CN104531262B - A kind of coal-fired superfine particulate matters control method based on modified kaolin - Google Patents
A kind of coal-fired superfine particulate matters control method based on modified kaolin Download PDFInfo
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- CN104531262B CN104531262B CN201410840918.7A CN201410840918A CN104531262B CN 104531262 B CN104531262 B CN 104531262B CN 201410840918 A CN201410840918 A CN 201410840918A CN 104531262 B CN104531262 B CN 104531262B
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Abstract
The invention discloses a kind of coal-fired superfine particulate matters control method based on modified kaolin, comprise the following steps: 1) prepare modified kaolin powder additive; 2) ratio being 3:100 ~ 5:100 in mass ratio by modified kaolin powder additive and coal dust is sent in coal pulverizer and is mixed; 3) coal dust being mixed with modified kaolin powder additive is sent into hearth combustion, catch by modified kaolin additive the superfine particulate matter that coal dust firing produces, modified kaolin powder additive be combined with superfine particulate matter the particle that formed by flue after caught by cleaning apparatus.Modified kaolin powder additive of the present invention is for kaolin before modified, and physics-chem characteristic there occurs change, significantly improves the capture ability of coal-fired superfine particulate matters, can improve the emission reduction effect of modified kaolin to fine particle further.
Description
Technical field
The invention belongs to coal burning pollution thing control field, more specifically, relate to a kind of coal-fired superfine particulate matters control method based on modified kaolin.
Background technology
In recent years, along with the development of China's new energy technology is with universal, coal develops the topmost energy as Chinese national economy, although some decline of its ratio, but based on the energy structure of the many coals of China, oil-poor, weak breath, coal will be still the topmost energy of China in the future for a long period of time.Coal is in use mainly based on coal fired power generation, and coal can produce many pollutents in combustion, as SO
x, NO
x, CO
2and particulate matter etc., great infringement is caused to environment and human body, produces Greenhouse effect, formation acid rain damages buildings and farm crop, atmosphere pollution affect environment and HUMAN HEALTH etc.The coal-fired particulate matter produced, especially fine particle is the important component part of atmospheric polluting material, in air, the particulate matter of enriched can produce haze phenomenon, and the haze in each city is seriously more aobvious in recent years, have a strong impact on daily life and healthy, therefore the people's detrimentally affect that will more and more pay attention to particulate matter and produce, is also constantly seeking particulate matter source of generation and suppressing method simultaneously.
Atmospheric particulates are called for short PM (ParticulateMatter), according to the aerodynamic diameter scope of particulate matter, and the particulate matter abbreviation that definable is different.PM2.5: refer to that aerodynamic diameter is less than or equal to the Atmospheric particulates of 2.5 μm, this kind of particulate matter can enter human body alveolar by blood system, is called fine particle again.Fine particle, because its particle diameter is little, specific surface area is large, therefore organic pollutants and multiple trace heavy metals is easily enriched with, as lead, cadmium, nickel, manganese, vanadium, bromine, zinc and PAHs etc., great harm can be caused to the neural system of human body, respiratory system, blood circulation, reproductive system etc.
Current research shows, coal-fired superfine particulate matters condenses primarily of gasification, mineral directly transform, coal tar broken and out-phase condensation etc. acts on and producing, reacted by adsorbent surface and the mechanism of melting, ultra-fine multi-modal particle can be stoped to be formed or superfine particulate matter (aerodynamic diameter is less than or equal to the particulate matter of 0.5 μm) is changed towards fine particle, thus the effective discharge controlling superfine particulate matter.Therefore by spraying into the method that additive is fine particle generation in a kind of effective minimizing burning in stove, kaolin is then considered to a kind of extraordinary Particulates from Coal Combustion sorbent material.Kaolin main component is sieve and silica-sesquioxide and Bound moisture, under the hot conditions that kaolin produces at coal dust firing, Alkali-Metal Na, the oxyhydroxide of K, the compound vapor such as vitriol and muriate can be adsorbed, reaction generates silico-aluminate, therefore, it is by absorption Na, K that kaolin reduces PM2.5 generation, and then suppresses the generation of ultra-fine multi-modal particle thing to realize.
In existing patent " removal methods of coal-fired superfine particulate matters " (zl201010109820.6), Mg base is removed agent and coal dust multifuel combustion, the coal-fired superfine particulate matter produced is removed by adsorbent, thus effectively decreases the discharge of coal-fired superfine particulate matters; Ba base is removed agent (BaO, Ba (OH) respectively in " discharge control method of coal-fired superfine particulate matters " (zl201110420438.1), " discharge control method of coal-fired superfine particulate matters " (zl201010201835.5), " a kind of discharge control method of coal-fired superfine particulate matters " (zl201210405695.2)
2, BaCO
3or Ba (HCO
3)
2), Fe base removes agent (FeO, Fe
2o
3, Fe (OH)
2or Fe (OH)
3), Mn base removes agent (MnO
2, Mn
3o
4, Mn (OH)
2or MnCO
3) with and composition thereof carry out Homogeneous phase mixing with coal dust, send into hearth combustion, the coal-fired fine particle produced is removed agent and catches and become greater particle size particle, removed by afterbody fly-ash separator subsequently, the method can reduce alkali metallic sodium and potassium discharge effectively, reduce basic metal to the high temperature corrosion of boiler, the toxic heavy metal element in flue gas can also be removed while removing PM2.5; Propose in " a kind of method of removing contaminations under oxygen-enriched combustion condition " (zl200910273086.4) to utilize kaolin as sorbent material, at O
2/ CO
2by chemical reaction and physical adsorption under burning, the multiple pollutants such as submicron particles (PM1), heavy metal and basic metal are carried out combining removing, and then reduce the discharge of fine particle.But kaolin is as a kind of coal-fired superfine particulate matters sorbent material, it needs further to be improved to the removal effect of particulate matter.
Kaolinic chemical formula is Al
2o
32SiO
22H
2o, main chemical compositions is Al
2o
3and SiO
2, its crystalline structure is the dioctahedron laminate structure of 1:1 type, is built into by the connection of common Sauerstoffatom by Si ~ O tetrahedron and the false octahedral layer of Al ~ (O, OH).In kaolinic practical structures, Si ~ O tetrahedral sheet four sides has to pass through slight relatively rotating and could match with " oxyhydrogen aluminum stone " sheet of " distortion " with warpage.In kaolinic crystalline structure, interlamellar spacing is less, and inter-layer bonding force is more weak, and there is unsaturated filling distortion.Because kaolinic structure exists above shortcoming, it is not very high to the adsorption rate of superfine particulate matter.
Along with environmental problem is more aobvious outstanding, the harm that the discharge of particulate matter produces is increasing, for the problem of the fine particle maximum discharge that existing fire coal produces, is badly in need of the coal-fired superfine particulate matters sorbent material seeking more highly effective.Show that kaolin can more effective emission-reducing coal superfine particulate matter from current research, it is about 31% to the adsorption rate of coal-fired superfine particulate matters, and adsorption rate is not high, superfine particulate matter discharge after environmental pollution larger.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of coal-fired superfine particulate matters control method based on modified kaolin, superfine particulate matter is removed by adding sorbent material, the adsorption rate of modified kaolin to superfine particulate matter can be significantly improved, the effective discharge reducing superfine particulate matter.
For achieving the above object, according to one aspect of the present invention, provide a kind of coal-fired superfine particulate matters control method based on modified kaolin, comprise the following steps:
1) prepare modified kaolin powder additive, described modified kaolin powder additive is one or more in sour modified kaolin powder, manganate modified kaolin powder and vitriol modified kaolin powder;
2) ratio being 3:100 ~ 5:100 in mass ratio by modified kaolin powder additive and coal dust is sent in coal pulverizer and is mixed;
3) coal dust being mixed with modified kaolin powder additive is sent into hearth combustion, catch by modified kaolin additive the superfine particulate matter that coal dust firing produces, modified kaolin powder additive be combined with superfine particulate matter the particle that formed by flue after caught by cleaning apparatus.
Preferably, described modified kaolin powder additive comprises sour modified kaolin powder, and described sour modified kaolin powder is hydrochloric Acid Modification kaolin powder, and the preparation process of hydrochloric Acid Modification kaolin powder is as follows:
1) kaolin is calcined 2 ~ 4h under 800 ~ 1000 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to every 7 ~ 10mL hydrochloric acid soln, kaolin after calcining is added in the hydrochloric acid soln of 3 ~ 5mol/L, centrifugation is carried out react 2 ~ 4h under the water bath with thermostatic control condition that temperature is 80 ~ 100 DEG C after, be separated through repeatedly centrifuge washing and remove chlorion, obtain hydrochloric Acid Modification kaolin;
3) hydrochloric Acid Modification kaolin is dried at 80 ~ 120 DEG C;
4) the hydrochloric Acid Modification kaolin of drying with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained hydrochloric Acid Modification kaolin powder after pulverizing, milling.
Preferably, described modified kaolin powder additive comprises manganate modified kaolin powder, and described manganate modified kaolin powder is potassium manganate modified kaolin powder, and the preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the potassium manganate modified kaolin of drying with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Preferably, described modified kaolin powder additive comprises vitriol modified kaolin powder, and described vitriol modified kaolin powder is Tai-Ace S 150 modified kaolin powder, and the preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state being left standstill 30 ~ 40min, the constant temperature oven inside holding l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by insulation after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Preferably, described modified kaolin powder additive also comprises potassium manganate modified kaolin powder, and modified kaolin powder additive comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of potassium manganate modified kaolin powder according to ratio of weight and number; The preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the potassium manganate modified kaolin of drying screens with 100 ~ 300 object screen clothes after pulverizing, milling after pulverizing, milling, and collects the powder by screen cloth, obtains potassium manganate modified kaolin powder.
Preferably, described modified kaolin powder additive also comprises Tai-Ace S 150 modified kaolin powder, and modified kaolin powder additive comprises according to ratio of weight and number: 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of Tai-Ace S 150 modified kaolin powder; The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Preferably, described modified kaolin powder additive also comprises potassium manganate modified kaolin powder and Tai-Ace S 150 modified kaolin powder; Modified kaolin powder additive comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of potassium manganate modified kaolin powder, 2 ~ 4 parts of Tai-Ace S 150 modified kaolin powder according to ratio of weight and number; Wherein
The preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the hydrochloric Acid Modification kaolin of drying screens with 100 ~ 300 object screen clothes after pulverizing, milling after pulverizing, milling, and collects the powder by screen cloth, obtains potassium manganate modified kaolin powder;
The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Preferably, described modified kaolin powder additive also comprises Tai-Ace S 150 modified kaolin powder, and modified kaolin powder additive comprises 1 ~ 2 part of potassium manganate modified kaolin powder, 1 ~ 2 part of Tai-Ace S 150 modified kaolin powder according to ratio of weight and number; The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
In general, the above technical scheme conceived by the present invention compared with prior art, owing to have employed modified kaolin, can obtain following beneficial effect:
1) modified kaolin powder additive absorption fine particle is by two kinds of approach: one, by modified kaolin surface and alkali metal vapour generation chemical reaction, catch alkali metal vapour by chemisorption, thus prevent these alkali metal vapours from condensing into ultra-fine multi-modal particle thing; They are two years old, the sodium silico-aluminate that modified kaolin surface is formed with alkali metal vapour chemical reaction, at high temperature easily melting forms surperficial liquid phase layer, be melt into liquid phase sodium silico-aluminate can further with inter-modal particulate matter generation liquid phase capture reaction, thus reduce further the formation of coal-fired superfine particulate matters.
2) modified kaolin powder additive is for kaolin before modified, and physics-chem characteristic there occurs change, significantly improves the capture ability of coal-fired superfine particulate matters, can improve the emission reduction effect of modified kaolin to fine particle further.
3) modified kaolin powder additive is easy to make, and raw material is sufficient, can do large-scale production and application.The product simultaneously produced is convenient to store transport, and component function is stablized, nontoxic.
3) modified kaolin powder additive can adsorb the composition of most fine particles such as basic metal, alkaline-earth metal and SOx effectively, and significantly reduction fine particle is discharged into the content in air.
Accompanying drawing explanation
Fig. 1 is workflow diagram of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Embodiment 1
The preparation of hydrochloric Acid Modification kaolin powder I:
1) kaolin is calcined 2h under 800 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to every 7mL hydrochloric acid soln, kaolin after calcining is added in the hydrochloric acid soln of 4mol/L, centrifugation is carried out react 3.5h under the water bath with thermostatic control condition that temperature is 80 DEG C after, be separated through repeatedly centrifuge washing and remove chlorion, obtain hydrochloric Acid Modification kaolin;
3) hydrochloric Acid Modification kaolin is dried at 80 DEG C;
4) the hydrochloric Acid Modification kaolin of drying with 100 object screen cloth screenings, is collected the powder by screen cloth, is obtained hydrochloric Acid Modification kaolin powder after pulverizing, milling.
Be the ratio of 3:100 according to hydrochloric Acid Modification kaolin powder I with coal dust weight ratio, hydrochloric Acid Modification kaolin powder I is fully mixed with coal dust (particle size range 45 ~ 100 μm), the coal dust being mixed with hydrochloric Acid Modification kaolin powder I is burnt in sedimentation furnace, experimental temperature is 1500 DEG C, be 0.15g/min to powder speed, the particle that coal dust produces after sedimentation furnace burning, entered cyclonic separator to be separated, remove the particle of aerodynamic diameter more than 10 μm, and then collected by the low pressure striker (DLPI) with 13 grades of particle diameter dividing functions, the particle that aerodynamic diameter is less than 10 μm collected by low pressure striker (DLPI), 13 grade particles particle diameters are respectively: 0.0281 μm, 0.0565 μm, 0.0944 μm, 0.154 μm, 0.258 μm, 0.377 μm, 0.605 μm, 0.936 μm, 1.58 μm, 2.36 μm, 3.95 μm, 6.6 μm, 9.8 μm, afterwards the particulate matter collected 1,000,000/balance (precision is 1 μ g) is sampled, the change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding hydrochloric Acid Modification kaolin powder I is 59.36%.
Embodiment 2
The preparation of hydrochloric Acid Modification kaolin powder II:
1) kaolin is calcined 2 ~ 4h under 950 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to every 10mL hydrochloric acid soln, kaolin after calcining is added in the hydrochloric acid soln of 3mol/L, centrifugation is carried out react 2h under the water bath with thermostatic control condition that temperature is 100 DEG C after, be separated through repeatedly centrifuge washing and remove chlorion, obtain hydrochloric Acid Modification kaolin;
3) hydrochloric Acid Modification kaolin is dried at 120 DEG C;
4) the hydrochloric Acid Modification kaolin of drying with 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained hydrochloric Acid Modification kaolin powder after pulverizing, milling.
Be the ratio of 4:100 according to hydrochloric Acid Modification kaolin powder II with coal dust weight ratio, hydrochloric Acid Modification kaolin powder II is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with hydrochloric Acid Modification kaolin powder II, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding hydrochloric Acid Modification kaolin powder II is 62.05%.
Embodiment 3
The preparation of hydrochloric Acid Modification kaolin powder III:
1) kaolin is calcined 4h under 1000 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to every 9mL hydrochloric acid soln, kaolin after calcining is added in the hydrochloric acid soln of 5mol/L, centrifugation is carried out react 4h under the water bath with thermostatic control condition that temperature is 75 DEG C after, be separated through repeatedly centrifuge washing and remove chlorion, obtain hydrochloric Acid Modification kaolin;
3) hydrochloric Acid Modification kaolin is dried at 110 DEG C;
4) the hydrochloric Acid Modification kaolin of drying with 200 object screen cloth screenings, is collected the powder by screen cloth, is obtained hydrochloric Acid Modification kaolin powder after pulverizing, milling.
Be the ratio of 5:100 according to hydrochloric Acid Modification kaolin powder III with coal dust weight ratio, hydrochloric Acid Modification kaolin powder III is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with hydrochloric Acid Modification kaolin powder III, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding hydrochloric Acid Modification kaolin powder III is 60.26%.
Embodiment 4
The preparation method of potassium manganate modified kaolin powder I is as follows:
1) kaolin is calcined 2h under 660 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20mL, kaolin after calcining is added in the potassium manganate solution of 2mol/L, centrifugation is carried out react 6.5h under the water bath with thermostatic control condition that temperature of reaction is 70 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 DEG C;
4) the potassium manganate modified kaolin of drying with 100 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 3:100 according to potassium manganate modified kaolin powder I with coal dust weight ratio, potassium manganate modified kaolin powder I is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with potassium manganate modified kaolin powder I, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding potassium manganate modified kaolin powder I is 50.56%.
Embodiment 5
The preparation method of potassium manganate modified kaolin powder II is as follows:
1) kaolin is calcined 2.5h under 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 30mL, kaolin after calcining is added in the potassium manganate solution of 3mol/L, centrifugation is carried out react 6h under the water bath with thermostatic control condition that temperature of reaction is 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 95 DEG C;
4) the potassium manganate modified kaolin of drying with 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 4:100 according to potassium manganate modified kaolin powder II with coal dust weight ratio, potassium manganate modified kaolin powder II is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with potassium manganate modified kaolin powder II, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding potassium manganate modified kaolin powder II is 52.48%.
Embodiment 6
The preparation method of potassium manganate modified kaolin powder III is as follows:
1) kaolin is calcined 3h under 600 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 25mL, kaolin after calcining is added in the potassium manganate solution of 2.5mol/L, centrifugation is carried out react 8h under the water bath with thermostatic control condition that temperature of reaction is 85 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 120 DEG C;
4) the potassium manganate modified kaolin of drying with 200 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 5:100 according to potassium manganate modified kaolin powder III with coal dust weight ratio, potassium manganate modified kaolin powder III is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with potassium manganate modified kaolin powder III, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding potassium manganate modified kaolin powder III is 53.05%.
Embodiment 7
The preparation method of Tai-Ace S 150 modified kaolin powder I is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 7 parts, 1 part, Tai-Ace S 150, gac 0.2 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state being left standstill 36min, the constant temperature oven inside holding lh of 90 DEG C is placed in;
4) by insulation after mixing additive at 200 DEG C of roasting temperature 1h;
5) the mixing additive after roasting with 100 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 3:100 according to Tai-Ace S 150 modified kaolin powder I with coal dust weight ratio, Tai-Ace S 150 modified kaolin powder I is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with Tai-Ace S 150 modified kaolin powder I, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding Tai-Ace S 150 modified kaolin powder I is 50.42%.
Embodiment 8
The preparation method of Tai-Ace S 150 modified kaolin powder II is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 parts, 1.5 parts, Tai-Ace S 150, gac 0.1 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state being left standstill 30min, the constant temperature oven inside holding 1.2h of 100 DEG C is placed in;
4) by insulation after mixing additive at 300 DEG C of roasting temperature 1h;
5) the mixing additive after roasting with 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 4:100 according to Tai-Ace S 150 modified kaolin powder II with coal dust weight ratio, Tai-Ace S 150 modified kaolin powder II is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with Tai-Ace S 150 modified kaolin powder II, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding Tai-Ace S 150 modified kaolin powder II is 52.24%.
Embodiment 9
The preparation method of Tai-Ace S 150 modified kaolin powder III is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 8 parts, 2 parts, Tai-Ace S 150, gac 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state being left standstill 40min, the constant temperature oven inside holding 2h of 95 DEG C is placed in;
4) by insulation after mixing additive at 260 DEG C of roasting temperature 1.2h;
5) the mixing additive after roasting with 200 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
Be the ratio of 5:100 according to Tai-Ace S 150 modified kaolin powder III with coal dust weight ratio, Tai-Ace S 150 modified kaolin powder III is fully mixed with coal dust (particle size range 45 ~ 100 μm); Burnt in sedimentation furnace by the coal dust being mixed with Tai-Ace S 150 modified kaolin powder III, subsequent operations process is identical with embodiment 1; The change of kaolin adsorptive power after contrast before modified, the adsorption rate obtaining the ultra-fine grain after adding Tai-Ace S 150 modified kaolin powder III is 53.25%.
Embodiment 10
1) get above-mentioned hydrochloric Acid Modification kaolin powder I 50kg, potassium manganate modified kaolin powder I 25kg, Tai-Ace S 150 modified kaolin powder I 25kg mixes as additive for fire coal I, then puts into mixing machinery and mixes;
2) be the ratio of 3:100 according to additive for fire coal I and the mass ratio of coal dust, the additive for fire coal I and the coal dust that prepare (particle size range 45 ~ 100 μm) are fully mixed;
3) coal dust being mixed with modified kaolin powder is burnt respectively in sedimentation furnace, experimental temperature is 1500 DEG C, be 0.15g/min to powder speed, the particle that coal dust produces after sedimentation furnace burning, entered cyclonic separator to be separated, remove the particle of aerodynamic diameter more than 10 μm, and then collected by the low pressure striker (DLPI) with 13 grades of particle diameter dividing functions; The particle that aerodynamic diameter is less than 10 μm collected by low pressure striker (DLPI), 13 grade particles particle diameters are respectively: 0.0281 μm, 0.0565 μm, 0.0944 μm, 0.154 μm, 0.258 μm, 0.377 μm, 0.605 μm, 0.936 μm, 1.58 μm, 2.36 μm, 3.95 μm, 6.6 μm, 9.8 μm, afterwards the particulate matter collected 1,000,000/balance (precision is 1 μ g) is sampled, compare the grain amount that the kaolin after interpolation before modified and raw coal generate;
4) contrast the change of kaolin adsorptive power before modified, obtaining the adsorption rate of superfine particulate matter is 62.38%.
Embodiment 11
1) get above-mentioned hydrochloric Acid Modification kaolin powder II 30kg, potassium manganate modified kaolin powder II 40kg, Tai-Ace S 150 modified kaolin powder II 30kg mixes as additive for fire coal II, then puts into mixing machinery and mixes;
2) be the ratio of 4:100 according to additive for fire coal II and the mass ratio of coal dust, the additive for fire coal II and the coal dust that prepare (particle size range 45 ~ 100 μm) are fully mixed;
3) step 3 of operating process and embodiment 10) identical;
4) contrast the change of kaolin adsorptive power before modified, obtaining adsorption rate is 61.53%.
Embodiment 12
1) get above-mentioned hydrochloric Acid Modification kaolin powder III 30kg, potassium manganate modified kaolin powder III 30kg, Tai-Ace S 150 modified kaolin powder III 40kg mixes as additive for fire coal III, then puts into mixing machinery and mixes;
2) be the ratio of 5:100 according to additive for fire coal III and the mass ratio of coal dust, the additive for fire coal III and the coal dust that prepare (particle size range 45 ~ 100 μm) are fully mixed;
3) step 3 of operating process and embodiment 10) identical;
4) contrast the change of kaolin adsorptive power before modified, obtaining adsorption rate is 63.58%.
Embodiment 13
Additive for fire coal I in embodiment 10 is carried out test in the back yard industry stove of a 30MW, comprises following steps:
1) be the ratio of 3:100 according to additive for fire coal I with coal mass ratio, the additive for fire coal I and the coal dust that prepare sent into coal pulverizer in the lump, makes the two fully mixing;
2) coal dust being mixed with additive for fire coal I is sent into burner hearth with First air, in the back yard industry stove of a 30MW, carry out test, carry out sampling at back-end ductwork by the low pressure striker (DLPI) with 13 grades of particle diameter dividing functions simultaneously and collect;
3) particle that aerodynamic diameter is less than 10 μm collected by low pressure striker (DLPI), afterwards the particulate matter collected 1,000,000/balance (precision is 1 μ g) is sampled, the grain amount that comparison interpolation composite additive and raw coal generate, the change of kaolin adsorptive power after contrast before modified.
4) the coal-fired superfine particulate matter produced is by the trapping of additive, transforms, along with flue gas enters in back-end ductwork, caught subsequently by electrostatic precipitator or sack cleaner to macrobead, thus reduces the discharge of coal-fired superfine particulate matters;
5) contrast the change of kaolin adsorptive power before modified, obtaining adsorption rate is 57.46%.
Embodiment 14
Additive for fire coal II in embodiment 11 is carried out test in the back yard industry stove of a 30MW, comprises following steps:
1) be the ratio of 4:100 according to additive for fire coal II with coal mass ratio, the additive for fire coal II and the coal dust that prepare sent into coal pulverizer in the lump, makes the two fully mixing;
2) coal dust being mixed with additive for fire coal II is sent into burner hearth with First air, in the back yard industry stove of a 30MW, carry out test, carry out sampling at back-end ductwork by the low pressure striker (DLPI) with 13 grades of particle diameter dividing functions simultaneously and collect;
Step 3), 4) identical with embodiment 13;
5) contrast the change of kaolin adsorptive power before modified, obtaining adsorption rate is 56.37%.
Embodiment 15
Additive for fire coal III in embodiment 12 is carried out test in the back yard industry stove of a 30MW, comprises following steps:
1) be the ratio of 5:100 according to additive for fire coal III with coal mass ratio, the additive for fire coal III and the coal dust that prepare sent into coal pulverizer in the lump, makes the two fully mixing;
2) coal dust being mixed with additive for fire coal III is sent into burner hearth with First air, in the back yard industry stove of a 30MW, carry out test, carry out sampling at back-end ductwork by the low pressure striker (DLPI) with 13 grades of particle diameter dividing functions simultaneously and collect;
Step 3), 4) identical with embodiment 13;
5) contrast the change of kaolin adsorptive power before modified, obtaining adsorption rate is 58.21%.
The invention solves the difficult problem that current particulate matter removing equipment is low to superfine particulate matter removal efficiency, propose a kind of easy to make, be convenient to store with transport modified kaolin powder additive.This modified kaolin powder additive can effectively total amount in superfine particulate matter of the growing amount of lower superfine particulate matter and heavy metal element and concentration, has great advantage for environment protection and HUMAN HEALTH.
In addition, the modified kaolin powder additive configured according to the method described above can be placed and never degenerate for many years, and simultaneously modified kaolin powder to mix in coal dust the quality guaranteed period of coal dust without impact.
In addition, the hydrochloric Acid Modification kaolin powder obtained by aforesaid method, potassium manganate modified kaolin powder and Tai-Ace S 150 modified kaolin powder, can also be combined between two and add in coal dust.
When the mixing of hydrochloric Acid Modification kaolin powder, Tai-Ace S 150 modified kaolin powder adds in coal dust, mixture comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of Tai-Ace S 150 modified kaolin powder by ratio of weight and the number of copies.
When the mixing of hydrochloric Acid Modification kaolin powder, potassium manganate modified kaolin powder adds in coal dust, mixture comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of potassium manganate modified kaolin powder by ratio of weight and the number of copies.
When the mixing of potassium manganate modified kaolin powder, Tai-Ace S 150 modified kaolin powder adds in coal dust, mixture comprises 1 ~ 2 part of potassium manganate modified kaolin powder, 1 ~ 2 part of Tai-Ace S 150 modified kaolin powder by ratio of weight and the number of copies.
When adding between two, also can improve the adsorption rate to superfine particulate matter.
In addition, sour modified kaolin, except can adopting hydrochloric Acid Modification kaolin, can also adopt sulfuric acid modified kaolin, phosphoric acid modification kaolin etc.
Manganate modified kaolin, except can adopting potassium manganate modified kaolin, can also adopt Rosensthiel's green modified kaolin, calcium manganate modified kaolin, the magnesium-modified kaolin of mangaic acid etc.
Vitriol modified kaolin, except can adopting Tai-Ace S 150 modified kaolin, can also adopt barium sulfate modified column kaolin, calcium sulfate modified kaolin, magnesium sulfate modified kaolin etc.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1., based on a coal-fired superfine particulate matters control method for modified kaolin, it is characterized in that: comprise the following steps:
1) prepare modified kaolin powder additive, described modified kaolin powder additive is one or more in sour modified kaolin powder, manganate modified kaolin powder and vitriol modified kaolin powder;
2) ratio being 3:100 ~ 5:100 in mass ratio by modified kaolin powder additive and coal dust is sent in coal pulverizer and is mixed;
3) coal dust being mixed with modified kaolin powder additive is sent into hearth combustion, catch by modified kaolin additive the superfine particulate matter that coal dust firing produces, modified kaolin powder additive be combined with superfine particulate matter the particle that formed by flue after caught by cleaning apparatus.
2. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 1, it is characterized in that: described modified kaolin powder additive comprises sour modified kaolin powder, described sour modified kaolin powder is hydrochloric Acid Modification kaolin powder, and the preparation process of hydrochloric Acid Modification kaolin powder is as follows:
1) kaolin is calcined 2 ~ 4h under 800 ~ 1000 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to every 7 ~ 10mL hydrochloric acid soln, kaolin after calcining is added in the hydrochloric acid soln of 3 ~ 5mol/L, centrifugation is carried out react 2 ~ 4h under the water bath with thermostatic control condition that temperature is 80 ~ 100 DEG C after, be separated through repeatedly centrifuge washing and remove chlorion, obtain hydrochloric Acid Modification kaolin;
3) hydrochloric Acid Modification kaolin is dried at 80 ~ 120 DEG C;
4) the hydrochloric Acid Modification kaolin of drying with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained hydrochloric Acid Modification kaolin powder after pulverizing, milling.
3. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 1, it is characterized in that: described modified kaolin powder additive comprises manganate modified kaolin powder, described manganate modified kaolin powder is potassium manganate modified kaolin powder, and the preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the potassium manganate modified kaolin of drying with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained potassium manganate modified kaolin powder after pulverizing, milling.
4. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 1, it is characterized in that: described modified kaolin powder additive comprises vitriol modified kaolin powder, described vitriol modified kaolin powder is Tai-Ace S 150 modified kaolin powder, and the preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state being left standstill 30 ~ 40min, the constant temperature oven inside holding l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by insulation after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained Tai-Ace S 150 modified kaolin powder after pulverizing, milling.
5. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 2, it is characterized in that: described modified kaolin powder additive also comprises potassium manganate modified kaolin powder, modified kaolin powder additive comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of potassium manganate modified kaolin powder according to ratio of weight and number; The preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the potassium manganate modified kaolin of drying screens with 100 ~ 300 object screen clothes after pulverizing, milling after pulverizing, milling, and collects the powder by screen cloth, obtains potassium manganate modified kaolin powder.
6. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 2, it is characterized in that: described modified kaolin powder additive also comprises Tai-Ace S 150 modified kaolin powder, and modified kaolin powder additive comprises according to ratio of weight and number: 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of Tai-Ace S 150 modified kaolin powder; The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained Tai-Ace S 150 modified kaolin powder after pulverizing, milling.
7. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 2, is characterized in that: described modified kaolin powder additive also comprises potassium manganate modified kaolin powder and Tai-Ace S 150 modified kaolin powder; Modified kaolin powder additive comprises 3 ~ 5 parts of hydrochloric Acid Modification kaolin powder, 2 ~ 4 parts of potassium manganate modified kaolin powder, 2 ~ 4 parts of Tai-Ace S 150 modified kaolin powder according to ratio of weight and number; Wherein
The preparation method of potassium manganate modified kaolin powder is as follows:
1) kaolin is calcined 2 ~ 3h under 600 ~ 700 DEG C of conditions;
2) the kaolinic input ratio of 1g is thrown according to the potassium manganate solution of every 20 ~ 30mL, kaolin after calcining is added in the potassium manganate solution of 2 ~ 3mol/L, centrifugation is carried out react 6 ~ 8h under the water bath with thermostatic control condition that temperature of reaction is 70 ~ 90 DEG C after, be separated through repeatedly centrifuge washing and remove potassium ion, obtain potassium manganate modified kaolin;
3) potassium manganate modified kaolin is dried at 80 ~ 120 DEG C;
4) the hydrochloric Acid Modification kaolin of drying screens with 100 ~ 300 object screen clothes after pulverizing, milling after pulverizing, milling, and collects the powder by screen cloth, obtains potassium manganate modified kaolin powder;
The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained Tai-Ace S 150 modified kaolin powder after pulverizing, milling.
8. a kind of coal-fired superfine particulate matters control method based on modified kaolin according to claim 3, it is characterized in that: described modified kaolin powder additive also comprises Tai-Ace S 150 modified kaolin powder, modified kaolin powder additive comprises 1 ~ 2 part of potassium manganate modified kaolin powder, 1 ~ 2 part of Tai-Ace S 150 modified kaolin powder according to ratio of weight and number; The preparation method of Tai-Ace S 150 modified kaolin powder is as follows:
1) preparation mixing additive, described mixing additive comprises according to ratio of weight and number: kaolin 6 ~ 8 parts, 1 ~ 2 part, Tai-Ace S 150, gac 0.1 ~ 0.5 part;
2) in mixing additive, add distilled water and stir, making mixing additive become pasty state;
3), after the mixing additive of pasty state leaves standstill 30 ~ 40min, the constant temperature oven insulation l ~ 2h of 90 ~ 100 DEG C is placed in;
4) by dry after mixing additive at 200 ~ 300 DEG C of roasting temperature 1 ~ 2h;
5) the mixing additive after roasting with 100 ~ 300 object screen cloth screenings, is collected the powder by screen cloth, is obtained Tai-Ace S 150 modified kaolin powder after pulverizing, milling.
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