CN103771542B - Preparation method for high-heat stability cobalt oxide with large specific surface - Google Patents
Preparation method for high-heat stability cobalt oxide with large specific surface Download PDFInfo
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- CN103771542B CN103771542B CN201410031002.7A CN201410031002A CN103771542B CN 103771542 B CN103771542 B CN 103771542B CN 201410031002 A CN201410031002 A CN 201410031002A CN 103771542 B CN103771542 B CN 103771542B
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Abstract
The invention discloses a preparation method for high-heat stability cobalt oxide with a large specific surface. According to the method, a polyhydric alcohol is introduced to adjust a precursor sedimentation process; multi-step temperature-changing aging enables the polyhydric alcohol to enter a precursor according to suitable manner and quantity to generate a strong mutual effect, so that the precursor with a specific structure property is obtained, the specific surface area is kept after roasting and the heat stability is good; the specific surface area of the cobalt oxide prepared by the invention is 240-280m<2>/g; after the cobalt oxide is roasted at an air atmosphere at 650 DEG C for 24 hours, the specific surface area is still greater than 180m<2>/g; the cobalt oxide can be used as a catalyst or a catalyst carrier in a plurality of catalytic reactions.
Description
Technical field
The present invention relates to a kind of preparation method of high thermal stability large specific surface cobalt/cobalt oxide, this cobalt/cobalt oxide, in the heterogeneous catalytic reaction of petrochemical complex and field of fine chemical, is mainly used as catalyzer or support of the catalyst.
Background technology
Co
3o
4be one of most important p-type semiconductor material, be widely used in optics, magnetics, lithium cell, chemical sensor and catalysis.In catalytic applications, Co
3o
4generally as catalyzer or the support of the catalyst of heterogeneous reaction, also can be used for photochemical catalysis or electrocatalysis.Such as, Co
3o
4can directly as catalyzer or be scattered in Al
2o
3, CeO
2, TiO
2on, or as carrier loaded Au, Pt, Pa etc., in multiple reactions such as CO catalytic oxidation, methane, propane, toluene, demonstrate good catalytic performance.
Co
3o
4prepare by the precipitator method, hydrothermal method, solvent-thermal method, masterplate method, micro emulsion method, thermal decomposition method and gas solid method.The precipitator method are simple to operate, and general soluble cobalt adds the presoma precipitation that precipitation agent first obtains oxyhydroxide or carbonate, obtains cobalt/cobalt oxide through high-temperature roasting.The Co of conventional preparation
3o
4specific surface area general not high, usually at 100m
2/ below g [Hu LH, Peng Q, Li YD.J Am Chem Soc, 2008,130:16136], [Hai F, et al.J Petrochem Univ, 2008,21:20], [Wang B, et al.Nat Gas Chem Indus, 2010,35:32], [Shao JJ, et al.J Fuel Chem Tech, 2012,40:229], [Xiong DS, et al.Acta Chimica Sinica, 2012,70:39], and thermostability is very poor, after experience high-temperature roasting or higher reaction temperatures, specific surface area declines a lot.Open source literature is had to report Co
3o
4specific surface area can reach 113m
2/ g [Cao CY, et al.Chin J Catal, 2012,33:1334] and 163m
2/ g [Xie XW, et al.Nature, 2009,458:746].
No matter be as catalyzer or carrier, specific surface area is all important performance perameter.Obviously, for the cobalt/cobalt oxide with same surface properties, larger specific surface area generally just shows as better catalytic performance or better carrying capacity.The preparation method that exploitation possesses the large specific surface cobalt/cobalt oxide of high thermal stability has significant application value.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the large specific surface cobalt/cobalt oxide of high thermal stability.
Technical scheme of the present invention is on the basis of traditional precipitator method, regulates presoma precipitation process by introducing polyvalent alcohol.The introducing of polyvalent alcohol can first form cobalt alkoxide species, presoma precipitation is generated afterwards by hydrolysis, polyvalent alcohol can make this process carry out at relatively high temperatures as heat-conducting medium simultaneously, the aging polyvalent alcohol that makes of the alternating temperature of multistep enters in presoma with amount by rights, to ensure that the specific surface area of presoma in roasting process subsequently farthest can be inherited by final cobalt/cobalt oxide.
The preparation method of a kind of high thermal stability large specific surface cobalt/cobalt oxide provided by the invention, comprise the steps: soluble cobalt and polyvalent alcohol mixing post-heating to 120 ~ 190 DEG C, stir, alkaline solution is dripped under protection of inert gas, the precipitation aging 6 ~ 24h first at the reaction temperatures generated, be down to aged at room temperature 2 ~ 12h, then be warming up to higher than precipitation generation temperature 10 ~ 20 DEG C of aging 2 ~ 12h; 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4 ~ 6h in air atmosphere at 350 ~ 500 DEG C, obtains high thermal stability large specific surface cobalt/cobalt oxide.
Cobalt in above-mentioned soluble cobalt is divalence cobalt, includes but not limited to Cobaltous diacetate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride or their hydrate; Polyvalent alcohol be ethylene glycol, glycerol, propylene glycol or their polymer one of them, or multiple mixture; The polyhydric alcohol solutions concentration of soluble cobalt is 0.01 ~ 0.2g/mL.
Above-mentioned alkaline solution be sodium carbonate, salt of wormwood, sodium bicarbonate the aqueous solution one of them, concentration is 0.1 ~ 0.2mol/L, and dripping quantity is 1 ~ 3 times of polyhydric alcohol solutions volume.
The specific surface area of high thermal stability large specific surface cobalt/cobalt oxide obtained above is 240 ~ 280m
2/ g, at experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is still greater than 180m
2/ g.
The multiple characterization methods such as employing XRD, IR, TEM, ultimate analysis monitor the change in above-mentioned preparation process, result shows, the cobalt hydroxide being precipitated as houghite stratiform of initial generation, the negatively charged ion that interlayer has carbanion and introduces with soluble cobalt; After multistep alternating temperature is aging, a large amount of polyvalent alcohols enters cobalt hydroxide interlayer and the interaction stronger with its generation, thus obtaining the presoma with ad hoc structure character, the final cobalt/cobalt oxide after this makes roasting has very large specific surface area, and thermostability is fine.
Effect of the present invention and benefit are: by introducing polyvalent alcohol and adopting the alternating temperature of multistep aging thus the large specific surface cobalt/cobalt oxide of acquisition high thermal stability.The present invention's operation is comparatively simple, is easy to extensive preparation.This cobalt/cobalt oxide can be used as catalyzer or support of the catalyst in multiple catalyzed reaction.Further illustrate with example below.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
The TEM figure of Fig. 1 cobalt/cobalt oxide.
The XRD figure of Fig. 2 cobalt/cobalt oxide.
The nitrogen adsorption desorption isotherm figure of Fig. 3 cobalt/cobalt oxide.
Embodiment
Embodiment 1
Be dissolved in by Cobaltous diacetate in ethylene glycol, concentration is 0.05g/mL, is heated to 150 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of ethylene glycol solution volume; The precipitation aging 24h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 160 DEG C of aging 6h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.
Utilize the means such as TEM, XRD, nitrogen adsorption desorption to characterize catalyzer, TEM figure, XRD figure, nitrogen adsorption desorption isotherm figure are shown in Fig. 1, Fig. 2 and Fig. 3.TEM figure shows the irregular fold flake that cobalt/cobalt oxide after 450 DEG C of roastings still keeps presoma to manifest, not common particulate state.Only there is Co at 36.85 degree in XRD figure
3o
4the diffraction peak of the strongest (311) crystal face, in conjunction with H
2-TPR is known, and after roasting, presoma almost changes Co into completely
3o
4, but degree of crystallinity is poor.Be 280m by nitrogen adsorption desorption isotherm through the cobalt/cobalt oxide specific surface area that multiple spot BET method calculates
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 207m
2/ g.
Comparative example 1
(adding without polyvalent alcohol) is soluble in water by Cobaltous diacetate, and concentration is 0.05g/mL, is heated to 80 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of aqueous solution volume; The precipitation aging 24h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 90 DEG C of aging 6h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 47m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 21m
2/ g.
Comparative example 2
Cobaltous diacetate is dissolved in ethylene glycol by (without Aging Step), and concentration is 0.05g/mL, is heated to 150 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of ethylene glycol solution volume; Generate precipitation suction filtration, washing immediately, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 143m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 66m
2/ g.
Comparative example 3
Cobaltous diacetate is dissolved in ethylene glycol by (aging without alternating temperature), and concentration is 0.05g/mL, is heated to 150 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of ethylene glycol solution volume; Aging 32h(is identical with digestion time total in embodiment 1 at the reaction temperatures for the precipitation generated); Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 206m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 128m
2/ g.
Embodiment 2
Be dissolved in by Cobaltous diacetate in glycerol, concentration is 0.02g/mL, is heated to 160 DEG C, and stir, under protection of inert gas, drip 0.1mol/L aqueous sodium carbonate, dripping quantity is 3 times of glycerin solution volume; The precipitation aging 24h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 170 DEG C of aging 6h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 257m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 183m
2/ g.
Embodiment 3
Cobalt chloride be dissolved in ethylene glycol, concentration is 0.03g/mL, is heated to 140 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of ethylene glycol solution volume; The precipitation aging 24h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 160 DEG C of aging 6h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 266m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 196m
2/ g.
Embodiment 4
Be dissolved in by Cobaltous diacetate in ethylene glycol, concentration is 0.05g/mL, is heated to 150 DEG C, and stir, under protection of inert gas, drip 0.2mol/L aqueous sodium carbonate, dripping quantity is 3 times of ethylene glycol solution volume; The precipitation aging 12h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 160 DEG C of aging 12h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 254m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 190m
2/ g.
Embodiment 5
Be dissolved in by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in propylene glycol, concentration is 0.02g/mL, is heated to 160 DEG C, and stir, under protection of inert gas, drip 0.2mol/L wet chemical, dripping quantity is 2 times of ethylene glycol solution volume; The precipitation aging 24h first at the reaction temperatures generated, is down to aged at room temperature 2h, then is warming up to 170 DEG C of aging 12h; Suction filtration, washing, 60 DEG C of temperature and lower than 1kPa pressure under dry; Roasting 4h in air atmosphere at 450 DEG C.The cobalt/cobalt oxide specific surface area of gained is 240m
2/ g.At experience 650 DEG C after 24h air atmosphere calcination process, specific surface area is 185m
2/ g.
Claims (3)
1. the preparation method of a high thermal stability large specific surface cobalt/cobalt oxide, it is characterized in that comprising the steps: soluble cobalt and polyvalent alcohol mixing post-heating to 120 ~ 190 DEG C, stir, alkaline solution is dripped under protection of inert gas, the precipitation generated, first aging 6 ~ 24 h at the reaction temperatures, are down to aged at room temperature 2 ~ 12 h, then are warming up to higher than aging 2 ~ 12 h of precipitation generation temperature 10 ~ 20 DEG C; 60 DEG C of temperature and lower than 1 kPa pressure under dry; At 350 ~ 500 DEG C, roasting 4 ~ 6 h in air atmosphere, obtains high thermal stability large specific surface cobalt/cobalt oxide; The polyhydric alcohol solutions concentration of above-mentioned soluble cobalt is 0.01 ~ 0.2 g/mL; Above-mentioned alkaline solution be sodium carbonate, salt of wormwood, sodium bicarbonate the aqueous solution one of them, concentration is 0.1 ~ 0.2 mol/L, and dripping quantity is 1 ~ 3 times of polyhydric alcohol solutions volume.
2. preparation method according to claim 1, is characterized in that: the cobalt in above-mentioned soluble cobalt is divalence cobalt, comprises Cobaltous diacetate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride or their hydrate; Polyvalent alcohol be ethylene glycol, glycerol, propylene glycol or their polymer one of them, or multiple mixture.
3. preparation method according to claim 1, is characterized in that: the specific surface area of high thermal stability large specific surface cobalt/cobalt oxide obtained above is 240 ~ 280 m
2/ g, at experience 650 DEG C after 24 h air atmosphere calcination process, specific surface area is still greater than 180 m
2/ g.
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| CN105399150B (en) * | 2015-11-24 | 2017-09-29 | 青岛能迅新能源科技有限公司 | Sour nickel nano material of a kind of cobalt and its preparation method and application |
| CN105399151B (en) * | 2015-11-24 | 2018-01-12 | 青岛能迅新能源科技有限公司 | A kind of preparation method of cobalt acid nickel nano material |
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