CN105921115A - SDS-MgCl2 composite modified fly ash and preparation method thereof - Google Patents

SDS-MgCl2 composite modified fly ash and preparation method thereof Download PDF

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CN105921115A
CN105921115A CN201610302082.4A CN201610302082A CN105921115A CN 105921115 A CN105921115 A CN 105921115A CN 201610302082 A CN201610302082 A CN 201610302082A CN 105921115 A CN105921115 A CN 105921115A
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flyash
sds
mgcl
composite modified
fly ash
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王维生
应成璋
罗宇晨
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Guangxi University
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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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • 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
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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Abstract

The invention discloses SDS-MgCl2 composite modified fly ash. The SDS-MgCl2 composite modified fly ash is prepared from, by weight, 18-22 parts of calcined fly ash, 3.5-5 parts of H2SO4, 0.8-1.2 parts of MgCl2.6H2O and 1.8-2.5 parts of SDS. A preparation method comprises the following steps that the raw materials are weighed or metered by weight separately, the calcined fly ash is added into the H2SO4 solution, and the materials are stirred to be prepared into fly ash suspension liquid; MgCl2.6H2O and SDS are put into the fly ash suspension liquid, oscillating, filtering, drying and grinding are conducted, and then the SDS-MgCl2 composite modified fly ash is obtained. After the fly ash is subjected to composite modification of SDS and MgCl2, the glass structure formed on the surface of the fly ash is destroyed, a large quantity of Al and Si active groups are generated, and compared with original fly ash, the specific surface area, the porosity and the average pore size of the composite modified fly ash are increased, and the adsorption capacity of the composite modified fly ash is improved.

Description

A kind of SDS-MgCl2Composite modified flyash and preparation method thereof
Technical field
The present invention relates to Material Field, specifically a kind of SDS-MgCl2Composite modified flyash and preparation method thereof.
Background technology
Mineral products industry is the important component part of China's economy, along with China's economy and the fast development of science and technology, Ren Menkai The mineral resources adopting utilization get more and more.China has the mineral such as miscellaneous nonferrous metal resources, lead, zinc, stannum, hydrargyrum The yield of resource and the equal position of reserves are at the forefront in the world, and other mineral metal products such as ferrum, manganese, copper, aluminum, nickel, gold, silver etc. are industrially Also there is substantial amounts of demand.The yield of these Ores is big, and the grade of ore of China is the most relatively low, includes a large amount of impurity, needs Could be used for smelting after ore dressing, therefore can produce substantial amounts of mine tailing.Mine tailing is the ore deposit that metal and nonmetal deposits mountain produces Stone, the waste residue discharged after the ore-dressing techniques such as broken, ore grinding and sorting select valuable concentrate, general and beneficiation reagent mixes Synthesis mud form enters air storage in Tailings Dam.Tailing heap is placed under open-air atmosphere, can take substantial amounts of soil, meanwhile, Containing numerous environmentally harmful materials in mine tailing.In ore dressing process, the most poisonous beneficiation reagent remains in mine tailing, tail Ore deposit itself also remains detection device for multi metallic elements, such as zinc, lead, cadmium and arsenic etc..A huge sum of money under the conditions of acid precipitation, in mine tailing Genus element easily is leached out and enters in subsoil water, surface water, soil and plant, jeopardizes the strong of the mankind eventually through food chain Health.
The heavy metal pollution of mine tailing is an important environment hidden danger, and these heavy metals are leached out such as rainwater Coming, surrounding enviroment are polluted, so suppressing heavy metal to be leached out from source, becoming the master controlling heavy metal pollution Want technology.The most at home and abroad in research, main control method has neutralisation, covers isolation method and deactivation method.
Flyash (flyash) is the fine ash being retained down from flue gas after coal burning, and also referred to as flying dust, is that firepower is sent out One of primary solids garbage that the coal-burning boilers such as power plant are discharged.During coal burning, particle diameter is less than the coal dust of 100 μm Grain is suspended in burner hearth, and temperature can reach 1300 DEG C, and organic carbon part is sufficiently burned, incombustible inorganic mineral part At high temperature in droplet-like, these drops cool down rapidly in flue gas, cannot form crystal structure because variations in temperature is too fast, Having eventually become the vitreous structure particulate matter based on Si-Al, these particulate matters are collected by fume dust remover, are Flyash
The primary solids garbage that flyash is discharged as coal-burning power plant, yield is big, cheap.After nineteen fifty, with The development of power industry, the yield of flyash increases sharply, and Systems in Certain Developed Countries has started to grind the application of flyash one after another Study carefully.At present, flyash has had become as the one of solid mineral material, is widely used in various industry, in the U.S., and flyash Utilization rate be 80%, and Japan can reach more than 90% for the utilization rate of flyash.The domestic application for flyash Research is started late, and before 1980, the utilization rate of China's flyash is less than 10%, along with the growth at a high speed of China's economy, powder The yield of coal ash and utilization rate are also quickly increasing, and to 2015, the annual production of China's flyash was up to 6.2 hundred million Ton, utilization rate is about 70%.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that a kind of SDS-MgCl2Composite modified flyash and preparation method thereof, And be applied to process the heavy metal in mine tailing, utilize the absorption property that it is good to reduce Zn in tailing leaching liquid2+Concentration, from source Head controls mine tailing heavy metal pollution.
To achieve these goals, present invention employs techniques below scheme:
A kind of SDS-MgCl2Composite modified flyash, is prepared by the raw material of following parts by weight:
Flyash 18 after calcining～22 parts, H2SO43.5～5 parts, MgCl2·6H2O 0.8～1.2 parts and SDS 1.8 ～2.5 parts.
Described SDS-MgCl2The preparation method of composite modified flyash, comprises the steps:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measures H2SO4Solution,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, grinds and i.e. obtain institute State SDS-MgCl2Composite modified flyash.
The calcining concrete operations of step (1) described flyash are, the flyash crossing 100～500 mesh sieves is placed in Muffle furnace In, at 700～1000 DEG C, calcine 1～3h.
Described H2SO4The mass concentration of solution is 1.7～3%.
The concussion operation of step (3) is specifically, shake 3～4 hours at room temperature.
Preferably, described SDS-MgCl2The preparation method of composite modified flyash,
The flyash crossing 200 mesh sieves is placed in Muffle furnace, at 800 DEG C, calcines 2h, weigh the flyash after 20g calcining Joining in the sulfuric acid solution of 200mL mass concentration 2%, stirring is configured to flyash suspension；
1.0g MgCl is added in flyash suspension2·6H2O and 2.0g SDS, at room temperature concussion 4 hours, filter, Clean filter cake 4 to 5 times with distilled water, gained filter cake is dried in 60 DEG C of baking ovens, grind, cross 100 mesh sieves, obtain described SDS- MgCl2Composite modified flyash.
Compared with prior art, the beneficial effect that the present invention possesses:
In simulation tailing leaching liquid experiment, experiment of single factor result shows, described SDS-MgCl2Composite modified flyash To Zn2+Clearance be up to 95.3%, process in actual tailing leaching liquid at modified coal ash, described SDS-MgCl2Compound Modified coal ash is to Zn2+Clearance be up to 90.4%, described SDS-MgCl2Composite modified flyash is to Zn2+Saturated suction Attached amount is 17.15mg/g, shows SDS-MgCl2The more former flyash of absorbability of composite modified flyash has had and has dramatically increased, The equilibrium adsorption capacity of former flyash is about 50 percent.Simulated Acid Rain test result indicate that SDS-MgCl2Composite modified powder Coal ash be suitable for acid rain take place frequently area use.Characterization result by SEM, XRD and IR and the analysis to mechanism of modification, powder Coal ash is through SDS and MgCl2After composite modified, the vitreous structure on flyash surface is destroyed, occur in that substantial amounts of Al and Si active group, the more former flyash of the specific surface area of composite modified flyash, porosity and average pore size has increased, compound More material can be adhered in the surface of modified coal ash, and absorbability gets a promotion.
Accompanying drawing explanation
Fig. 1 for process simulation tailing leaching liquid research in dosage to Zn2+The impact of removal effect.
Fig. 2 for process simulation tailing leaching liquid research in pH to Zn2+The impact of removal effect.
Fig. 3 for process simulation tailing leaching liquid research in the response time to Zn2+The impact of removal effect.
Fig. 4 for process simulation tailing leaching liquid research in temperature to Zn2+The impact of removal effect.
When Fig. 5 is 25 DEG C, flyash is to Zn2+Absorption isotherm.
Fig. 6 is the SEM photograph of three kinds of flyash, and a is former flyash, and b is modified coal ash A, and c is modified coal ash B.
Fig. 7 is the XRD figure of three kinds of flyash, and a is former flyash, and b is modified coal ash A, and c is modified coal ash B.
Fig. 8 is the infrared spectrogram of three kinds of flyash, and a is former flyash, and b is modified coal ash A, and c is modified coal ash B。
Fig. 9 be in the applied research of actual tailing leaching liquid flyash dosage to Zn2+The impact of removal effect.
Figure 10 be in the applied research of actual tailing leaching liquid pH to Zn2+The impact of removal effect.
Figure 11 be in the applied research of actual tailing leaching liquid the response time to Zn2+The impact of removal effect.
Figure 12 be in the applied research of actual tailing leaching liquid temperature to Zn2+The impact of removal effect.
Figure 13 is Simulated Acid Rain experiment.
Detailed description of the invention
Below by embodiment, technical scheme is further elaborated.
Embodiment 1
1 materials and methods
1.1 experiment material
Flyash, derives from power plant, state's electricity Nanning, and polished mistake 100 mesh sieve saves backup；HDTMA, SDS, sulphuric acid, Magnesium dichloride hexahydrate, ammonium chloride is analytical pure.
The preparation of 1.2 modified coal ash
HDTMA-NH4The composite modified flyash of Cl: be placed in Muffle furnace by flyash, calcines 2 hours at 800 DEG C.Join The sulfuric acid solution of mass concentration 2% processed, the HDTMA solution of 55mmol/L.Weigh the flyash after 20g calcining and join 200mL Sulfuric acid solution stirs, is configured to suspension；In 40 DEG C of water-baths, in flyash suspension, slowly add 1.0gNH4Cl, limit Edged stirs；Lentamente 200mL HDTMA solution is added drop-wise in above-mentioned suspension in 60 DEG C of water-baths after 30min, water-bath 2h； After water-bath terminates, cooling, filter, clean filter cake 4 to 5 times with distilled water, gained filter cake is dried in 60 DEG C of baking ovens, grind, Cross 100 mesh sieves, obtain composite modified flyash A.
SDS-MgCl2Composite modified flyash: be placed in Muffle furnace by flyash, calcines 2 hours at 800 DEG C.Preparation The sulfuric acid solution of mass concentration 2%.Weigh the flyash after 20g calcining and add the stirring of 200mL sulfuric acid solution, the fine coal being configured to Ash suspension；1.0gMgCl is added in flyash suspension2·6H2O and 2.0gSDS, at room temperature concussion 4 hours, filter, Clean filter cake 4 to 5 times with distilled water, gained filter cake is dried in 60 DEG C of baking ovens, grind, cross 100 mesh sieves, obtain described SDS- MgCl2Composite modified flyash, contrasts, by described SDS-with composite modified flyash A in the present embodiment for convenience MgCl2Composite modified flyash is referred to as composite modified flyash B.
1.3 experimental procedure
1.3.1 modified coal ash processes simulation tailing leaching liquid experiment
Learnt by the experiment of early stage tailing leaching, be 4.0 at pH, under conditions of temperature is 25 DEG C, 50g mine tailing be dipped in In 500mL deionized water, Zn2+The highest leaching content be 53.2mg/L.Therefore simulation experiment is with ZnCl2For raw material, prepare two parts 500mLZn2+Concentration is the simulation tailing leaching liquid of 50mg/L, and regulation pH is 4.0, and temperature is 25 DEG C, weighs 2.0g respectively and is combined Modified coal ash A and composite modified flyash B, is added to simulate in tailing leaching liquid, continuous stirring 1h, takes out solution and crosses 0.45 μm filter membrane, measures Zn in filtrate2+Content.
1.3.2 modified coal ash processes the experiment of actual tailing leaching liquid
Weigh 2.5g composite modified flyash A and composite modified flyash B respectively, be positioned in 20mL centrifuge tube, add 10mL deionized water is configured to suspension, is uniformly added drop-wise to 50g mine tailing surface, and the mine tailing after processing is put in beaker, adds 500mL deionized water, regulation pH is 4.0, and temperature is 25 DEG C, continuous stirring 10h, after reaction terminates, takes out solution and crosses 0.45 μm Filter membrane, measures Zn in filtrate2+Content.Experimentation suspends stirring every 1h, regulates pH value of solution.
2 results and discussion
2.1 modified coal ash process simulation tailing leaching liquid experiment
2.1.1 the flyash dosage impact on treatment effect
Initial condition pH be 4.0, temperature be 25 DEG C, the response time investigate two kinds of modified coal ash and former fine coal when being 1h The dosage of ash is to Zn2+The impact of removal effect, experimental result is shown in Fig. 1.As shown in Figure 1, along with three kinds of flyash dosages Increase, Zn2+Clearance all gradually step up.When dosage is identical, to Zn2+The power of removal ability is ordered as modified fine coal Ash A > modified coal ash B > former modified coal ash.When dosage is 2.0g, the adsorption capacity of flyash, already close to saturated, changes Flyash A is to Zn for property2+Clearance reach 95.8%, modified coal ash B is to Zn2+Clearance reach 94.3%, now sexual valence Ratio is the highest.
2.1.2 the pH impact on treatment effect
Due to Zn2+It is easier in acid condition leach, and Tailings Dam is in acid rain prone areas, therefore pH model in experiment Enclosing selection 3-7, other initial condition flyash dosage 2.0g, temperature 25 DEG C, response time 1h, experimental result is shown in Fig. 2.By scheming 2 understand, and when pH is 3.0, the removal effect of three kinds of flyash is the most poor, and this illustrates when pH is relatively low, the H of higher concentration in solution+Can suppress the activity of flyash neutral and alkali oxide, thus reduce the absorbability of flyash, when pH is 4-7, clearance has aobvious Write and improve, illustrate that modified coal ash is suitable for using under mildly acidic conditions.
2.1.3 the response time impact on treatment effect
Initial condition flyash dosage be 2.0g, pH be 4.0, temperature be 25 DEG C time investigate the response time to Zn2+Go Except the impact of effect, experimental result is shown in Fig. 3.From the figure 3, it may be seen that along with the prolongation in response time, Zn2+Clearance increase, former Flyash reacts when 30min and basically reaches balance, Zn2+Clearance be 51.4%, two kinds of modified coal ash are anti-when 40min Should basically reach balance, modified coal ash A is to Zn2+Clearance be 96.3%, modified coal ash B is to Zn2+Clearance be 95.7%.
2.1.4 the temperature impact on treatment effect
Initial condition flyash dosage be 2.0g, pH be 4.0, the response time be 1h time investigate temperature to Zn2+Remove The impact of effect, experimental result is shown in Fig. 4.As shown in Figure 4, along with the rising of temperature, three kinds of flyash are to Zn2+Clearance all omit Having reduction, this is due to Powder ash adsorption Zn2+It is an exothermic process, but clearance excursion is less than 5%, and temperature is described To Zn2+Clearance impact little.
2.1.5 adsorption isothermal curve experiment
Set flyash dosage as 2.0g, pH as 4.0, temperature as 25 DEG C, the response time as 1h, take Zn respectively2+Concentration Be 10,15,20,25,30,35,40,45,50, the simulated wastewater solution 500mL of 60mg/L, carry out adsorption test, result is shown in Fig. 5 With table 1.
As shown in Figure 5, along with Zn2+The increase of initial concentration, adsorption capacity first increases sharply, and then speedup slows down until satisfying With.For further determining that flyash is to Zn2+Characterization of adsorption, this experiment uses Langmuir equation and Freundlich equation pair Experimental data carries out linear fit.
Langmuir equation: C/Q=1/ (QmKL)+1/Qm×C
Freundlich equation: lnQ=lnKF+1/n×lnC
In formula: Q is adsorbance during balance, mg/g；Zn in solution when C is saturated2+Concentration, mg/L；QmFor saturated absorption Capacity, mg/g；KLFor Langmuir adsorption coefficient, KFIt is Freundlich adsorption coefficient with 1/n.
As shown in Table 1, coefficient R is all higher than 0.98, illustrates that three kinds of flyash are to Zn2+Absorption meet Langmuir side Journey and Freundlich equation, adsorption process is monolayer adsorption.The relatively K of 3 kinds of flyashLValue understands, modified coal ash A Absorbability the strongest, the absorbability of two kinds of modified coal ash all much larger than former flyash, 1/n between 0.5 to 1, explanation The absorption of three kinds of flyash is easy to carry out.Former flyash is to Zn2+Saturated extent of adsorption be 8.07mg/g, modified coal ash A pair Zn2+Saturated extent of adsorption be 17.39mg/g, modified coal ash B is to Zn2+Saturated extent of adsorption be 17.15mg/g, illustrate use The treatment effect of modified coal ash is better than the former flyash of use.
During 1 25 DEG C of table, flyash is to Zn2+Langmuir and Freundlich absorption isotherm fitting parameter table
2.1.6 sign and the mechanism of modification of modified coal ash is inquired into
Using the former flyash of sem analysis and the surface texture of two kinds of modified coal ash, amplification is 400 times and 1000 Times, result is shown in Fig. 6, contrasts 3 pictures and understands, and former flyash surface compact, two kinds of modified coal ash surfaces are all modified agent bag Wrap up in, define fluffy floccule, illustrate that modifying agent is successfully attached to flyash surface.
Using the former flyash of XRD analysis and the interlayer structure of modified coal ash, sweep limits is from 5 degree to 80 degree, and result is shown in Fig. 7.As shown in Figure 7, it is quartz diffraction maximum near 26 degree, is Al near 34 degree2O3Diffraction maximum, at two, diffraction maximum has and substantially adds By force, illustrate that the Si-Al of flyash is destructurized, occur in that the Al with absorbability3+。
Using infrared spectrometric analyzer to characterize former flyash and modified coal ash, result is shown in Fig. 8.As shown in Figure 8, Flyash before modification after absworption peak shape enter that this is consistent, do not produce the general band of new feature.3400cm-1Place goes out peak and belongs to Si-OH, 1100cm-1Place goes out peak and belongs to Si-O-Si, and the peak intensity of modified coal ash is significantly increased, Si-OH and Si-O-is described Si structure increases, and changes the Si-Al structure of former flyash.
2.2 modified coal ash are containing the application in Zn2+ tailing leaching liquid
2.2.1 the flyash dosage impact on treatment effect
Initial condition pH be 4.0, temperature be 25 DEG C, the response time investigate two kinds of modified coal ash and former powder when being 10h The dosage of coal ash is to Zn2+The impact of removal effect, experimental result is shown in Fig. 9.As shown in Figure 9, when dosage is 2.5g, three kinds Flyash is to Zn2+Clearance basically reach stable, former flyash is to Zn2+Clearance be 43.5%, modified coal ash A pair Zn2+Clearance be 90.8%, modified coal ash B is to Zn2+Clearance be 89.3%.Owing to experimentation constantly having Zn2+ Leaching from mine tailing, therefore the optimum dosage of flyash is more than simulation experiment.
2.2.2 the pH impact on treatment effect
Initial condition flyash dosage be 2.5g, temperature be 25 DEG C, the response time investigate pH when being 10h to processing effect The impact of fruit, experimental result is shown in Figure 10.As shown in Figure 10, experimental result is close with simulation experiment, when pH is 3.0, and three kinds of fine coal The removal effect of ash is the most poor, and when pH is 4-7, clearance is significantly increased, and illustrates that modified coal ash is suitable in solutions of weak acidity Lower use.
2.2.3 the response time impact on treatment effect
Initial condition flyash dosage be 2.5g, pH be 4.0, temperature be 25 DEG C time investigate the response time to Zn2+Go Except the impact of effect, experimental result is shown in Figure 11.As shown in Figure 11, at initial period, along with the prolongation in response time, Zn2+Go Except rate is being gradually increased, owing to mine tailing constantly having Zn2+Leaching, therefore the response time is longer than simulation experiment, and former flyash exists During 4h, reaction basically reaches balance, Zn2+Clearance be 42.3%, two kinds of modified coal ash react when 8h basically reach flat Weighing apparatus, Zn2+Clearance be respectively 88.2% and 87.2%.
2.2.4 the reaction temperature impact on treatment effect
Initial condition flyash dosage be 2.5g, pH be 4.0, the response time be 10h time investigate temperature to Zn2+Remove The impact of effect, experimental result is shown in Figure 12.As shown in Figure 12, experimental result and simulation experiment approximate, along with the rising of temperature, and three Plant flyash to Zn2+Clearance slightly reduce, this illustrates Powder ash adsorption Zn2+It is an exothermic process, but temperature is to Zn2+ Clearance impact little.
2.2.5 orthogonal test
For studying the Best of modified coal ash, spy devises orthogonal experiment, is deposited in dew for a long time due to mine tailing In it environment, Zn2+The time leached with acid rain cannot determine, does not therefore consider the response time in orthogonal experiment, select dosage, Temperature, pH carry out 3 factor 3 horizontal quadratures experiments, and experimental result is shown in Table 2 and table 3.As shown in Table 2, modified coal ash A's is optimal Scheme is A2B1C1,Major influence factors is dosage, and pH is minimum on the impact of clearance, i.e. the dosage of modified coal ash A is 2.5g, pH value is 4.0, to Zn in tailing leaching liquid when temperature is 25 DEG C2+Removal effect best.As shown in Table 3, modified fine coal The preferred plan of ash B is A2B3C1,Major influence factors is dosage, and pH is minimum on the impact of clearance, i.e. modified coal ash B Dosage be 2.5g, pH value is 5.0, to Zn in tailing leaching liquid when temperature is 25 DEG C2+Removal effect best.
Table 2 modified coal ash A Orthogonal experiment results table
Table 3 modified coal ash B Orthogonal experiment results table
2.2.6 Simulated Acid Rain experiment
Form according to average ion in the acid rain of Guangxi province, use SO4 2-With NO3 -Mol ratio 7:1, SO4 2-Concentration 100 μ mol·L-1；Ca2+With NH4 +Mol ratio 1:1, Ca2+Concentration 60 μm ol L-1, prepare Simulated Acid Rain solution.In pH4.0 (moderate acid Rain), pH4.4 (Hechi Prefecture's pH value of acid rain meansigma methods) and three kinds of pH gradients of pH5.6 (slight acid rain) descend, 50g mine tailing is dipped in In 500mL simulated solution, add 2.5g flyash, investigate former flyash and two kinds of modified coal ash to Zn2+Removal effect, its He is reaction condition temperature 25 DEG C, response time 10h, and experimental result is shown in Figure 13.As shown in Figure 13, under three kinds of pH gradients, two kinds The removal effect of modified coal ash is all preferable, it can therefore be concluded that when Tailings Dam location occurs acid rain, modified coal ash Still can there is preferable treatment effect.
Conclusion
Two kinds of composite modified fine coal are to Zn in simulation tailing leaching liquid2+The highest clearance be respectively 96.8% He 95.3%, to Zn in actual tailing leaching liquid2+The highest clearance be respectively 91.9% and 90.4%, modified coal ash A is to Zn2 +Saturated extent of adsorption be 17.39mg/g, modified coal ash B is to Zn2+Saturated extent of adsorption be 17.15mg/g.Can by orthogonal experiment The Best knowing modified coal ash A is dosage 2.5g/50g, reaction temperature 25 DEG C, pH value 4.0, response time 10h； The Best of modified coal ash B is dosage 2.5g/50g, reaction temperature 25 DEG C, pH value 5.0, response time 10h.By Simulated Acid Rain experiment understand, modified coal ash be suitable for acid rain take place frequently area use.Modified coal ash is by SEM, IR and XRD Modified coal ash is characterized, shows that modifying agent has been attached to flyash surface, change the surface texture of flyash, from And enhance the absorption property of flyash.
Embodiment 2
A kind of SDS-MgCl2Composite modified flyash, is prepared by the raw material of following parts by weight:
18 parts of flyash after calcining, H2SO43.5 parts, MgCl2·6H2O 0.8 part and SDS 1.8 parts.
Described SDS-MgCl2The preparation method of composite modified flyash, comprises the steps:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measuring mass concentration is The H of 1.7%2SO4Solution, H2SO4H in solution2SO4Net content be 3.5 weight portions,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, grinds and i.e. obtain institute State SDS-MgCl2Composite modified flyash.
The calcining concrete operations of step (1) described flyash are, are placed in Muffle furnace by the flyash crossing 100 mesh sieves, 3h is calcined at 700 DEG C.
The concussion operation of step (3) is specifically, shake 3 hours at room temperature.
Embodiment 3
A kind of SDS-MgCl2Composite modified flyash, is prepared by the raw material of following parts by weight:
22 parts of flyash after calcining, H2SO45 parts, MgCl2·6H2O 1.2 parts and SDS 2.5 parts.
Described SDS-MgCl2The preparation method of composite modified flyash, comprises the steps:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measuring mass concentration is The H of 2.5%2SO4Solution, H2SO4H in solution2SO4Net content be 5 weight portions,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, grinds and i.e. obtain institute State SDS-MgCl2Composite modified flyash.
The calcining concrete operations of step (1) described flyash are, are placed in Muffle furnace by the flyash crossing 500 mesh sieves, 2h is calcined at 1000 DEG C.
The concussion operation of step (3) is specifically, shake 4 hours at room temperature.
Embodiment 4
A kind of SDS-MgCl2Composite modified flyash, is prepared by the raw material of following parts by weight:
20 parts of flyash after calcining, H2SO44.5 parts, MgCl2·6H2O 1 part and SDS 2.2 parts.
Described SDS-MgCl2The preparation method of composite modified flyash, comprises the steps:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measuring mass concentration is The H of 3%2SO4Solution so that H2SO4H in solution2SO4Net content be 4.5 weight portions,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, grinds and i.e. obtain institute State SDS-MgCl2Composite modified flyash.
The calcining concrete operations of step (1) described flyash are, are placed in Muffle furnace by the flyash crossing 200 mesh sieves, 1h is calcined at 800 DEG C.
The concussion operation of step (3) is specifically, shake 3.5 hours at room temperature.
Embodiment 5
A kind of SDS-MgCl2Composite modified flyash, is prepared by the raw material of following parts by weight:
20 parts of flyash after calcining, H2SO43.5 parts, MgCl2·6H2O1.2 part and SDS 1.8 parts.
Described SDS-MgCl2The preparation method of composite modified flyash, comprises the steps:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measuring mass concentration is The H of 2.3%2SO4Solution, H2SO4H in solution2SO4Net content be 3.5 weight portions,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, grinds and i.e. obtain institute State SDS-MgCl2Composite modified flyash.
The calcining concrete operations of step (1) described flyash are, are placed in Muffle furnace by the flyash crossing 400 mesh sieves, 2.5h is calcined at 900 DEG C.
The concussion operation of step (3) is specifically, shake 3 hours at room temperature.

Claims (6)

1. a SDS-MgCl2Composite modified flyash, it is characterised in that be prepared by the raw material of following parts by weight:
Flyash 18 after calcining～22 parts, H2SO43.5～5 parts, MgCl2·6H2O 0.8～1.2 parts and SDS 1.8～2.5 Part.
2. SDS-MgCl as claimed in claim 12The preparation method of composite modified flyash, it is characterised in that include walking as follows Rapid:
(1) according to described parts by weight, the flyash after calcining, MgCl are weighed2·6H2O and SDS, measures H2SO4Solution,
(2) flyash after calcining is joined H2SO4In solution, stirring is configured to flyash suspension；
(3) in flyash suspension, MgCl is added2·6H2O and SDS, then shakes, and filters, and dries, and grinds described in i.e. obtaining SDS-MgCl2Composite modified flyash.
3. SDS-MgCl as claimed in claim 22The preparation method of composite modified flyash, it is characterised in that step (1) institute The calcining concrete operations stating flyash are, are placed in Muffle furnace, at 700～1000 DEG C by the flyash crossing 100～500 mesh sieves Calcining 1～3h.
4. SDS-MgCl as claimed in claim 22The preparation method of composite modified flyash, it is characterised in that described H2SO4 The mass concentration of solution is 1.7～3%.
5. SDS-MgCl as claimed in claim 22The preparation method of composite modified flyash, it is characterised in that step (3) Concussion operation is specifically, shake 3～4 hours at room temperature.
6. SDS-MgCl as claimed in claim 22The preparation method of composite modified flyash, it is characterised in that
The flyash crossing 200 mesh sieves is placed in Muffle furnace, at 800 DEG C, calcines 2h, weigh the flyash after 20g calcining and add In the sulfuric acid solution of 200mL mass concentration 2%, stirring is configured to flyash suspension；
1.0g MgCl is added in flyash suspension2·6H2O and 2.0g SDS, at room temperature concussion 4 hours, filter, with steaming Distilled water cleans filter cake 4 to 5 times, is dried by gained filter cake in 60 DEG C of baking ovens, grinds, and crosses 100 mesh sieves, obtains described SDS- MgCl2Composite modified flyash.
CN201610302082.4A 2016-05-09 2016-05-09 SDS-MgCl2 composite modified fly ash and preparation method thereof Pending CN105921115A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104826578A (en) * 2015-05-29 2015-08-12 浙江海洋学院 Fly ash modified adsorbent and preparing method thereof and method of treating oily sewage

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Publication number Priority date Publication date Assignee Title
CN104826578A (en) * 2015-05-29 2015-08-12 浙江海洋学院 Fly ash modified adsorbent and preparing method thereof and method of treating oily sewage

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周建兵等: "十二烷基磺酸钠(SDS)改性蒙脱石对Cu2+、Cd2+吸附研究", 《环境科学学报》 *
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