CN106693976A - Method for preparing heterogeneous organic metal catalyst Ni/C oxide - Google Patents
Method for preparing heterogeneous organic metal catalyst Ni/C oxide Download PDFInfo
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- CN106693976A CN106693976A CN201611202133.2A CN201611202133A CN106693976A CN 106693976 A CN106693976 A CN 106693976A CN 201611202133 A CN201611202133 A CN 201611202133A CN 106693976 A CN106693976 A CN 106693976A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention discloses a method for preparing a heterogeneous organic metal catalyst Ni/C oxide. A water-soluble nickel salt solution and a low-molecular-weight organic acid solution are mixed and stirred at normal temperature, standing is conducted for 6-8 hours, then a liquid supernatant is removed, sediments are dried at the temperature of 80 DEG C. Pulverization is conducted after drying, the organic metal catalyst Ni/C oxide is prepared by calcining in an air atmosphere in a box-type atmosphere protection furnace. Compared with other technologies, the method is simple to operate and cheap in medicament price and saves cost; the molar concentration of the low-molecular-weight organic acid is controlled to be slightly larger than that of nickel nitrate, so that metal ion residues in a solution can be reduced, and the pollution to the environment is reduced; in the application process of the prepared catalyst, the recycle technology is simple, no complex operation is needed, and the catalyst is low in cost, simple, efficient and environmentally friendly, and has a very broad application prospects and a very large research value.
Description
Technical field
The invention belongs to material chemistry technical field, it is related to the preparation of heterogeneous catalysis, and in particular to a kind of heterogeneous
The preparation method of organo-metallic catalyst Ni/C oxides.
Background technology
Heterocatalysis is the important component in catalysis technique, and its concrete mode is to bear the component with catalysis activity
It is loaded on the carrier of stabilization.Heterocatalysis effectively improves catalyst in homogeneous catalysis and is difficult to reclaim and easily causes secondary pollution
Problem, improves the recycling rate of waterused of catalyst, reduces catalysis cost, enjoys researchers to pay close attention to.
In current research, the selection of carrier has vital influence.Titanium dioxide（Chemical formula：TiO2）, oxygen
Change aluminium（Chemical formula：Al2O3）Silica gel, zeolite, kaolin etc. are conventional carriers, there is very many researchs and application.But it is such
It is not big enough to there is specific surface area in conventional carrier, and pore passage structure is simple, the carrier defect such as feature functional group is less in itself, causes this
The load factor of a little Carriers Active components is relatively low and does not form concerted catalysis effect.Additionally, CNT, Graphene etc.
It is the study hotspot of researcher, although but such material improves the defect of conventional carrier often expensive, with current
Technology is difficult to large-scale promotion in actual applications.
In recent years, organic metal is increasingly paid close attention to as the emerging field of materials chemistry aspect by people, compared to
Organic metal has very big advantage for traditional material：（1）With larger specific surface area；（2）With larger porosity
With open skeleton structure；（3）Organic gold can conveniently be regulated and controled by the species for changing metal ion and organic backbone
The concrete structure of category.In consideration of it, organo metallic material is being separated, gas storage, energy storage aspect has big advantage, and is applied
Also there is very big prospect in catalytic field.
Chinese patent CN 104667980A disclose that " a kind of metal organic framework compound carried metal-char combustion thing is received
Rice grain catalyst and its preparation method and application ", the method is by the use of MIL-101 as carrier, with organic acid-transition metal
The catalyst of metal-carbon oxide is prepared using hydro-thermal method for active component.CN1962059A discloses a kind of " three-dimensional meso-hole
Structure non-homogeneous phase organo-metallic catalyst and its preparation method and application ", the method is common mesoporous using diphenylphosphine modification
Material is allowed to, with ordered mesopore structure, then as carrier loaded organo-metallic catalyst, and be applied in aqueous medium
The isomerization reaction of homoallylic alcohol.CN 103785471A disclose that " short-bore road ordered mesoporous organic metal Rh (I) is heterogeneous to urge
The preparation method of agent ", deacidification, surfactant, alcohol, two under the tangible heating condition of the method（Three ethoxy silicon substrates）Ethene and have
Machine metal Rh (I) silane mixture, fully reaction, filtering, solid obtain that short-bore road is order mesoporous to be had through extraction, washing and after drying
Machine metal Rh (I) heterogeneous catalysis.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of heterogenous organic metal catalyst Ni/C oxygen
The preparation method of compound.The method is by normal temperatures, water-soluble nickel salt solution and small molecular organic acid solution being mixed
After reaction obtains sediment drying, grinding, calcining is obtained heterogenous organic metal catalyst Ni/C oxides.
A kind of preparation method of heterogenous organic metal catalyst Ni/C oxides of the present invention, it is characterised in that use with
Lower technical scheme：At normal temperatures, water-soluble nickel salt solution and small molecular organic acid solution are mixed；After standing 6 ~ 8 hours
Supernatant is removed, sediment is dried at 80 DEG C；Ground after drying, in box atmosphere protection stove, calcined under air atmosphere, produced
Thing is heterogenous organic metal catalyst Ni/C oxides.
Water-soluble nickel salt solution of the present invention is nickel nitrate solution（Chemical formula：Ni(NO3)2）.
Small molecular organic acid solution of the present invention is oxalic acid（Chemical formula：H2C2O4）.
Metal salt solution of the present invention is 1 with small molecular organic acid solution mol ratio:1~1:1.5.
Calcining heat under air atmosphere of the present invention is 200 ~ 600 DEG C.
Obtained heterogenous organic metal catalyst Ni/C oxide applications of the present invention are degraded in active oxidation agent and are contaminated
Material waste water.
Compared with prior art, the present invention has advantages below：
（1）The present invention is simple to operate compared with other technologies, and medicament is cheap, cost-effective；
（2）Compared with other technologies, by making small molecular organic acid slightly excessive, the metal ion that can be reduced in solution is residual for the present invention
Stay, reduce the pollution to environment；
（3）Catalyst recovery technology of the present invention is simple, without complex operations, beneficial to the reuse of catalyst.
Brief description of the drawings
Fig. 1 is method for preparing catalyst of the invention.
Process chart of Fig. 2 present invention for catalytic degradation waste water from dyestuff.
Fig. 3 is 1 ~ 5 pair of design sketch of acid orange 7 of the embodiment of the present invention
Specific embodiment
Catalytic effect of the invention is further explained with reference to embodiment, but the claimed scope of the invention is not
It is only limitted to this.
Tested as object using acid orange 7, answered for activating potassium hydrogen persulfate using catalyst of the invention
Salt is closed, activation effect is evaluated with the degradation rate of acid orange 7.
Embodiment 1, as shown in Fig. 2 being processed the aqueous solution containing acid orange 7 with the method for the present invention.
It is the simulated wastewater 500ml of 0.02mM to acid orange 7 concentration is added in reactor；To adding persulfuric acid in reactor
The heterogenous organic metal catalyst Ni/C oxides calcined at hydrogen potassium complex salt and 200 DEG C, make ammonium persulfate-sodium bisulfate
Initial concentration is 0.4mM（It is 20 with the mol ratio of acid orange 7:1）, the concentration of heterogenous organic metal catalyst Ni/C oxides
It is 0.1mg/L；Heterogenous organic metal catalyst Ni/C oxides activation ammonium persulfate-sodium bisulfate is decomposed and produces sulfate radical certainly
By base, the acid orange 7 in potentiometric titrations oxidative degradation water.
Treatment effect as shown in Fig. 3 F1, at 20 DEG C ± 2 DEG C, acid orange 7 degradation rate only up to 30% in 30min.
Embodiment 2, is the simulated wastewater 500ml of 0.02mM to acid orange 7 concentration is added in reactor；Add in reactor
Enter the heterogenous organic metal catalyst Ni/C oxides calcined at ammonium persulfate-sodium bisulfate and 300 DEG C, make potassium hydrogen persulfate
The initial concentration of complex salt is 0.4mM（It is 20 with the mol ratio of acid orange 7:1）, the heterogenous organic metal calcined at 200 DEG C
The concentration of catalyst is 0.1mg/L.
Treatment effect as shown in Fig. 3 F2, at 20 DEG C ± 2 DEG C, acid orange 7 in 30min degradation rate up to more than 99.9%.
Embodiment 3, is the simulated wastewater 500ml of 0.02mM to acid orange 7 concentration is added in reactor；Add in reactor
Enter the heterogenous organic metal catalyst calcined at ammonium persulfate-sodium bisulfate and 400 DEG C, make the first of ammonium persulfate-sodium bisulfate
Beginning concentration is 0.4mM（It is 20 with the mol ratio of acid orange 7:1）, the heterogenous organic metal catalyst of calcining is dense at 400 DEG C
It is 0.1mg/L to spend.
Treatment effect as shown in Fig. 3 F3, at 20 DEG C ± 2 DEG C, acid orange 7 in 30min degradation rate up to more than 99.9%.
Embodiment 4, is the simulated wastewater 500ml of 0.02mM to acid orange 7 concentration is added in reactor；Add in reactor
Enter the heterogenous organic metal catalyst calcined at ammonium persulfate-sodium bisulfate and 500 DEG C, make the first of ammonium persulfate-sodium bisulfate
Beginning concentration is 0.4mM（It is 20 with the mol ratio of acid orange 7:1）, the heterogenous organic metal catalyst of calcining is dense at 500 DEG C
It is 0.1mg/L to spend.
Treatment effect as shown in Fig. 3 F4, at 20 DEG C ± 2 DEG C, acid orange 7 in 40min degradation rate up to more than 99.9%.
Embodiment 5, is the simulated wastewater 500ml of 0.02mM to acid orange 7 concentration is added in reactor；Add in reactor
Enter the heterogenous organic metal catalyst calcined at ammonium persulfate-sodium bisulfate and 600 DEG C, make the first of ammonium persulfate-sodium bisulfate
Beginning concentration is 0.4mM（It is 20 with the mol ratio of acid orange 7:1）, the heterogenous organic metal catalyst of calcining is dense at 600 DEG C
It is 0.1mg/L to spend.
As shown in Fig. 3 F5, at 20 DEG C ± 2 DEG C, acid orange 7 in 40min degradation rate up to more than 99.9%.
Claims (7)
1. a kind of preparation method of heterogenous organic metal catalyst Ni/C oxides is characterized in that, preparation process by entering as follows
OK：At normal temperatures, water-soluble nickel salt solution and small molecular organic acid solution are mixed；Supernatant is removed after standing 6 ~ 8 hours
Liquid, sediment is dried at 80 DEG C；Ground after drying, calcined in box atmosphere protection stove, under air atmosphere and organic gold is obtained
Metal catalyst Ni/C oxides.
2. according to right 1, it is characterised in that the water-soluble nickel salt solution is nickel nitrate solution（Chemical formula：Ni
(NO3)2）.
3. according to right 1, it is characterised in that the small molecular organic acid solution is oxalic acid（Chemical formula：H2C2O4）.
4. according to right 1, it is characterised in that the metal salt solution is 1 with small molecular organic acid solution mol ratio:1~1:
1.5。
5. according to right 1, it is characterised in that the calcining heat under the air atmosphere is 200 ~ 600 DEG C.
6. according to the method that one of right 1 ~ 5 is described, it is characterised in that the obtained heterogenous organic metal catalyst Ni@C
Oxide applications are in active oxidation agent degradation of dye waste water.
7. according to right 6, it is characterised in that the oxidant includes：Such as ammonium persulfate-sodium bisulfate（Chemical formula：
2KHSO5·KHSO4·K2SO4）, sodium peroxydisulfate（Chemical formula：Na2S2O8）, potassium peroxydisulfate（Chemical formula：K2S2O8）, hydrogen peroxide（Change
Formula：H2O2）In the combination of one or more.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611202133.2A CN106693976B (en) | 2016-12-23 | 2016-12-23 | A kind of preparation of the heterogeneous organo-metallic catalyst containing Ni for active oxidation agent degradation of dye waste water |
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|---|---|---|---|
| CN201611202133.2A CN106693976B (en) | 2016-12-23 | 2016-12-23 | A kind of preparation of the heterogeneous organo-metallic catalyst containing Ni for active oxidation agent degradation of dye waste water |
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| CN106693976A true CN106693976A (en) | 2017-05-24 |
| CN106693976B CN106693976B (en) | 2019-08-13 |
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| CN201611202133.2A Expired - Fee Related CN106693976B (en) | 2016-12-23 | 2016-12-23 | A kind of preparation of the heterogeneous organo-metallic catalyst containing Ni for active oxidation agent degradation of dye waste water |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609607A (en) * | 2015-02-11 | 2015-05-13 | 四川大学 | Method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene to work in coordination with persulfate |
| CN104667870A (en) * | 2015-02-11 | 2015-06-03 | 四川大学 | Method for removing endocrine disrupter in water by utilizing persulfate and ferro-manganese loaded dual-phase compound graphene oxide |
| CN106673171A (en) * | 2016-12-23 | 2017-05-17 | 四川大学 | Method for promoting peroxymonosulfate to generate sulfate radicals for degrading organic matters |
-
2016
- 2016-12-23 CN CN201611202133.2A patent/CN106693976B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609607A (en) * | 2015-02-11 | 2015-05-13 | 四川大学 | Method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene to work in coordination with persulfate |
| CN104667870A (en) * | 2015-02-11 | 2015-06-03 | 四川大学 | Method for removing endocrine disrupter in water by utilizing persulfate and ferro-manganese loaded dual-phase compound graphene oxide |
| CN106673171A (en) * | 2016-12-23 | 2017-05-17 | 四川大学 | Method for promoting peroxymonosulfate to generate sulfate radicals for degrading organic matters |
Non-Patent Citations (1)
| Title |
|---|
| 徐鸽等: "《化学工程与工艺专业实验（第二版）》", 31 August 2013 * |
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Granted publication date: 20190813 Termination date: 20191223 |