CN109529885B - Cobalt sulfide/biomass charcoal composite material, preparation method thereof and application of cobalt sulfide/biomass charcoal composite material as elemental mercury oxidation catalyst - Google Patents
Cobalt sulfide/biomass charcoal composite material, preparation method thereof and application of cobalt sulfide/biomass charcoal composite material as elemental mercury oxidation catalyst Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a cobalt sulfide/biomass charcoal composite material, a preparation method thereof and application of the composite material as a simple substance mercury oxidation catalyst. The preparation process comprises the following steps: mixing and reacting a cobalt salt solution and thiourea to obtain a cobalt complex solution; placing a biomass raw material in a cobalt complex solution for dipping treatment, and drying to obtain a precursor material; and (3) putting the precursor material in a protective atmosphere for heat treatment to obtain the material. The cobalt sulfide/biomass charcoal composite material shows higher elemental mercury oxidation catalytic activity under mild conditions, is particularly suitable for removing elemental mercury in flue gas and can be used for removing elemental mercury in SO2When the catalyst exists, the high-efficiency oxidation conversion of elemental mercury under the chlorine-free condition is realized, the conversion rate can reach 100 percent, and the problem that the traditional demercuration catalyst is used for preparing high-concentration SO2Deactivation under conditions and the need for higher concentrations of HCl to achieve efficient conversion of elemental mercury to divalent mercury.
Description
Technical Field
The invention relates to a catalytic material, in particular to a cobalt sulfide/biomass charcoal composite catalytic material for elemental mercury catalytic oxidation, a preparation method of the cobalt sulfide/biomass charcoal composite material, and application of the cobalt sulfide/biomass charcoal composite material in the aspect of elemental mercury oxidation catalysis, and belongs to the field of mercury pollution emission control.
Background
Mercury is a toxic heavy metal with durability, accumulation, easy migration, and high biological enrichment, and has been listed as the only pollutant that affects the world, in addition to greenhouse gases. In 2013, 19 months 1, the United nations environmental planning agency establishes the Water Accident for controlling the global mercury pollution problem, and 147 member countries including China are required to take action together on reducing the mercury emission. In 2016, the decision of approving "water guarantee about mercury" is passed in China, and the approval is formally carried out in the same year, 8 months, so that the mercury pollution prevention and performance work can be comprehensively carried out in China. The convention formally takes effect in 2017, 8 and 16.
In the mercury-containing flue gas, three kinds of mercury with different forms exist, and the mercury has different chemical properties and different removal difficulty degrees: particulate mercury Hg (p) and oxidized mercury (Hg)2+) The mercury (Hg) with stable property can be captured by the existing dust-removing equipment in a large amount0) The inertness is high and most of them are difficult to trap and thus to discharge into the atmosphere. The main direction of research at present is to improve the conversion rate of elemental mercury into mercury in other forms, and the important principle for developing the flue gas mercury emission control technology is to synchronously remove mercury by using the existing flue gas pollution control device, so the core of the method is the catalytic oxidation of elemental mercury, namely, the catalytic oxidation is carried out by using a catalyst after a flue gas dust removal device. The rate of the bivalent mercury generated by the oxidation of the elemental mercury is increased, so that the bivalent mercury is removed in a flue gas washing device or a desulfurization device.
The nonferrous smelting mercury emission is the second largest mercury emission source next to the coal, and compared with other flue gas (such as coal-fired flue gas), the nonferrous smelting flue gas has SO2And a high elemental mercury concentration, SO2Easily cause catalyst poisoning and deactivation. In addition, catalytic oxidation of elemental mercury typically requires HCl mediation, but the nonferrous smelting fumes have very low HCl content. Therefore, the traditional catalyst is difficult to be directly applied to the process of mercury removal from non-ferrous smelting flue gas, and the development of the composite metal catalyst which is environment-friendly, efficient, low in cost, high in sulfur resistance and low in HCl dependence is urgent.
Co9S8Have attracted attention due to their complex structures and characteristics. At present, the method，Co9S8Mainly used as an important hydrodesulfurization catalyst, magnetic material and the like. And Co9S8For example, Chinese patent (CN104229731A) discloses a Co9S 8/graphene composite hydrogen storage material and a preparation method thereof, the maximum hydrogen storage capacity of the hydrogen storage material can reach 3.73 wt%, the Co9S 8/graphene composite hydrogen storage material is prepared into a battery, the hydrogen storage capacity is still kept above 88% after 20 times of circulation, and the discharge capacity is still kept above 80% under the condition of 1000mA/g discharge current density. However, no report about the use of the catalyst as a catalytic oxidation demercuration catalyst exists at present.
At present, Co9S8It is generally synthesized by solid-phase reaction, for example, mixing solid elemental sulfur and elemental cobalt in stoichiometric ratio in a silica tube, and Co can be synthesized at high temperature9S8A compound is provided. In recent years, the hydrothermal method for synthesizing nano Co at low temperature is reported9S8And (4) polycrystallization. Also adopts a high-energy ball milling method to prepare Co9S8For example, cobalt powder and sulfur powder are subjected to high-energy ball milling to obtain Co9S8And (3) powder. However, the prior art does not show that Co is prepared by taking cobalt salt and thiourea as raw materials9S8The related reports of (1).
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a cobalt sulfide/biomass charcoal composite material formed by loading cobalt sulfide on biomass charcoal in situ, wherein the cobalt sulfide of the composite material has good dispersibility and shows high oxidation catalytic activity on elemental mercury.
The invention also aims to provide a method for preparing the cobalt sulfide/biomass charcoal composite material, which has the advantages of simple method, readily available raw materials and lower cost.
The third purpose of the invention is to provide an application of the cobalt sulfide/biomass charcoal composite material, which is used as an elemental mercury oxidation catalyst, shows higher catalytic activity under mild conditions, is particularly suitable for removing elemental mercury in flue gas, and is cobalt sulfide/biomass charcoal composite materialCarbon composite material utilizes O existing in flue gas at low temperature2And trace HCl can realize the high-efficiency conversion of zero-valent mercury; more importantly in SO2When the catalyst exists, the high-efficiency conversion of elemental mercury under the chlorine-free condition can be realized, the conversion rate can reach 100 percent, and the composite catalyst solves the problem that the traditional demercuration catalyst is used for high-concentration SO2Deactivation under conditions and the need for higher concentrations of HCl to achieve efficient conversion of elemental mercury to divalent mercury.
In order to achieve the technical purpose, the invention provides a cobalt sulfide/biomass charcoal composite material which is formed by loading cobalt sulfide on biomass charcoal.
The biomass charcoal in the cobalt sulfide/biomass charcoal composite material has rich pore structures and larger specific surface area, and can well disperse cobalt sulfide, so that the cobalt sulfide shows higher catalytic activity.
In the preferred scheme, the mass percentage content of cobalt sulfide in the cobalt sulfide/biomass charcoal composite material is 30-40%; the cobalt sulfide is cobalt nickel pyrite type Co9S8。
The invention also provides a preparation method of the cobalt sulfide/biomass charcoal composite material, which comprises the following steps:
1) mixing and reacting a cobalt salt solution and thiourea to obtain a cobalt complex solution;
2) placing a biomass raw material in a cobalt complex solution for dipping treatment, and drying to obtain a precursor material;
3) and (3) putting the precursor material in a protective atmosphere for heat treatment to obtain the material.
In the preparation process of the cobalt sulfide/biomass charcoal composite material, the biomass raw material is firstly used for loading the cobalt-thiourea complex, the fiber porous structure of the biomass raw material is used for adsorbing and loading the cobalt-thiourea complex, the dispersion and stable loading of the cobalt-thiourea complex are realized, and then the biomass raw material is carbonized to generate the biomass charcoal material on one hand and the Co is generated by high-temperature reaction on the other hand9S8And growing on the biomass charcoal in situ to obtain the stable composite material.
In a preferred embodiment, the molar ratio of the cobalt salt to the thiourea in the cobalt salt solution is (0.1-1): 1. Within this ratio range, a stable cobalt-thiourea complex can be obtained.
In a preferable scheme, the concentration of the cobalt salt solution is 0.05-1 mol/L. Cobalt salts refer to water soluble cobalt salts such as cobalt nitrate and the like.
In the preferable scheme, the addition amount of the biomass raw material relative to the cobalt complex solution is 20-100 g/L.
In a more preferable scheme, the biomass raw material comprises at least one of shaddock peel, rice straw and corn straw. These biomass feedstocks are pretreated by conventional dry comminution.
Preferably, the dipping time is 18-32 h. The impregnation process mainly allows the cobalt complex solution to completely penetrate the biomass raw material.
Preferably, the heat treatment process comprises the following steps: heating to 500-900 ℃ at the speed of 2-10 ℃/min, and preserving heat for 2-4 h.
The preparation method of the cobalt sulfide/biomass charcoal composite material comprises the following specific preparation steps:
1) analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.05-1 mol/L, wherein the obtained solution is marked as A;
2) to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2The molar concentration ratio of (0.1-1) to (1), stirring for 2-4 h, and marking the obtained solution as B;
3) adding 1-5 g of biomass (one or more of shaddock peel, rice straw and corn straw) into the solution B, mixing and soaking, standing for 18-32 h, and drying in an oven at 80 ℃ to obtain a sample C;
4) placing the sample C in a tubular furnace at 500-900 ℃, and roasting for 2-4 h in a nitrogen atmosphere, wherein the heating rate is 2-10 ℃/min;
5) and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material.
The invention also provides an application of the cobalt sulfide/biomass charcoal composite material as an elemental mercury oxidation catalyst.
The cobalt sulfide/biomass charcoal composite material is particularly suitable for being used as an oxidation catalyst to catalyze and oxidize elemental mercury in flue gas, and the elemental mercury is oxidized into bivalent mercury which is easy to absorb and fix. The flue gas generally refers to flue gas containing mercury, such as smelting flue gas, power station boiler flue gas, industrial kiln flue gas and the like. The temperature range of the flue gas is 50-200 ℃, and mercury (Hg) is0) The concentration is 0.1 to 1000 mug/Nm3. Other constituents of flue gases, e.g. O20.1-15% (volume concentration), N230-80% (volume concentration), SO20.01-8% (volume concentration), CO20-10% (volume concentration), HCl: 2 to 10 ppm.
The method for removing gaseous elementary mercury by catalytic oxidation of the cobalt sulfide/biomass charcoal composite material comprises the following steps: introducing the flue gas into a device (such as a fixed bed reactor) filled with a cobalt sulfide/biomass charcoal composite material catalyst for catalytic oxidation reaction; the reaction space velocity is adjusted by controlling the adding amount of the cobalt sulfide/biomass charcoal composite material catalyst in the fixed bed reactor, the mass of the added catalyst is 50-100 mg, and the space velocity can reach 100000-250000 h under the catalytic atmosphere condition-1Greatly improving the smoke treatment capacity.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the cobalt sulfide/biomass charcoal composite material is used as a catalyst to catalyze and oxidize zero-valent mercury to generate divalent mercury, and a new idea for catalytically treating mercury-containing flue gas is developed.
2. The cobalt sulfide/biomass charcoal composite material has the advantages of simple preparation process, easily obtained raw materials and mild conditions, and is beneficial to industrial production.
3. The cobalt sulfide/biomass charcoal composite material provided by the invention has low dependence on HCl gas, and when the HCl concentration is reduced to 2ppm, the catalytic efficiency is maintained at 100%.
4. According to the inventionThe cobalt sulfide/biomass charcoal composite material has chlorine-free high-efficiency demercuration performance, and SO is generated in the presence of oxygen at 50 DEG C2When the concentration is 5%, the catalytic effect is stable, and the removal efficiency reaches 100%; solves the problem that the traditional demercuration catalyst has high concentration SO2Deactivation under conditions and the need for higher concentrations of HCl to achieve efficient conversion of elemental mercury to divalent mercury.
5. The cobalt sulfide/biomass charcoal composite material has stable catalytic performance, and can still maintain 100% of removal efficiency after running for 24 hours under the catalytic condition.
6. The cobalt sulfide/biomass charcoal composite material provided by the invention is used for preparing the biomass charcoal carrier material by utilizing the biomass raw material, so that the cobalt sulfide is good in dispersity, the catalytic activity of the cobalt sulfide is improved, the biomass raw material is easy to obtain, and the recycling of agricultural wastes can be realized.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the cobalt sulfide/biomass charcoal composite prepared in example 2.
Fig. 2 is a scanning electron microscopy spectroscopy (EDS) photograph of the cobalt sulfide/biomass charcoal composite prepared in example 2.
Fig. 3 is a diagram illustrating the effect of a cobalt sulfide/biomass charcoal composite material on the catalytic oxidation activity of elemental mercury by a catalyst under different atmosphere conditions and the effect of HCl with different concentrations on the activity of the catalyst.
Fig. 4 is a diagram showing the catalytic oxidation effect of a catalyst on elemental mercury in a cobalt sulfide/biomass charcoal composite material under different temperature conditions.
Fig. 5 is a diagram of the catalytic stability test effect of the cobalt sulfide/biomass charcoal composite material on a catalyst under a long-time condition.
Fig. 6 is a diagram of the effect of the cobalt sulfide/biomass charcoal composite material on sulfur resistance activity test.
FIG. 7 is a diagram showing the effect of chlorine-free catalytic activity test on the cobalt sulfide/biomass charcoal composite material.
Detailed Description
The following examples are intended to illustrate the present invention in further detail with reference to the accompanying drawings, and are not intended to limit the scope of the invention as claimed.
Example 1
Analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.1mol/L, and the obtained solution is marked as A; to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2The molar concentration ratio of the components is 0.1:1, stirring is carried out for 3 hours, and the obtained solution is marked as B; adding 1g of biomass (shaddock peel) into the solution B, mixing and soaking, standing for 24h, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a 900 ℃ tubular furnace, roasting for 2h in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min; and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material.
Example 2
Analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.1mol/L, and the obtained solution is marked as A; to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2The molar concentration ratio of the components is 0.5:1, stirring is carried out for 3 hours, and the obtained solution is marked as B; adding 3g of biomass (shaddock peel) into the solution B, mixing and soaking, standing for 24h, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a 800 ℃ tubular furnace, roasting for 2h under the nitrogen atmosphere, wherein the heating rate is 5 ℃/min; and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material. Analyzing the obtained sample by adopting a Japanese science D/Max 2500 VB + XX type X-ray diffractometer, and finding that the crystal phase of the obtained product is cobalt-nickel-pyrite type Co9S8The XRD diffraction pattern corresponded well to the position of the main peak on a standard card (PDF No.86-2273), as shown in FIG. 1 below. By observing the appearance of the sample by using JSM-IT300LA model scanning electron microscope of Jeol company and carrying out energy spectrum analysis, the fact that the cobalt sulfide is successfully loaded on the biomass carrier and has dispersity can be obviously foundPreferably, as shown in FIG. 2 below.
Example 3
Analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.1mol/L, and the obtained solution is marked as A; to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2The molar concentration ratio of the components is 0.5:1, stirring is carried out for 3 hours, and the obtained solution is marked as B; adding 3g of biomass (corn straws) into the solution B, mixing and soaking, standing for 24 hours, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a 700 ℃ tubular furnace, roasting for 2h in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min; and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material.
Example 4
Analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.1mol/L, and the obtained solution is marked as A; to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2The molar concentration ratio of the components is 0.5:1, stirring is carried out for 3 hours, and the obtained solution is marked as B; adding 5g of biomass (shaddock peel) into the solution B, mixing and soaking, standing for 24h, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a tube furnace at 600 ℃, roasting for 2h under the nitrogen atmosphere, and raising the temperature at the rate of 5 ℃/min; and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material.
Example 5
Analytically pure cobalt nitrate (Co (NO)3)2·6H2O) into deionized water to prepare Co2+A red solution with the concentration of 0.1mol/L, and the obtained solution is marked as A; to solution A, analytically pure thiourea (SC (NH) was added2)2) To make Co in the mixed solution2+And SC (NH)2)2In a molar concentration ratio of 1:1, stirring3h, marking the obtained solution as B; adding 5g of biomass (rice straws) into the solution B, mixing and soaking, standing for 24h, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a 500 ℃ tubular furnace, roasting for 2h in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min; and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the black cobalt sulfide/biomass charcoal composite material.
Example 6
Testing the oxidation activity of the catalyst and the influence of HCl with different concentrations on the activity of the catalyst:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 2) packing of 50mg with N2As Hg0The flow rate of the carrier gas is controlled to be 200mL/min, and Hg in the smoke gas0The concentration was 260. mu.g/m3Left and right, another path N2The total flow of gas was kept at 600mL/min as the balance gas and the experimental temperature was 150 ℃. Setting experimental atmosphere conditions, reaction 1: no oxidizing gas is added, and only nitrogen serving as carrier gas and balance gas is introduced; reaction 2: introducing 6% of O2The rest gas is N2(ii) a Reaction 3: introducing 6% of O22ppm HCl and the balance N2(ii) a Reaction 4: introducing 6% of O210ppm HCl, the remainder being N2. After the flue gas is treated, the catalyst treatment efficiency is recorded after the mercury concentration reaches a stable value. The results are shown in FIG. 3.
Example 7
Temperature effect on catalyst activity test:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 2) packing of 50mg with N2As Hg0The flow rate of the carrier gas is controlled to be 200mL/min, and Hg in the smoke gas0The concentration was 260. mu.g/m3Left and right, another path N2Keeping the total flow of gas at 600mL/min as balance gas, introducing 6% O in oxidizing atmosphere2And 10ppm HCl. Setting reaction temperature conditions, reaction 1: 50 ℃; reaction 2: 100 ℃; reaction 3: 150 ℃; reaction 4: at 200 ℃. After the flue gas is treated, the catalyst treatment efficiency is recorded after the mercury concentration reaches a stable value. The results are shown in FIG. 4.
Example 8
And (3) testing the catalytic stability:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 2) packing of 50mg with N2As Hg0The flow rate of the carrier gas is controlled to be 200mL/min, and Hg in the smoke gas0The concentration was 240. mu.g/m3Left and right, another path N2Keeping the total flow of gas at 600mL/min as balance gas, introducing 6% O in oxidizing atmosphere2And 10ppm HCl, the reaction temperature is 50 ℃, the reaction time is 24h, and the test data are shown in FIG. 5.
Example 9
Testing the sulfur resistance activity of the catalyst:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 2) packing of 50mg with N2As Hg0The flow rate of the carrier gas is controlled to be 200mL/min, and Hg in the smoke gas0The concentration was 240. mu.g/m3Left and right, another path N2The total flow of gas was kept at 600mL/min as the balance gas and the experimental temperature was 150 ℃. Setting experimental atmosphere conditions, reaction 1: introducing 6% of O210ppm HCl and the balance N2(ii) a Reaction 2: introducing 6% of O2，10ppm HCl，0.5％SO2The rest gas is N2(ii) a Reaction 3: introducing 6% of O2，10ppm HCl，2％SO2The rest gas is N2(ii) a Reaction 4: introducing 6% of O2， 10ppm HCl，5％SO2The rest gas is N2. After the flue gas is treated, the catalyst treatment efficiency is recorded after the mercury concentration reaches a stable value. The results are shown in FIG. 6.
Example 10
Testing the chlorine-free catalytic activity of the catalyst:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 2) packing of 50mg with N2As Hg0The flow rate of the carrier gas is controlled to be 200mL/min, and Hg in the smoke gas0The concentration was 240. mu.g/m3Left and right, another path N2The total flow of gas was kept at 600mL/min as the balance gas and the experimental temperature was 50 ℃. Setting experimental atmosphere conditions, reaction 1: 0.5% SO was introduced2The rest of the gasIs N2(ii) a Reaction 2: 2% SO was introduced2The rest gas is N2(ii) a Reaction 3: introducing 6% of O2，0.5％SO2The rest gas is N2. After the flue gas is treated, the catalyst treatment efficiency is recorded after the mercury concentration reaches a stable value. The results are shown in FIG. 7.
Claims (8)
1. The application of the cobalt sulfide/biomass charcoal composite material is characterized in that: the cobalt sulfide/biomass charcoal composite material is formed by loading cobalt sulfide on biomass charcoal; the cobalt sulfide/biomass charcoal composite material is used as a simple substance mercury oxidation catalyst;
the mass percentage content of the cobalt sulfide is 30-40%; the cobalt sulfide is cobalt nickel pyrite type Co9S8。
2. The use of a cobalt sulphide/biomass char composite as claimed in claim 1, wherein: the cobalt sulfide/biomass charcoal composite material is prepared by the following preparation method, and comprises the following steps:
1) mixing and reacting a cobalt salt solution and thiourea to obtain a cobalt complex solution;
2) placing a biomass raw material in a cobalt complex solution for dipping treatment, and drying to obtain a precursor material;
3) and (3) putting the precursor material in a protective atmosphere for heat treatment to obtain the material.
3. The use of a cobalt sulphide/biomass char composite as claimed in claim 2, wherein: the molar ratio of the cobalt salt to the thiourea in the cobalt salt solution is (0.1-1): 1.
4. The use of a cobalt sulphide/biomass char composite as claimed in claim 3, wherein: the cobalt salt concentration of the cobalt salt solution is 0.05-1 mol/L.
5. The use of a cobalt sulphide/biomass char composite as claimed in claim 2, wherein: the adding amount of the biomass raw material relative to the cobalt complex solution is 20-100 g/L.
6. The use of a cobalt sulphide/biomass char composite as claimed in claim 5, wherein: the biomass raw material comprises at least one of shaddock peel, rice straw and corn straw.
7. The use of a cobalt sulphide/biomass char composite as claimed in claim 2, wherein: the dipping time is 18-32 h.
8. The use of a cobalt sulphide/biomass char composite as claimed in claim 2, wherein: the heat treatment process comprises the following steps: heating to 500-900 ℃ at the speed of 2-10 ℃/min, and preserving heat for 2-4 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 CO₂Utilization》.2018,第27卷第196页摘要. * |
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