CN108940239A - The method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite - Google Patents
The method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite Download PDFInfo
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- CN108940239A CN108940239A CN201811144201.3A CN201811144201A CN108940239A CN 108940239 A CN108940239 A CN 108940239A CN 201811144201 A CN201811144201 A CN 201811144201A CN 108940239 A CN108940239 A CN 108940239A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
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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
- B01D53/06—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 with moving adsorbents, e.g. rotating beds
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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
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/11—Clays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of methods for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite, by Coal-fired capacity and modified attapulgite powder quality ratio (43000-50000): in the way of in the of 1, modified attapulgite powder is sprayed into the burner hearth that burning has coal；And according to exhaust gas volumn (standard state, wet basis, the 6%O before electric precipitation2, unit: m3/ s) and modified attapulgite liquid volume ratio (5000000-8000000): 1 mode, the spraying modified concave convex rod liquid in electric precipitation channel；The modified attapulgite powder is to use concentration to carry out acid for 3.5-3.9mol/L sulfuric acid to be modified；The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, suspension is made, and suspension is placed in 60-70 DEG C, 1:60 in mass ratio is added acidic thickener and is made.The method based on modified attapulgite control coal-burning power plant's fine particle and heavy metal can reduce fine particle and heavy metal that coal-burning power plant is generated in burning.
Description
Technical field
Present invention relates particularly to a kind of methods for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite.
Background technique
It is right that coal-burning power plant gives off a large amount of pollutants (oxysulfide, nitrogen oxides, fine particle and heavy metal etc.)
Atmospheric environment and human health generate significant damage.Coal-fired flue-gas can take off after dedusting, limestone-gypsum wet desulfuration
Except most of dust and heavy metal, but be discharged into atmosphere flue gas there are still fine particle and quality it is considerable, with mercury, lead,
Chromium and cadmium etc. are the heavy metal of essential element.
The existing control technology to fine particle discharge mainly has electric reunion, acoustic agglomeration, magnetic coagulation, heat reunion, turbulent flow (side
Interlayer) flowing reunion and chemical agglomeration etc..Wherein, it is known as chemical agglomeration using the method for adsorbent capture submicron particles,
Agglomeration Mechanism is mainly physical absorption and chemical reaction.Currently, being ground both at home and abroad to coal-fired fine particle using chemical agglomeration method
Study carefully content and is concentrated mainly on the influence reunited using the common adsorbent such as kaolinite, bauxite to particulate matter and its to one kind
Or the removing effect of several heavy metal species, the research of chemical agglomeration trapping and few is carried out using novel agglomerator.Finding economy has
The agglomerator of effect is the key that physics and chemical agglomeration method promote particulate matter reunion trapping.
Attapulgite also known as green attapulgite or Palygorskite are that the aqueous rich magnesium aluminosilicate of a kind of layer of chain structure is viscous
Native ore.Crystal shape be rodlike, fibrous, needle-shaped clay mineral, i.e. two layers of oxygen-octahedron, one layer of alumina octahedral,
Standard chemical formula is Mg5Si8O20(HO)2(OH2)4·4H2O, but actually chemical component is with SiO2、MgO、Al2O3Based on, wherein
Contain a certain amount of Fe2O3、MnO、TiO2Deng.It is recessed since concave convex rod itself has very unique layer chain crystal structure
There are many special physico-chemical properties, such as adsorptivity, rheological characteristic, catalytic, ion exchange, plasticity etc. for convex stick.Concave convex rod
These characteristics, so that concave convex rod is widely used in the numerous areas such as petroleum, chemical industry, medicine, environmental protection, printing.Its biggish ratio
It is adapted to apply in the control of coal-fired fine particle compared with adsorption site existing for area and its surface.
The attapulgite of natural output is often associated with the mineral such as montmorillonite, kaolinite, hydromica, quartz, carbonate.Suitably
Acid processing on the one hand can play dredging duct, removal carbonate and impurity, increase activated adoption bit number of points the effects of.Separately
On the one hand, due to the cationic interchangeability of concave convex rod, the lesser H of radius+Concave convex rod interlayer portion K can be displaced+、Na+、
Ca2+And Mg2+Plasma increases empty volume.
Summary of the invention
The purpose of the present invention is to solve the shortcomings of the prior art place, provide it is a kind of it is new modified have be provided simultaneously with object
Reason and chemical modification concave convex rod promote the trapping to fine particle and heavy metal, to reach the fine grained for reducing coal-burning power plant's discharge
The purpose of object and heavy metal.
The purpose of the present invention is achieved by the following technical programs.
A method of coal-burning power plant's fine particle and heavy metal being controlled based on modified attapulgite, according to Coal-fired capacity and modification
Concave convex rod powder mass ratio (43000-50000): 1 mode sprays into modified attapulgite powder in coal-burning power plant's burner hearth；And it presses
According to exhaust gas volumn (standard state, wet basis, the 6%O before electric precipitation2, unit: m3/ s) and modified attapulgite liquid volume ratio (5000000-
8000000): 1 mode, the spraying modified concave convex rod liquid in electric precipitation channel；
The modified attapulgite powder uses concentration to carry out acid activation for 3.5-3.9mol/L sulfuric acid；
The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, and suspension is made, and
Suspension is placed in 60-70 DEG C, 1:60 in mass ratio is added acidic thickener and is made.
Further, the process flow of coal-burning power plant is as follows: hearth combustion -- spraying into modified attapulgite powder --, and SCR is de-
Nitre -- sprays into -- electric precipitation -- limestone-gypsum wet desulfuration -- the chimney discharge of modified attapulgite liquid.
Further, the modified attapulgite powder preparation the following steps are included:
(1) concave convex rod ground, be sized to 2-4mm, then with deionized water according to (5-15): 150 mass ratio mixes,
Mud in suspension is formed, then fully dispersed by ultrasonication, upper suspension is taken to handle 5- in the centrifuge of 3000r/min
10min, standing vacuumize；
(2) concave convex rod solution is placed in container, and the sulfuric acid for putting into 3.5-3.9mol/L carries out acid activation, carries out 10-20min
Ultrasonic treatment, be filtered by vacuum after being then allowed to stand；
(3) concave convex rod after acid activation is placed in container, and changed according to 1:100 ratio investment vinyltriethoxysilane
Property, temperature controls at 65-75 DEG C, carries out the ultrasonic treatment of 10-20min, then filter, dries after mechanical stirring 3 hours, powder
It is broken and be sized to 2-4mm.
Further, the modified attapulgite powder is sprayed into according to mass ratio 1:50000 in the anthracitic burner hearth that burns.
Further, the modified attapulgite powder is sprayed into according to mass ratio 1:48000 in the burner hearth of bituminous coal.
Further, the modified attapulgite powder is sprayed into according to mass ratio 1:43000 in the burner hearth of combusting brown coal.
The beneficial effects of the present invention are:
(1) acid activation processing can part depolymerization concave convex rod stick crystalline substance beam, change the specific surface area of concave convex rod, removal carbonate etc.
Minerals impurity.H simultaneously+The Mg contained in concave convex rod can be replaced2+、Al3+And Fe3+Equal metal ions, improve the sun of concave convex rod from
Sub- interchangeability improves its adsorptivity.
(2) what is be affected in limestone-gypsum wet desulfuration slurries to desulfuration efficiency is chloride ion and nitrate ion,
This formula uses sulfuric acid then not generate new pollution as acid modified, can to avoid use conventional acid modified hydrochloric acid, chlorine in nitric acid
Ion and nitrate ion influence desulfuration efficiency, and can increase the quality of gypsum using sulfuric acid modified concave convex rod.
(3) the vinyltriethoxysilane cooperation modification used can be in inorganic filler and organic polymer basis material
Interface between erect " molecular bridge " the materials " coupling " of two kinds of property great disparities together, play enhancing and mention high performance work
With, and the mode of cooperative mechanical stirring, greatly increase its adsorptivity.
(4) by spraying modified attapulgite liquid double combinations before spraying modified attapulgite powder and electric precipitation in burning boiler
Efficiently to reduce fine particle and heavy metal discharge.Wherein modified attapulgite is as strong adsorbent, and at modified attapulgite
Physics and chemical reaction occurs, to increase particle size to reduce fine particle output, covers of gaseous state heavy metal
Grain object can be removed by devices such as electric precipitation and limestone-gypsum wet desulfurations.
(5) concave convex rod has that rich reserves, affordable, preparation is simple, is easily achieved large-scale production, and can increase
The advantages that by-produced gypsum quality, environmental benefit is good.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1
A method of coal-burning power plant's fine particle and heavy metal being controlled based on modified attapulgite, according to Coal-fired capacity and modified bumps
The mode of stick powder quality ratio 50000:1 has penetrating modified attapulgite powder in anthracitic burner hearth in burning；And it is removed according to electricity
Exhaust gas volumn (standard state, wet basis, 6%O before dirt2, unit: m3/ s) and modified attapulgite liquid volume ratio 8000000:1 mode, in electricity
Spraying modified concave convex rod liquid in dedusting channel；
The preparation of the modified attapulgite powder the following steps are included:
(1) concave convex rod ground, be sized to 4mm, then mixed with deionized water according to the mass ratio of 5:150, formed outstanding
Mud scum slurry, then it is fully dispersed by ultrasonication, take upper suspension to handle 10min in the centrifuge of 3000r/min, it is quiet
It sets and vacuumizes；
(2) concave convex rod solution is placed in container, and the sulfuric acid for putting into 3.9mol/L carries out acid activation, carries out the ultrasound of 10min
Processing, is filtered by vacuum after being then allowed to stand；
(3) concave convex rod after acid activation is placed in container, and changed according to 1:100 ratio investment vinyltriethoxysilane
Property, temperature controls at 75 DEG C, carries out the ultrasonic treatment of 20min, then filter, dries after mechanical stirring 3 hours, crushes and sieve
Divide to 2-4mm.
The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, is made and is suspended
Liquid, and suspension is placed in 70 DEG C, 1:60 in mass ratio is added acidic thickener and is made.
The process flow of coal-burning power plant is as follows: hearth combustion -- sprays into modified attapulgite powder -- SCR denitration -- penetrating to change
Property concave convex rod liquid -- electric precipitation -- limestone-gypsum wet desulfuration -- chimney discharge.
Embodiment 2
A method of coal-burning power plant's fine particle and heavy metal being controlled based on modified attapulgite, according to Coal-fired capacity and modified bumps
The mode of stick powder quality ratio 48000:1 sprays into modified attapulgite powder in the burner hearth that burning has bituminous coal；And according to electric precipitation
Preceding exhaust gas volumn (standard state, wet basis, 6%O2, unit: m3/ s) and modified attapulgite liquid volume ratio 6500000:1 mode, it is removed in electricity
Spraying modified concave convex rod liquid in dirt channel；
The preparation of the modified attapulgite powder the following steps are included:
(1) concave convex rod ground, be sized to 2mm, then mixed with deionized water according to the mass ratio of 15:150, formed outstanding
Mud scum slurry, then it is fully dispersed by ultrasonication, take upper suspension to handle 5min in the centrifuge of 3000r/min, it is quiet
It sets and vacuumizes；
(2) concave convex rod solution is placed in container, and the sulfuric acid for putting into 3.5mol/L carries out acid activation, carries out the ultrasound of 20min
Processing, is filtered by vacuum after being then allowed to stand；
(3) concave convex rod after acid activation is placed in container, and changed according to 1:100 ratio investment vinyltriethoxysilane
Property, temperature controls at 65 DEG C, carries out the ultrasonic treatment of 20min, then filter, dries after mechanical stirring 3 hours, crushes and sieve
Divide to 2-4mm.
The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, is made and is suspended
Liquid, and suspension is placed in 60 DEG C, 1:60 in mass ratio is added acidic thickener and is made.
The process flow of coal-burning power plant is as follows: hearth combustion -- sprays into modified attapulgite powder -- SCR denitration -- penetrating to change
Property concave convex rod liquid -- electric precipitation -- limestone-gypsum wet desulfuration -- chimney discharge.
Embodiment 3
A method of coal-burning power plant's fine particle and heavy metal being controlled based on modified attapulgite, according to recessed according to Coal-fired capacity and modification
The mode of convex stick powder quality ratio 43000:1 sprays into modified attapulgite powder in the burner hearth that burning has lignite；And it is removed according to electricity
Exhaust gas volumn (standard state, wet basis, 6%O before dirt2, unit: m3/ s) and modified attapulgite liquid volume ratio 5000000:1 mode, in electricity
Spraying modified concave convex rod liquid in dedusting channel；
The preparation of the modified attapulgite powder the following steps are included:
(1) attapulgite ground, be sized to 3mm, then mixed with deionized water according to the mass ratio of 10:150, formed
Mud in suspension, then it is fully dispersed by ultrasonication, take upper suspension to handle 7min in the centrifuge of 3000r/min,
Standing vacuumizes；
(2) concave convex rod solution is placed in container, and the sulfuric acid for putting into 3.7mol/L carries out acid activation, carries out the ultrasound of 15min
Processing, is filtered by vacuum after being then allowed to stand；
(3) concave convex rod after acid activation is placed in container, and changed according to 1:100 ratio investment vinyltriethoxysilane
Property, temperature controls at 60 DEG C, carries out the ultrasonic treatment of 20min, then filter, dries after mechanical stirring 3 hours, crushes and sieve
Divide to 2-4mm.
The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, is made and is suspended
Liquid, and suspension is placed in 60 DEG C, 1:60 in mass ratio is added acidic thickener and is made.
The process flow of coal-burning power plant is as follows: hearth combustion -- sprays into modified attapulgite powder -- SCR denitration -- penetrating to change
Property concave convex rod liquid -- electric precipitation -- limestone-gypsum wet desulfuration -- chimney discharge.
Comparative example
Existing concave convex rod surface modifying treatment specifically first carries out calcination processing to concave convex rod, then presses ethyl alcohol, water
It carries out being mixed to prepare treatment fluid according to weight ratio 1:13, calcined concave convex rod is immersed in treatment fluid, ultrasonic disperse processing
It is filtered out after 30min, drying.
Experimental example
It selects with a collection of concave convex rod as experimental raw, then respectively with above-described embodiment 1, embodiment 2, embodiment 3 and comparison
The corresponding method of example is modified processing, and wherein embodiment 1, embodiment 2, embodiment 3 are modified concave-convex using spraying into burner hearth
Stick powder and the spraying modified concave convex rod liquid in electric precipitation channel, comparative example only spray into modified attapulgite powder in burner hearth,
The mass concentration that fine particle is calculated using fine particle sampling instrument collects particle, ICP- using bearing type particle sampling instrument
Content of beary metal in MS test analysis fine particle, specific correlation data are as shown in the table.
It can be obtained by the above results, it can be significant using modified attapulgite powder made from this programme and modified attapulgite liquid
Fine particle is reduced, mass concentration reduces 56-64%, meanwhile, the heavy metal concentrations such as As, Pb 62- in fine particle can be reduced
72%, compared to use of the existing modified attapulgite in coal-burning power plant, effect is considerably better.
The beneficial effects of the present invention are: (1) acid activation processing can part depolymerization concave convex rod stick crystalline substance beam, change concave convex rod
Specific surface area, the removal minerals impurity such as carbonate.H simultaneously+The Mg contained in concave convex rod can be replaced2+、Al3+And Fe3+Equal gold
Belong to ion, improves the cationic interchangeability of concave convex rod, improve its adsorptivity.(2) right in limestone-gypsum wet desulfuration slurries
What desulfuration efficiency was affected is chloride ion and nitrate ion, this formula uses sulfuric acid then not generate new dirt as acid modified
Dye, can to avoid use conventional acid modified hydrochloric acid, chloride ion and nitrate ion influence desulfuration efficiency in nitric acid, and use sulphur
The modified concave convex rod of acid can increase the quality of gypsum.(3) the vinyltriethoxysilane cooperation modification used can be in nothing
" molecular bridge " is erected between machine filler and the interface of organic polymer basis material to exist the material " coupling " of two kinds of property great disparities
Together, play the role of enhance and mention it is high performance, and cooperative mechanical stirring mode, greatly increase its adsorptivity.(4) pass through
Spray modified attapulgite liquid double combinations efficiently reduce carefully before spraying modified attapulgite powder and electric precipitation in burning boiler
Particulate matter and heavy metal discharge.Wherein modified attapulgite is as strong adsorbent, and physics and chemistry occur at modified attapulgite
Reaction, to increase particle size to reduce fine particle output, the particulate matter for covering gaseous state heavy metal can pass through electricity
The devices such as dedusting and limestone-gypsum wet desulfuration remove.(5) concave convex rod has rich reserves, affordable, preparation simple, easy
In accomplishing scale production, and by-produced gypsum quality can be increased, the advantages that environmental benefit is good.
The foregoing is a specific embodiment of the present invention.It should be pointed out that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (6)
1. a kind of method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite, it is characterised in that: according to combustion
Coal amount and modified attapulgite powder quality ratio (43000-50000): 1 mode sprays into modified concave-convex in coal-burning power plant's burner hearth
Stick powder；And according to exhaust gas volumn (standard state, wet basis, the 6%O before electric precipitation2, unit: m3/s) and modified attapulgite liquid volume ratio
(5000000-8000000): 1 mode, the spraying modified concave convex rod liquid in electric precipitation channel；
The modified attapulgite powder is to use concentration to carry out acid for 3.5-3.9mol/L sulfuric acid to be modified；
The modified attapulgite liquid is dispersed in deionized water solution using modified attapulgite powder, and suspension is made, and
Suspension is placed in 60-70 DEG C, 1:60 in mass ratio is added acidic thickener and is made.
2. the method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite as described in claim 1, special
Sign, which is that the process flow of coal-burning power plant is as follows: hearth combustion, -- to be sprayed into modified attapulgite powder -- SCR denitration -- and sprays into modification
-- electric precipitation -- limestone-gypsum wet desulfuration -- the chimney discharge of concave convex rod liquid.
3. the method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite as described in claim 1, special
Sign is: the modified attapulgite powder is sprayed into according to mass ratio 1:50000 in the anthracitic burner hearth that burns.
4. the method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite as described in claim 1, special
Sign is: the modified attapulgite powder is sprayed into according to mass ratio 1:48000 in the burner hearth of bituminous coal.
5. the method for controlling coal-burning power plant's fine particle and heavy metal based on modified attapulgite as described in claim 1, special
Sign is: the modified attapulgite powder is sprayed into according to mass ratio 1:43000 in the burner hearth of combusting brown coal.
6. according to any one of claims 1 to 5 control coal-burning power plant's fine particle and heavy metal based on modified attapulgite
Method, which is characterized in that the preparation of the modified attapulgite powder the following steps are included:
(1) concave convex rod ground, be sized to 2-4mm, then with deionized water according to (5-15): 150 mass ratio mixes,
Mud in suspension is formed, then fully dispersed by ultrasonication, upper suspension is taken to handle 5- in the centrifuge of 3000r/min
10min, standing vacuumize；
(2) concave convex rod solution is placed in container, and the sulfuric acid for putting into 3.5-3.9mol/L carries out acid activation, carries out 10-20min
Ultrasonic treatment, be filtered by vacuum after being then allowed to stand；
(3) concave convex rod after acid activation is placed in container, and changed according to 1:100 ratio investment vinyltriethoxysilane
Property, temperature controls at 65-75 DEG C, carries out the ultrasonic treatment of 10-20min, then filter, dries after mechanical stirring 3 hours, powder
It is broken and be sized to 2-4mm.
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