CN106943855A - The method of modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour - Google Patents
The method of modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour Download PDFInfo
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- CN106943855A CN106943855A CN201710287824.5A CN201710287824A CN106943855A CN 106943855 A CN106943855 A CN 106943855A CN 201710287824 A CN201710287824 A CN 201710287824A CN 106943855 A CN106943855 A CN 106943855A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
Abstract
A kind of method that the present invention provides modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour, is slightly calcined to kaolin first, then carries out Ca (OH)2And CH3COONa solution dipping is modified, and then sprays into modified kaolin and metal vapors is once adsorbed in high-temperature burner hearth, subsequent modified kaolin enters high-temperature flue, in O2/H2Being rich under oxygen radical effect for O plasma exciatiaons, second adsorption is carried out to metal vapors.Finally, the kaolin powder of enriching heavy metal and alkali metal is trapped by cleaner.This method lifts adsorption capacity of the kaolin to metal chloride vapors by the synergy of modified kaolin powder and low temperature plasma, realizes that kaolin efficiently controls sub-micron heavy metals emission and mitigates ash erosion, heat-transfer surface dust stratification and high temperature corrosion.
Description
Technical field
The invention belongs to atmosphere pollution control field, and in particular to a kind of modified kaolin coordinated with plasma absorption weight
The method of metal and alkali metal vapour.
Background technology
During the solid fuel ignitions such as coal, rubbish and biomass, the half volatile such as Pb, Cd, Zn, Cu, Na, K metal member
Partly or entirely volatilization forms metal vapors to element at high temperature, and burner hearth is left with flue gas.Flue gas temperature after heat transmission equipment drops
Low, metal vapors is condensed by the effect such as homogeneous nucleation and heterogeneous nucleation, is easily enriched in Submicron Particles（PM1）
Or even superfine particulate matter（PM0.1）In.The tiny particle of these particle diameters is difficult to efficiently be trapped by cleaner, heavy metal therein
Element is the main source of particulate matter toxicity, and alkali metal is to constitute one of main matrix of particulate matter, serious harm human body
Health.For high Na coals and herbaceous biomass, the alkali metal vapour of high-temperature flue gas middle and high concentration, which is also resulted in flue, to be changed
The generation of the problems such as hot device dust stratification, high temperature corrosion and ash erosion, severe jamming boiler operatiopn.
Forefathers' research finds that the natural minerals such as kaolin can chemically react with half volatile metal under high temperature, raw
Into nonvolatile alumino-silicate.Therefore, the kaolin powder of ultra micro rice is sprayed into high temperature furnace（PM>1）Can be with chemisorbed metallic
Steam, then efficiently trapped by cleaner, be converted into after metal volatilization tiny particles content or corrosion heating surface so as to cut off
Path.But, the appearance of chlorine element can substantially reduce trapping energy of the natural minerals such as kaolin to metal vapors under high-temperature atmosphere
Power.The essence that chlorine element suppresses mineral trap heavy metals is that chlorine element causes heavy metal element to exist in the form of chloride,
And the reaction rate of natural minerals and metal chloride vapors will be significantly lower than its reaction rate with metal oxide steam.Rubbish
Inevitable based on chloride containing the metal form in a large amount of organochlorines and inorganic chlorine, therefore stove in rubbish, coal and biomass, this will
Cause conventional natural minerals adsorbent high temperature adsorption heavy metal and alkali metal inefficiency without practical value.Lack at present
The weary high temperature adsorption technology with anti-chlorine performance.
The content of the invention
The present invention in furnace injection natural non-metallic mineral high temperature adsorption stove on the basis of metal vapors technology there is provided
A kind of method of modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour.This method passes through modified kaolin powder
End and the synergy of low temperature plasma, lifting kaolin realize kaolin to the adsorption capacity of metal chloride vapors
Efficiently control sub-micron heavy metals emission and mitigation ash erosion, heat-transfer surface dust stratification and high temperature corrosion.
The concrete technical scheme of the present invention is as follows：A kind of modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal
The method of steam, this method comprises the following steps：Into incinerator, 900 DEG C of high temperature above area injection modified kaolin powder, change
Property the flue gas that is produced with burning of kaolin powder enter in flue, while 600-800 DEG C of warm area injection O into flue2/H2O etc. from
Daughter, is set after forming the heavy metal in cooperation-removal effect, last modified kaolin powder adsorption flue gas and alkali metal by dedusting
Standby trapping, wherein, the modified kaolin powder is by kaolin first through slight calcining, then by Ca (OH)2And CH3COONa's is mixed
Solution adsorptive is closed to be prepared from.
The modified kaolin powder is prepared by following methods：
（1）The kaolin powder of 5 ~ 30 μm of selection；
（2）Above-mentioned kaolin powder is placed in 5 ~ 10 min of calcining at 350 ~ 400 DEG C, slight calcined kaolin is obtained；
（3）Above-mentioned slight calcined kaolin powder is dispersed in maceration extract, the maceration extract is to be dissolved with Ca (OH)2With
CH3Ca (OH) in the COONa aqueous solution, maceration extract2Concentration is 0.001 ~ 0.005 mol/L, CH3COONa concentration be 0.001 ~
The solid-to-liquid ratio of 0.005 mol/L, kaolin powder and maceration extract is 2 ~ 5 g/L, and dip time is 6 ~ 10 h, and dipping temperature is 10
~30℃；
（4）By the solid generated in above-mentioned maceration extract by filtering, deionized water elution, dry and broken, obtained modified kaolinite
Native powder, wherein elution number of times be no less than 2 times, drying temperature be 120 ~ 240 DEG C, drying time be 5 ~ 8 h, crush particle diameter be 5 ~
30 μm。
The modified kaolin powderject quality is 500-1000 mg/Nm with flue gas volume ratio3。
The O2/H2O plasmas be oxygen and vapor gaseous mixture by plasma reactor produce containing oxygen-containing
The plasma of free radical, plasma temperature is 400 ~ 700 DEG C, wherein O in gaseous mixture2: H2O volume ratio is 15 ~ 19：
1, the ratio of the vapor addition and flue gas is 400 ~ 1000 mg/Nm3。
Nozzle is arranged in burner hearth, modified kaolin is spurted into more than 900 DEG C warm areas in stove, an adsorbing metal first
Steam：Kaolin powder enters in flue with flue gas, spout is arranged in flue, by O2/H2O plasma jets enter in flue
600 ~ 800 DEG C of warm areas, in O2/H2In the presence of O plasmas, second adsorption metal vapors.The concrete principle of the present invention is as follows：
（1）Kaolin is modified, its metal chloride Molecular Adsorption ability is improved.First by slightly calcining, remove high
Ridge soil surface portion site weaker hydroxyl of bond energy because of fault of construction, supported active position is provided for dipping ion；Then super
In low concentration maceration extract, Ca2+And Na+By electrostatic interaction absorption in active sites；Then other positions are removed by eluting
Ca2+And Na+；Eventually pass the modified kaolin dried and form that Ca and Na decentralization is high, load capacity is low.Kaolin high temperature adsorption gold
The activity unit for belonging to oxide and chloride molecule is surface A l rings.When kaolin sprays into high temperature adsorption area, kaolin surface
In Ca the and Na depth insertion kaolin surface Al rings of load, periphery Al rings are caused to produce certain distortion so as to activity raising.Table
The Ca and Na of face load have catalytic action to vapor, make kaolin surface be easier to form hydroxyl, so as to promote metal chlorine
The adsorption reaction of compound molecule.Ca and Na presence is also beneficial to improve chloride molecule and its adsorption reaction intermediate product molecule
In the energy of adsorption of kaolin surface.
（2）Collaboration uses O2/H2O plasmas, can further improve its metal chloride adsorption capacity.O2/H2O etc.
Gas ions can provide a large amount of high activity oxy radicals, participate directly in metal chloride Molecular Adsorption, without experience water
Vapour molecule is decomposed into the overactivity energy process of hydroxyl.Therefore, O2/H2O plasmas provide for metal chloride Molecular Adsorption
A large amount of reactants, it is the bottleneck in hydroxyl this adsorption reaction step to have got around water-molecule dissociation.Meanwhile, the Ca of kaolin surface
Contribute to hinder the compound of oxygen-content active group with Na, extend its existence time.Active group is easily combined at high temperature, therefore
Temperature is selected less than injection in the flue of burner hearth.
Beneficial effect：
（1）Non-structural damage type modification is carried out to it on the basis of primary kaolin adsorbent, by slightly calcine with it is ultralow
Concentration Electrostatic Absorption, realizes Ca, Na ion surface insertion of high degree of dispersion and low-load amount, improves the chlorine of kaolin surface Al rings
Compound adsorption activity；And calcining heat is low in modification procedure, the time is short, and energy consumption is low；Dipping solution acid-base property is weak, corrosion-free
Property.
（2）On the basis of traditional mineral injection, plasma body cooperative removing heavy metal and alkali metal vapour are introduced.O2/
H2The oxygen radical that O plasmas are rich in promotes the reaction of kaolin adsorbing metal chloride vapor, enhances kaolinite
The chlorine resistance of soil at high temperature, the present invention passes through the synergy of modified kaolin powder and low temperature plasma, lifting height
Ridge soil realizes that kaolin efficiently controls sub-micron heavy metals emission and mitigated in stove to tie to the adsorption capacity of metal chloride vapors
Slag, heat-transfer surface dust stratification and high temperature corrosion..
Embodiment
It is below a kind of embodiment of the present invention, but embodiments of the present invention not limited to this.
Waste incineration experiment is carried out on processing quantity of refuse 0.5t circulating fluidized bed incinerators at one, emulsion zone temperature is
700-800 DEG C, freeboard temperature is 850-1000 DEG C, and afterbody is equipped with sack cleaner.Fuel Selection simcity house refuse,
Its concrete component is as shown in table 1.Add the heavy metal in the house refuse of heavy metal acetate simcity, addO-on therapy such as table 2
It is shown.
Each component in the simcity house refuse of table 1（Mass percent, %）
| Title | Flour | Dish leaf | Paper | Wood chip | Plastics | Cotton | PVC | NaCl |
| Content | 40 | 15 | 15 | 12 | 12 | 3 | 1.5 | 1.5 |
The addition and adding ingredient of heavy metal (account for domestic waste butt gross weight in the simcity house refuse of table 2
Ratio, mg/kg),
| Heavy metal | Addition | Adding ingredient |
| Zn | 8000 | (CH3COO)2Zn•2H2O |
| Cu | 2000 | (CH3COO)2Cu• H2O |
| Pb | 1500 | (CH3COO)2Pb•3H2O |
| Cd | 500 | (CH3COO)2Cd•2H2O |
Prepare modified kaolin：The kaolin powder of 5 ~ 30 μm of selection, then calcines 5 min at 400 DEG C first, then
It is even to be scattered in 0.002 mol/L Ca (OH)2With 0.002 mol/L CH3In the COONa aqueous solution, kaolin powder and the aqueous solution
Solid-to-liquid ratio is 5g/L, and 15 DEG C impregnate 6 h at room temperature, and the solid of generation finally is eluted into 3 times by filtering, deionized water, dried
With broken, obtained 5 ~ 30 μm modified kaolin powder.
Embodiment 1
Above-mentioned obtained modified kaolin is spurted into about 900 DEG C of positions of burner hearth freeboard temperature, powderject quality and flue gas body
Product is than being 600 mg/Nm3.Meanwhile, by volume ratio 94:6 O2/H2O, which is passed through after plasma producing apparatus, to be spurted into flue about
600 DEG C of positions, about 700 DEG C of plasma temperature, vapor addition quality is 1 g/Nm with flue gas volume ratio3。
Comparative example 1
5 ~ 30 μm of unmodified kaolin powder is spurted into about 900 DEG C of positions of burner hearth freeboard temperature, powderject quality with
Flue gas volume ratio is 600 mg/Nm3.Non- coordinated with plasma.
Comparative example 2
Modified kaolin is spurted into about 900 DEG C of positions of burner hearth freeboard temperature, powderject quality is 600 with flue gas volume ratio
mg/Nm3.Non- coordinated with plasma.
Comparative example 3
5 ~ 30 μm of unmodified kaolin powder is spurted into about 900 DEG C of positions of burner hearth freeboard temperature, powderject quality with
Flue gas volume ratio is 600 mg/Nm3.Meanwhile, it is 94 by volume ratio:6 O2/H2O is passed through after plasma producing apparatus and spurted into
About 600 DEG C of positions in flue, about 700 DEG C of plasma temperature, vapor addition quality is 1 g/Nm with flue gas volume ratio3。
Comparative example 4
Sprayed without high-temperature adsorbing agent and low temperature plasma.
Embodiment 1, comparative example 1 to the sack cleaner exiting flue gas flying dust of comparative example 4 are sampled respectively, analysis heavy metal
（Zn、Cu、Pb、Cd）And alkali metal（Na）Concentration of emission, as a result as shown in table 3.
The heavy metal and alkali metal concentration of emission of the sack cleaner of table 3 outlet（µg/Nm3）
| Heavy metal | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Zn | 578 | 1842 | 1104 | 962 | 2254 |
| Cu | 799 | 1487 | 1408 | 1078 | 1534 |
| Pb | 93 | 681 | 501 | 391 | 861 |
| Cd | 175 | 492 | 379 | 244 | 577 |
| Na | 751 | 2572 | 1987 | 1158 | 4148 |
By the heavy metal in embodiment 1 and alkali metal concentration of emission significantly lower than heavy metal of the comparative example 1 into comparative example 4 and
Alkali metal concentration of emission.The result of comparative example 1 and comparative example 2 shows that modified kaolin is favorably improved metal vapors absorption effect
Rate；The result of comparative example 1 and comparative example 3 shows that coordinated with plasma particle is favorably improved metal vapors adsorption efficiency；Implement
The Comparative result of example 1 and other comparative examples shows that modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour are imitated
It is really optimal.
Claims (4)
1. a kind of method of modified kaolin coordinated with plasma Adsorption of Heavy Metals and alkali metal vapour, it is characterised in that this method
Comprise the following steps：900 DEG C of high temperature above area injection modified kaolin powder into incinerator, modified kaolin powder is with burning
The flue gas of generation enters in flue, while the 600-800 DEG C of warm area injection O into flue2/H2O plasmas, form cooperation-removal
Trapped after heavy metal and alkali metal in effect, last modified kaolin powder adsorption flue gas by cleaner, wherein, it is described to change
Property kaolin powder by kaolin first through slight calcining, then by Ca (OH)2And CH3It is prepared by COONa mixed solution adsorptive
Form.
2. the method for modified kaolin coordinated with plasma Adsorption of Heavy Metals according to claim 1 and alkali metal vapour,
It is characterized in that the modified kaolin powder is prepared by following methods：
（1）The kaolin powder of 5 ~ 30 μm of selection；
（2）Above-mentioned kaolin powder is placed in 5 ~ 10 min of calcining at 350 ~ 400 DEG C, slight calcined kaolin is obtained；
（3）Above-mentioned slight calcined kaolin powder is dispersed in maceration extract, the maceration extract is to be dissolved with Ca (OH)2With
CH3Ca (OH) in the COONa aqueous solution, maceration extract2Concentration is 0.001 ~ 0.005 mol/L, CH3COONa concentration be 0.001 ~
The solid-to-liquid ratio of 0.005 mol/L, kaolin powder and maceration extract is 2 ~ 5 g/L, and dip time is 6 ~ 10 h, and dipping temperature is 10
~30℃；
（4）By the solid generated in above-mentioned maceration extract by filtering, deionized water elution, dry and broken, obtained modified kaolinite
Native powder, wherein elution number of times be no less than 2 times, drying temperature be 120 ~ 240 DEG C, drying time be 5 ~ 8 h, crush particle diameter be 5 ~
30 μm。
3. the method for modified kaolin coordinated with plasma Adsorption of Heavy Metals according to claim 1 and alkali metal vapour,
It is characterized in that：The modified kaolin powderject quality is 500-1000 mg/Nm with flue gas volume ratio3。
4. the method for modified kaolin coordinated with plasma Adsorption of Heavy Metals according to claim 1 and alkali metal vapour,
It is characterized in that：The O2/H2O plasmas pass through containing that plasma reactor is produced for the gaseous mixture of oxygen and vapor
The plasma of oxygen radical, plasma temperature is 400 ~ 700 DEG C, wherein O in gaseous mixture2 : H2O volume ratio is
15~19:1, the ratio of the vapor addition and flue gas is 400 ~ 1000 mg/Nm3。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108715519A (en) * | 2018-06-01 | 2018-10-30 | 南京师范大学镇江创新发展研究院 | A kind of method that incineration of refuse flyash harmless resource utilization utilizes |
| CN111333354A (en) * | 2020-03-09 | 2020-06-26 | 常熟理工学院 | Method for preparing non-sintered cement by using municipal domestic waste and product |
| CN111735056A (en) * | 2020-05-27 | 2020-10-02 | 东南大学 | Heavy metal collecting agent for garbage incinerator, garbage incineration treatment system and treatment method |
| CN112090270A (en) * | 2020-08-31 | 2020-12-18 | 上海交通大学 | Method for inhibiting generation of flue gas sulfur trioxide and cooperatively removing mercury |
| CN112108109A (en) * | 2020-09-29 | 2020-12-22 | 华中科技大学 | Preparation method of kaolin-based composite heavy metal additive and product thereof |
| CN115254897A (en) * | 2022-07-25 | 2022-11-01 | 南京师范大学镇江创新发展研究院 | Process for preparing formed fuel based on rural domestic garbage and agricultural waste |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715519A (en) * | 2018-06-01 | 2018-10-30 | 南京师范大学镇江创新发展研究院 | A kind of method that incineration of refuse flyash harmless resource utilization utilizes |
| CN111333354A (en) * | 2020-03-09 | 2020-06-26 | 常熟理工学院 | Method for preparing non-sintered cement by using municipal domestic waste and product |
| CN111333354B (en) * | 2020-03-09 | 2021-10-19 | 常熟理工学院 | Method for preparing non-sintered cement by using municipal domestic waste and product |
| CN111735056A (en) * | 2020-05-27 | 2020-10-02 | 东南大学 | Heavy metal collecting agent for garbage incinerator, garbage incineration treatment system and treatment method |
| CN111735056B (en) * | 2020-05-27 | 2023-06-02 | 东南大学 | Heavy metal trapping agent for garbage incinerator, garbage incineration treatment system and treatment method |
| CN112090270A (en) * | 2020-08-31 | 2020-12-18 | 上海交通大学 | Method for inhibiting generation of flue gas sulfur trioxide and cooperatively removing mercury |
| CN112090270B (en) * | 2020-08-31 | 2022-01-11 | 上海交通大学 | Method for inhibiting generation of flue gas sulfur trioxide and cooperatively removing mercury |
| CN112108109A (en) * | 2020-09-29 | 2020-12-22 | 华中科技大学 | Preparation method of kaolin-based composite heavy metal additive and product thereof |
| CN115254897A (en) * | 2022-07-25 | 2022-11-01 | 南京师范大学镇江创新发展研究院 | Process for preparing formed fuel based on rural domestic garbage and agricultural waste |
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