CN107001038B - 通过喷雾热解制备金属氧化物的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 15
- 238000005118 spray pyrolysis Methods 0.000 title claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000443 aerosol Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000012387 aerosolization Methods 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
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- 150000001875 compounds Chemical class 0.000 description 4
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
-
- 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/34—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of sprayed or atomised solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/308—Thermal decomposition of nitrates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical Kinetics & Catalysis (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
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Abstract
本发明提供通过喷雾热解制备金属氧化物粉末的方法,其中将包含氨和气溶胶的混合物引入反应空间的高温区域内,并且在其中在含氧气氛下反应,并且随后将固体分离出来,其中气溶胶通过用雾化气雾化含有金属化合物的溶液而获得。
Description
技术领域
本发明涉及通过喷雾热解制备金属氧化物的方法。
背景技术
喷雾热解和火焰喷雾热解是确定的制备金属氧化物的方法。在喷雾热解中,将细小液滴形式的金属化合物引入高温区,在其中它们被氧化和/或水解以产生金属氧化物。该方法的特殊形式是火焰喷雾热解,其中液滴被供应到由燃烧气体和含氧气体点燃而形成的火焰。
本领域技术人员可以获得许多反应参数,以改变所制备的金属氧化物的物理化学性质。例如,温度、金属化合物的浓度、反应混合物的停留时间和流速影响金属氧化物的结构。
特别是在工业规模转化时,发现形成了不需要的产物,例如以中空珠粒的形式,或者金属氧化物颗粒的尺寸分布非常宽。因此,人们正在寻找尽量减少这些缺点的方法。
发明内容
本发明提供一种通过喷雾热解制备金属氧化物粉末的方法,其中,包含氨和气溶胶的混合物被引入到反应空间的高温区内,并在其中的含氧气氛下反应,然后将固体分离出来,其中通过雾化气,优选氮气或空气,雾化含有金属化合物的溶液而获得所述气溶胶。
根据本发明的方法可以排除通过喷雾热解制备组成是LixLa3Zr2MyO8.5+0.5x+z的金属氧化物粉末的方法,其中6.5≤x≤8,0≤y≤0.5,对于M=Hf、Ga、Ge、Nb、Si、Sn、Sr、Ta、Ti,z=2y;对于M=Sc、V、Y,z=1.5y;对于M=Ba、Ca、Mg、Zn,z=y,其中包含氨和气溶胶(其中气溶胶含有金属化合物和雾化气)的混合物被引入反应空间的高温区内,在其中的含氧气氛下反应,并且随后分离固体。
类似地,根据本发明的方法可以排除制备组成是LixLa3Zr2AlyO8.5+0.5x+1.5y的金属氧化物粉末的方法,其中6≤x≤7,0.2≤y≤0.5,其中溶液或各自含有一种或多种锂、镧、铝和锆的化合物的多种溶液,其以对应于化学计量的浓度并且以细小液滴的形式引入在反应空间内燃烧的火焰中,火焰通过将含氧气体和与氧反应时形成水的燃烧气体引入反应空间并在其中点燃而形成,并且随后将固体与雾状或气态物质分离。
氨的浓度优选是使用的金属的0.5-5.0kg NH3/kg,更优选1.5-3.5kg/kg。在这些范围内,对于待制备的金属氧化物颗粒的均匀性的影响最大。
在优选的实施方案中,向其内引入混合物的高温区域是通过含氧气体和燃烧气体反应所形成的火焰,燃烧气体优选是在与氧的反应中形成水的燃烧气体。
所使用的燃烧气体可以是氢气、甲烷、乙烷、丙烷、丁烷及其混合物。优选使用氢气。
含氧气体通常是空气。在根据本发明的方法中,应选择氧气的量,从而至少足以使燃烧气体和所有金属化合物完全转化。使用过量的氧气通常是有利的。该过量值合适地表示成存在的氧气与燃烧气体燃烧所需要的氧气的比例,并被定义为λ。λ优选是1.5-6.0,更优选2.0-4.0。
图1、2A和2B显示将原料引入反应空间内的可能布置示意图,其中:1=含金属化合物的溶液,2=雾化气,3=氨,4=空气,5=燃烧气体,A=反应室壁。
在特定的实施方案中,火焰和混合物在反应空间内至少部分地在空间上彼此分离。图2B显示了这种布置的示意图,其中钟罩B包围引入到反应空间内的混合物。由此制备的金属氧化物颗粒在粒度分布方面具有特别高的均匀性。
在该实施方案中,当火焰的平均速度v火焰大于混合物的平均速度v混合物时,可以进一步提高均匀性方面的积极效果。更优选地,2≤v火焰/v混合物≤10;最优选地,3≤v火焰/v混合物≤5。速度图是标准化的速度。通过将具有单位m3(STP)/h的体积流量除以横截面积来得到它们。
在根据本发明的方法中,将一种或多种溶液以细小液滴的形式引入反应空间内。优选地,细小液滴的中值液滴尺寸是1-120μm,更优选30-100μm。通常使用单个或多个喷嘴产生液滴。
为了达到溶解度,并且为了获得溶液雾化所需的合适粘度,可以加热溶液。原则上,可以使用可氧化的所有可溶性金属化合物。
优选地,金属化合物的金属成分选自Ag、Al、B、Ba、Ca、Cd、Co、Cr、Cu、Fe、Ga、Ge、Hf、In、Li、Mg、Mn、Mo、Nb、Ni、Pd、Rh、Ru、Sc、Si、Sn、Sr、Ta、Ti、V、Y和Zn。原则上,也可以使用多种金属成分,从而得到混合氧化物。
这些可以是无机金属化合物,例如硝酸盐、氯化物、溴化物,或有机金属化合物,例如醇盐或羧酸盐。所使用的醇盐优选可以是乙醇盐、正丙醇盐、异丙醇盐、正丁醇盐和/或叔丁醇盐。所使用的羧酸盐可以是基于乙酸、丙酸、丁酸、己酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、辛酸、2-乙基己酸、戊酸、癸酸和/或月桂酸的化合物。在有机金属化合物组中,优选使用2-乙基己酸酯或月桂酸酯。溶液可以包含一种或多种无机金属化合物、一种或多种有机金属化合物或无机和有机金属化合物的混合物。
在优选的实施方案中,至少一种金属化合物是硝酸盐。由此制备的金属氧化物颗粒在粒度分布方面具有特别高的均匀性。
优选地,溶剂可以选自水、C5-C20烷烃、C1-C15烷烃羧酸和/或C1-C15烷醇。所使用的有机溶剂或所使用的有机溶剂混合物的成分可以优选是醇,例如甲醇、乙醇、正丙醇、异丙醇、正丁醇或叔丁醇;二醇,例如乙二醇、戊二醇、2-甲基戊烷-2,4-二醇;C1-C12羧酸,例如乙酸、丙酸、丁酸、己酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、辛酸、2-乙基己酸、戊酸、癸酸、月桂酸。此外,可以使用苯、甲苯、石脑油和/或汽油。
优选使用水溶液,水溶液被理解为是指其中水是溶剂混合物的主要成分或其中仅水是溶剂的溶液。
所用溶液的浓度没有特别限制。如果仅存在一种含有所有混合氧化物组分的溶液,则基于氧化物的总和,浓度通常是1-50重量%,优选3-30重量%,最优选5-20重量%。
实施例
根据DIN ISO 9277,确定BET表面积。d50来自体积-平均尺寸分布的累积分布曲线。这通常由激光衍射确定。在本发明的上下文中,来自Cilas的Cilas 1064仪器用于此目的。d50是50%的颗粒在所示尺寸范围内的值。
使用的金属化合物是各自的硝酸盐。在每种情况下,进行没有氨的实施例(后缀0;比较例)和有氨的实施例(后缀1;本发明的实施例)。
实施例Mn0
用5m3(STP)/h的空气作为雾化气,将2kg/h的锰浓度是15.3重量%的硝酸锰溶液通过两相喷嘴雾化进在反应空间内燃烧的火焰。火焰是由10m3(STP)/h的氢气和30m3(STP)/h的空气反应形成的。冷却后,在过滤器中将金属氧化物粉末与气态物质分离。
类似地进行实施例Co0、Ni0、Zr0、La0、Al0和Ce0。原料的数量列于表中。
实施例Mn1
与Mn0一样,不同的是,除了溶液和喷雾空气之外,另外将0.6kg/h的氨雾化到反应空间内。
类似地进行实施例Co1、Ni1、Zr1、La1、Al1和Ce1。原料数量列于表中。
通过根据本发明的方法制备的金属氧化物粉末具有更低的BET表面积和平均粒度分布值。
Claims (6)
1.通过喷雾热解制备金属氧化物粉末的方法,其特征在于:
将包含氨和气溶胶的混合物引入反应空间的高温区域内,其中,所述气溶胶通过用雾化气雾化含有金属化合物的溶液而获得,并且
在其中在含氧气氛下反应,并且
随后将固体分离出来;
其中,向其中引入所述混合物的所述高温区域是通过含氧气体和燃烧气体的反应而形成的火焰。
2.如权利要求1所述的方法,其特征在于:
氨的浓度是使用的金属的0.5-5.0kg NH3/kg。
3.如权利要求2所述的方法,其特征在于:
所述火焰和所述混合物在反应空间内至少部分地在空间上彼此分离。
4.如权利要求3所述的方法,其特征在于:
以下公式适用于所述火焰的平均速度与所述混合物的平均速度的比率:
2≤v火焰/v混合物≤10。
5.如权利要求1-4任一项 所述的方法,其特征在于:
至少一种金属化合物是硝酸盐。
6.如权利要求1-5任一项 所述的方法,其特征在于:
所述金属化合物的金属成分选自Ag、Al、B、Ba、Ca、Cd、Co、Cr、Cu、Fe、Ga、Ge、Hf、In、Li、Mg、Mn、Mo、Nb、Ni、Pd、Rh、Ru、Sc、Si、Sn、Sr、Ta、Ti、V、Y和Zn。
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