CN110327880A - Bromide fire retardant and biomass prepare method, product and the application of mercury control activated carbon - Google Patents

Bromide fire retardant and biomass prepare method, product and the application of mercury control activated carbon Download PDF

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CN110327880A
CN110327880A CN201910543934.2A CN201910543934A CN110327880A CN 110327880 A CN110327880 A CN 110327880A CN 201910543934 A CN201910543934 A CN 201910543934A CN 110327880 A CN110327880 A CN 110327880A
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biomass
fire retardant
activated carbon
mercury
bromide fire
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CN110327880B (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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Huazhong University of Science and Technology
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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
    • B01D53/02—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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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  • Carbon And Carbon Compounds (AREA)
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Abstract

The invention belongs to active carbon preparation fields, and disclose a kind of bromide fire retardant and biomass prepares method, product and the application of mercury control activated carbon.The method includes being mixed by preset quality ratio with bromide fire retardant particle after biomass drying is crushed by S1；KOH solution is added into mixture and carries out hydro-thermal reaction under an inert atmosphere by S2, obtains pyrolytic carbon solidliquid mixture；After the pyrolytic carbon solidliquid mixture is carried out drying grinding by S3, carbonization reaction is carried out under an inert atmosphere, obtains mercury control activated carbon.The product is prepared using the above method.The present invention should be able to mutually obtain the demercuration adsorbent with higher demercuration efficiency, greatly improve active carbon to Elemental Mercury Hg by the way that bromine system flame retardant waste plastic, biomass and KOH to be pyrolyzed under the conditions of being sufficiently mixed0Chemical adsorption capacity be therefore particularly suitable for the application of power-plant flue gas demercuration etc to promote demercuration efficiency.

Description

Bromide fire retardant and biomass prepare method, product and the application of mercury control activated carbon
Technical field
The invention belongs to active carbon preparation technical fields, prepare more particularly, to a kind of bromide fire retardant and biomass Method, product and the application of mercury control activated carbon.
Background technique
Currently, mercury emissions caused by the annual mankind's activity in the whole world have reached 1000-6000 tons, global atmosphere mercury row is accounted for The 30-55% put.Coal-burning power plant is most important human factor mercury emissions source, accounts for the half of total artificial mercury emission.Beauty The relevant mercury emissions in coal-burning power plant are applied with additional limitation by state's publication clean air mercury regulation (CAMR) in 2005.2012 U.S.EPA (EPA) promulgates mercury and air toxics standard (MATS) regulation, formed limitation coal-burning power plant's mercury, sour gas and its The ultimate criterion of his noxious material discharge.China fossil-fuel power plant atmospheric pollutant emission standard (GB13223- promulgated in 2011 2011) regulation mercury and mercuric compounds emission limit is 0.03mg/m3.Mercury pollution has become another whole world after climate change Property environmental problem, mercury pollution are prevented and treated imperative and have caused more and more extensive concern.
In coal-fired plant flue gas, mercury occurs in the form of these three by following: Elemental Mercury (Hg0), oxidation state mercury (Hg2+) and Grain state mercury (Hgp).Oxidation state mercury (Hg2+) soluble easily in water, it can be removed by wet desulphurization (WFGD) equipment high efficiency, particle mercury (Hgp) can also be removed by electrostatic precipitator (ESP) or bag filter (FF).However, Elemental Mercury (Hg0) there is high volatilization Property and it is practically insoluble in water, is difficult to remove by flue gas after-treatment device.The removing of Elemental Mercury becomes in mercury control technology Key points and difficulties where.In recent years, development goes out many technologies to remove Elemental Mercury (Hg0), main includes inhaling Attached method, catalytic oxidation, photocatalytic oxidation, photochemistry removal method, plasma removal method and wet oxidation method etc..Mercury is inhaled Attached technical method is simple, feasibility is high, and the technology is by powdered active carbon from deduster equipment (PCD) injected upstream flue In, it is collected after activated carbon adsorption gaseous mercury by deduster.Domestic and foreign scholars to carbon-based, calcium base, metal oxide, natural crystal and Carried active carbon has conducted extensive research.Wherein, flue active carbon gunite (ACI) is that current coal fired power plant reduces mercury emissions The technology of most mature and feasible, US Coal-fired Power Plants have generally carried out the emission control of mercury using the method.American National energy skill Demercuration performance of the art laboratory (NETL) in multiple power plant's on-the-spot test NORIT FGD commercial activated carbons, the results showed that Hg is de- Except efficiency is 70%~90%.But in the prior art, complicated for the preparation method of the active carbon of Adsorption of Mercury, operating cost Height is worked together the problems such as bigger than high and regenerating active carbon difficulty there is also charcoal/mercury.
Therefore, this field urgently proposes that a kind of preparation process is simple, and equipment and production cost are low, and the feature of environmental protection is good, reaches simultaneously To the mercury control activated carbon of solid waste resource recovery disposition and the double effects of coal-burning power plant's pollutant control.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides bromide fire retardant and biomass preparation are de- Method, product and the application of mercury active carbon, by the way that bromine system flame retardant waste plastic, biomass and KOH are being sufficiently mixed condition Lower carry out hydro-thermal process, and the parameters such as the process conditions in preparation process such as pyrolysis temperature, mixing mass ratio are designed, phase The demercuration adsorbent with higher demercuration efficiency should be able to be obtained, greatly improves active carbon to Elemental Mercury Hg0Chemisorption Ability is therefore particularly suitable for the application of power-plant flue gas demercuration etc to promote demercuration efficiency.
To achieve the goals above, according to one aspect of the present invention, a kind of bromide fire retardant and biomass by hydro-thermal are provided The method for preparing mercury control activated carbon, comprising the following steps:
After biomass drying is crushed by S1, mixed by preset quality ratio with bromide fire retardant particle；
KOH solution is added in the mixture that S2 is obtained to step S1, obtains mixed solution, by the mixed solution in inertia Hydro-thermal reaction is carried out under atmosphere, obtains pyrolytic carbon solidliquid mixture；
After the pyrolytic carbon solidliquid mixture is carried out drying grinding by S3, carbonization reaction is carried out under an inert atmosphere, is obtained Mercury control activated carbon；
Wherein, in step S2, in the mixed solution, the molar ratio of potassium ion and bromide ion is 1:1~5:1.
Further, in step S1, bromide fire retardant is in tetrabromobisphenol A, hexabromocyclododecane and polybrominated diphenyl ethers It is one or more.
Further, in step S1, the diameter of the broken biomass of drying and the diameter of bromide fire retardant particle Respectively less than 250 μm；The broken biomass of drying and the preset quality ratio of bromide fire retardant particle are 1:1~4:1, into one Step, the broken biomass of drying and the preset quality ratio of bromide fire retardant particle are 2:1.
Further, in step S2, the condition of the hydro-thermal reaction be with 5 DEG C/min~30 DEG C/min heating rate from Room temperature rises to 260 DEG C~320 DEG C, and 2h~4h is kept the temperature within the temperature range of 260 DEG C~320 DEG C, wherein pyrolytic reaction process In pressure be set as 4.5MPa~15.5MPa.
Further, in step S3, the pyrolytic carbon solidliquid mixture obtain after drying grinding diameter be 50 μm~ 100 μm of powder.
Further, in step S3, the temperature of the carbonization reaction is 700 DEG C~900 DEG C, further, the charing The temperature of reaction is 800 DEG C；The time of the carbonization reaction is 30min~60min.
Further, in step S3, the carrier gas flux of the inert atmosphere is 0.1L/min~1L/min, the indifferent gas Atmosphere is one of nitrogen or helium or a variety of.
Other side according to the invention provides a kind of mercury control activated carbon that the above method is prepared.
Other side according to the invention provides a kind of application of above-mentioned mercury control activated carbon in power-plant flue gas demercuration.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below Technological merit:
(1) present invention is not only low in cost, former by preparing mercury control activated carbon using bromide fire retardant and biomass as raw material Expect from a wealth of sources, while having the advantages that preparation process is simple, production cost is low, to realize that solid waste resource recovery is disposed With the double goal of coal-burning power plant's pollutant control；Pass through the component ratio of optimization potassium and bromine, in pyrolytic process, KOH simultaneously KBr can be generated with the Br radical reaction of release, and be equably supported in hydro-thermal charcoal, reach effect identical with chemical modification Fruit greatly improves active carbon to Elemental Mercury Hg0Chemical adsorption capacity, to promote demercuration efficiency.
(2) Br free radical is released in bromide fire retardant hydrothermal reaction process of the present invention, is reacted with KOH and generates KBr, energy It is enough to be equably supported in hydro-thermal charcoal, reach effect identical with chemical modification, greatly improves active carbon to Elemental Mercury Hg0's Chemical adsorption capacity, to promote demercuration efficiency.
(3) addition of KOH of the present invention enhances the solvability of brominated flame-retardant, promotes brominated flame-retardant in hydro-thermal charcoal Decomposition during change releases more Br free radicals, accelerates debrominate ability, and generates a large amount of microcellular structure, The performance of hydrothermal activity charcoal is greatly improved, meanwhile, the molar ratio of potassium ion and bromide ion is 1:1~5:1, by adjusting bromine system The specific gravity of fire retardant and biomass and KOH can optimize the performance of mercury control activated carbon to a certain extent.Meanwhile In the present invention, the molar ratio of potassium ion and bromide ion is preferably 1:1, and with this condition, KOH just can be completely free with Br In conjunction with, debrominate ability can be accelerated, generate a large amount of microcellular structure, and can save material, reduce other impurities generation and In the presence of.
(4) present invention does not need to be modified by adding chemical reagent during preparing demercuration adsorbent, can keep away Exempt from secondary pollution caused by using chemical reagent, and the oxidation of other halogens such as Br ratio Cl in bromine system flame retardant waste plastic Property it is stronger, have better demercuration effect.
(5) mercury control activated carbon acquired in the method for the present invention, has microcellular structure abundant, thus large specific surface area is protected The demercuration adsorbent demercuration efficiency of preparation is demonstrate,proved 60% or more, highest demercuration efficiency can achieve 88.8% or more.
Detailed description of the invention
Fig. 1 is the method flow diagram that a kind of bromide fire retardant of the present invention and biomass prepare mercury control activated carbon；
Fig. 2 is the experimental provision structural schematic diagram that hydro-thermal reaction is related in step S2 of the present invention；
Fig. 3 is the fixed-bed reactor structural schematic diagram that carbonization reaction is related in step S3 of the present invention；
Fig. 4 is the apparatus structure schematic diagram that demercuration adsorbent prepared by the present invention carries out mercury adsorption experiment.
1- recirculated water, 2- pump, 3- three-way valve, the discharge of 4- cold water, the input of 5- cold water, 6- first flowmeter, 7- heat insulation layer, 8- Heater, 9- water heating apparatus, 10- ice water, 11- data processor, the first valve of 12-, 13- gas sampled, 14- second flow Meter, 15- resistance furnace, 16- sample, the first temperature controller of 17-, 18- crystal reaction tube, 19- product liquid recover, 20- tail Treatment apparatus, 21- mass flow controller, the second shut-off valve of 22-, 23- Elemental Mercury generator, 24- second temperature controller, 25- third temperature controller, 26- mercury control activated carbon, 27- fixed bed reactors, 28- drying tube, 29-VM3000 survey mercury online Instrument, 30- flue gas analyzer.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
As shown in Figure 1, a kind of method of bromide fire retardant and biomass water hot preparation mercury control activated carbon of the present invention, this method It is bromide fire retardant, biomass and KOH to be subjected to mixing hydro-thermal reaction in a kettle, and reaction product is subjected to pyrocarbon Change, is a kind of cheap high activity demercuration adsorbent preparation method to prepare high activity demercuration adsorbent.Its specifically include with Lower step:
After biomass drying is crushed by S1, mixed by preset quality ratio with bromide fire retardant particle；
KOH solution is added in the mixture that S2 is obtained to step S1, obtains mixed solution, by the mixed solution in inertia Hydro-thermal reaction is carried out under atmosphere, obtains pyrolytic carbon solidliquid mixture；
After the pyrolytic carbon solidliquid mixture is carried out drying grinding by S3, carbonization reaction is carried out under an inert atmosphere, is obtained Mercury control activated carbon；
Wherein, in step S2, in the mixed solution, the molar ratio of potassium ion and bromide ion is 1:2~10:1, as this The molar ratio of the preferred embodiment of invention, potassium ion and bromide ion is 1:1~5:1, and further, potassium ion and bromide ion rub You are than being 1:1.
Wherein, hydro-thermal reaction carries out in experimental provision as shown in Figure 2 in step S2 of the present invention, in step S3 of the present invention Carbonization reaction carries out in experimental provision as shown in Figure 3.
Further, in step S1, bromide fire retardant is in tetrabromobisphenol A, hexabromocyclododecane and polybrominated diphenyl ethers It is one or more.
Further, in step S1, the diameter of the broken biomass of drying and the diameter of bromide fire retardant particle Respectively less than 250 μm；The broken biomass of drying and the preset quality ratio of bromide fire retardant particle are 1:1~4:1, into one Step, the broken biomass of drying and the preset quality ratio of bromide fire retardant particle are 2:1.
Further, in step S2, the condition of the hydro-thermal reaction be with 5 DEG C/min~30 DEG C/min heating rate from Room temperature rises to 260 DEG C~320 DEG C, and 2h~4h is kept the temperature within the temperature range of 260 DEG C~320 DEG C, wherein pyrolytic reaction process In pressure be set as 4.5MPa~15.5MPa.
Further, in step S3, the pyrolytic carbon solidliquid mixture obtain after drying grinding diameter be 50 μm~ 100 μm of powder.
Further, in step S3, the temperature of the carbonization reaction is 700 DEG C~900 DEG C, further, the charing The temperature of reaction is 800 DEG C；The time of the carbonization reaction is 30min~60min.
Further, in step S3, the carrier gas flux of the inert atmosphere is 0.1L/min~1L/min, the indifferent gas Atmosphere is one of nitrogen or helium or a variety of.
Other side according to the invention provides a kind of mercury control activated carbon that the above method is prepared.
Other side according to the invention provides a kind of application of above-mentioned mercury control activated carbon in power-plant flue gas demercuration.
In the present invention, selected biomass may include a variety of, such as lignocellulose-like biomass, hair beech, moso bamboo The biomass such as powder, bamboo scraps, stalk can be used as raw material of the invention, but be not limited to above-mentioned biomass.
Embodiment 1
The present embodiment is using tetrabromobisphenol A (TBBPA) and moso bamboo powder as reaction raw materials, mixing water hot preparation mercury control activated carbon Method the following steps are included:
Step (1) cleans biomass with deionized water, 12 hours dry in 105 DEG C of baking ovens.
Step (2) is sieved after being crushed the biomass that step (1) obtains with 60 mesh sieve.
Step (3) weighs the biomass and tetrabromobisphenol A (TBBPA) each 10g that step (2) obtains according to weight ratio 1:1, After mixing, the solution containing 4.13gKOH is added into mixture, after being sufficiently mixed uniformly, is placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 500ml/min, the oxygen in removing system The foreign gas of equal other influences hydro-thermal reaction.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 4 DEG C/min by room temperature to 320 DEG C, 3h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 800 DEG C, carbonizes 30min, obtain by step (7) To mercury control activated carbon.
As shown in figure 4, the dosage of mercury control activated carbon is 200mg, adsorption temp is the experimental provision of Elemental Mercury adsorption experiment 140 DEG C, N2Flow is 1.5L/min.The demercuration rate of active carbon is as shown in table 1.
The demercuration rate of 1 active carbon of table
Embodiment 2
The present embodiment is using tetrabromobisphenol A (TBBPA) and moso bamboo powder as reaction raw materials, mixing water hot preparation mercury control activated carbon Method the following steps are included:
Step (1) cleans biomass with deionized water, 12 hours dry in 105 DEG C of baking ovens.
Step (2) is sieved after being crushed the biomass that step (1) obtains with 60 mesh sieve.
Step (3) weighs biomass 5g and tetrabromobisphenol A (TBBPA) each 15g that step (2) obtains, after mixing, to mixed It closes and the solution containing 4.06gKOH is added in object, after being sufficiently mixed uniformly, be placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 500ml/min, the oxygen in removing system The foreign gas of equal other influences hydro-thermal reaction.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 4 DEG C/min by room temperature to 320 DEG C, 3h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 800 DEG C, carbonizes 30min, obtain by step (7) To mercury control activated carbon.
As shown in figure 4, the dosage of mercury control activated carbon is 200mg, adsorption temp is the experimental provision of simple substance mercury removal experiment 140 DEG C, N2Flow is 1.5L/min.The demercuration rate of mercury control activated carbon is as shown in table 2.
The demercuration rate of 2 active carbon of table
Embodiment 3
For the present embodiment using hexabromocyclododecane (HBCD) and moso bamboo powder as reaction raw materials, mixing water hot preparation demercuration is active The method of charcoal the following steps are included:
Step (1) cleans biomass with deionized water, 12 hours dry in 105 DEG C of baking ovens.
Step (2) is sieved after being crushed the biomass that step (1) obtains with 60 mesh sieve.
Step (3) weighs biomass that step (2) obtains according to weight ratio 1:1 and hexabromocyclododecane (HBCD) is each After mixing, the solution containing 4.13g KOH is added into mixture, after being sufficiently mixed uniformly, is placed in hydrothermal reactor by 10g.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 500ml/min, the oxygen in removing system The foreign gas of equal other influences hydro-thermal reaction.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 4 DEG C/min by room temperature to 320 DEG C, 3h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 800 DEG C, carbonizes 30min, obtain by step (7) To mercury control activated carbon.
As shown in figure 4, the dosage of mercury control activated carbon is 200mg, adsorption temp is the experimental provision of simple substance mercury removal experiment 140 DEG C, N2Flow is 1.5L/min.The demercuration rate of active carbon is as shown in table 3.
The demercuration rate of 3 active carbon of table
Embodiment 4
For the present embodiment using polybrominated diphenyl ethers (PBDEs) and moso bamboo powder as reaction raw materials, mixing water hot preparation demercuration is active The method of charcoal the following steps are included:
Step (1) cleans biomass with deionized water, 12 hours dry in 105 DEG C of baking ovens.
Step (2) is sieved after being crushed the biomass that step (1) obtains with 60 mesh sieve.
Step (3) weighs the biomass and polybrominated diphenyl ethers (PBDEs) each 10g that step (2) obtains according to weight ratio 1:1, After mixing, the solution containing 4.13g KOH is added into mixture, after being sufficiently mixed uniformly, is placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 500ml/min, the oxygen in removing system The foreign gas of equal other influences hydro-thermal reaction.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 4 DEG C/min by room temperature to 320 DEG C, 3h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 800 DEG C, carbonizes 30min, obtain by step (7) To mercury control activated carbon.
As shown in figure 4, the dosage of mercury control activated carbon is 200mg, adsorption temp is the experimental provision of simple substance mercury removal experiment 140 DEG C, N2Flow is 1.5L/min.The demercuration rate of active carbon is as shown in table 4.
The demercuration rate of 4 active carbon of table
Embodiment 5
The present embodiment is using tetrabromobisphenol A (TBBPA) and biomass as reaction raw materials, mixing water hot preparation mercury control activated carbon Method the following steps are included:
Step (1) cleans biomass with deionized water, dries 15 hours in an oven.
Step (2) is sieved after being crushed the biomass that step (1) obtains with 60 mesh sieve.
Step (3), weighs the step of mass ratio is 1:4 (2) obtained biomass and tetrabromobisphenol A (TBBPA) is mixed It closes, KOH solution is added into said mixture, wherein in mixed liquor, the molar ratio of potassium ion and bromide ion is 1:2.It is sufficiently mixed After closing uniformly, it is placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 40min into reaction kettle with the flow of 100ml/min, the oxygen in removing system The foreign gas of equal other influences hydro-thermal reaction.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 30 DEG C/min by room temperature to 320 DEG C, 2h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 800 DEG C, carbonizes 30min, obtain by step (7) To mercury control activated carbon.
Embodiment 6
The present embodiment is using hexabromocyclododecane and biomass as reaction raw materials, the side of mixing water hot preparation mercury control activated carbon Method the following steps are included:
Step (1) cleans biomass with deionized water, dries 10 hours in an oven.
Step (2) sieves the biomass that step (1) obtains with 60 mesh sieve.
Step (3), weighs the step of mass ratio is 1:3 (2) obtained biomass and hexabromocyclododecane is mixed, to KOH solution is added in said mixture, wherein in mixed liquor, the molar ratio of potassium ion and bromide ion is 5:1.It is sufficiently mixed After even, it is placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 20min into reaction kettle with the flow of 1000ml/min, the oxygen in removing system The foreign gas of the other influences hydro-thermal reaction such as gas.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 15 DEG C/min by room temperature to 300 DEG C, 3h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 700 DEG C, carbonizes 45min, obtain by step (7) To mercury control activated carbon.
Embodiment 7
The present embodiment is using polybrominated diphenyl ethers and biomass as reaction raw materials, the method for mixing water hot preparation mercury control activated carbon The following steps are included:
Step (1) cleans biomass with deionized water, dries 15 hours in an oven.
Step (2) sieves the biomass that step (1) obtains with 60 mesh sieve.
Step (3), weighs the step of mass ratio is 1:2 (2) obtained biomass and polybrominated diphenyl ethers is mixed, upwards It states and KOH solution is added in mixture, wherein in mixed liquor, the molar ratio of potassium ion and bromide ion is 10:1.It is sufficiently mixed uniformly Afterwards, it is placed in hydrothermal reactor.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 1000ml/min, the oxygen in removing system The foreign gas of the other influences hydro-thermal reaction such as gas.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 30 DEG C/min by room temperature to 260 DEG C, 4h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 900 DEG C, carbonizes 60min, obtain by step (7) To mercury control activated carbon.
Embodiment 8
The present embodiment is using polybrominated diphenyl ethers and biomass as reaction raw materials, the method for mixing water hot preparation mercury control activated carbon The following steps are included:
Step (1) cleans biomass with deionized water, dries 15 hours in an oven.
Step (2) sieves the biomass that step (1) obtains with 60 mesh sieve.
Step (3), weighs the step of mass ratio is 1:2 (2) obtained biomass and polybrominated diphenyl ethers is mixed, upwards It states and KOH is added in mixture, wherein in mixed liquor, the molar ratio of potassium ion and bromide ion is 3:1.After being sufficiently mixed uniformly, set In hydrothermal reactor.
Step (4) is passed through high pure nitrogen 30min into reaction kettle with the flow of 1000ml/min, the oxygen in removing system The foreign gas of the other influences hydro-thermal reaction such as gas.
Step (5) sets the temperature of hydro-thermal reaction are as follows: with the heating rate of 30 DEG C/min by room temperature to 260 DEG C, 4h is kept the temperature, is then cooled to room temperature.
Gained solidliquid mixture drying after hydro-thermal reaction is ground into 50 μm~100 μm powder by step (6).
The dry reagent contained that step (6) obtains is put into the tube furnace that temperature is 900 DEG C, carbonizes 60min, obtain by step (7) To mercury control activated carbon.
Preparation process of the present invention is simple, and equipment and production cost are low, and the feature of environmental protection is good, while reaching solid waste resource recovery The double effects of disposition and coal-burning power plant's pollutant control have fabulous social benefit, economic benefit and environmental benefit.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (9)

1. a kind of method of bromide fire retardant and biomass water hot preparation mercury control activated carbon, which comprises the following steps:
After biomass drying is crushed by S1, mixed by preset quality ratio with bromide fire retardant particle；
KOH solution is added in the mixture that S2 is obtained to step S1, the molar ratio for obtaining potassium ion and bromide ion is 1:1~5:1 Mixed solution, the mixed solution is subjected to hydro-thermal reaction under an inert atmosphere, obtains pyrolytic carbon solidliquid mixture；
After the pyrolytic carbon solidliquid mixture is carried out drying grinding by S3, carbonization reaction is carried out under an inert atmosphere, obtains demercuration Active carbon.
2. the method according to claim 1, wherein bromide fire retardant is tetrabromobisphenol A, hexabromo in step S1 One of cyclododecane and polybrominated diphenyl ethers are a variety of.
3. the method according to claim 1, wherein in step S1, the broken biomass of drying it is straight The diameter of diameter and bromide fire retardant particle is respectively less than 250 μm；The broken biomass of drying and bromide fire retardant particle Preset quality ratio is 1:1~4:1, further, the default matter of the drying broken biomass and bromide fire retardant particle Amount is than being 2:1.
4. the method according to claim 1, wherein in step S2, the condition of the hydro-thermal reaction be with 5 DEG C/ Min~30 DEG C/min heating rate rises to 260 DEG C~320 DEG C from room temperature, and protects within the temperature range of 260 DEG C~320 DEG C Warm 2h~4h, wherein the pressure during pyrolytic reaction is set as 4.5MPa~15.5MPa.
5. the method according to claim 1, wherein the pyrolytic carbon solidliquid mixture is dried in step S3 The powder that diameter is 50 μm~100 μm is obtained after dry grinding.
6. the method according to claim 1, wherein in step S3, the temperature of the carbonization reaction is 700 DEG C~ 900 DEG C, further, the temperature of the carbonization reaction is 800 DEG C；The time of the carbonization reaction is 30min~60min.
7. the method according to claim 1, wherein in step S3, the carrier gas flux of the inert atmosphere is 0.1L/min~1L/min, the inert atmosphere are one of nitrogen or helium or a variety of.
8. a kind of mercury control activated carbon that the method according to claim 1 to 7 is prepared.
9. a kind of application of mercury control activated carbon as claimed in claim 8 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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