 2 , ytterbium oxide Yb 2 0 3 , magnesia (MgO), calcium oxide (CaO), scandium oxide (SC2O3), zirconia (Zr0 2 ), yttrium oxide (Y2O3), boron oxide (B2O3), combinations from SiC and (AI2O3), or aluminum titanate. More pre ferred reinforcing components are B2O3, Zr0 2 and Y2O3.
- Preferred zirconia-reinforced alumina is AI2O3 with from 10 to 20 mole-% Zr0 2 .
- Preferred exam ples of reinforced zirconia are selected from Zr0 2 reinforced with from 10 to 20 mole-% CaO, in particular 16 mole-%, from 10 to 20 mole-% MgO, preferably 16 mole-%, or from 5 to 10 mole-% Y2O3, preferably 8 mole-%, or from 1 to 5 mole-% Y2O3, preferably 4 mole-%.
- An example of a preferred ternary mixture is 80 mole-% AI2O3, 18.4 mole-% Zr0 2 and 1.6 mole-% Y2O3.
- Preferred fiber materials are oxide ceramic materials, carbide ceramic materials, nitride ceramic materials, SiBCN fibers, basalt, boron nitride, tungsten carbide, aluminum nitride, titania, barium titanate, lead zirconate-titanate and boron carbide. Even more preferred fiber materials are AI2O3, mullite, SiC, and Zr0 2 fibers.
- the fibers are made from aluminum oxide
- the ceramic matrix composite comprises a ceramic matrix material selected from aluminum oxide, quartz, mullite, cordier- ite and combinations of at least two of the foregoing. Preferred is aluminum oxide.
- creep resistant fibers are fibers that exhibit minimum - or no - permanent elongation or other permanent deformation at temperatures up to 1 ,400°C.
- ceramic fibers may have a diameter in the range of from 7 to 12 pm. Their length may be in the range of from 1 mm up to 1 km or even longer, so- called endless fibers. In one embodiment, several fibers are combined with each other to yarns, rovings (German: Multifilamentgarn), textile strips, hoses, or the like.
- ceramic fibers used in the present invention have a tensile strength of at least 50 MPa, preferably at least 70 MPa, more preferably at least 100 MPa, and even more preferably at least 120 MPa.
- a maximum value of the tensile strength of ceramic fibers used in the present invention is 3,100 MPa or even 10,000 MPa.
- the tensile strength may be determined with a tensile tester. Typical measuring conditions are cross-head speeds of 1.2 to 1.3 cm/min, for example 1.27 cm/min, and 7.61 cm gauge.
- the matrix is made from an oxide ceramic material or a carbide.
- Preferred oxide ceramic materials for the matrix are AI2O3, mullite, SiC, ZrC>2 and spinel, MgAhCU.
- Particularly preferred components are SiC/SiC, Zr02/ZrC>2, ZrC AhCh, AhCh/ZrC ⁇ , AI2O3/AI2O3 and mullite/mullite.
- the fiber material is in each foregoing case the first and the matrix the second material.
- such ceramic matrix composite comprises 20 to 60 % by volume ceramic fiber.
- Ceramic matric composites are porous. In many cases, the total solids content of such ceramic matrix composite is from 50 to 80% of the theoretical, the rest is air or gas due to the pores.
- such ceramic matrix composite has a porosity in the range of from 20 % to 50 %; thus, such ceramic matrix composite is not gas tight in the sense of DIN 623-2.
- the ceramic matrix composite comprises fibers from aluminum oxide and a ceramic selected from aluminum oxide, quartz, mullite, cordierite and combinations of at least two of the foregoing, for example aluminum oxide and mullite or aluminum oxide and cordierite. Even more preferably, the ceramic matrix composite comprises fibers from aluminum oxide and aluminum oxide ceramic.
- layer (D) has a thickness in the range of from 0.5 mm to 15 mm, preferably 2 mm to 8 mm.
- layer (D) covers the entire surface of element (B) that would be otherwise exposed to the reactants.
- the surface of layer (D) in contact with the particu late solids inside the drum reactor is not evenly cylindrical but shaped, having circumferential, axial or otherwise oriented strips or a checked pattern or any other pattern.
- the surface of layer (D) in contact with the particu late solids inside the drum reactor is coated, for example with a ceramic coating.
- the coating of layer (D) may have a barrier function or an abrasion protection function, or both functions.
- Rotary drum reactors further contain one or more elements (C), for example 2 to 3.
- Such inter nals) (C) are attached to the inner wall, or to the front and end surfaces of a non-rotating part of said rotating drum reactor. Preferably, they are attached to the inner wall.
- Internal(s) (C) may be selected from baffles, plough shares, blades or shovels. Internals (C) may expand entirely from the wall to the center of the rotary drum or they may expand partially from the wall to center of the rotating drum. Preferably, from 1 to 10 internals (C) are distributed along the axis of the rotating drum and from 1 to 10 internals (C) are distributed along the cir cumference of the rotating drum. In total, from 2 to 100 internals (C) may be distributed inside the rotating drum, preferably, and preferably from 4 to 20 internals (C) may be distributed inside the rotating drum in a symmetric orientation.
- the length of the drum is from 0.5 to 20 m, prefera bly from 1 to 10 m.
- the diameter of the drum is in the range of from 0.25 to 5 m.
- a further aspect of the present invention relates to rotary drum reactors in which the inventive process may be advantageously performed.
- Such rotary drum reactors are also referred to as inventive rotary drum reactors.
- inventive rotary drum reactors contain the following elements, hereinafter also referred to as elements (A) to (D):
- At least some of the internals (C) serve as scrapers by removing incrustations of, e.g., sintered particulate solids from the inner walls.
- Such internals (C) that serve as scrapers are preferably those that are at the end of the reaction zone of an inventive rotary drum reactor.
- inventive rotary drum reactors may further comprise elements such as gaskets, an entry system for introduction of particulate sold and a removal system for react ed particulate solid.
- Particulate solid - for example a mixture from lithium source and precursor for an electrode ac tive material - enters through the left.
- the respective electrode active material leaves bottom right.
- the gaskets support the axis.
- A evacuated space between the outer and the inner wall
- FIG. 1 Example of an inventive drum reactor. Flow of gas and motion of particles are co-current. Four pairs of baffles (C). B2: Electric heating system.
- A evacuated space between the outer and the inner wall
- the 4 pairs of internals move the particles in the course of the rotation of the rotary drum reac- tor.
- M motor to effect the rotation of the drum.
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Abstract
Process for performing an endothermic reaction in a rotary drum reactor at a temperature in the range of from 300 to 1500°C, comprising the step of introducing at least one particulate material into said rotary drum reactor and moving it through the rotary drum reactor with a flow of a gas, wherein said rotary drum reactor comprises the following elements: (A) a double-wall steel drum wherein the space of the outer and the inner wall is evacuated, (B) with an electrical heating system attached to the inner wall, (C) internal(s) attached to the inner wall, or to the front and end surfaces of a non-rotating part of said rotating drum, (D) and, optionally, a corrosion protection layer attached to the electric heating system.
Description
Process for Performing Endothermic Reactions, and Reaction Vessel Suitable therefore
The present invention is directed towards a process for performing an endothermic reaction in a rotary drum reactor at a temperature in the range of from 300 to 1500°C, said process compris ing the step of introducing at least one particulate material into said rotary drum reactor and moving it through the rotary drum reactor with a flow of a gas, wherein said rotary drum reactor contains the following elements:
(A) a double-wall steel drum wherein the space of the outer and the inner wall is evacuated,
(B) with an electrical heating system attached to the inner wall,
(C) internal(s) attached to the inner wall, or to the front and end surfaces of a non-rotating part of said rotating drum,
(D) and, optionally, a corrosion protection layer attached to the electric heating system.
Endothermic reactions as well as strongly exothermic reactions pose a lot of requirements for the reaction technology. Particularly challenging are reactions that combine endothermic reac tion enthalpy, high reaction temperatures, and particulate solids that exhibit a certain fragility. A key element of the reaction technology is the reactor.
An example of reactor for performing endothermic reactions at high temperature is the rotary kiln technology. Rotary kilns such as those used for cement productions can cope with highly corrosive materials. The reaction good is exposed directly to hot gas stemming from the com bustion of gas, oil, pulverized petroleum coke or pulverized coal, and to radiation. The hot gas comprises CO2 that does not impose any quality restrictions to the reaction good. The tube that forms the body of said kiln is therefore protected from the corrosive reaction good with ceram ics.
Several endothermic reactions, however, need to be performed in the absence of carbon diox ide because carbon dioxide is detrimental to the desired product. For that reason, such reac tions need to apply indirect heating. However, in cases of indirect heating, layers of ceramic usually impair the heating due to their low heat conductivity.
It was therefore an objective of the present invention to provide a process by which particulate materials may be reacted in an endothermic reaction. It was further an objective to provide a reactor for performing such a process.
Accordingly, the process as defined at the outset has been found, hereinafter also referred to as “inventive process” or“process according to the present invention”. The inventive process is a continuous process.
As indicated above, the inventive process is performed at a temperature in the range of from 300 to 1500°C, preferred are 400 to 1100°C and even more preferred are 500 to 900°C. The temperature in this context refers to the highest temperature as measured in a distance of 1 cm to the inner wall.
The contemplated reaction is endothermic, for example a de-hydration or carbon dioxide re moval or a combination of at least one of the foregoing and the introduction of lithium, for exam ple the lithiation reaction of a precursor of a cathode active material.
Further examples of suitable endothermic reactions are the dehydration of inorganic oxyhydrox- ides and hydroxides in the formation of catalysts, e.g., copper oxide based catalysts, alumina based catalysts, and zeolite-based catalysts. Further examples are carrier-based reactions such as, but not limited to carbonaceous granule carrier-based reactions, for example carbona ceous granule carrier-based hydrogen cyanide synthesis from methane and ammonia, CO syn thesis according to the Boudouard reaction, iron-containing shaped body-based reactions such as, but not limited to dehydrogenation of alkanes to olefins, e.g., propylene from propane or butadiene from butane or n-butane, and aldehyde synthesis from alkanols.
The inventive process is carried out in a rotary drum reactor. Rotary drum reactors in the con text of the present invention are vessels that rotate along a longitudinal axis that may be hori zontal or tilted by 0.1 to 15 degrees and that have a length to diameter ratio in the range of from 0.1 to 20, preferably from 0.5 to 20.
In one embodiment of the present invention, rotary drum reactors may have a length in the range of from 1 to 20 meters, preferably 4 to 10 meters.
In one embodiment of the present invention, top and bottom phase of rotary drum reactors are preferably spherical.
In one embodiment of the present invention, rotary drum reactors in the context of the present invention are cylindrically shaped, preferably as right cylinders.
In one embodiment of the present invention, the rotary drum reactor is operated with 0.01 to 20 rounds per minute, preferred are 1 to 10 rounds per minute, and, in each case, continuously or in intervals. When operation in an interval mode is desired it is possible, for example, to stop the rotation after one to 5 rounds for one to 60 minutes, and then to again perform 1 to 5 rounds and again stop for 1 to 60 minutes, and so forth.
More details are described further down below.
The inventive process comprises the step of introducing a particulate solid into the rotary drum reactor and moving it through said rotary drum reactor with a flow of gas. The flow of gas may be co-current or preferably counter-current. For example, the gas flow comprises air that is co- currently or counter-currently with respect to the particulate solids. In this context, the particular solid may serve as a carrier, a catalyst, as seed or as reacting good. In specific embodiments, two different particulate solids are introduced into the rotary drum reactor.
Said particulate solid may have an average diameter (d50) in the range of from 1 pm to 1 mm, preferably 2 pm to 100 pm. Said particulate solid may have an irregular shape but in a preferred embodiment, said particulate solid has a regular shape, for example spheroidal or even spheri cal. The aspect ratio may be in the range of from 1 and 10, preferably from 1 to 3.
In embodiments wherein electrode active materials of lithium ion batteries are made, said par ticulate solid preferably has an average particle diameter (d50) in the range of from 2 to 20 pm and even more preferably from 3 to 15 pm. In such embodiments, two different particulate solids are introduced simultaneously into the rotary drum reactor is a mixture of a lithium source, for example LiOH, U2CO3, U2O, UNO3, anhydrous or as hydrate, if applicable, for example as Li OH H20, and a precursor, for example a mixed hydroxide or mixed oxyhydroxide or mixed oxide or mixed carbonate of transition metals, especially of nickel and at least one metal selected from manganese and cobalt. Further metals may be present in the precursor such as, but not limited to Mg, Ca, Al, Ba, B, Ti, Zr, Nb, Ta, W, Mo, and Y. In such embodiments, the stoichiome try of the transition metals in the precursor corresponds to the stoichiometry of the transition metals in the targeted cathode active material.
In a preferred embodiment, two different particulate solids are introduced simultaneously into said rotary drum reactor, one being selected from an inorganic lithium compound selected from U2O, LiOH and U2CO3, anhydrous or as hydrate, if applicable, and the other being selected from a mixed oxide, mixed carbonate, mixed hydroxide or mixed oxyhydroxide of nickel and at least one transition metal selected from cobalt and manganese and containing, optionally, at least one further metal selected from Mg, Ca, Al, Ba, B, Ti, Zr, Nb, W, Mo, and Y.
In one embodiment of the present invention, the metal part of mixed oxide, mixed carbonate, mixed hydroxide or mixed oxyhydroxide of nickel and at least one transition metal selected from cobalt and manganese corresponds to general formula (I)
NialVTbMric (I) where the variables are each defined as follows:
M1 is Co or a combination of Co and at least one metal selected from Ti, Zr, Al and Mg, a is in the range from 0.15 to 0.95, preferably from 0.6 to 0.92 or from 0.15 to 0.3 b is in the range from zero to 0.35, preferably 0.05 to 0.2, c is in the range from zero to 0.8, preferably 0.05 to 0.2, and a + b + c = 1.0 and at least one of b and c is greater than zero.
In one embodiment of the present invention, the average residence time of the particulate solid is in the range of from 10 minutes to 12 hours, preferably 1 to 6 hours. In this context, the aver age residence time refers to the average residence time of the particulate material in the rotary drum reactor.
In one embodiment of the present invention, the particulate solid is introduced into the rotary drum reactor at ambient temperature. In another embodiment of the present invention, the par ticulate solid is introduced into the rotary drum reactor at a temperature of from 100°C to 300°C.
In one embodiment of the present invention, said particulate solid is moved through the rotary drum reactor with a co-current flow of gas. In another embodiment of the present invention, said flow of gas and said particulate solid are moved through the rotary drum reactor counter- currently. The co-current flow has the disadvantage that, in case of electrode active materials for lithium ion batteries, the almost finished cathode active material is in contact with gas com parably rich in humidity and carbon dioxide. This disadvantage is avoided if flow of gas and mo tion of particulate solid are counter-current.
In one embodiment of the present invention, the gas temperature at the inlet to the reactor is in the range of from 10°C to 800°C, preferably from 20°C to 400°C
In one embodiment of the present invention, the average superficial velocity of the gas is in the range of from 0.005 m/s to 1 m/s, preferably 0.05 m/s to 0.2 m/s. With a higher superficial gas velocity, dust evolution may exceed a tolerable level.
Generally, the gas may be inert or oxidizing or a reactant, such as in the case of alkanols in the case of aldehyde formation. In embodiments wherein an electrode active material is made the gas is oxidizing, for example pure oxygen, oxygen-enriched air or air, oxygen-enriched air and air being preferred. An example of oxygen-enriched air is a mixture of 1 :0.5 by volume to 1 :5 by volume air : oxygen, determined at ambient conditions.
In one embodiment of the present invention, the inventive process is performed at ambient pressure or ± 50 mbar, preferably ambient pressure up to 20 mbar above ambient pressure.
In one embodiment of the present invention, the filling level of said rotary drum reactor is in the range of from 5 to 70%, preferred are 20 to 65%. The filling level is determined under neglecting the voids between particles of particulate solid.
According to the present invention, the rotary drum reactor contains the following elements:
(A) a double-wall steel drum, hereinafter also referred to as steel drum (A) or element (A), wherein the space of the outer and the inner wall is evacuated,
(B) with an electrical heating system attached to the inner wall, hereinafter also referred to as heating system (B) or element (B),
(C) internal(s) attached to the inner wall or to the front and end surfaces of a non-rotating part of said rotating drum, hereinafter also referred to as internal(s) (C) or element (C),
(D) and, optionally, a corrosion protection layer attached to the electric heating system, hereinafter also referred to as layer (D) or element (D).
Elements (A) to (D) will be described in more detail below.
Element (A) is a double-wall steel drum. In one embodiment of the present invention, the dis tance between the outer and the inner wall is in the range of from 1 to 20 cm, preferably 5 to 10 cm, determined at ambient temperature. The distance is an average value.
Each wall may have a thickness in the range of from 5 to 30 mm, preferred between 7 and 20 mm. The inner and the outer wall may have the same or different thicknesses. Preferably, the outer wall is 1.5 to 3 times thicker than the inner wall.
Outer and inner wall may be kept apart by spacers. Such spacers may have a round or polygo nal shape. The length of the spacers may be in the range of from 10 to 100 mm, preferred are 20 to 70 mm.
In one embodiment of the present invention, both outer and inner wall are from stainless steel.
The space between outer and inner wall is evacuated.“Evacuated” in the context of the present invention shall not be restricted to vacuum but also include a reduced pressure, that the pres sure in this space is in the range of from 1 to 100 mbar. The residual gas may be selected from nitrogen or noble gasses such as argon. However, the residual gas may be selected from air or oxygen and thereby cause a passivation of the hot surface of the inner wall of the drum.
The space between outer and inner wall may be empty or contain loose elements. Preferably, the space between outer and inner wall contains rock wool or porous stone.
The rotary drum reactor further comprises a heating system (B). The heating system (B) is elec tric and attached to the inner wall of the rotary drum reactor, and it may be selected from heat ing selected from resistance heating, inductive heating, and micro-wave heating.
In one embodiment of the present invention, the heating system (B) covers the inner surface of the inner wall of the drum to the extent of 70 to 100% of the inner surface of the inner wall.
In one embodiment of the present invention, the heating system (B) is attached to the inner wall through bolts or screws. In another embodiment of the present invention, the heating system (B) is drum shaped and has the same outer diameter as the inner diameter of the inner drum, upon heating and thermal expansion, the heating system is pressed to the wall of the drum due to the thermal expansion.
The region of rotary drum reactors that is exposed to the heating system is the reaction zone of such rotary drum reactor.
In one embodiment of the present invention, a corrosion protection layer (D) is attached to the heating system (B). Said layer (D) may be made from a ceramic matrix composite or an alloy selected from steels and nickel-based alloys and cobalt refractory alloys, or a metal selected from tungsten, molybdenum, iron, and nickel.
A ceramic matrix composite contains ceramic fibers, and it additionally comprises a ceramic matrix material. The fibers are in an ordered or non-ordered orientation, for example 0 90° layup or randomly criss-cross. Ceramic fibers and ceramic matrix material may have identical or different chemical compositions. In the context of the present invention, ceramic matrix compo sites comprise fibers embedded in ceramic oxide or non-oxide matrices. The bonding forces between the fibers and the matrix are comparatively low. Oxide matrix materials such as alumi num oxide are preferably in particulate form.
Ceramic fibers and ceramic matrix materials may each be selected from oxide and non-oxide ceramics. Examples of non-oxide ceramics are carbides and borides and nitrides. Particular examples of non-oxide ceramics are silicon carbide, silicon boride, silicon nitride, silicon-boron- nitride, hereinafter also referred to as SiBN, silicon carbon nitride, hereinafter also referred to as SiCN, and in particular combinations from SiC and Si3N4. Preferred are oxide ceramics, here inafter also referred to as oxide-based ceramics. Oxide ceramics are oxides of at least one ele ment selected from Be, Mg, Ca, Sr, Ba, rare earth metals, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Ga, Si, Ge, Sn, Re, Ru, Os, Ir, In, Y, and mixtures of at least two of the foregoing. Oxide-based ceramics may be selected from doped ceramics, wherein one main component is doped with up to 1 molar % components other than the main component, and from reinforced ceramics, wherein one component is the main component, for example at least 50 molar %, and one or more further components - reinforcing components - are present in ranges from 1.1 to 25 molar %. Further examples are titanates and silicates. Titanates and sili cates each may have a stoichiometric composition.
Preferred example of titanates is aluminum titanate. Preferred example of silicates is magnesi um silicate.
Examples of reinforced ceramics are reinforced alumina and reinforced zirconia. They may con tain two or more different reinforcement oxides and may thus be referred to as binary or ternary mixtures. The following binary and ternary mixtures are preferred: aluminum oxide reinforced with 1.1 to 25% by weight of one of the following: cerium oxide Ce02, ytterbium oxide Yb203, magnesia (MgO), calcium oxide (CaO), scandium oxide (SC2O3), zirconia (Zr02), yttrium oxide (Y2O3), boron oxide (B2O3), combinations from SiC and (AI2O3), or aluminum titanate. More pre ferred reinforcing components are B2O3, Zr02 and Y2O3.
Preferred zirconia-reinforced alumina is AI2O3 with from 10 to 20 mole-% Zr02. Preferred exam ples of reinforced zirconia are selected from Zr02 reinforced with from 10 to 20 mole-% CaO, in particular 16 mole-%, from 10 to 20 mole-% MgO, preferably 16 mole-%, or from 5 to 10 mole-% Y2O3, preferably 8 mole-%, or from 1 to 5 mole-% Y2O3, preferably 4 mole-%. An example of a preferred ternary mixture is 80 mole-% AI2O3, 18.4 mole-% Zr02 and 1.6 mole-% Y2O3.
Preferred fiber materials are oxide ceramic materials, carbide ceramic materials, nitride ceramic materials, SiBCN fibers, basalt, boron nitride, tungsten carbide, aluminum nitride, titania, barium titanate, lead zirconate-titanate and boron carbide. Even more preferred fiber materials are AI2O3, mullite, SiC, and Zr02 fibers.
In one embodiment the fibers are made from aluminum oxide, and the ceramic matrix composite comprises a ceramic matrix material selected from aluminum oxide, quartz, mullite, cordier- ite and combinations of at least two of the foregoing. Preferred is aluminum oxide.
Preferred are creep resistant fibers. In the context of the present invention, creep resistant fibers are fibers that exhibit minimum - or no - permanent elongation or other permanent deformation at temperatures up to 1 ,400°C.
In one embodiment of the present invention, ceramic fibers may have a diameter in the range of from 7 to 12 pm. Their length may be in the range of from 1 mm up to 1 km or even longer, so- called endless fibers. In one embodiment, several fibers are combined with each other to yarns, rovings (German: Multifilamentgarn), textile strips, hoses, or the like. In a preferred embodiment of the present invention ceramic fibers used in the present invention have a tensile strength of at least 50 MPa, preferably at least 70 MPa, more preferably at least 100 MPa, and even more preferably at least 120 MPa. A maximum value of the tensile strength of ceramic fibers used in the present invention is 3,100 MPa or even 10,000 MPa. The tensile strength may be determined with a tensile tester. Typical measuring conditions are cross-head speeds of 1.2 to 1.3 cm/min, for example 1.27 cm/min, and 7.61 cm gauge.
In one embodiment of the present invention, the matrix is made from an oxide ceramic material or a carbide. Preferred oxide ceramic materials for the matrix are AI2O3, mullite, SiC, ZrC>2 and spinel, MgAhCU.
Particularly preferred components are SiC/SiC, Zr02/ZrC>2, ZrC AhCh, AhCh/ZrC^, AI2O3/AI2O3 and mullite/mullite. The fiber material is in each foregoing case the first and the matrix the second material.
In one embodiment of the present invention, such ceramic matrix composite comprises 20 to 60 % by volume ceramic fiber.
Ceramic matric composites are porous. In many cases, the total solids content of such ceramic matrix composite is from 50 to 80% of the theoretical, the rest is air or gas due to the pores.
In one embodiment of the present invention, such ceramic matrix composite has a porosity in the range of from 20 % to 50 %; thus, such ceramic matrix composite is not gas tight in the sense of DIN 623-2.
In one embodiment of the present invention, the ceramic matrix composite comprises fibers from aluminum oxide and a ceramic selected from aluminum oxide, quartz, mullite, cordierite and combinations of at least two of the foregoing, for example aluminum oxide and mullite or aluminum oxide and cordierite. Even more preferably, the ceramic matrix composite comprises fibers from aluminum oxide and aluminum oxide ceramic.
In one embodiment of the present invention, layer (D) has a thickness in the range of from 0.5 mm to 15 mm, preferably 2 mm to 8 mm.
In one embodiment of the present invention, layer (D) covers the entire surface of element (B) that would be otherwise exposed to the reactants.
In one embodiment of the present invention, the surface of layer (D) in contact with the particu late solids inside the drum reactor is not evenly cylindrical but shaped, having circumferential, axial or otherwise oriented strips or a checked pattern or any other pattern.
In one embodiment of the present invention, the surface of layer (D) in contact with the particu late solids inside the drum reactor is coated, for example with a ceramic coating. The coating of layer (D) may have a barrier function or an abrasion protection function, or both functions.
Rotary drum reactors further contain one or more elements (C), for example 2 to 3. Such inter nals) (C) are attached to the inner wall, or to the front and end surfaces of a non-rotating part of said rotating drum reactor. Preferably, they are attached to the inner wall.
Internal(s) (C) may be selected from baffles, plough shares, blades or shovels. Internals (C) may expand entirely from the wall to the center of the rotary drum or they may expand partially from the wall to center of the rotating drum. Preferably, from 1 to 10 internals (C) are distributed along the axis of the rotating drum and from 1 to 10 internals (C) are distributed along the cir cumference of the rotating drum. In total, from 2 to 100 internals (C) may be distributed inside the rotating drum, preferably, and preferably from 4 to 20 internals (C) may be distributed inside the rotating drum in a symmetric orientation.
In one embodiment of the present invention, the length of the drum is from 0.5 to 20 m, prefera bly from 1 to 10 m.
In one embodiment of the present invention, the diameter of the drum is in the range of from 0.25 to 5 m.
By performing the inventive process, a reduction of heating time required is achieved. Further more, only a small share of fines is generated.
A further aspect of the present invention relates to rotary drum reactors in which the inventive process may be advantageously performed. Such rotary drum reactors are also referred to as inventive rotary drum reactors. Inventive rotary drum reactors contain the following elements, hereinafter also referred to as elements (A) to (D):
(A) a double-wall steel drum wherein the space between the outer and the inner wall is evac uated,
(B) with an electrical heating system attached to the inner wall,
(C) internal(s) attached to the inner wall, or to the front and end surfaces of a non-rotating part of said rotating drum,
(D) and, optionally, a corrosion protection layer attached to the electric heating system. Elements (A) to (D) have been described in more detail above.
In one embodiment of the present invention, at least some of the internals (C) serve as scrapers by removing incrustations of, e.g., sintered particulate solids from the inner walls. Such internals (C) that serve as scrapers are preferably those that are at the end of the reaction zone of an inventive rotary drum reactor.
In a preferred embodiment, inventive rotary drum reactors may further comprise elements such as gaskets, an entry system for introduction of particulate sold and a removal system for react ed particulate solid.
The invention is further explained by a drawing.
Brief description of the drawing (Figure 1):
Gas enters the exemplified rotary drum reactor through“gas in” and leaves through“gas out”. Particulate solid - for example a mixture from lithium source and precursor for an electrode ac tive material - enters through the left. The respective electrode active material leaves bottom right.
The gaskets support the axis.
Brief description of the drawings: Figure 1 :
A: evacuated space between the outer and the inner wall
B1 : electric heating system
C: internals
L: Filling level Figure 2: Example of an inventive drum reactor. Flow of gas and motion of particles are co-current. Four pairs of baffles (C). B2: Electric heating system.
A: evacuated space between the outer and the inner wall
The 4 pairs of internals move the particles in the course of the rotation of the rotary drum reac- tor. M: motor to effect the rotation of the drum.
Claims
1. Process for performing an endothermic reaction in a rotary drum reactor at a temperature in the range of from 300 to 1500°C, said process comprising the step of introducing at least one particulate material into said rotary drum reactor and moving it through the rota ry drum reactor with a flow of a gas, wherein said rotary drum reactor contains the follow ing elements:
(A) a double-wall steel drum wherein the space of the outer and the inner wall is evacu ated,
(B) with an electrical heating system attached to the inner wall,
(C) internal(s) attached to the inner wall, or to the front and end surfaces of a non
rotating part of said rotating drum,
(D) and, optionally, a corrosion protection layer attached to the electric heating system.
2. Process according to claim 1 wherein such rotary drum reactor comprises a layer (D) made from a ceramic matrix composite or an alloy selected from steels and nickel-based alloys and cobalt refractory alloys, or a metal selected from tungsten, molybdenum, iron, and nickel.
3. Process according to claim 2 wherein the ceramic matrix composite comprises fibers from aluminum oxide or mullite and a ceramic selected from aluminum oxide, mullite, zirconia, yttria, cordierite and combinations of at least two of the foregoing.
4. Process according to any of claims 1 to 3 wherein the reaction enthalpy under standard conditions is in the range of from 50 to 600 kJ/kg particulate matter.
5. Process according to any of claims 1 to 4 wherein two different particulate solids are in troduced simultaneously into said rotary drum reactor, one being selected from an inor ganic lithium compound selected from U2O, LiOH and U2CO3 and the other being selected from a mixed oxide, carbonate, hydroxide or oxyhydroxide of nickel and at least one tran sition metal selected from cobalt and manganese and containing, optionally, at least one further metal selected from Mg, Ca, Al, Ba, B, Ti, Zr, Nb, W, Mo, and Y.
6. Process according to any of the preceding claims where the filling level of said rotary drum reactor is in the range of from 5 to 70%.
7. Process according to any of the preceding claims wherein the gas flow comprises air or oxygen-enriched air or oxygen moving counter-currently with respect to the particulate sol- ids.
8. Process according to any of the preceding claims wherein at least some of the internals (C) serve as scrapers.
9. Process according to any of the preceding claims wherein the average residence time of the particulate material is in the range of from 10 minutes to 12 hours.
10. Rotary drum reactor containing the following elements:
(A) a double-wall steel drum wherein the space between the outer and the inner wall is evacuated,
(B) with an electrical heating system attached to the inner wall,
(C) internal(s) attached to the inner wall, or to the front and end surfaces of a non
rotating part of said rotating drum,
(D) and, optionally, a corrosion protection layer attached to the electric heating system.
11. Rotary drum reactor according to claim 10 wherein such drum reactor comprises a layer (D) made from a ceramic matrix composite or an alloy selected from steels and nickel- based alloys and cobalt refractory alloys, or a metal selected from tungsten, molybdenum, iron, and nickel.
12. Rotary drum reactor according to claim 11 wherein the ceramic matrix composite com prises fibers from aluminum oxide or mullite and a ceramic selected from aluminum oxide, mullite, zirconia, yttria, cordierite and combinations of at least two of the foregoing.
13. Rotary drum reactor according to any of claims 10 to 12 wherein the average distance of the two walls of double-wall steel drum are in the range of from 1 to 20 cm, determined at ambient temperature.
14. Rotary drum reactor according to any of claims 10 to 13 wherein the otherwise evacuated space contains rock wool or porous stone.
15. Rotary drum reactor according to any of claims 10 to 14 wherein the drum is heated
through electrical heating selected from resistance heating, inductive heating, and micro- wave heating.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111394A (en) * | 1959-03-13 | 1963-11-19 | Nuclear Materials & Equipment | Apparatus for treating chemical compounds |
WO2007141558A2 (en) * | 2006-06-09 | 2007-12-13 | Statoilhydro Asa | Carbon nano-fibre production |
CN201686500U (en) * | 2010-03-22 | 2010-12-29 | 昆明理工大学 | Microwave rotary kiln used for calcining chemical uranium concentrate |
CN105789614A (en) * | 2016-04-22 | 2016-07-20 | 柳州凯通新材料科技有限公司 | Preparation method of layered nickel cobalt lithium manganate cathode material |
-
2020
- 2020-05-13 WO PCT/EP2020/063287 patent/WO2020234075A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111394A (en) * | 1959-03-13 | 1963-11-19 | Nuclear Materials & Equipment | Apparatus for treating chemical compounds |
WO2007141558A2 (en) * | 2006-06-09 | 2007-12-13 | Statoilhydro Asa | Carbon nano-fibre production |
CN201686500U (en) * | 2010-03-22 | 2010-12-29 | 昆明理工大学 | Microwave rotary kiln used for calcining chemical uranium concentrate |
CN105789614A (en) * | 2016-04-22 | 2016-07-20 | 柳州凯通新材料科技有限公司 | Preparation method of layered nickel cobalt lithium manganate cathode material |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 201127, Derwent World Patents Index; AN 2011-B31570, XP002793756 * |
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