CN103936083A - Nickel magnesium composite oxide and preparation method thereof - Google Patents
Nickel magnesium composite oxide and preparation method thereof Download PDFInfo
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- CN103936083A CN103936083A CN201310023125.1A CN201310023125A CN103936083A CN 103936083 A CN103936083 A CN 103936083A CN 201310023125 A CN201310023125 A CN 201310023125A CN 103936083 A CN103936083 A CN 103936083A
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Abstract
The invention relates to a nickel magnesium composite oxide and a preparation method thereof, mainly solving problems of the low specific surface area, less pore content and nonuniform microcosmic particles of nickel magnesium composite oxides in the prior art. According to a technical scheme, the nickel magnesium composite oxide comprises a) 0.1-30 parts by weight of nickel oxide and b) 100 parts by weight of magnesium oxide, wherein the BET specific surface area of the nickel magnesium composite oxide is larger than 25 m<2>/g, the pore content is higher than 0.12 cm<3>/g, and the microcosmic particle size is between 0.5 [mu]m and 5.0 [mu]m. By adoption of the technical scheme, the problems are solved well. The preparation method thereof can be used for industrial production of the nickel magnesium composite oxide.
Description
Technical field
The present invention relates to a kind of nickel-magnesia mixed oxide and preparation method thereof.
Background technology
Composite oxide of metal, the oxide compound especially with perovskite typed, spinel type or green stone type crystal structure, there is good optics, electricity, magnetic performance, important laserable material, pyroelectricity material, piezoelectric and strong magnetic material, in traditional industry and modern high technology, all there is important purposes, apply very extensive.Wherein, nickel-magnesia mixed oxide because its preparation is simple, excellent property, environmental protection, the advantage such as cheap, can be used as sensor, catalyzer and sorbent material etc.In addition, in gas chemical industry's industry, via methane reforming reaction preparing synthetic gas, then by the process of synthetic gas synthesis of organic chemical product as an important channel of methyl hydride catalyzed conversion and be subject to extensive concern.Loading type nickel-based reforming catalyst has the activity and selectivity suitable with loaded noble metal catalyst, and price is more cheap again, thereby having good application prospect, many investigators have carried out a large amount of research on various carriers, auxiliary agent and preparation condition etc. to the impact of catalyst performance.Existing research points out, MgO is a kind of good base catalysis agent carrier, and the nickel-magnesia mixed oxide that the NiO/ MgO catalyzer of nickel-loaded or single stage method obtain has higher reformation catalytic activity and stability.But still there is shortcomings in above-mentioned nickel-magnesia mixed oxide, low such as specific surface area, voids content is few and microscopic particles is inhomogeneous etc., these drawbacks limit their further application.
For example, in the Chinese patent that is CN95111008.X at application number, through preparing porous oxidation magnesium carrier, preparation steeping fluid, with steeping fluid, flood above-mentioned carrier, in the prepared metal composite of the complex steps such as dry and roasting, nickel enters the surface of magnesium oxide skeleton, but the method for this dipping can not guarantee all nickel and all form sosoloid with magnesium oxide skeleton, and magnesium oxide microscopic particles size is also inhomogeneous, from all having distribution to millimeter rank below 70 microns, therefore this composite oxides anti-caking power at high temperature greatly reduces, work-ing life in catalytic applications is corresponding shortening also.
Chinese patent CN102133529 discloses a kind of method that method of utilizing alkali-titration is prepared Ni-based steam reforming catalyzer, utilize soluble magnesium nitrate, aluminum nitrate to be precipitated thing, after suction filtration, washing, dry and roasting, obtain the carrier of composite oxides, then utilize a certain amount of nickel of pickling process load and obtain finished catalyst after the steps such as dry and roasting again.But the porosity via the method gained catalyzer is lower, also cannot guarantee the homogeneity of microscopic particles.Moreover, in above-described these patents, all used the pickling process of complex steps, so not only improved preparation cost, and made preparation technology more complicated.
Summary of the invention
One of technical problem to be solved by this invention is the problem that nickel-magnesia mixed oxide specific surface area is low, voids content is few and microscopic particles is inhomogeneous existing in prior art, and a kind of new nickel-magnesia mixed oxide is provided.These composite oxides have that specific surface area is high, voids content is high and the uniform feature of microscopic particles.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the nickel-magnesia mixed oxide corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows: a kind of nickel-magnesia mixed oxide, in parts by weight, comprises following component: a) nickel oxide of 0.1 ~ 30 part; B) magnesium oxide of 100 parts; Wherein, described nickel-magnesia mixed oxide BET specific surface area is greater than 25 meters
2/ gram, pore space is greater than 0.12 centimetre
3/ gram, microscopic particles size is between 0.5 ~ 5.0 micron.
Preferably, in parts by weight, in described nickel-magnesia mixed oxide, the content of nickel oxide is 0.5 ~ 20 part.
Preferably, described nickel-magnesia mixed oxide BET specific surface area is more than or equal to 50 meters
2/ gram.
More preferably, described nickel-magnesia mixed oxide BET specific surface area is 50 ~ 150 meters
2/ gram.
Described in described nickel-magnesia mixed oxide BET specific surface area, nickel-magnesia mixed oxide pore space is more than or equal to 0.4 centimetre
3/ gram.
More preferably, described nickel-magnesia mixed oxide pore space is 0.4 ~ 0.7 centimetre
3/ gram.
Preferably, described nickel-magnesia mixed oxide microscopic particles size is between 0.8 ~ 4.0 micron.
Preferably, in parts by weight, in described nickel-magnesia mixed oxide, also comprise 0.1 ~ 10 part at least one in ferric oxide, cobalt oxide, aluminum oxide, cupric oxide, titanium oxide, manganese oxide, sodium oxide, potassium oxide or calcium oxide that be selected from.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of preparation method of nickel-magnesia mixed oxide, comprises the following steps:
A) nickel source, magnesium source, precipitation agent, dispersion agent and water are formed to mixture, the pH value of adjusting mixture is 7～12, under 5 ~ 90 ℃ of conditions of temperature, stirs 5 ~ 40 hours, obtains precursor A; Wherein, in precursor A, the weight ratio of each material is nickel source: magnesium source: precipitation agent: dispersion agent: water=(0.001～0.3): 1:(0.5～5): (0.05～5): (2～20);
B) precursor A, through burin-in process, obtains precursor B;
C) precursor B, through washing, dry, calcining, obtains described nickel-magnesia mixed oxide;
Wherein, described nickel source is selected from least one in nickelous nitrate, nickelous chloride, single nickel salt, nickel acetate, nickelous bromide, sulfuric acid oxygen nickel, six hydration nickel, hexamine nickel or nickle carbonoxide; Magnesium source is selected from least one in magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium fluoride or bischofite; Precipitation agent is selected from least one in sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, carbonic acid, sodium oxalate, oxalic acid or oxalic acid potassium; Dispersion agent is selected from least one in succinate sodium 2-ethylhexyl, cetyl trimethylammonium bromide, polyethylene oxide-propylene oxide block copolymer, polyoxyethylene glycol or polyvinyl alcohol.
Preferably, nickel source is selected from least one in nickelous nitrate, nickelous chloride or single nickel salt; Magnesium source is selected from least one in magnesium nitrate, magnesium chloride or magnesium sulfate; Dispersion agent is selected from least one in succinate sodium 2-ethylhexyl, cetyl trimethylammonium bromide, polyethylene oxide-propylene oxide block copolymer or polyoxyethylene glycol.
Preferably, in step a) precursor A, the weight ratio of each material is nickel source: magnesium source: precipitation agent: dispersion agent: water=(0.005～0.2): 1:(0.3～2): (0.2～3): (3～10), the pH value of adjusting mixture is 8～10, and temperature is 30 ~ 60 ℃.
Preferably, step b) aging temperature is 100 ~ 200 ℃, and aging pressure is 0.1 ~ 5MPa, and digestion time is 4 ~ 40 hours.
More preferably, step b) aging temperature is 120 ~ 160 ℃, and aging pressure is 0.2 ~ 3MPa, and digestion time is 8 ~ 20 hours.
Preferably, step c) drying temperature is 60～150 ℃, and be 1～10 hour time of drying, and calcining temperature is 300～1200 ℃, and calcination time is 3～10 hours.
More preferably, step c) drying temperature is 80～120 ℃, and be 2～8 hours time of drying, and calcining temperature is 500～1000 ℃, and calcination time is 5～10 hours.
Preferably, also comprise at least one being selected from source of iron, cobalt source, aluminium source, Tong Yuan, titanium source, manganese source, sodium source, Huo Gai source, potassium source described in step a) in mixture, the weight ratio in its consumption and magnesium source is (0.001 ~ 0.1): 1.
Preferably, described source of iron is selected from iron nitrate; Described cobalt source is selected from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Described aluminium source is selected from aluminum nitrate; Described copper source is selected from copper sulfate; Described titanium source is selected from Titanium Nitrate; Described manganese source is selected from manganous nitrate; Described sodium source is selected from sodium-chlor; Described potassium source is selected from Repone K; Described calcium source is selected from nitrocalcite.
Preferably, in step a), adding alkali take to adjust the pH value of mixture is 7～12, and alkali is selected from least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, quadrol, triethylamine or fatty ammonium hydroxide.
More preferably, alkali is selected from least one in sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Preferably, water and alcohol wash respectively for step c) precursor B washing; Wherein, the weight ratio of water and precursor B is (1 ~ 200): 1, and the weight ratio of alcohol and precursor B is (0.5～15): 1.
More preferably, the weight ratio of water and precursor B is (10 ~ 50): 1, and the weight ratio of alcohol and precursor B is (0.5～5): 1.
In the present invention, due to nickel oxide and magnesian presoma are added in preparation system simultaneously, guaranteed that nickel oxide can form homogeneous phase composite oxides with magnesium oxide; And due to the existence of dispersion agent, can guarantee that in presoma, microparticle can not occur to reunite and size homogeneous, and can be by regulating the add-on of dispersion agent to obtain the nickel-magnesia mixed oxide with different specific surface areas and granularity; By changing calcining temperature and time, also can regulate the porosity of product.In addition, in preparation process, the presoma of nickel and magnesium is that original position adds simultaneously, has therefore avoided the back loading process of complex steps.These above measures, nickel-magnesia mixed oxide microparticle size heterogeneity, specific surface area have been solved in traditional preparation method and porosity is low and the difficult problem such as complicated process of preparation simultaneously, obtain efficient, stable nickel-magnesia mixed oxide, obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of gained nickel-magnesia mixed oxide in [embodiment 3].
Fig. 2 is the transmission electron microscope photo of gained nickel-magnesia mixed oxide in [comparative example].
In Fig. 1, the particle size homogeneous of gained nickel-magnesia mixed oxide, is distributed between 0.5 ~ 5.0 micron.
In Fig. 2, the particle size relative different of gained nickel-magnesia mixed oxide is larger, and macrobead size surpasses 14 microns, and short grained size only has 0.5 micron.
Embodiment
[embodiment 1]
Under 40 ℃ of constant temperature, by 0.5 gram of nickelous nitrate, 15.1 gram magnesium nitrate, 14.5 gram salt of wormwood, 7.4 grams of polyoxyethylene glycol are mixed in 75 grams of water, and stir, finally add 0.1 gram of sodium hydroxide, regulate pH=13 ~ 14, mixing solutions is stirred 20 hours at 50 ℃ of constant temperature, then product is carried out to burin-in process, treatment temp is 150 ℃, time is 15 hours, pressure is 0.3MPa, the cooling rear water respectively of product and alcohol wash, then solid product is dried to 6 hours at 100 ℃, finally in air atmosphere 500 ℃ calcining 10 hours, obtain nickel-magnesia mixed oxide of the present invention.
[embodiment 2～6]
By [embodiment 1] described synthesis step, only change nickel source add-on, can synthesize and obtain nickel content and be respectively 0.1%, 0.5%, 1%, 5%, 15% nickel-magnesia mixed oxide.Nickel-magnesia mixed oxide formula, preparation condition and composition constitutional features are in Table 1 ~ table 4.
[embodiment 7～15]
By [embodiment 1] described synthesis step, (wherein succinate sodium 2-ethylhexyl, sodium hydroxide, potassium hydroxide, ammoniacal liquor, TPAOH, tetraethyl ammonium hydroxide, cetyl trimethylammonium bromide and polyethylene oxide-propylene oxide block copolymer are respectively referred to as AOT, NaOH, KOH, NH to change nickel source, magnesium source, precipitation agent, dispersion agent and alkali
3h
2o, TPAOH TEAOH, CTAB, P123 and F127) kind and quality, regulate preparation condition, all can synthesize and obtain nickel-magnesia mixed oxide of the present invention.Nickel-magnesia mixed oxide formula, preparation condition and structure composition characteristic are in Table 1 ~ table 4.
[embodiment 16～24]
By [embodiment 1] described synthesis step, add source of iron, cobalt source, aluminium source, Tong Yuan, titanium source, manganese source, sodium source, Huo Gai source, potassium source presoma, all can synthesize and obtain nickel-magnesia mixed oxide of the present invention, nickel-magnesia mixed oxide formula and structure composition characteristic are in Table 5.
[comparative example]
Utilize pickling process to prepare nickel-magnesia mixed oxide.Under 40 ℃ of constant temperature, 0.8 gram of nickelous nitrate and 3.5 grams of salt of wormwood mixing are added in 6 grams of water, after dissolution of solid, add 16 grams of magnesium oxide to stir, by at 40 ℃ of mixture constant temperature, stir 10 hours, water is slowly volatilized, then by product at 100 ℃ dry 6 hours, finally in air atmosphere 500 ℃ calcining 5 hours, obtain nickel-magnesia mixed oxide prepared by pickling process.Gained nickel-magnesia mixed oxide structure composition characteristic is in Table 5.
Table 1
Table 2
Table 3
| Embodiment | Water and material ratio | Alcohol and material ratio | Drying temperature (℃) | Time of drying (hour) | Calcining temperature (℃) |
| 1 | 10 | 5.0 | 100 | 6 | 500 |
| 2 | 10 | 5.0 | 100 | 6 | 500 |
| 3 | 10 | 0.5 | 100 | 6 | 500 |
| 4 | 10 | 1.0 | 100 | 6 | 300 |
| 5 | 10 | 1.5 | 60 | 1 | 400 |
| 6 | 15 | 2.0 | 70 | 2 | 500 |
| 7 | 1 | 3.0 | 80 | 3 | 600 |
| 8 | 5 | 4.0 | 90 | 4 | 700 |
| 9 | 20 | 5.0 | 100 | 5 | 800 |
| 10 | 40 | 2.0 | 110 | 6 | 900 |
| 11 | 60 | 2.0 | 120 | 7 | 1000 |
| 12 | 100 | 2.0 | 130 | 8 | 1100 |
| 13 | 120 | 2.0 | 140 | 9 | 1200 |
| 14 | 150 | 2.0 | 150 | 10 | 600 |
| 15 | 20 | 2.0 | 90 | 6 | 600 |
Table 4
Table 5
Claims (10)
1. a nickel-magnesia mixed oxide, in parts by weight, comprises following component: a) nickel oxide of 0.1 ~ 30 part; B) magnesium oxide of 100 parts; Wherein, described nickel-magnesia mixed oxide BET specific surface area is greater than 25 meters
2/ gram, pore space is greater than 0.12 centimetre
3/ gram, microscopic particles size is between 0.5 ~ 5.0 micron.
2. nickel-magnesia mixed oxide according to claim 1, is characterized in that in parts by weight, and the content of nickel oxide is 0.5 ~ 20 part.
3. nickel-magnesia mixed oxide according to claim 1, is characterized in that described nickel-magnesia mixed oxide BET specific surface area is more than or equal to 50 meters
2/ gram, pore space is more than or equal to 0.4 centimetre
3/ gram.
4. nickel-magnesia mixed oxide according to claim 3, is characterized in that described nickel-magnesia mixed oxide BET specific surface area is 50 ~ 150 meters
2/ gram, pore space is 0.4 ~ 0.7 centimetre
3/ gram.
5. nickel-magnesia mixed oxide according to claim 1, is characterized in that microscopic particles size is between 0.8 ~ 4.0 micron.
6. nickel-magnesia mixed oxide according to claim 1, it is characterized in that in parts by weight, in described nickel-magnesia mixed oxide, also comprise 0.1 ~ 10 part at least one in ferric oxide, cobalt oxide, aluminum oxide, cupric oxide, titanium oxide, manganese oxide, sodium oxide, potassium oxide or calcium oxide that be selected from.
7. the preparation method of nickel-magnesia mixed oxide claimed in claim 1, comprises the following steps:
A) nickel source, magnesium source, precipitation agent, dispersion agent and water are formed to mixture, the pH value of adjusting mixture is 7～12, under 5 ~ 90 ℃ of conditions of temperature, stirs 5 ~ 40 hours, obtains precursor A; Wherein, in precursor A, the weight ratio of each material is nickel source: magnesium source: precipitation agent: dispersion agent: water=(0.001～0.3): 1:(0.5～5): (0.05～5): (2～20);
B) precursor A, through burin-in process, obtains precursor B;
C) precursor B, through washing, dry, calcining, obtains described nickel-magnesia mixed oxide;
Wherein, described nickel source is selected from least one in nickelous nitrate, nickelous chloride, single nickel salt, nickel acetate, nickelous bromide, sulfuric acid oxygen nickel, six hydration nickel, hexamine nickel or nickle carbonoxide; Magnesium source is selected from least one in magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium fluoride or bischofite; Precipitation agent is selected from least one in sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, carbonic acid, sodium oxalate, oxalic acid or oxalic acid potassium; Dispersion agent is selected from least one in succinate sodium 2-ethylhexyl, cetyl trimethylammonium bromide, polyethylene oxide-propylene oxide block copolymer, polyoxyethylene glycol or polyvinyl alcohol.
8. the preparation method of nickel-magnesia mixed oxide according to claim 7, the weight ratio that it is characterized in that each material in step a) precursor A is nickel source: magnesium source: precipitation agent: dispersion agent: water=(0.005～0.2): 1:(0.3～2): (0.2～3): (3～10), the pH value of adjusting mixture is 8～10, and temperature is 30 ~ 60 ℃.
9. the preparation method of nickel-magnesia mixed oxide according to claim 7, is characterized in that step b) aging temperature is 100 ~ 200 ℃, and aging pressure is 0.1 ~ 5MPa, and digestion time is 4 ~ 40 hours; Step c) drying temperature is 60～150 ℃, and be 1～10 hour time of drying, and calcining temperature is 300～1200 ℃, and calcination time is 3～10 hours.
10. the preparation method of nickel-magnesia mixed oxide according to claim 7, it is characterized in that in mixture, also comprising at least one being selected from source of iron, cobalt source, aluminium source, Tong Yuan, titanium source, manganese source, sodium source, Huo Gai source, potassium source described in step a), the weight ratio in its consumption and magnesium source is (0.001 ~ 0.1): 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293591A (en) * | 2015-11-10 | 2016-02-03 | 沈阳化工大学 | Method for preparing magnesium-nickel metal compound oxide with active magnesium oxide as raw material |
| CN105858691A (en) * | 2016-05-18 | 2016-08-17 | 四川大学 | Method for preparing flower-like magnesium oxide microsphere according to precipitation method |
| CN106732608A (en) * | 2016-11-23 | 2017-05-31 | 太原理工大学 | A kind of preparation method of nickeliferous mesoporous catalyst |
| CN107224977A (en) * | 2016-03-25 | 2017-10-03 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation catalyst and preparation method thereof, application |
| CN110465281A (en) * | 2018-07-10 | 2019-11-19 | 吉林大学 | A kind of nickel magnesium sosoloid method for preparing catalyst |
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| CN102451689A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing nickel-based catalyst precursor |
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| CN102451689A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing nickel-based catalyst precursor |
| CN102863032A (en) * | 2012-09-11 | 2013-01-09 | 河北工业大学 | Preparation method of porous nano-nickel oxide material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293591A (en) * | 2015-11-10 | 2016-02-03 | 沈阳化工大学 | Method for preparing magnesium-nickel metal compound oxide with active magnesium oxide as raw material |
| CN107224977A (en) * | 2016-03-25 | 2017-10-03 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation catalyst and preparation method thereof, application |
| CN105858691A (en) * | 2016-05-18 | 2016-08-17 | 四川大学 | Method for preparing flower-like magnesium oxide microsphere according to precipitation method |
| CN106732608A (en) * | 2016-11-23 | 2017-05-31 | 太原理工大学 | A kind of preparation method of nickeliferous mesoporous catalyst |
| CN110465281A (en) * | 2018-07-10 | 2019-11-19 | 吉林大学 | A kind of nickel magnesium sosoloid method for preparing catalyst |
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