CN104925757A - Coprecipitation preparation method for nickel-cobalt-tungsten-molybdenum composite oxide - Google Patents
Coprecipitation preparation method for nickel-cobalt-tungsten-molybdenum composite oxide Download PDFInfo
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- CN104925757A CN104925757A CN201510261994.7A CN201510261994A CN104925757A CN 104925757 A CN104925757 A CN 104925757A CN 201510261994 A CN201510261994 A CN 201510261994A CN 104925757 A CN104925757 A CN 104925757A
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Abstract
The invention discloses a coprecipitation preparation method for nickel-cobalt-tungsten-molybdenum composite oxide. The coprecipitation preparation method comprises the following steps of preparing cobalt salt or nickel salt solution, adding one of molybdenum salt solution and tungsten salt solution or mixed solution of molybdenum salt and tungsten salt to one of the cobalt salt solution and the nickel salt solution or mixed solution of cobalt salt and nickel salt, and stirring for more than 30 minutes so as to enable composite oxide of corresponding metal to precipitate; then, filtering, washing and drying, and finally, calcining at 300 to 800 DEG C to obtain cobalt-molybdenum, nickel-molybdenum, cobalt-tungsten, nickel-tungsten, cobalt-molybdenum-tungsten, nickel-molybdenum-tungsten or nickel-cobalt-tungsten-molybdenum composite oxide. The coprecipitation preparation method disclosed by the invention has the advantages that inorganic salts are adopted as raw materials, and precipitator does not need to be added; the synthesis process is simple, the period is short, the cost is low and no harmful gas is emitted; the nickel-cobalt-tungsten-molybdenum composite oxide can be used for preparing petroleum hydrofining catalysts and can also be used for preparing propane oxidative dehydrogenation catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of composite oxides, particularly a kind of not additional precipitation agent obtains the co-precipitation preparation method of nickel cobalt molybdenum tungsten composite oxides.
Background technology
At present, the preparation method of the composite oxides of nickel cobalt molybdenum tungsten has solid phase method, hydrothermal synthesis method, sol-gel method etc.All there is many deficiencies in above synthetic method: in Solid phase synthesis, each raw material reaction is incomplete, and product component is uneven, and powder reuniting is very serious, later stage needs to grind again, is inevitably mixed into again the impurity that the apparatus such as abrading-ball, ball mill brings in process of lapping.Due to needs condition of high voltage, so high to equipment requirements, also there is potential safety hazard in hydrothermal method.All very expensive when sol-gel method raw material is metal alkoxide, acetate, cost is very high; When adopting vitriol, nitrate as raw material, then have the obnoxious flavour such as sulphur and nitrogen oxide when gel is calcined and discharge; Meanwhile, the method technological process needs precise hard_drawn tuhes, otherwise is difficult to obtain gel; Powder productive rate is also lower, is not suitable for mass scale operation.
Liu Zhi bravely waits people to prepare rose vitriol and ammonium molybdate solution respectively, after the above two kinds of solution of mixing, by the pH value to 4. about 0 of nitric acid and ammoniacal liquor regulator solution, then stir, heating evaporation to thick, be transferred in crucible, in an oven in 110 DEG C of drying 12 h, then in air atmosphere, in 200 DEG C of roasting 2 h in retort furnace, 500 DEG C of roasting 7 h, naturally cool to room temperature, obtain required catalyst cobalt molybdenum oxide.This technology needs regulable control pH value, and need the roasting in two stages, the cycle is very long, the more important thing is the discharge that must have oxysulfide obnoxious flavour in calcination process.
At present, catalyst field is more common in the preparation of cobalt nickel molybdenum tungsten Series oxides, and the general carrier that adopts floods in cobalt nickel molybdenum tungsten metal salt solution, then roasting.But cobalt nickel molybdenum tungsten metal-salt mostly is sulfate and nitrate, therefore, must have sulphur, oxynitride noxious gas emission in calcination process.
The three components composite oxides of cobalt, nickel and molybdenum or tungsten, the rare report of current document, cobalt, nickel, molybdenum, tungsten Four composition composite oxides then rarer report.
Summary of the invention
For the problems referred to above, the object of this invention is to provide a kind of simple for process, the cycle is short, cost is low, free of contamination compound precipitation legal system is for nickel cobalt molybdenum tungsten composite oxides.
The present invention, in preparation process, by improving cobalt salt, nickel salt, molybdenum salt, tungsten salt solution to suitable concentration, without the need to additional precipitation agent, can obtain the serial composite oxides of nickel cobalt molybdenum tungsten completely.
To achieve these goals, the concrete technical scheme that the present invention adopts is:
(1) nickel salt, cobalt salt, molybdenum salt or tungsten salt are dissolved in deionized water, are mixed with the solution that strength of solution is 0.2 ~ 2.0 mol/L respectively;
(2) molybdenum salts solution is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, obtain cobalt molybdenum and nickel molybdenum two components precipitate respectively; Tungsten salt solution is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, obtain cobalt tungsten and nickel tungsten two components precipitate respectively; The mixing solutions of molybdenum salt and tungsten salt is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, respectively obtained cobalt molybdenum tungsten and nickel molybdenum tungsten three components precipitation; The mixing solutions of molybdenum salt and tungsten salt joins in the mixing solutions of cobalt salt and nickel salt, Keep agitation 30 minutes, then obtained nickel cobalt molybdenum tungsten Four composition precipitation; By the precipitation obtained through filtering, washing, dry, obtain oxide precursor powder; Or in a kind of or cobalt salt heat-resistant inorganic oxide carrier joined in corresponding cobalt salt solution or nickel salt solution and the mixing solutions of nickel salt, stir more than 30 minutes, after adding the mixing solutions of a kind of or molybdenum salt and the tungsten salt in molybdenum salts solution or tungsten salt solution, the composite oxides precipitation of respective metal will be obtained, then filter, wash, dry, obtain oxide precursor powder;
(3) presoma is calcined 0.5-4.0 hour at 300 ~ 800 DEG C, namely obtain the cobalt molybdenum oxide of non-loading type and loading type, nickel molybdenum oxide, cobalt tungsten oxide, nickel tungsten oxide, cobalt molybdenum tungsten oxide, nickel molybdenum tungsten oxide or nickel cobalt molybdenum tungsten oxide powder.
Described molybdenum salt comprises Sodium orthomolybdate or ammonium paramolybdate; Described tungsten salt comprises sodium wolframate or ammonium metawolframate; Described cobalt salt comprises cobalt chloride, rose vitriol or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Described nickel salt comprises nickelous chloride, single nickel salt or nickelous nitrate.
Described heat-resistant inorganic oxide carrier is one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, alumina-silica magnesium, silica-alumina, silica-magnesias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, synthesis zeolite, non-zeolitic molecular sieves or clay.
Outstanding advantages of the present invention is: raw material adopts inorganic salt, need not additional precipitation agent, and synthesis technique is simple, and the cycle is short, and cost is low, non-environmental-pollution.
Nickel cobalt molybdenum tungsten series composite oxides prepared by the present invention can be used for preparing oil Hydrobon catalyst, also can be used for oxidative dehydrogenation of propane catalyzer.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of cobalt molybdenum oxide.
Fig. 2 is the scanning electron microscope diagram of nickel molybdenum oxide.
Fig. 3 is the scanning electron microscope diagram of cobalt molybdenum tungsten oxide.
Fig. 4 is the scanning electron microscope diagram of nickel molybdenum tungsten oxide.
Fig. 5 is the scanning electron microscope diagram of cobalt nickel molybdenum tungsten oxide.
Embodiment
Invention is further illustrated by specific embodiment below in conjunction with accompanying drawing.
Embodiment 1:
Accurately take rose vitriol (CoSO
47H
2o) 1.124g, Sodium orthomolybdate (Na
2moO
42H
2o) 0.968g, is dissolved in 10ml distilled water respectively, is made into the solution that concentration is 0.4 mol/L; Then by Na
2moO
4dropwise is added drop-wise to CoSO
4in solution, stir simultaneously, observe in solution and generate purple precipitation immediately.All solution all drips rear continuation and stirs 0.5h, after reaction terminates, carry out suction filtration, and it is colourless to be washed with distilled water to filtrate, the clean post-drying of washing of precipitate to product, by presoma at 400 DEG C of calcining 2h, obtains cobalt molybdenum oxide.As can be seen from the scanning electron microscope diagram of Fig. 1, the primary particle size of cobalt molybdenum composite oxides is less than 100nm, and crystal grain is self-assembled into bar-shaped, excellent long about 500nm, excellent diameter about 100nm.
Embodiment 2:
Accurately take nickelous chloride (NiCl
36H
2o) 19.01g, Sodium orthomolybdate (Na
2moO
42H
2o) 9.68g, is dissolved in 100ml distilled water respectively, is made into the solution that concentration is 0.8 and 0.4mol/L, then by Na
2moO
4dropwise drips NiCl
3solution in, stir simultaneously, observe in solution and generate greenish precipitate immediately.All solution all drips rear continuation and stirs half an hour, after reaction terminates, carry out suction filtration, and it is colourless to be washed with distilled water to filtrate, the clean post-drying of washing of precipitate to product, by presoma at 500 DEG C of calcining 2h, obtains nickel molybdenum oxide.As can be seen from the scanning electron microscope diagram of Fig. 2, nickel molybdenum composite oxides particle diameter is less than 50nm, and crystal grain is self-assembled into bar-shaped, excellent long about 50-200nm, excellent diameter about 50nm.
Embodiment 3:
Accurately take rose vitriol (CoSO
47H
2o) 11.2360g, Sodium orthomolybdate (Na
2moO
42H
2o) 4.8653g and sodium wolframate (Na
2wO
42H
2o) 6.6270g, is dissolved in 50ml distilled water respectively, is made into the solution that concentration is 0.8,0.4 and 0.4 mol/L respectively, then by Na
2moO
4solution and Na
2wO
4solution mixes, then mixing solutions is dropwise added drop-wise to NiCl
3in solution, stir simultaneously, observe in solution and generate purple precipitation immediately.All solution all drips rear continuation and stirs 0.5h, after reaction terminates, carry out suction filtration, and it is colourless to be washed with distilled water to filtrate, the clean post-drying of washing of precipitate to product, by presoma at 300 DEG C of calcining 2h, obtains cobalt molybdenum tungsten oxide.From the scanning electron microscope diagram of Fig. 3, cobalt molybdenum tungsten composite oxides primary particle size is less than 50nm, the lamellar structure that little crystal grain formation arranged together is large.
Embodiment 4:
Accurately take nickelous chloride (NiCl
36H
2o) 9.51g, Sodium orthomolybdate (Na
2moO
42H
2o) 4.84g and sodium wolframate (Na
2wO
42H
2o) 6.60g, is dissolved in 100ml distilled water respectively, is made into the solution that concentration is 0.4,0.2 and 0.2 mol/L respectively, then by Na
2moO
4solution and Na
2wO
4solution mixes, then mixing solutions is dropwise added drop-wise to NiCl
3in solution, stir simultaneously, observe in solution and generate greenish precipitate immediately.All solution all drips rear continuation and stirs 0.5h, after reaction terminates, carry out suction filtration, and it is colourless to be washed with distilled water to filtrate, the clean post-drying of washing of precipitate to product, by presoma at 600 DEG C of calcining 2h, obtains nickel molybdenum tungsten oxide.From the scanning electron microscope diagram of Fig. 4, nickel molybdenum tungsten composite oxides crystal grain is less than 100nm, and little crystal grain forms irregular lumps, and agglomerate is about 50-200nm.
Embodiment 5:
Accurately take rose vitriol (CoSO
47H
2o) 11.24, nickelous chloride (NiCl
36H
2o) 9.51g, Sodium orthomolybdate (Na
2moO
42H
2o) 4.84g and sodium wolframate (Na
2wO
42H
2o) 6.60g, is dissolved in respectively in 100ml distilled water, is made into concentration respectively, and the solution of 0.4,0.4,0.2 and 0.2 mol/L, then by Na
2moO
4solution and Na
2wO
4solution mixes, then mixing solutions is dropwise added drop-wise to CoSO
4and NiCl
3in solution, stir simultaneously, observe in solution and generate lead precipitation.All solution all drips rear continuation and stirs 0.5h, after reaction terminates, carry out suction filtration, and it is colourless to be washed with distilled water to filtrate, the clean post-drying of washing of precipitate to product, by presoma at 600 DEG C of calcining 2h, obtains nickel molybdenum tungsten oxide.From the Scanning Electron microphotograph of Fig. 5, nickel cobalt molybdenum tungsten composite oxides are corynebacterium, particle diameter 100-300nm.
Those of ordinary skill in the art can understand, and in protection scope of the present invention, modifies for above-described embodiment, and it is all possible for adding and replacing, and it does not all exceed protection scope of the present invention.
Claims (7)
1. a co-precipitation preparation method for nickel cobalt molybdenum tungsten composite oxides, is characterized in that, comprise the following steps:
(1) preparation of solution: be dissolved in deionized water by nickel salt, cobalt salt, molybdenum salt or tungsten salt, is mixed with the solution that concentration is 0.2 ~ 2.0 mol/L respectively;
(2) preparation of presoma: molybdenum salts solution is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, obtains cobalt molybdenum and nickel molybdenum two components precipitate respectively; Tungsten salt solution is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, obtain cobalt tungsten and nickel tungsten two components precipitate respectively; The mixing solutions of molybdenum salt and tungsten salt is joined in cobalt salt solution or nickel salt solution, Keep agitation 30 minutes, respectively obtained cobalt molybdenum tungsten or nickel molybdenum tungsten three components precipitation; The mixing solutions of molybdenum salt and tungsten salt is joined in the mixing solutions of cobalt salt and nickel salt, Keep agitation 30 minutes, then obtained nickel cobalt molybdenum tungsten Four composition precipitation; By the precipitation obtained through filtering, washing, dry, obtain oxide precursor powder;
(3) preparation of oxide compound: by oxide precursor at 300 ~ 800 DEG C of calcining 0.5-4.0 hour, namely obtain cobalt molybdenum oxide, nickel molybdenum oxide, cobalt tungsten oxide, nickel tungsten oxide, cobalt molybdenum tungsten oxide, nickel molybdenum tungsten oxide or nickel cobalt molybdenum tungsten oxide powder.
2. co-precipitation preparation method according to claim 1, it is characterized in that in step (2), heat-resistant inorganic oxide carrier being joined in the mixing solutions of a kind of or cobalt salt in cobalt salt solution or nickel salt solution and nickel salt, stir more than 30 minutes, after adding the mixing solutions of a kind of or molybdenum salt and the tungsten salt in molybdenum salts solution or tungsten salt solution, the composite oxides precipitation of respective metal will be obtained, then filter, wash, dry, obtain oxide precursor powder.
3. co-precipitation preparation method according to claim 1, is characterized in that described molybdenum salt comprises Sodium orthomolybdate or ammonium paramolybdate.
4. co-precipitation preparation method according to claim 1, is characterized in that described tungsten salt comprises sodium wolframate or ammonium metawolframate.
5. co-precipitation preparation method according to claim 1, is characterized in that described cobalt salt comprises cobalt chloride, rose vitriol or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
6. co-precipitation preparation method according to claim 1, is characterized in that described nickel salt comprises nickelous chloride, single nickel salt or nickelous nitrate.
7. co-precipitation preparation method according to claim 1, it is characterized in that, described heat-resistant inorganic oxide carrier is one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, alumina-silica magnesium, silica-alumina, silica-magnesias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, synthesis zeolite, non-zeolitic molecular sieves or clay.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107790161A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | The method for preparing hydrotreating catalyst |
| CN110038581A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing Hydrobon catalyst |
| CN110038625A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing hydrocracking catalyst |
| CN115430839A (en) * | 2022-08-25 | 2022-12-06 | 云南电网有限责任公司电力科学研究院 | Preparation method of nickel-molybdenum intermetallic compound and prepared nickel-molybdenum intermetallic compound |
-
2015
- 2015-05-21 CN CN201510261994.7A patent/CN104925757A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SAGRARIO M. MONTEMAYOR ET AL.: "Electrochemical characteristics of lithium insertion in several 3D metal tungstates (MWO4,M=Mn,Co,Ni and Cu) prepared by aqueous reactions", 《CERAMICS INTERNATIONAL》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107790161A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | The method for preparing hydrotreating catalyst |
| CN107790161B (en) * | 2016-08-29 | 2020-03-17 | 中国石油化工股份有限公司 | Process for preparing hydroprocessing catalysts |
| CN110038581A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing Hydrobon catalyst |
| CN110038625A (en) * | 2018-01-16 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing hydrocracking catalyst |
| CN110038581B (en) * | 2018-01-16 | 2022-04-08 | 中国石油化工股份有限公司 | Method for preparing hydrofining catalyst |
| CN110038625B (en) * | 2018-01-16 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN115430839A (en) * | 2022-08-25 | 2022-12-06 | 云南电网有限责任公司电力科学研究院 | Preparation method of nickel-molybdenum intermetallic compound and prepared nickel-molybdenum intermetallic compound |
| CN115430839B (en) * | 2022-08-25 | 2023-07-07 | 云南电网有限责任公司电力科学研究院 | Preparation method of nickel-molybdenum intermetallic compound and prepared nickel-molybdenum intermetallic compound |
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