CN110327880B - Method for preparing demercuration activated carbon from brominated flame retardant and biomass, product and application - Google Patents

Method for preparing demercuration activated carbon from brominated flame retardant and biomass, product and application Download PDF

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CN110327880B
CN110327880B CN201910543934.2A CN201910543934A CN110327880B CN 110327880 B CN110327880 B CN 110327880B CN 201910543934 A CN201910543934 A CN 201910543934A CN 110327880 B CN110327880 B CN 110327880B
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biomass
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CN110327880A (en
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于洁
巴彩玲
伍俊宇
孙路石
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Huazhong University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D—SEPARATION
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    • B01D2257/60—Heavy metals or heavy metal compounds
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Abstract

The invention belongs to the field of activated carbon preparation, and discloses a method for preparing demercuration activated carbon from a brominated flame retardant and biomass, a product and application thereof. The method comprises the steps of S1, drying and crushing the biomass, and mixing the biomass with brominated flame retardant particles according to a preset mass ratio; s2, adding a KOH solution into the mixture, and carrying out hydrothermal reaction under an inert atmosphere to obtain a pyrolytic carbon solid-liquid mixture; s3, drying and grinding the pyrolytic carbon solid-liquid mixture, and then carrying out carbonization reaction in an inert atmosphere to obtain the demercuration activated carbon. The product is prepared by the method. According to the invention, the bromine-containing flame-retardant waste plastic, the biomass and the KOH are pyrolyzed under the condition of full mixing, so that the mercury removal adsorbent with higher mercury removal efficiency can be obtained correspondingly, and the effect of activated carbon on elemental mercury Hg is greatly improved0The chemical adsorption capacity of the mercury removing agent is improved, so that the mercury removing agent is particularly suitable for application occasions such as power plant flue gas mercury removal.

Description

Method for preparing demercuration activated carbon from brominated flame retardant and biomass, product and application
Technical Field
The invention belongs to the technical field of activated carbon preparation, and particularly relates to a method for preparing demercuration activated carbon from a brominated flame retardant and biomass, a product and application of the demercuration activated carbon.
Background
At present, the mercury emission caused by human activities worldwide reaches 1000-. Coal-fired power plants are the most important anthropogenic mercury emission sources, and account for half of the total anthropogenic mercury emission. The Clean Air Mercury Regulation (CAMR) was released in 2005 in the united states, placing additional restrictions on mercury emissions associated with coal-fired power plants. The U.S. Environmental Protection Agency (EPA) in 2012 promulgates mercury and air poison standards (MATS) regulations, forming the final standard for limiting the emissions of mercury, acid gases, and other toxic substances from coal-fired power plants. The emission limit of mercury and compounds thereof is 0.03mg/m specified by the emission standard of atmospheric pollutants (GB13223-2011) of thermal power plants issued in 2011 in China3. Mercury pollution has become a secondary climateWith another global environmental problem after change, mercury pollution control is imperative and has attracted increasing attention.
In coal fired power plant flue gas, mercury occurs in three forms: elemental mercury (Hg)0) Mercury (Hg) in its oxidized state2+) And particulate mercury (Hg)p). Oxidized mercury (Hg)2+) Is easily dissolved in water, can be efficiently removed by wet desulphurization (WFGD) equipment, and has granular mercury (Hg)p) It can also be removed by an electrostatic precipitator (ESP) or a bag-type dust collector (FF). However, elemental mercury (Hg)0) Has high volatility and is hardly soluble in water and is difficult to remove by a flue gas post-treatment device. The removal of elemental mercury has become a key and difficult point in mercury emission control technology. In recent years, many technologies have been developed at home and abroad to remove elemental mercury (Hg)0) The method mainly comprises an adsorption method, a catalytic oxidation method, a photocatalytic oxidation method, a photochemical removal method, a plasma removal method, a wet oxidation method and the like. The mercury adsorption technology is simple in method and high in feasibility, powdered activated carbon is sprayed into a flue from the upstream of dust remover equipment (PCD), and the activated carbon adsorbs gaseous mercury and is collected by a dust remover. Scholars at home and abroad have conducted a great deal of research on carbon-based, calcium-based, metal oxides, natural ores and supported activated carbon. Among them, flue Activated Carbon Injection (ACI) is the most mature and feasible technology for reducing mercury emissions of coal-fired power plants at present, and is commonly used by coal-fired power plants in the united states for mercury emission control. The demercuration performance of NORIT FGD commercial activated carbon is tested by a National Energy Technology Laboratory (NETL) in a plurality of power plants on site, and the result shows that the Hg removal efficiency is 70-90%. However, in the prior art, the preparation method of the activated carbon for adsorbing mercury is complex, the operation cost is high, and the problems of high carbon/mercury ratio, high activated carbon regeneration difficulty and the like exist in colleagues.
Therefore, the field needs to provide the mercury-removing activated carbon which has simple preparation process, low equipment and production cost and good environmental protection property, and simultaneously achieves the double effects of resource treatment of solid wastes and pollutant treatment of coal-fired power plants.
Disclosure of Invention
Addressing the above deficiencies or improvements in the prior artAccording to the method, the product and the application of preparing the demercuration activated carbon by using the brominated flame retardant and the biomass, the demercuration adsorbent with high demercuration efficiency can be correspondingly obtained by carrying out hydrothermal treatment on the brominated flame-retardant waste plastic, the biomass and the KOH under the condition of full mixing and designing the process conditions in the preparation process such as pyrolysis temperature, mixing mass ratio and other parameters, so that the method greatly improves the effect of the activated carbon on preparing the elemental mercury Hg by using the activated carbon0The chemical adsorption capacity of the mercury removing agent is improved, so that the mercury removing agent is particularly suitable for application occasions such as power plant flue gas mercury removal.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for hydrothermally preparing demercuration activated carbon by using a brominated flame retardant and biomass, comprising the following steps:
s1, drying and crushing the biomass, and mixing the biomass with brominated flame retardant particles according to a preset mass ratio;
s2, adding a KOH solution into the mixture obtained in the step S1 to obtain a mixed solution, and carrying out hydrothermal reaction on the mixed solution in an inert atmosphere to obtain a pyrolytic carbon solid-liquid mixture;
s3, drying and grinding the pyrolytic carbon solid-liquid mixture, and then carrying out a carbonization reaction in an inert atmosphere to obtain demercuration activated carbon;
in step S2, the molar ratio of potassium ions to bromide ions in the mixed solution is 1: 1-5: 1.
Further, in step S1, the brominated flame retardant is one or more of tetrabromobisphenol a, hexabromocyclododecane and polybrominated diphenyl ether.
Further, in step S1, the diameter of the dried and crushed biomass and the diameter of the brominated flame retardant particles are both less than 250 μm; the preset mass ratio of the dried and crushed biomass to the brominated flame retardant particles is 1: 1-4: 1, and further the preset mass ratio of the dried and crushed biomass to the brominated flame retardant particles is 2: 1.
Further, in step S2, the hydrothermal reaction is performed under the condition that the temperature is increased from room temperature to 260-320 ℃ at a rate of 5-30 ℃/min, and the temperature is maintained within the temperature range of 260-320 ℃ for 2-4 h, wherein the pressure during the pyrolysis reaction is set to 4.5-15.5 MPa.
Further, in step S3, the pyrolytic carbon solid-liquid mixture is dried and ground to obtain powder with a diameter of 50 μm to 100 μm.
Further, in step S3, the temperature of the carbonization reaction is 700 ℃ to 900 ℃, and further, the temperature of the carbonization reaction is 800 ℃; the time of the carbonization reaction is 30 min-60 min.
Further, in step S3, a carrier gas flow rate of the inert atmosphere is 0.1L/min to 1L/min, and the inert atmosphere is one or more of nitrogen or helium.
According to another aspect of the invention, the mercury-removing activated carbon prepared by the method is provided.
According to another aspect of the invention, the application of the demercuration activated carbon in power plant flue gas demercuration is provided.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the method for preparing the demercuration activated carbon by using the brominated flame retardant and the biomass as the raw materials has the advantages of low cost, wide raw material source, simple preparation process and low production cost, thereby realizing the dual purposes of resource treatment of solid wastes and pollutant treatment of coal-fired power plants; meanwhile, by optimizing the component ratio of potassium to bromine, in the pyrolysis process, KOH can react with released Br free radicals to generate KBr, and the KBr is uniformly loaded in hydrothermal carbon, so that the effect same as that of chemical modification is achieved, and the effect of activated carbon on elemental mercury Hg is greatly improved0Thereby improving the mercury removal efficiency.
(2) The Br free radical released in the hydrothermal reaction process of the brominated flame retardant disclosed by the invention reacts with KOH to generate KBr, and the KBr can be uniformly loaded in hydrothermal carbon, so that the same effect as chemical modification is achieved, and the effect of activated carbon on elemental mercury Hg is greatly improved0Thereby improving the mercury removal efficiency.
(3) The addition of KOH enhances the dissolving capacity of the bromine-containing flame retardant, promotes the decomposition of the bromine-containing flame retardant in the hydrothermal carbonization process, releases more Br free radicals, accelerates the debromination capacity, generates a large number of microporous structures, greatly improves the performance of the hydrothermal activated carbon, simultaneously has the molar ratio of potassium ions to bromide ions of 1: 1-5: 1, and can optimize the performance of the demercuration activated carbon to a certain extent by adjusting the specific gravity of the bromine-containing flame retardant, the biomass and the KOH. Meanwhile, in the invention, the preferred molar ratio of potassium ions to bromide ions is 1:1, and under the condition, KOH can be just completely and freely combined with Br, thereby not only accelerating the debromination capability and generating a large number of micropore structures, but also saving raw materials and reducing the generation and existence of other impurities.
(4) In the process of preparing the demercuration adsorbent, modification is not required to be carried out by adding a chemical reagent, secondary pollution caused by using the chemical reagent can be avoided, and Br in the brominated flame-retardant waste plastic has stronger oxidability than other halogen elements such as Cl and the like, so that the demercuration adsorbent has a better demercuration effect.
(5) The demercuration activated carbon obtained by the method has rich microporous structures and large specific surface area, so that the demercuration efficiency of the prepared demercuration adsorbent is ensured to be more than 60%, and the highest demercuration efficiency can be more than 88.8%.
Drawings
FIG. 1 is a flow chart of a method for preparing demercuration activated carbon by using a brominated flame retardant and biomass according to the invention;
FIG. 2 is a schematic structural diagram of an experimental apparatus involved in the hydrothermal reaction in step S2 according to the present invention;
FIG. 3 is a schematic structural view of a fixed bed reaction apparatus involved in the carbonization reaction in step S3 according to the present invention;
fig. 4 is a schematic structural diagram of a device for mercury adsorption experiments by the mercury removal adsorbent prepared by the invention.
1-circulating water, 2-pump, 3-three-way valve, 4-cold water discharge, 5-cold water input, 6-first flowmeter, 7-heat insulating layer, 8-heater, 9-hydrothermal equipment, 10-ice water, 11-data processor, 12-first valve, 13-sampling gas, 14-second flowmeter, 15-resistance furnace, 16-sample, 17-first temperature controller, 18-quartz reaction tube, 19-liquid product recoverer, 20-tail gas processor, 21-mass flow controller, 22-second stop valve, 23-elemental mercury generator, 24-second temperature controller, 25-third temperature controller, 26-demercuration activated carbon, 27-fixed bed reactor, 28-drying tube, 29-VM3000 online mercury detector, 30-flue gas analyzer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the method for preparing the demercuration activated carbon by the bromine-based flame retardant and the biomass in a hydrothermal mode is characterized in that the bromine-based flame retardant, the biomass and KOH are subjected to mixed hydrothermal reaction in a reaction kettle, and a reaction product is subjected to high-temperature carbonization, so that the high-activity demercuration adsorbent is prepared, and the method is a low-cost preparation method of the high-activity demercuration adsorbent. The method specifically comprises the following steps:
s1, drying and crushing the biomass, and mixing the biomass with brominated flame retardant particles according to a preset mass ratio;
s2, adding a KOH solution into the mixture obtained in the step S1 to obtain a mixed solution, and carrying out hydrothermal reaction on the mixed solution in an inert atmosphere to obtain a pyrolytic carbon solid-liquid mixture;
s3, drying and grinding the pyrolytic carbon solid-liquid mixture, and then carrying out a carbonization reaction in an inert atmosphere to obtain demercuration activated carbon;
in step S2, the molar ratio of potassium ions to bromide ions in the mixed solution is 1:2 to 10:1, and as a preferred embodiment of the present invention, the molar ratio of potassium ions to bromide ions is 1:1 to 5:1, and further the molar ratio of potassium ions to bromide ions is 1: 1.
In step S2 of the present invention, the hydrothermal reaction was carried out in the experimental apparatus shown in FIG. 2, and in step S3 of the present invention, the carbonization reaction was carried out in the experimental apparatus shown in FIG. 3.
Further, in step S1, the brominated flame retardant is one or more of tetrabromobisphenol a, hexabromocyclododecane and polybrominated diphenyl ether.
Further, in step S1, the diameter of the dried and crushed biomass and the diameter of the brominated flame retardant particles are both less than 250 μm; the preset mass ratio of the dried and crushed biomass to the brominated flame retardant particles is 1: 1-4: 1, and further the preset mass ratio of the dried and crushed biomass to the brominated flame retardant particles is 2: 1.
Further, in step S2, the hydrothermal reaction is performed under the condition that the temperature is increased from room temperature to 260-320 ℃ at a rate of 5-30 ℃/min, and the temperature is maintained within the temperature range of 260-320 ℃ for 2-4 h, wherein the pressure during the pyrolysis reaction is set to 4.5-15.5 MPa.
Further, in step S3, the pyrolytic carbon solid-liquid mixture is dried and ground to obtain powder with a diameter of 50 μm to 100 μm.
Further, in step S3, the temperature of the carbonization reaction is 700 ℃ to 900 ℃, and further, the temperature of the carbonization reaction is 800 ℃; the time of the carbonization reaction is 30 min-60 min.
Further, in step S3, a carrier gas flow rate of the inert atmosphere is 0.1L/min to 1L/min, and the inert atmosphere is one or more of nitrogen or helium.
According to another aspect of the invention, the mercury-removing activated carbon prepared by the method is provided.
According to another aspect of the invention, the application of the demercuration activated carbon in power plant flue gas demercuration is provided.
In the present invention, the biomass selected may include various biomass such as lignocellulose biomass, beech, bamboo powder, bamboo sawdust, straw, etc., but is not limited to the above biomass.
Example 1
The method for preparing the demercuration activated carbon by mixing tetrabromobisphenol A (TBBPA) and moso bamboo powder serving as reaction raw materials and performing hydrothermal reaction comprises the following steps of:
step (1), the biomass was washed with deionized water and dried in an oven at 105 ℃ for 12 hours.
And (2) crushing the biomass obtained in the step (1), and screening by using a 60-mesh sieve.
And (3) weighing 10g of the biomass obtained in the step (2) and 10g of tetrabromobisphenol A (TBBPA) according to the weight ratio of 1:1, mixing, adding a solution containing 4.13g of KOH into the mixture, fully and uniformly mixing, and placing in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 500ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: heating from room temperature to 320 ℃ at the heating rate of 4 ℃/min, preserving heat for 3h, and then cooling to room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 800 ℃, and carbonizing for 30min to obtain the demercuration activated carbon.
As shown in FIG. 4, the amount of the demercuration activated carbon is 200mg, the adsorption temperature is 140 deg.C, and N is2The flow rate was 1.5L/min. The mercury removal rate of the activated carbon is shown in table 1.
TABLE 1 Dehydrargyrum Rate of activated carbon
Figure BDA0002103395420000071
Example 2
The method for preparing the demercuration activated carbon by mixing tetrabromobisphenol A (TBBPA) and moso bamboo powder serving as reaction raw materials and performing hydrothermal reaction comprises the following steps of:
step (1), the biomass was washed with deionized water and dried in an oven at 105 ℃ for 12 hours.
And (2) crushing the biomass obtained in the step (1), and screening by using a 60-mesh sieve.
And (3) weighing 15g of biomass obtained in the step (2) and 15g of tetrabromobisphenol A (TBBPA) respectively, mixing, adding a solution containing 4.06g of KOH into the mixture, fully and uniformly mixing, and placing the mixture in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 500ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: heating from room temperature to 320 ℃ at the heating rate of 4 ℃/min, preserving heat for 3h, and then cooling to room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 800 ℃, and carbonizing for 30min to obtain the demercuration activated carbon.
As shown in FIG. 4, the amount of the activated carbon for removing mercury is 200mg, the adsorption temperature is 140 deg.C, and N is2The flow rate was 1.5L/min. The demercuration ratio of the demercuration activated carbon is shown in table 2.
TABLE 2 Dehydrargyrum Rate of activated carbon
Figure BDA0002103395420000081
Example 3
In this embodiment, a method for preparing demercuration activated carbon by mixing Hexabromocyclododecane (HBCD) and moso bamboo powder as reaction raw materials and performing hydrothermal reaction includes the following steps:
step (1), the biomass was washed with deionized water and dried in an oven at 105 ℃ for 12 hours.
And (2) crushing the biomass obtained in the step (1), and screening by using a 60-mesh sieve.
And (3) weighing 10g of the biomass obtained in the step (2) and 10g of Hexabromocyclododecane (HBCD) respectively according to the weight ratio of 1:1, mixing, adding a solution containing 4.13g of KOH into the mixture, fully mixing uniformly, and placing in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 500ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: heating from room temperature to 320 ℃ at the heating rate of 4 ℃/min, preserving heat for 3h, and then cooling to room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 800 ℃, and carbonizing for 30min to obtain the demercuration activated carbon.
As shown in FIG. 4, the amount of the activated carbon for removing mercury is 200mg, the adsorption temperature is 140 deg.C, and N is2The flow rate was 1.5L/min. The mercury removal rate of the activated carbon is shown in table 3.
TABLE 3 Dehydrargyrum Rate of activated carbon
Figure BDA0002103395420000091
Example 4
In this embodiment, the method for preparing the demercuration activated carbon by mixing the polybrominated diphenyl ethers (PBDEs) and the phyllostachys pubescens powder as reaction raw materials and performing hydrothermal reaction comprises the following steps:
step (1), the biomass was washed with deionized water and dried in an oven at 105 ℃ for 12 hours.
And (2) crushing the biomass obtained in the step (1), and screening by using a 60-mesh sieve.
And (3) weighing 10g of the biomass obtained in the step (2) and 10g of polybrominated diphenyl ethers (PBDEs) respectively according to the weight ratio of 1:1, mixing, adding a solution containing 4.13g of KOH into the mixture, fully mixing uniformly, and placing in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 500ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: heating from room temperature to 320 ℃ at the heating rate of 4 ℃/min, preserving heat for 3h, and then cooling to room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 800 ℃, and carbonizing for 30min to obtain the demercuration activated carbon.
As shown in FIG. 4, the amount of the activated carbon for removing mercury is 200mg, the adsorption temperature is 140 deg.C, and N is2The flow rate was 1.5L/min. The mercury removal rate of the activated carbon is shown in table 4.
TABLE 4 Dehydrargyrum Rate of activated carbon
Figure BDA0002103395420000101
Example 5
The method for preparing the demercuration activated carbon by mixing tetrabromobisphenol A (TBBPA) and biomass as reaction raw materials and performing hydrothermal reaction comprises the following steps:
step (1), the biomass was washed with deionized water and dried in an oven for 15 hours.
And (2) crushing the biomass obtained in the step (1), and screening by using a 60-mesh sieve.
And (3) weighing and mixing the biomass obtained in the step (2) and tetrabromobisphenol A (TBBPA) in a mass ratio of 1:4, and adding a KOH solution into the mixture, wherein the molar ratio of potassium ions to bromine ions in the mixed solution is 1: 2. After being fully and uniformly mixed, the mixture is placed in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 100ml/min for 40min, and removing oxygen and other impurity gases influencing hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: heating from room temperature to 320 ℃ at the heating rate of 30 ℃/min, preserving heat for 2h, and then cooling to room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 800 ℃, and carbonizing for 30min to obtain the demercuration activated carbon.
Example 6
In the embodiment, the method for preparing the demercuration activated carbon by mixing hexabromocyclododecane and biomass as reaction raw materials and performing hydrothermal reaction comprises the following steps:
step (1), the biomass is washed with deionized water and dried in an oven for 10 hours.
And (2) sieving the biomass obtained in the step (1) by using a 60-mesh sieve.
And (3) weighing and mixing the biomass obtained in the step (2) and hexabromocyclododecane in a mass ratio of 1:3, and adding a KOH solution into the mixture, wherein the molar ratio of potassium ions to bromide ions in the mixed solution is 5: 1. After being fully and uniformly mixed, the mixture is placed in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 1000ml/min for 20min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 15 ℃/min, preserving the temperature for 3h, and then cooling to the room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 700 ℃, and carbonizing for 45min to obtain the demercuration activated carbon.
Example 7
The method for preparing the demercuration activated carbon by using polybrominated diphenyl ethers and biomass as reaction raw materials and mixing with water and heat comprises the following steps:
step (1), the biomass was washed with deionized water and dried in an oven for 15 hours.
And (2) sieving the biomass obtained in the step (1) by using a 60-mesh sieve.
And (3) weighing the biomass obtained in the step (2) in a mass ratio of 1:2 and polybrominated diphenyl ether, mixing, and adding a KOH solution into the mixture, wherein the molar ratio of potassium ions to bromide ions in the mixed solution is 10: 1. After being fully and uniformly mixed, the mixture is placed in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 1000ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: raising the temperature from room temperature to 260 ℃ at the temperature raising rate of 30 ℃/min, preserving the temperature for 4h, and then cooling to the room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 900 ℃, and carbonizing for 60min to obtain the demercuration activated carbon.
Example 8
The method for preparing the demercuration activated carbon by using polybrominated diphenyl ethers and biomass as reaction raw materials and mixing with water and heat comprises the following steps:
step (1), the biomass was washed with deionized water and dried in an oven for 15 hours.
And (2) sieving the biomass obtained in the step (1) by using a 60-mesh sieve.
And (3) weighing the biomass obtained in the step (2) in a mass ratio of 1:2 and polybrominated diphenyl ether, mixing, and adding KOH into the mixture, wherein the molar ratio of potassium ions to bromide ions in the mixed solution is 3: 1. After being fully and uniformly mixed, the mixture is placed in a hydrothermal reactor.
And (4) introducing high-purity nitrogen into the reaction kettle at the flow rate of 1000ml/min for 30min, and removing oxygen and other impurity gases affecting the hydrothermal reaction in the system.
And (5) setting the temperature of the hydrothermal reaction as follows: raising the temperature from room temperature to 260 ℃ at the temperature raising rate of 30 ℃/min, preserving the temperature for 4h, and then cooling to the room temperature.
And (6) drying and grinding the solid-liquid mixture obtained after the hydrothermal reaction into powder of 50-100 microns.
And (7) putting the dried reactant obtained in the step (6) into a tubular furnace at the temperature of 900 ℃, and carbonizing for 60min to obtain the demercuration activated carbon.
The invention has simple preparation process, low equipment and production cost and good environmental protection, simultaneously achieves the double effects of resource disposal of solid wastes and pollutant treatment of coal-fired power plants, and has excellent social benefit, economic benefit and environmental benefit.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (11)

1. A method for preparing demercuration activated carbon by using a brominated flame retardant and biomass in a hydrothermal mode is characterized by comprising the following steps:
s1, drying and crushing the biomass, and mixing the biomass with brominated flame retardant particles according to a preset mass ratio;
s2, adding a KOH solution into the mixture obtained in the step S1 to obtain a mixed solution with the molar ratio of potassium ions to bromide ions being 1: 1-5: 1, and carrying out hydrothermal reaction on the mixed solution in an inert atmosphere to obtain a pyrolytic carbon solid-liquid mixture; wherein the hydrothermal reaction condition is that the temperature is increased from room temperature to 260-320 ℃ at the temperature increase rate of 5-30 ℃/min, and the temperature is kept within the temperature range of 260-320 ℃ for 2-4 h;
s3, drying and grinding the pyrolytic carbon solid-liquid mixture, and then carrying out carbonization reaction in an inert atmosphere to obtain the demercuration activated carbon.
2. The method of claim 1, wherein in step S1, the brominated flame retardant is one or more of tetrabromobisphenol A, hexabromocyclododecane, and polybrominated diphenyl ethers.
3. The method of claim 1, wherein in step S1, the diameter of the dried and crushed biomass and the diameter of the brominated flame retardant particles are both less than 250 μm; the preset mass ratio of the dried and crushed biomass to the brominated flame retardant particles is 1: 1-4: 1.
4. The method of claim 3, wherein the predetermined mass ratio of the oven-dried crushed biomass to the brominated flame retardant particles is 2: 1.
5. The method according to claim 1, wherein the pressure during the pyrolysis reaction is set to 4.5 to 15.5 MPa.
6. The method of claim 1, wherein in step S3, the pyrolytic carbon solid-liquid mixture is dried and ground to obtain powder with a diameter of 50 μm to 100 μm.
7. The method according to claim 1, wherein in step S3, the temperature of the carbonization reaction is 700-900 ℃; the time of the carbonization reaction is 30 min-60 min.
8. The method of claim 7, wherein the temperature of the carbonization reaction is 800 ℃.
9. The method of claim 1, wherein in step S3, the carrier gas flow rate of the inert atmosphere is 0.1L/min-1L/min, and the inert atmosphere is one or more of nitrogen or helium.
10. A demercuration activated carbon prepared by the method of any one of claims 1-9.
11. Use of the demercuration activated carbon of claim 10 in power plant flue gas demercuration.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006105456A2 (en) * 2005-03-30 2006-10-05 Bp Corporation North America Inc. Process for removing color bodies from hydrocarbon-based fuels using actived carbon
CN106000317A (en) * 2016-08-01 2016-10-12 华北电力大学（保定） Efficient demercuration absorbent for biomass char
CN107051391A (en) * 2017-06-29 2017-08-18 安徽天顺环保设备股份有限公司 One kind carries the sulfur-rich activated carbon flue gas demercuration adsorbent of bromine and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006105456A2 (en) * 2005-03-30 2006-10-05 Bp Corporation North America Inc. Process for removing color bodies from hydrocarbon-based fuels using actived carbon
CN106000317A (en) * 2016-08-01 2016-10-12 华北电力大学（保定） Efficient demercuration absorbent for biomass char
CN107051391A (en) * 2017-06-29 2017-08-18 安徽天顺环保设备股份有限公司 One kind carries the sulfur-rich activated carbon flue gas demercuration adsorbent of bromine and preparation method

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