CN106582651A - Preparation method for porous carrier-loaded nano-cobalt catalyst - Google Patents

Preparation method for porous carrier-loaded nano-cobalt catalyst Download PDF

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CN106582651A
CN106582651A CN201710015380.XA CN201710015380A CN106582651A CN 106582651 A CN106582651 A CN 106582651A CN 201710015380 A CN201710015380 A CN 201710015380A CN 106582651 A CN106582651 A CN 106582651A
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CN106582651B (en
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李进军
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Wuhan University WHU
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    • 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
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/143—X-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

The invention provides a preparation method for a porous carrier-loaded nano-cobalt catalyst. The basic preparation process comprises the steps of dropwise adding a soluble cobalt salt solution into an ammonium hydroxide solution, stirring and oxidizing in the air, and forming a coordination compound of Co<3+>, NH<3> and OH<-> in the solution; taking the solution as a precursor solution of the catalyst, adding porous silica gel, a zeolite molecular sieve or active carbon and other carriers; and enabling the cobalt coordination compound to be chemically adsorbed on the surface of the carrier, and performing subsequent thermal treatment to obtain the load type nano-cobalt catalyst. According to the preparation method, low cost of the raw materials, mild preparation conditions, short preparation time, convenient operation, and adjustable grain diameters of the product are realized; and the prepared load type nano-cobalt catalyst can be used in multiple kinds of industrial catalysis or environment catalysis processes.

Description

A kind of preparation method of the nanometer cobalt catalyst of porous carrier load
Technical field
The invention belongs to nanocatalyst preparing technical field, and in particular to a kind of nanometer cobalt catalysis of porous carrier load The preparation method of agent.
Background technology
Supported cobalt catalysts have obtained wide in the reaction such as waste gas purification, Fiscber-Tropscb synthesis, alkene polycondensation, hydrocarbon reformation General application.
The conventional method for preparing supported cobalt catalysts is infusion process, and infusion process is fairly simple, generally that cobalt salt is water-soluble Liquid is immersed in the duct of porous carrier, and by being dried with after roasting, cobalt salt decomposes, and is deposited on channel surfaces.Infusion process lack Point is that the particle diameter of the cobalt species for obtaining is difficult to control to, and is often reunited serious, and surface area is relatively low.The Co catalysts of area load are received Meter Hua, improves the surface area of cobalt, is the target that association area staff lays siege to；Document CN104043453B has reported one The cobaltosic oxide nano composite catalyst of carbon black loadings is planted, its basic preparation process is by the ethanol of soluble cobalt or second two Alcoholic solution mix with acidifying white carbon black, and the reaction of 50 DEG C～160 DEG C condensing refluxes is after 8～12 hours, then separate, be dried, heat treatment Product is obtained, the method needs organic solvent, higher temperature and long period；Document CN103816905B has reported a kind of carbon and has received Mitron loads the preparation method of nanometer cobalt catalyst, and its basic preparation process is first under high-temperature and high-pressure conditions by cobalt salt, organic Solvent and organic ligand reaction 8-120 hours, prepare the metallic organic framework product Co-MOF of cobalt, and preparation condition is more Harshness, uses more Organic substance；Document CN102658144A has reported a kind of graphene oxide interlayer load four oxidation of nanometer The preparation method of three Co catalysts, its basic preparation process are that graphene oxide and divalent cobalt are dispersed in hexanol solution In, 50-150 DEG C of reacting by heating 5-20 hour, obtains product in the basic conditions, the preparation method be also required to organic solvent and The longer response time.
If the process of synthesis loaded nano Co catalysts can be realized in water phase, and does not use organic solvent, and And relatively mild reaction condition is adopted, shorten the response time, be beneficial to the extension production of catalyst；Additionally, except charcoal is carried Outside body, if nanometer cobalt catalyst can be loaded on other a variety of carriers, the use of catalyst will can be extended Scope.
The content of the invention
The present invention provides a kind of preparation method of the nanometer cobalt catalyst of porous carrier load, with the solubility being readily obtained Divalent cobalt is raw material, with Bio-sil, zeolite molecular sieve and activated carbon as carrier, is entered in aqueous under normal temperature and pressure conditionses Prepared by row, the load capacity of cobalt is 0.5～15%, and the mean diameter of cobalt species is 2～12 nanometers, and load capacity and particle diameter can bases Preparation condition carries out modulation.
Concrete technical scheme of the present invention is as follows：
A kind of 1 preparation method of the nanometer cobalt catalyst of porous carrier load, preparation process are as follows：（1）By solubility bivalence cobalt The solution of salt is added dropwise in the ammonia spirit of stirring, is persistently stirred 2-4 hours in atmosphere, is obtained precursor solution；Before described The concentration for driving ammonia in liquid solution is 30～60 for the mol ratio of 3～6 mol/Ls, ammonia and cobalt；
（2）Carrier is added to into step（1）In the precursor solution for obtaining, the dosage of carrier is 50～200 g/l of presomas Solution, persistently stirs 0.5-1.5 hours, obtains the carrier of the complex ion of surface enrichment cobalt；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt sequentially passes through filtration, is dried and roasting, is loaded Type nanometer cobalt catalyst.
As preference：The preparation process also includes step（4）：With step（3）The loaded nano cobalt for preparing Catalyst is used as carrier, repeat step（1）-（3）, obtain the higher loaded nano Co catalysts of load capacity.
As preference：The step（1）Middle solubility divalent cobalt is cobaltous sulfate, cobalt nitrate or cobaltous chloride.
As preference：The step（2）Middle carrier is Bio-sil, zeolite molecular sieve or activated carbon.
As preference：The zeolite molecular sieve includes 13X molecular sieves, 10X molecular sieves, USY molecular sieve, ZSM-5 molecules Sieve, Beta molecular sieves and mordenite molecular sieve.
As preference：When the carrier is Bio-sil or zeolite molecular sieve, roasting is carried out in air atmosphere, roasting Temperature is 200-700 DEG C, and roasting time is 0.5-2 hours, obtains loaded nano Cobalto-cobaltic oxide catalyst.
As preference：500 DEG C of reduction treatments in atmosphere of hydrogen by loaded nano Cobalto-cobaltic oxide catalyst 1-2 hours, obtain load-type nanometer metal Co catalysts.
As preference：When the carrier is activated carbon, roasting is carried out in nitrogen or atmosphere of hydrogen, and sintering temperature is 500 DEG C, roasting time is 0.5-3 hours, obtains load-type nanometer metal Co catalysts.
The present invention provides a kind of preparation method of the nanometer cobalt catalyst of porous carrier load, and its basic preparation process is：Can Dissolubility cobalt salt solution is added drop-wise in ammonia spirit, and stirring oxidation, forms Co in solution in atmosphere3+、NH3With OH-Coordination compound, Using this solution as the precursor solution of catalyst, the carriers such as Bio-sil, zeolite molecular sieve or activated carbon, the cooperation of cobalt are added Thing is chemisorbed on carrier surface, by follow-up heat treatment, obtains loaded nano Co catalysts.
The outstanding advantages of the method for preparing loaded nano Co catalysts provided by the present invention are：
（1）Preparation is carried out in aqueous, it is not necessary to use organic solvent；
（2）Preparation process is carried out under room temperature, normal pressure, simple to operate, easily extension production；
（3）Required low in raw material price, low cost；
（4）The product that roasting is obtained has Cobalto-cobaltic oxide structure, rather than unreducible low activity cobalt Si composite oxide；
（5）Particle diameter can be with modulation；
（6）Applicable carrier scope is wide.
Description of the drawings
Fig. 1. impact of the solution ion strength to Co adsorbances；
Fig. 2. the X-ray diffraction spectrogram of the nano-cobaltic-cobaltous oxide of Bio-sil load；
Fig. 3. the high-resolution-ration transmission electric-lens figure of the nano-cobaltic-cobaltous oxide of Bio-sil load；
Fig. 4. the high-resolution-ration transmission electric-lens figure of the nano-cobaltic-cobaltous oxide of zeolite molecular sieve load；
Fig. 5. the high-resolution-ration transmission electric-lens figure of activated carbon supported nano-cobaltic-cobaltous oxide.
Specific embodiment
Preparation process is broadly divided into following step：
（1）The solution of solubility divalent cobalt is added dropwise in the ammonia spirit of stirring, in atmosphere persistently stir 3 hours, two Valency cobalt ion is oxidized to trivalent cobalt ion, with solution in amino molecule and hydroxide ion act on to be formed the dissolved complexation from Son, obtains the precursor solution of black, and in the solution, the concentration of ammonia is 30～60 for the mol ratio of 3～6 mol/Ls, ammonia and cobalt；
（2）Carrier is added to into step（1）In the precursor solution for obtaining, the dosage of carrier is 50～200 g/l of presomas Solution, persistently stirs one hour, and the complex ion of cobalt adsorbs in carrier surface, and experiment shows, the change of ionic strength does not affect Adsorbance（Accompanying drawing 1）, illustrate to happens is that chemisorbed, inner-sphere complex is formed in adsorbent surface；
（3）The carrier filtration of the complex ion of cobalt, drying and roasting will have been adsorbed, the catalysis of loaded nano cobalt obtained Agent, the mean diameter of cobalt species is 2～6nm, and the mass loading amount of cobalt is 0.5～7.6%.
In order to increase the particle diameter of the load capacity and appropriate increase cobalt of cobalt, supported cobalt catalysts prepared by above-mentioned steps can be with The complex ion of chemisorbed cobalt and amino molecule and hydroxyl particle again, repeat step（2）With（3）, obtain loaded nano Co catalysts, the mean diameter of cobalt species increase to 3～12nm, and the mass loading amount of cobalt increases to 1～15%.
The preparation method of described loaded nano Co catalysts, solubility divalent cobalt include cobaltous sulfate, cobalt nitrate and Cobaltous chloride.
The preparation method of described loaded nano Co catalysts, carrier include Bio-sil, zeolite molecular sieve and activity Charcoal, wherein zeolite molecular sieve include 13X molecular sieves, 10X molecular sieves, USY molecular sieve, ZSM-5 molecular sieve, Beta molecular sieves and silk Geolyte molecular sieve.
The preparation method of described loaded nano Co catalysts, when carrier is Bio-sil or zeolite molecular sieve, roasting Burning is carried out in air atmosphere, and sintering temperature is 200-700 DEG C, and roasting time is 0.5-2 hours, obtains four oxygen of loaded nano Change three Co catalysts（Accompanying drawing 2）.By loaded nano Cobalto-cobaltic oxide catalyst in atmosphere of hydrogen 500 DEG C of reduction treatment 1-2 Hour, load-type nanometer metal Co catalysts can be obtained.
The preparation method of described loaded nano Co catalysts, when carrier is activated carbon, roasting is in nitrogen or hydrogen Carry out in atmosphere, sintering temperature is 500 DEG C, and roasting time is 0.5-3 hours, obtains load-type nanometer metal Co catalysts.
With reference to embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1
（1）The ammonia spirit that 7.5 mL concentration are 10 mol/L, magnetic agitation, 17.5 mL concentration of Deca is added to be in beaker Co (the NO of 0.14 mol/L3)2Solutions Solution, completion of dropping continue stirring 3 hours in atmosphere, Co are formed in solution3+、NH3 With OH-Coordination compound, with this dark solution（About 25 mL）As the precursor solution of catalyst, wherein NH3Concentration is about 3 Mol/L, NH3/ Co mol ratios are about 30.
（2）1.25 g Bio-sils are added in this precursor solution（About 50 g/L of dosage）, a hour is stirred, Obtain the carrier of the complex ion of surface enrichment cobalt；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt is filtered successively, is dried, then in atmosphere in 200 DEG C roasting 2 hours, obtains load type Co3O4Catalyst, about 7 nm of mean diameter（Accompanying drawing 3）, the mass loading amount about 7.6% of cobalt.
Embodiment 2
Method such as embodiment 1 prepares precursor solution, by the load type Co of the load capacity obtained by embodiment 1 about 7.6%3O4 Catalyst is added in precursor solution again, after absorption, is filtered, is dried, and 200 DEG C of roastings 2 hours obtain support type Co3O4Catalyst, about 12 nm of mean diameter（Accompanying drawing 3）, the mass loading amount about 15% of cobalt.
Embodiment 3
By the load type Co of the load capacity obtained by embodiment 1 about 7.6%3O4Catalyst is reduced 1 hour for 500 DEG C in hydrogen, is obtained To load type metal Co catalyst, about 5 nm of mean diameter.
Embodiment 4
（1）The ammonia spirit that 12.5 mL concentration are 12 mol/L, magnetic agitation, 12.5 mL concentration of Deca is added to be in beaker The CoSO of 0.2 mol/L4Solutions Solution, completion of dropping continue stirring 2 hours in atmosphere, Co are formed in solution3+、NH3With OH-Coordination compound, with this dark solution（About 25 mL）As the precursor solution of catalyst, wherein NH3Concentration is about 6 mol/ L, NH3/ Co mol ratios are about 60.
（2）5 g Bio-sils are added in this precursor solution（About 200 g/L of dosage）, stir 0.5 hour, obtain The carrier of the complex ion of cobalt to surface enrichment；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt is filtered successively, is dried, then in atmosphere in 700 DEG C roasting 0.5 hour, obtains load type Co3O4Catalyst, about 2 nm of mean diameter, the mass loading amount about 2.5% of cobalt.
Embodiment 5
Method such as embodiment 4 prepares precursor solution, by the load type Co of the load capacity obtained by embodiment 4 about 2.5%3O4 Catalyst is added in precursor solution again, after absorption, is filtered, is dried, and 700 DEG C of roastings 0.5 hour obtain support type Co3O4Catalyst, about 3 nm of mean diameter, the mass loading amount about 4% of cobalt.
Embodiment 6
（1）The ammonia spirit that 8 mL concentration are 14 mol/L, magnetic agitation are added in beaker, 17 mL concentration of Deca is 0.16 The CoCl of mol/L2Solutions Solution, completion of dropping continue stirring 4 hours in atmosphere, Co are formed in solution3+、NH3With OH-'s Coordination compound, with this dark solution（About 25 mL）As the precursor solution of catalyst, wherein NH3Concentration is about 4.5 mol/L, NH3/ Co mol ratios are about 40.
（2）2 g 13X molecular sieves are added in this precursor solution（About 80 g/L of dosage）, 1.5 hours are stirred, Obtain the carrier of the complex ion of surface enrichment cobalt；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt is filtered successively, is dried, then in atmosphere in 500 DEG C roasting 1 hour, obtains load type Co3O4Catalyst, about 5 nm of mean diameter（Accompanying drawing 4）, the mass loading amount about 4% of cobalt.
If changing carrier into 10X molecular sieves, the load type Co for obtaining3O4About 5 nm of catalyst mean diameter, the quality of cobalt Load capacity about 2.6%.
If changing carrier into ZSM-5 molecular sieve, the load type Co for obtaining3O4About 4 nm of catalyst mean diameter, the matter of cobalt Amount load capacity about 0.5%.
If changing carrier into USY molecular sieve, the load type Co for obtaining3O4About 5 nm of catalyst mean diameter, the quality of cobalt Load capacity about 1%.
If changing carrier into Beta molecular sieves, the load type Co for obtaining3O4About 5 nm of catalyst mean diameter, the matter of cobalt Amount load capacity about 1%.
If changing carrier into mordenite molecular sieve, the load type Co for obtaining3O4About 6 nm of catalyst mean diameter, cobalt Mass loading amount about 1%.
Embodiment 7
By the 13X obtained by embodiment 6 molecular sieve carried Co3O4Catalyst 500 DEG C of reductase 12 hours in hydrogen, are loaded Type metal Co catalyst, about 4 nm of mean diameter.
Embodiment 8
（1）The ammonia spirit that 8 mL concentration are 14 mol/L, magnetic agitation are added in beaker, 17 mL concentration of Deca is 0.16 Co (the NO of mol/L3)2Solutions Solution, completion of dropping continue stirring 3 hours in atmosphere, Co are formed in solution3+、NH3With OH- Coordination compound, with this dark solution（About 25 mL）As the precursor solution of catalyst, wherein NH3Concentration is about 4.5 mol/ L, NH3/ Co mol ratios are about 40.
（2）2 g activated carbons are added in this precursor solution（About 80 g/L of dosage）, a hour is stirred, is obtained The surface enrichment carrier of the complex ion of cobalt；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt is filtered successively, is dried, then in 500 in hydrogen DEG C roasting 0.5 hour, obtains load type metal Co catalyst, about 2.5 nm of mean diameter（Accompanying drawing 5）, the mass loading amount of cobalt is about 6%。
If roasting condition is changed in nitrogen 500 DEG C of roastings 3 hours, load type metal Co catalyst, average grain are obtained About 2 nm of footpath.
It should be appreciated that the part that this specification is not elaborated belongs to prior art.
It should be appreciated that the above-mentioned description for preferred embodiment is more detailed, therefore can not be considered to the present invention The restriction of scope of patent protection, one of ordinary skill in the art are being wanted without departing from right of the present invention under the enlightenment of the present invention Ask under protected ambit, replacement can also be made or deformed, be each fallen within protection scope of the present invention, it is of the invention Scope is claimed to be defined by claims.

Claims (8)

1. the preparation method of the nanometer cobalt catalyst of a kind of porous carrier load, it is characterised in that preparation process is as follows：（1）Will The solution of solubility divalent cobalt is added dropwise in the ammonia spirit of stirring, is persistently stirred 2-4 hours in atmosphere, is obtained presoma Solution；In the precursor solution, the concentration of ammonia is 30～60 for the mol ratio of 3～6 mol/Ls, ammonia and cobalt；
（2）Carrier is added to into step（1）In the precursor solution for obtaining, the dosage of carrier is 50～200 g/l of presomas Solution, persistently stirs 0.5-1.5 hours, obtains the carrier of the complex ion of surface enrichment cobalt；
（3）By surface enrichment obtained by upper step, the carrier of the complex ion of cobalt sequentially passes through filtration, is dried and roasting, is loaded Type nanometer cobalt catalyst.
2. preparation method as claimed in claim 1, it is characterised in that the preparation process also includes step（4）：With step （3）The loaded nano Co catalysts for preparing are used as carrier, repeat step（1）-（3）, obtain the higher load of load capacity Type nanometer cobalt catalyst.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the step（1）Middle solubility divalent cobalt is sulfur Sour cobalt, cobalt nitrate or cobaltous chloride.
4. preparation method as claimed in claim 1 or 2, it is characterised in that the step（2）Middle carrier is Bio-sil, boiling Stone molecular sieve or activated carbon.
5. preparation method as claimed in claim 4, it is characterised in that the zeolite molecular sieve includes 13X molecular sieves, 10X point Sub- sieve, USY molecular sieve, ZSM-5 molecular sieve, Beta molecular sieves and mordenite molecular sieve.
6. preparation method as claimed in claim 4, it is characterised in that when the carrier is Bio-sil or zeolite molecular sieve, Roasting is carried out in air atmosphere, and sintering temperature is 200-700 DEG C, and roasting time is 0.5-2 hours, obtains loaded nano four Co 3 O catalyst.
7. preparation method as claimed in claim 6, it is characterised in that described that loaded nano Cobalto-cobaltic oxide catalyst exists In atmosphere of hydrogen, 500 DEG C of reduction treatment 1-2 hours, obtain load-type nanometer metal Co catalysts.
8. preparation method as claimed in claim 4, it is characterised in that when the carrier is activated carbon, roasting is in nitrogen or hydrogen Atmosphere is carried out in enclosing, and sintering temperature is 500 DEG C, and roasting time is 0.5-3 hours, obtains load-type nanometer metal Co catalysts.
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CN108380899A (en) * 2018-04-04 2018-08-10 陕西理工大学 A kind of preparation method of cobalt nano magnetic material
CN108452783A (en) * 2018-04-04 2018-08-28 福州大学 The preparation method of fish scale-shaped metal oxide nano two-dimensional material is grown in a kind of nanometer sheet
CN112058217A (en) * 2020-09-04 2020-12-11 山东大学 Silicon-based adsorption material capable of being rapidly regenerated and method for microwave in-situ degradation of organic pollutants
CN112517066A (en) * 2020-12-18 2021-03-19 武汉大学 Supported nano iron-based catalyst and preparation method and application thereof
CN114873690A (en) * 2022-04-24 2022-08-09 河北海力香料股份有限公司 Method for treating wastewater containing dimethyl formamide

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