CN109529885A - A kind of cobalt sulfide/biomass carbon composite material and preparation method and as elemental mercury oxidation catalyst application - Google Patents
A kind of cobalt sulfide/biomass carbon composite material and preparation method and as elemental mercury oxidation catalyst application Download PDFInfo
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- CN109529885A CN109529885A CN201811377852.7A CN201811377852A CN109529885A CN 109529885 A CN109529885 A CN 109529885A CN 201811377852 A CN201811377852 A CN 201811377852A CN 109529885 A CN109529885 A CN 109529885A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
Abstract
The invention discloses a kind of cobalt sulfide/biomass carbon composite material and preparation method and as elemental mercury oxidation catalyst application, which is supported on biomass carbon by cobalt sulfide and is constituted.Its preparation process: by cobalt salt solution and thiocarbamide hybrid reaction, cobalt complex solution is obtained；Biomass material is placed in cobalt complex solution after impregnation, it is dry, obtain persursor material；Persursor material is placed under protective atmosphere be heat-treated to get.Cobalt sulfide/biomass carbon composite material shows higher elemental mercury oxidation catalytic activity in a mild condition, can be in SO particularly suitable for the removing of Elemental Mercury in flue gas2In the presence of realize that conversion ratio solves traditional demercuration catalyst in high concentration SO up to 100% without the efficient oxidation conversion of Elemental Mercury under the conditions of chlorine2Under the conditions of the problem of inactivating and higher concentration HCl is needed just to be able to achieve Elemental Mercury to mercuric Efficient Conversion.
Description
Technical field
The present invention relates to a kind of catalysis materials, and in particular to a kind of cobalt sulfide/biology for Elemental Mercury catalysis oxidation
Matter charcoal composite catalyzing material further relates to cobalt sulfide/biomass carbon composite material preparation method and cobalt sulfide/biology
Application of the matter carbon composite in terms of elemental mercury oxidation catalysis belongs to mercury pollution emission control field.
Background technique
Mercury is the toxic heavy metal with persistence, cumulative bad, property easy to migrate and high biological enrichment, has been listed in and has removed
The pollutants that unique a kind of pair of global range has an impact outside greenhouse gases.On January 19th, 2013, United Nations Environment Programme
" Minamata pact " has been formulated in order to control whole world mercury pollution problem, it is desirable that 147 member states including China are reducing mercury
It takes action jointly in discharge.In April, 2016, China have passed through the decision about approval " the Minamata pact about mercury ", and in
The same year August is formally criticized about, and comprehensive mercury pollution of carrying out is prevented and treated work of honouring an agreement by China as a result,.Pact is formal on August 16th, 2017
It comes into force.
In mercury fume, there are the mercury of three kinds of different shapes, it is also different to remove complexity for different chemical property:
Grain state mercury Hg (p) and oxidation state mercury (Hg2+) property stabilization can largely be trapped by existing cleaner, and Elemental Mercury (Hg0) lazy
Property it is high, be largely difficult to trap to be discharged into atmosphere.Elemental Mercury is improved to study at present to the conversion ratio of other form mercury
Main way, exploitation smoke mercury emission control technology cardinal principle be synchronized using existing flue gas polution control device it is de-
Mercury, therefore its core is the catalysis oxidation of Elemental Mercury, i.e., is aoxidized after fume dust remover using catalyst.It improves single
Matter mercury oxidation generates mercuric rate, removes it in flue washing device or desulfurizer.
Nonferrous smelting mercury emissions are to be only second to the coal-fired second largest mercury emissions source, and Flue Gas of Nonferrous Smelting and other flue gases are (such as
Coal-fired flue-gas) it compares, there is SO2High feature, SO with elemental mercury concentration2Catalyst poisoning is easily led to lose activity.In addition, single
The catalysis oxidation of matter mercury usually requires HCl mediation, but HCl content is extremely low in Flue Gas of Nonferrous Smelting.It can be seen that traditional catalyst
Be difficult to directly apply to during Flue Gas of Nonferrous Smelting demercuration, develop a kind of environmental protection, efficiently, cheap, resistance to SO_2 is high and HCl according to
The composite metal catalyst for relying property low is extremely urgent.
Co9S8Due to its complicated structure and characteristic, attract attention.Currently, Co9S8Mainly as one
Kind important hydrodesulfurization catalyst agent and magnetic material etc..And Co9S8Composite material be used as more electrode material for electro-catalysis lead
Domain etc., if Chinese patent (CN104229731A) discloses a kind of Co9S8/ graphene composite hydrogen storage material and preparation method thereof,
Hydrogen storage material maximum hydrogen storage capability is prepared into battery up to 3.73wt%, by Co9S8/ graphene composite hydrogen storage material, is recycling
After 20 times, hydrogen storage ability remains at 88% or more, and under the conditions of the discharge current density of 1000mA/g, discharge capability is still
It is maintained at 80% or more.But there is presently no the relevant reports used as catalysis oxidation demercuration catalyst.
Currently, Co9S8Solid reaction process synthesis is generallyd use, for example, in silica tube, stoichiometrically hybrid solid
Elemental sulfur and simple substance cobalt, Co can be synthesized at high temperature9S8Compound.Also there is the synthesis of document report hydro-thermal method low temperature in recent years
Nano Co9S8Polycrystalline.There are also prepare Co using high energy ball mill method9S8, as obtained Co after cobalt powder and sulphur powder high-energy ball milling9S8Powder
End.But the prior art yet there are no using cobalt salt and thiocarbamide as raw material and prepare Co9S8Relevant report.
Summary of the invention
In view of the defects existing in the prior art, the first purpose of this invention is to be to provide one kind by cobalt sulfide original position
It is supported on the cobalt sulfide/biomass carbon composite material constituted on biomass carbon, the cobalt sulfide good dispersion of the composite material,
High oxidation catalytic activity is shown to Elemental Mercury.
Another object of the present invention is to be to provide that a kind of method is simple, raw material are easy to get, lower-cost prepares cobalt
Sulfide/biomass carbon composite material method.
Third object of the present invention is to be to provide a kind of application of cobalt sulfide/biomass carbon composite material, is made
For elemental mercury oxidation catalyst application, higher catalytic activity is shown in a mild condition, particularly suitable for single in flue gas
The removing of matter mercury, cobalt sulfide/biomass carbon composite material utilize O present in flue gas at low temperatures2With micro HCl
It can realize the Efficient Conversion of nonvalent mercury；More importantly in SO2In the presence of the height of Elemental Mercury under the conditions of no chlorine may be implemented
Effect conversion, for conversion ratio up to 100%, which solves traditional demercuration catalyst in high concentration SO2Under the conditions of inactivate
The problem of with needing higher concentration HCl to be just able to achieve Elemental Mercury to mercuric Efficient Conversion.
In order to achieve the above technical purposes, the present invention provides a kind of cobalt sulfide/biomass carbon composite materials, by cobalt
Sulfide is supported on biomass carbon and constitutes.
Biomass carbon has pore structure abundant and biggish in cobalt sulfide/biomass carbon composite material of the invention
Specific surface area can disperse cobalt sulfide well, cobalt sulfide is made to show higher catalytic activity.
Preferred scheme, in cobalt sulfide/biomass carbon composite material the mass percentage content of cobalt sulfide be 30~
40%；The cobalt sulfide is hengleinite type Co9S8。
The present invention also provides a kind of preparation methods of cobalt sulfide/biomass carbon composite material comprising following steps:
1) by cobalt salt solution and thiocarbamide hybrid reaction, cobalt complex solution is obtained；
2) biomass material is placed in cobalt complex solution after impregnation, it is dry, obtain persursor material；
3) persursor material is placed under protective atmosphere be heat-treated to get.
In cobalt sulfide/biomass carbon composite material preparation process of the invention, biomass material is first passed through to load
Cobalt-thiourea complex realizes cobalt-thiocarbamide using the fiber multihole structure of biomass material come absorption carriage cobalt-thiourea complex
Complex dispersion and steady load, then by pyroreaction, the charing on the one hand carrying out biomass material generates biomass raw material of wood-charcoal
Material, another aspect pyroreaction generate Co9S8, and growth in situ obtains stable composite material on biomass carbon.
Preferred scheme, the molar ratio of cobalt salt and thiocarbamide is (0.1~1) in cobalt salt solution: 1.It, can in the proportional region
To obtain stable cobalt-thiourea complex.
Preferred scheme, the concentration of the cobalt salt solution are 0.05~1mol/L.Cobalt salt refers to water-soluble cobalt salt, such as
Cobalt nitrate etc..
Preferred scheme, biomass material are 20~100g/L with respect to the additional amount of cobalt complex solution.
More preferably scheme, the biomass material include at least one of pomelo peel, rice straw, corn stover.This
A little biomass materials pass through conventional drying and crushing pretreatment.
Preferred scheme, dip time are 18~32h.Dipping process mainly makes cobalt complex solution permeate biomass completely
Raw material.
Preferred scheme, heat treatment process are as follows: be warming up to 500~900 DEG C with 2~10 DEG C/min rate, keep the temperature 2~4h.
Cobalt sulfide/biomass carbon composite material preparation method of the invention includes preparation step in detail below:
1) by analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.05
The red solution of~1mol/L, acquired solution are denoted as A；
2) analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+With SC (NH2)2Mole
Concentration ratio is (0.1~1): 1,2~4h is stirred, acquired solution is denoted as B；
3) 1~5g biomass (one of pomelo peel, rice straw, corn stover or a variety of) is added in solution B
It is mixed with dipping, stands 18~32h, be dried to obtain sample C in 80 DEG C of baking ovens；
4) sample C is placed in 500~900 DEG C of tube furnace, roasts 2~4h, heating rate 2 in a nitrogen atmosphere
~10 DEG C/min；
5) cooled to room temperature, the cobalt that taking-up obtains black from roasting pipe vulcanize in a nitrogen atmosphere after roasting
Object/biomass carbon composite material.
The present invention also provides the applications of cobalt sulfide/biomass carbon composite material, are used as elemental mercury oxidation catalyst
Using.
Cobalt sulfide/biomass carbon composite material of the invention carrys out catalysis oxidation flue gas particularly suitable as oxidation catalyst
In Elemental Mercury, by elemental mercury oxidation at being easy to be absorbed fixed bivalent mercury.Flue gas refers generally to mercurous flue gas, such as smelts cigarette
Gas, flue gas in power station boiler, Industrial Boiler flue gas, industrial furnace smoke etc..Flue-gas temperature range is 50~200 DEG C, mercury (Hg0)
Concentration is 0.1~1000 μ g/Nm3.Other compositions in flue gas, such as O2: 0.1%~15% (volumetric concentration), N2: 30%~80%
(volumetric concentration), SO2: 0.01%~8% (volumetric concentration), CO2: 0%~10% (volumetric concentration), HCl:2~10ppm.
Cobalt sulfide of the invention/biomass carbon composite material catalytic oxidative desulfurization gaseous elemental mercury method: by flue gas
It is passed through filled in cobalt sulfide/biomass carbon composite catalyst device (such as fixed bed reactors), carries out catalysis oxygen
Change reaction；It is adjusted by control cobalt sulfide/additional amount of the biomass carbon composite catalyst in fixed bed reactors
Reaction velocity, the quality that catalyst is added is 50~100mg, in the case where being catalyzed atmospheric condition air speed can reach 100000~
250000h-1, greatly improve treatment quantity.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1, cobalt of the invention sulfide/biomass carbon composite material is as the catalyst to catalysis oxidation nonvalent mercury generates divalent
Mercury has opened up the new approaches of catalytic treatment mercury fume.
2, cobalt of the invention sulfide/biomass carbon composite material preparation process is simple, and raw material is easy to get and mild condition,
Be conducive to industrialized production.
3, cobalt of the invention sulfide/biomass carbon composite material is low to the dependence of HCl gas, when HCl concentration drops to
When 2ppm, catalytic efficiency maintains 100%.
4, cobalt of the invention sulfide/biomass carbon composite material has chlorine-free highly effective demercuration performance, and at 50 DEG C, oxygen is deposited
Under conditions, SO2When concentration is 5%, catalytic effect is stablized, and removal efficiency is up to 100%；Solves traditional demercuration catalyst
In high concentration SO2Under the conditions of the problem of inactivating and higher concentration HCl is needed just to be able to achieve Elemental Mercury to mercuric Efficient Conversion.
5, cobalt of the invention sulfide/biomass carbon composite material stable in catalytic performance, runs for 24 hours still under catalytic condition
It can maintain 100% removal efficiency.
6, cobalt of the invention sulfide/biomass carbon composite material prepares biomass carbon carrier material using biomass material
Material, can make cobalt sulfide good dispersion, improve its catalytic activity, and biomass material is easy to get, and agricultural wastes may be implemented
Recycling.
Detailed description of the invention
[Fig. 1] is cobalt sulfide/biomass carbon composite material X-ray diffraction (XRD) map prepared by embodiment 2.
[Fig. 2] is cobalt sulfide/biomass carbon composite material sem energy spectrum analysis (EDS) prepared by embodiment 2
Photo.
[Fig. 3] is that cobalt sulfide/biomass carbon composite material catalyst under the conditions of different atmosphere is catalyzed oxygen to Elemental Mercury
Change the influence test effect figure of activity and various concentration HCl to catalyst activity.
[Fig. 4] is the catalysis of catalyst to Elemental Mercury under condition of different temperatures of cobalt sulfide/biomass carbon composite material
Oxidation effectiveness figure.
[Fig. 5] is the test of cobalt sulfide/biomass carbon composite material catalyst under the conditions of long-time catalytic stability
Effect picture.
[Fig. 6] is cobalt sulfide/biomass carbon composite material sulfur resistive active testing effect picture.
[Fig. 7] is cobalt sulfide/biomass carbon composite material without chlorine catalytic activity test effect figure.
Specific embodiment
Following embodiment is intended to be described in further detail the content of present invention in conjunction with attached drawing, not limits right of the present invention
Claimed range.
Embodiment 1
By analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.1mol/L
Red solution, acquired solution is denoted as A；Analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+
With SC (NH2)2Molar concentration rate be 0.1:1, stir 3h, acquired solution is denoted as B；1g biomass (pomelo peel) is added to molten
It is mixed with dipping in liquid B, stands for 24 hours, be dried to obtain sample C in 80 DEG C of baking ovens；Sample C is placed in 900 DEG C of tube furnace,
2h is roasted under nitrogen atmosphere, heating rate is 5 DEG C/min；Cooled to room temperature in a nitrogen atmosphere after roasting is managed from roasting
Middle taking-up obtains cobalt sulfide/biomass carbon composite material of black.
Embodiment 2
By analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.1mol/L
Red solution, acquired solution is denoted as A；Analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+
With SC (NH2)2Molar concentration rate be 0.5:1, stir 3h, acquired solution is denoted as B；3g biomass (pomelo peel) is added to molten
It is mixed with dipping in liquid B, stands for 24 hours, be dried to obtain sample C in 80 DEG C of baking ovens；Sample C is placed in 800 DEG C of tube furnace,
2h is roasted under nitrogen atmosphere, heating rate is 5 DEG C/min；Cooled to room temperature in a nitrogen atmosphere after roasting is managed from roasting
Middle taking-up obtains cobalt sulfide/biomass carbon composite material of black.It is penetrated using 2500 VB+XX type X of Rigaku D/Max
Line diffractometer analysis gained sample finds that the crystal phase of products therefrom is hengleinite type Co9S8, XRD diffracting spectrum and standard
Card (PDF No.86-2273) peak position can be corresponded to well, is illustrated in fig. 1 shown below.Use Jeol company JSM-IT300LA
Type scanning electron microscopic observation sample topography and progress energy spectrum analysis, can obviously find that cobalt sulfide is successfully supported on biomass carrier
On, and good dispersion, it is illustrated in fig. 2 shown below.
Embodiment 3
By analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.1mol/L
Red solution, acquired solution is denoted as A；Analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+
With SC (NH2)2Molar concentration rate be 0.5:1, stir 3h, acquired solution is denoted as B；3g biomass (corn stover) is added to
It is mixed with dipping in solution B, stands for 24 hours, be dried to obtain sample C in 80 DEG C of baking ovens；Sample C is placed in 700 DEG C of tube furnace
In, 2h is roasted in a nitrogen atmosphere, and heating rate is 5 DEG C/min；Cooled to room temperature in a nitrogen atmosphere after roasting, from roasting
Burn the cobalt sulfide/biomass carbon composite material for taking out in pipe and obtaining black.
Embodiment 4
By analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.1mol/L
Red solution, acquired solution is denoted as A；Analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+
With SC (NH2)2Molar concentration rate be 0.5:1, stir 3h, acquired solution is denoted as B；5g biomass (pomelo peel) is added to molten
It is mixed with dipping in liquid B, stands for 24 hours, be dried to obtain sample C in 80 DEG C of baking ovens；Sample C is placed in 600 DEG C of tube furnace,
2h is roasted under nitrogen atmosphere, heating rate is 5 DEG C/min；Cooled to room temperature in a nitrogen atmosphere after roasting is managed from roasting
Middle taking-up obtains cobalt sulfide/biomass carbon composite material of black.
Embodiment 5
By analytically pure cobalt nitrate (Co (NO3)2·6H2O it) is add to deionized water, Co is made2+Concentration is 0.1mol/L
Red solution, acquired solution is denoted as A；Analytically pure thiocarbamide (SC (NH is added into solution A2)2), make Co in mixed solution2+
With SC (NH2)2Molar concentration rate be 1:1, stir 3h, acquired solution is denoted as B；5g biomass (rice straw) is added to molten
It is mixed with dipping in liquid B, stands for 24 hours, be dried to obtain sample C in 80 DEG C of baking ovens；Sample C is placed in 500 DEG C of tube furnace,
2h is roasted under nitrogen atmosphere, heating rate is 5 DEG C/min；Cooled to room temperature in a nitrogen atmosphere after roasting is managed from roasting
Middle taking-up obtains cobalt sulfide/biomass carbon composite material of black.
Embodiment 6
The influence test of catalyst oxidation activity and various concentration HCl to catalyst activity:
Experiment carries out in fixed bed reactors, and catalyst (preparation of embodiment 2) amount of fill is 50mg, using N2As
Hg0Carrier gas, control its flow 200mL/min, Hg in flue gas0Concentration is 260 μ g/m3Left and right, another way N2It is protected as Balance Air
Holding total gas flow rate is 600mL/min, and experimental temperature is 150 DEG C.Setting experiment atmospheric condition, reaction 1: is added without any oxidation
Gas is only passed through the nitrogen as carrier gas and Balance Air；Reaction 2: it is passed through 6%O2, remaining gas N2；Reaction 3: it is passed through 6%
O2, 2ppm HCl, remaining gas N2；Reaction 4: it is passed through 6%O2, 10ppmHCl, remaining gas N2.After fume treatment, mercury is dense
Degree records catalyst treatment efficiency after reaching stable.As a result as shown in Figure 3.
Embodiment 7
Temperature influences to test on catalyst activity:
Experiment carries out in fixed bed reactors, and catalyst (preparation of embodiment 2) amount of fill is 50mg, using N2As
Hg0Carrier gas, control its flow 200mL/min, Hg in flue gas0Concentration is 260 μ g/m3Left and right, another way N2It is protected as Balance Air
Holding total gas flow rate is 600mL/min, is passed through oxidizing atmosphere 6%O2And 10ppmHCl.Reaction temperature condition is set, reaction 1:
50℃；2:100 DEG C of reaction；3:150 DEG C of reaction；4:200 DEG C of reaction.After fume treatment, mercury concentration records catalysis after reaching stable
Agent treatment effeciency.As a result as shown in Figure 4.
Embodiment 8
Catalytic stability test:
Experiment carries out in fixed bed reactors, and catalyst (preparation of embodiment 2) amount of fill is 50mg, using N2As
Hg0Carrier gas, control its flow 200mL/min, Hg in flue gas0Concentration is 240 μ g/m3Left and right, another way N2It is protected as Balance Air
Holding total gas flow rate is 600mL/min, is passed through oxidizing atmosphere 6%O2And 10ppmHCl, reaction temperature are 50 DEG C, the reaction time
For 24 hours, test data is as shown in Figure 5.
Embodiment 9
Catalyst sulfur resistive active testing:
Experiment carries out in fixed bed reactors, and catalyst (preparation of embodiment 2) amount of fill is 50mg, using N2As
Hg0Carrier gas, control its flow 200mL/min, Hg in flue gas0Concentration is 240 μ g/m3Left and right, another way N2It is protected as Balance Air
Holding total gas flow rate is 600mL/min, and experimental temperature is 150 DEG C.Setting experiment atmospheric condition, reaction 1: is passed through 6%O2,
10ppm HCl, remaining gas N2；Reaction 2: it is passed through 6%O2, 10ppm HCl, 0.5%SO2, remaining gas N2；Reaction 3:
It is passed through 6%O2, 10ppm HCl, 2%SO2, remaining gas N2；Reaction 4: it is passed through 6%O2, 10ppm HCl, 5%SO2, remaining
Gas is N2.After fume treatment, mercury concentration records catalyst treatment efficiency after reaching stable.As a result as shown in Figure 6.
Embodiment 10
Catalyst is tested without chlorine catalytic activity:
Experiment carries out in fixed bed reactors, and catalyst (preparation of embodiment 2) amount of fill is 50mg, using N2As
Hg0Carrier gas, control its flow 200mL/min, Hg in flue gas0Concentration is 240 μ g/m3Left and right, another way N2It is protected as Balance Air
Holding total gas flow rate is 600mL/min, and experimental temperature is 50 DEG C.Setting experiment atmospheric condition, reaction 1: is passed through 0.5%SO2,
Remaining gas is N2；Reaction 2: it is passed through 2%SO2, remaining gas N2；Reaction 3: it is passed through 6%O2, 0.5%SO2, remaining gas is
N2.After fume treatment, mercury concentration records catalyst treatment efficiency after reaching stable.As a result as shown in Figure 7.
Claims (10)
1. a kind of cobalt sulfide/biomass carbon composite material, it is characterised in that: be supported on structure on biomass carbon by cobalt sulfide
At.
2. a kind of cobalt sulfide/biomass carbon composite material according to claim 1, it is characterised in that: the cobalt vulcanization
The mass percentage content of object is 30~40%；The cobalt sulfide is hengleinite type Co9S8。
3. a kind of preparation method of cobalt sulfide/biomass carbon composite material of any of claims 1 or 2, it is characterised in that: packet
Include following steps:
1) by cobalt salt solution and thiocarbamide hybrid reaction, cobalt complex solution is obtained；
2) biomass material is placed in cobalt complex solution after impregnation, it is dry, obtain persursor material；
3) persursor material is placed under protective atmosphere be heat-treated to get.
4. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 3, it is characterised in that:
The molar ratio of cobalt salt and thiocarbamide is (0.1~1) in cobalt salt solution: 1.
5. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 4, it is characterised in that:
The cobalt salt concentration of the cobalt salt solution is 0.05~1mol/L.
6. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 3, it is characterised in that:
Biomass material is 20~100g/L with respect to the additional amount of cobalt complex solution.
7. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 6, it is characterised in that:
The biomass material includes at least one of pomelo peel, rice straw, corn stover.
8. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 3, it is characterised in that:
Dip time is 18~32h.
9. a kind of preparation method of cobalt sulfide/biomass carbon composite material according to claim 3, it is characterised in that:
Heat treatment process are as follows: be warming up to 500~900 DEG C with 2~10 DEG C/min rate, keep the temperature 2~4h.
10. the application of cobalt sulfide/biomass carbon composite material of any of claims 1 or 2, it is characterised in that: as simple substance
Mercury oxidation catalyst application.
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| CN111408362A (en) * | 2020-03-23 | 2020-07-14 | 山东鲁北国际新材料研究院有限公司 | Sea urchin-shaped cobalt sulfide-charcoal composite material and preparation method and application thereof |
| CN112264046A (en) * | 2020-09-15 | 2021-01-26 | 金陵科技学院 | Co derived from coordination compound9S8Porous carbon composite catalyst and preparation method thereof |
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| CN114100576A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Cobalt disulfide/carbon composite material and preparation method and application thereof |
| BE1029905A1 (en) | 2023-01-30 | 2023-06-02 | Univ Jiangxi Sci & Technology | METHOD FOR PREPARING AND APPLYING A POROUS CARBON LOADED COPPER-COBALT COMPOSITE LOW CHLORINE DEMERCURY CATALYST TO A CARBON FIBER FABRIC |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130239469A1 (en) * | 2012-03-14 | 2013-09-19 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
| CN106908498A (en) * | 2017-04-07 | 2017-06-30 | 安徽工业大学 | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite |
| CN108301017A (en) * | 2018-03-12 | 2018-07-20 | 郑州大学 | A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof |
| CN108588752A (en) * | 2018-04-26 | 2018-09-28 | 郑州大学 | A kind of water electrolysis hydrogen production catalyst Co9S8/ rGO and preparation method thereof |
-
2018
- 2018-11-19 CN CN201811377852.7A patent/CN109529885B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130239469A1 (en) * | 2012-03-14 | 2013-09-19 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
| CN106908498A (en) * | 2017-04-07 | 2017-06-30 | 安徽工业大学 | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite |
| CN108301017A (en) * | 2018-03-12 | 2018-07-20 | 郑州大学 | A kind of water electrolysis hydrogen production catalyst Co9S8@CNT and preparation method thereof |
| CN108588752A (en) * | 2018-04-26 | 2018-09-28 | 郑州大学 | A kind of water electrolysis hydrogen production catalyst Co9S8/ rGO and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| GIHOON KWON ET AL.: "One step fabrication of carbon supported cobalt pentlandite (Co9S8) via the thermolysis of lignin and Co3O4", 《JOURNAL OF CO₂ UTILIZATION》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492090A (en) * | 2019-09-29 | 2019-11-22 | 西北师范大学 | A kind of biomass carbon cladding cobalt sulfide-eight vulcanizes the preparation and application of nine cobalt composite materials |
| CN110492090B (en) * | 2019-09-29 | 2022-05-24 | 西北师范大学 | Preparation and application of biomass carbon-coated cobalt sulfide-cobalt octasulfide composite material |
| CN111129531A (en) * | 2020-01-06 | 2020-05-08 | 西安航空职业技术学院 | Preparation method of cobalt-nitrogen co-doped biomass carbon zinc-air battery catalyst |
| KR102257706B1 (en) * | 2020-02-24 | 2021-05-27 | 아주대학교산학협력단 | Biomass-based porous carbon-supported metal catalyst, method for preparing the same, and method for preparing tetrahydrofuran from furan using the catalyst |
| CN111408362A (en) * | 2020-03-23 | 2020-07-14 | 山东鲁北国际新材料研究院有限公司 | Sea urchin-shaped cobalt sulfide-charcoal composite material and preparation method and application thereof |
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| CN114100576A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Cobalt disulfide/carbon composite material and preparation method and application thereof |
| CN114100576B (en) * | 2021-11-24 | 2023-07-18 | 中南大学 | Cobalt disulfide/carbon composite material and preparation method and application thereof |
| BE1029905A1 (en) | 2023-01-30 | 2023-06-02 | Univ Jiangxi Sci & Technology | METHOD FOR PREPARING AND APPLYING A POROUS CARBON LOADED COPPER-COBALT COMPOSITE LOW CHLORINE DEMERCURY CATALYST TO A CARBON FIBER FABRIC |
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