CN104724744A - Method for preparing solid-state polyaluminium chloride flocculating agent by utilizing fly ash as raw material - Google Patents

Method for preparing solid-state polyaluminium chloride flocculating agent by utilizing fly ash as raw material Download PDF

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CN104724744A
CN104724744A CN201510026718.2A CN201510026718A CN104724744A CN 104724744 A CN104724744 A CN 104724744A CN 201510026718 A CN201510026718 A CN 201510026718A CN 104724744 A CN104724744 A CN 104724744A
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CN104724744B (en
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王晖
孙忠
红艳
温龙英
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Inner Mongolia University
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Abstract

The invention discloses a method for preparing a solid polyaluminium chloride flocculating agent by utilizing fly ash as a raw material. According to the method, a solid-state high-efficiency flocculating agent polyaluminium chloride [Al13(OH)24(H2O)24Cl15.13H2O] (P-Al13 in short) crystal is prepared from the fly ash as the raw material by virtue of an intermediate product amorphous aluminum hydroxide. The method comprises the steps of enabling sodium carbonate and the fly ash to perform high-temperature solid phase reaction to obtain a clinker, performing acid leaching on the clinker to obtain an aluminum-containing solution, enabling the aluminum-containing solution and the sodium hydroxide to react to obtain an amorphous aluminum hydroxide intermediate product, enabling the amorphous aluminum hydroxide intermediate product and hydrochloric acid to perform a hydrolysis-polymerization reaction at more than 70 DEG C under normal pressure to achieve a certain alkalization degree, performing low-temperature natural crystallization to separate a P-Al13 product, and combining residual mother solution with the acid leaching solution to circularly reutilize, so that zero emission is achieved, and the obtained solid product meets the national standard (GB15892-2009) superior product specification. The method has the advantages of low aluminum ion loss rate and high P-Al13 conversion rate. Based on a flocculation test, the flocculation effect of the product P-Al13 is remarkably better than that of Keggin-Al13 ([AlO4Al12(OH)24(H20)12]<7+>).

Description

A kind of method taking flyash as raw material and develop solid-state polymerization aluminum chloride flocculant
Technical field
The present invention relates to total utilization of PCA and solid-state High-purity Polyaluminum Chloride preparation method, refer in particular to a kind of method taking flyash as raw material and develop solid-state polymerization aluminum chloride flocculant.
Background technology
Flyash is the complicated multiphase solid refuse that left behind after coal burns in burning boiler.Often burn one ton of coal, will produce 250-300kg flyash.If a large amount of flyash can not get utilization effectively and reasonably, a large amount of human and material resources, financial resources will be wasted and it is stacked and processes.The primary chemical composition of flyash is Al 2o 3, SiO 2, therefore, if can by Al wherein 2o 3be used, can not only turn waste into wealth, good economic benefit, environmental benefit and social benefit can also be produced simultaneously.
At present, flyash is mainly used in: the field such as material of construction, agricultural (plantation) cultivation, concrete construction, chemical and the water treatment that grew up in recent years.
The product that in water treatment procedure, consumption is maximum is polymerize aluminum chloride (PAC).PAC is AlCl 3mixture that formed through hydrolysis-polymerization, that be made up of the various hydrolysates that the polymerization degree is different.Generally be divided into Ala, Alb, Alc tri-kinds of polymeric species.The wherein Al of intermediate degree of polymerisation bbe considered to flocculation composition best in flocculation agent, Al bwith Al 13there is very large dependency, therefore, pursue Al in flocculation agent 13content maximizes, and becomes the common objective of domestic and international investigator.
The method of domestic and international production PAC has a variety of, and end is got up, and its principle is identical: be all create conditions, and makes aluminium salt constantly be hydrolyzed-be polymerized to starting point, but because of influence factor in preparation process numerous, obtained product is with Al 13be other form main be auxiliary mixture, generally do not reach Al bthe maximized desired result of content, and product water dissolubility is poor, needs predissolve.
And utilize coal ash for manufacturing for being considered to the most effective flocculation morphology in polymeric aluminum, there is the Al of superior water purification performance 13but report is had no.Al 13because of its nano molecular size and high electric charge, be considered to nanometer species minimum and the most stable in polymeric aluminum chlorides solution.But domestic and international each technical field attempts various synthesis preparation method so far, the high density with industrial application value all cannot be obtained, high Al 13the polymeric aluminum solution of content and rafifinal 13 solid product.
Within 2006, Sun Zhong is in Chinese J.Struct.Chem.25 (10): 1217-1227 reports and Keggin-Al 13there is same polymeric degree, the Al that composition structure is different 13(OH) 24(H 2o) 24cl 1513H 2o (P-Al 13), its polycation is with 15 positive charges, and number of patent application: 200510064782.6 disclose under 200 DEG C of autoclave conditions, has prepared high-purity P-Al with aluminium hydroxide, crystal aluminum chloride, water for raw material 13, and prove P-Al 13under different pH value, all Keggin-Al is compared in performance 13better go turbid ability, wider effective flocculation adds the water pH value of scope and adaptation.Show thus, P-Al 13a kind of superior performance, rising efficient flocculant.To exploitation Huanghe water, process various waste water, save groundwater resource significant.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method taking flyash as raw material and develop solid-state polymerization aluminum chloride flocculant, this method take waste coal ash as initial feed, prepare amorphous hydroted alumina, again under the mild conditions of normal pressure, lesser temps, development high purity, the solid-state efficient flocculant Al that form is single, flocculating property is superior 13(OH) 24(H 2o) 24cl 1513H 2o.
For solving the problems of the technologies described above, the present invention is realized by following scheme: a kind of method taking flyash as raw material and develop solid-state polymerization aluminum chloride flocculant, is characterized in that: take flyash as raw material, by intermediate product amorphous hydroted alumina development Al 13(OH) 24(H 2o) 24cl 1513H 2(P-Al is counted in letter to O 13), comprise following five steps:
1. high temperature solid state reaction: by flyash and sodium carbonate by 0.8 ~ 2.0: 1 quality mix than porphyrize, calcination 30 ~ 150min at 750 ~ 950 DEG C in retort furnace, after clinker cooling to room temperature, fully grinding is for subsequent use;
2. acid-leaching reaction: in above-mentioned grog, adds the hydrochloric acid of 3 ~ 12mol/L, and every gram of grog correspondence adds the hydrochloric acid of 4 ~ 20mL volume, after fully stirring, filters and obtain pickling liquor after room temperature leaves standstill 5 ~ 30min;
3. the preparation feedback of amorphous hydroted alumina: under room temperature to 70 DEG C condition, drip concentration and be greater than the sodium hydroxide solution of 4mol/L in pickling liquor, be adjusted to pH=5 ~ 6.5, be precipitated and be amorphous hydroted alumina, product after filtration after washing and drying porphyrize for subsequent use;
4. P-Al 13preparation feedback: by amorphous hydroted alumina under reflux conditions with 8 ~ 12mol/L hydrochloric acid reaction, temperature of reaction is at 70 ~ 120 DEG C, condition of normal pressure issues unboiled water solution-polyreaction 2 ~ 3 hours, obtain storing solution, its basicity (hydroxide aluminium ratio) is made to be 0.4 ~ 1.5, after filtered while hot, filtrate moves into crystallizer, evaporative crystallization at room temperature ~ 50 DEG C, waits to separate out Al 13(OH) 24(H 2o) 24cl 1513H 2be separated after O crystal or powder, solid product, through washing, dries product at room temperature ~ 50 DEG C, obtained solid-state efficient flocculant Al 13(OH) 24(H 2o) 24cl 1513H 2o, filtrate reusable edible;
5. Recycling Mother Solution: by P-Al 13the mother liquor of preparation feedback gained be all incorporated to recycle in the pickling liquor of acid-leaching reaction gained, the object of aluminum ion maximize conversion, zero release can be realized.Experimental principle of the present invention:
The principal crystalline phase material of flyash is mullite, and amorphous phase material is alumina silicate glass body.They are insoluble in bronsted lowry acids and bases bronsted lowry at normal temperatures.But under heating condition, can react with alkaline matter.As under the high temperature conditions, flyash and sodium carbonate can react generation nepheline.Nepheline is acid soluble material, can be decomposed generate silica gel and Al by acid 3+, realize effective separation of sial, obtain containing aluminum solutions.
Determining at temperature, regulate the pH value of aluminum solutions in suitable scope with sodium hydroxide solution, can obtain amorphous hydroted alumina, this aluminium hydroxide can realize being hydrolyzed-polyreaction with hydrochloric acid under normal pressure, lesser temps, can obtain containing P-Al after reaction reaches certain basicity 13solution.After degree of reaching capacity, Al 13(OH) 24(H 2o) 24cl 1513H 2o nature crystallization, filters and obtains product, and mother liquor recycling capable of circulation.
High temperature solid state reaction described in present method refers to: mix through pyroreaction by flyash with sodium carbonate, is the nepheline phase being soluble in acid by the thing inversion of phases in flyash; Acid-leaching reaction refers to: by the acid dipping of above-mentioned grog salt, Silicified breccias is effectively separated, and obtaining take iron ion as the liquor alumini chloridi of major impurity ion; The preparation feedback of amorphous hydroted alumina refers to: regulate pH to obtain in pickling liquor sodium hydroxide; P-Al 13preparation feedback refer to: with amorphous hydroted alumina be raw material be hydrolyzed with hydrochloric acid in atmospheric conditions-polyreaction obtains storing solution, left at room temperature, P-Al after degree of reaching capacity 13hydrochloride, by nature crystallization, obtains product after filtration; Recycling Mother Solution refers to: by P-Al 13the mother liquor of preparation feedback gained be all incorporated to recycle in the pickling liquor of acid-leaching reaction gained, the object of aluminum ion maximize conversion, zero release can be realized.
The mass ratio of the aluminous fly-ash described in present method and sodium carbonate, and dominant phase mullite and sodium carbonate complete reaction in flyash are guaranteed in the determination of calcining temperature and time, and not cause premised on energy dissipation.
The sour consumption of the hydrochloric acid leaching grog described in present method is that, rate of loss maximum according to the leaching yield of aluminium in flyash is minimised as according to drawing, the recyclable recycling of excessive hydrochloric acid.
Temperature amorphous hydroted alumina being prepared by pickling liquor sodium hydroxide direct precipitation method described in present method is: room temperature to 70 DEG C, the pH value of adjustment is between 5 ~ 6.5.
Described in present method with amorphous hydroted alumina be raw material in 70 ~ 120 DEG C of temperature ranges, be hydrolyzed-polyreaction 2 ~ 3 hours under condition of normal pressure with hydrochloric acid, obtain storing solution.
The used in amounts of the amorphous hydroted alumina described in present method and hydrochloric acid ensures that the storing solution basicity (hydroxide aluminium ratio) of end reaction is 0.4 ~ 1.5.
The al species of the amorphous hydroted alumina described in present method to can be implemented under lesser temps and condition of normal pressure with hydrochloric acid reaction and reaches preparation P-Al 13basicity.
The reaction solution of the amorphous hydroted alumina described in present method and hydrochloric acid, naturally can separate out P-Al under DEG C condition of room temperature ~ 50 13crystallization, directly obtains solid-state efficient flocculant after filtration, without the need to other solidification equipment any and technique.
Preparation P-Al described in present method 13required raw material is only amorphous hydroted alumina and hydrochloric acid, does not need other any catalyzer or reagent, does not namely introduce other any foreign ion except Al (III) in preparation process.
P-Al described in present method 13residue mother liquor reusable edible after hydrochloride crystallization, is at the bottom of a kind of aluminum ion rate of loss, transformation efficiency is high, the preparation P-Al of zero release 13method.
Advantage of the present invention: be that amorphous hydroted alumina development efficient flocculant Al prepared by raw material with aluminous fly-ash 13(OH) 24(H 2o) 24cl 1513H 2o has following outstanding advantage:
1. the present invention utilizes solid waste coal ash for manufacturing to be ready for use on the efficient flocculant of water treatment, achieve and turn waste into wealth, the effect of waste recycling, is a kind of approach realizing the comprehensive utilization of flyash high added value, can produces good economic benefit, environmental benefit and social benefit.
2. the present invention uses discarded flyash and common hydrochloric acid and sodium hydroxide reagent, therefore with low cost.
3. P-Al of the present invention 13preparation feedback temperature is lower, and the reaction times is shorter, without the need to pressurization, process easy handling, can obtain form single, highly purified solid-state polymerization aluminium 13 Al 13(OH) 24(H 2o) 24cl 1513H 2o, and can realize often making must, quality product is secure.P-Al 13at the bottom of the aluminum ion rate of loss of preparation process, P-Al 13transformation efficiency is high.
4. present method to can be implemented under condition of normal pressure with aluminium hydroxide is that P-Al prepared by raw material 13.
5. present method makes P-Al by adjusted saturation ratio 13nature crystallization, obtains solid-state efficient flocculant, without the need to other solidification equipment any and technique.
6. present method prepares P-Al 13other foreign ion except Al (III) is not introduced in process.
7. its composition P-Al that effectively flocculates of present method products therefrom 13content is up to more than 91%, and excellent aqueous solubility, does not have water-insoluble, meets national standard (GB15892-2009) premium grads specification.
8. products obtained therefrom P-Al of the present invention 13flocculating effect is better than Keggin-Al 13([AlO 4al 12(OH) 24(H 2o) 12] 7+).Contrast experiment is as shown in table 1.From table, P-Al prepared by the present invention 13with Keggin-Al 13compare, no matter high concentrtion stablizes water sample and the astable water sample of low turbidity, all show and compare Keggin-Al 13superior flocculating effect.
Table 1, P-Al 13with Keggin-Al 13 aflocculating experiment bresult
Annotation a: Keggin-Al 13preparation adopts slowly drips alkaline process: under constant temperature oil bath 80 DEG C, strong magnetic agitation condition, to AlCl 3slowly drip NaOH solution in solution, rate of addition controls at about 0.6mL/min.Be cooled to room temperature after dropwising, slaking certain hour must contain Keggin-Al 13polymerization PAC solution, Al bcontent about 80%, 27al-NMR characterizes proves that it is mainly Keggin-Al 13.Annotation b: flocculating experiment adopts chamber test method: instrument adopts JJ-4 type six electric mixer, 500mL simulated water sample is injected beaker, start and stir, in water sample, a certain amount of flocculation agent is dropped under rapid stirring (rotating speed is 200r/min), change at a slow speed (rotating speed is 40r/min) into after continuing rapid stirring 1min and stir 15min, stop stirring and standing sedimentation 15min.Precipitation terminates to draw primary water sample liquid from 1cm under liquid level, adopts 2100N type turbidimeter to detect its residual turbidity.)
Accompanying drawing illustrates:
Accompanying drawing 1 is the process flow sheet of present method.
Accompanying drawing 2 is intermediate product amorphous hydroted alumina XRD spectra.
Accompanying drawing 3 is XRD spectra first time separating out product.
Accompanying drawing 4 is the XRD spectra that second time separates out product.
Accompanying drawing 5 is XRD spectra third time separating out product.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but not to the affected any type of restriction of the present invention.
1, high-temperature fusion reaction: the flyash of Huhehaote power plant and sodium carbonate are pressed the mass ratio of 1.2: 1, mixes the two porphyrize in mortar, 850 DEG C of calcination 110min in retort furnace.After clinker cooling to room temperature, fully grinding is for subsequent use.(flyash Al 2o 3content is 49.2%)
2, acid-leaching reaction: get above-mentioned grog 75.2g in beaker, add 380mL concentrated hydrochloric acid and 30mL distilled water, after fully stirring, room temperature leaves standstill 5min, filters and obtains pickling liquor (now the extraction yield of aluminium can reach 95.7%).
3, the preparation of amorphous hydroted alumina: at ambient temperature, drip in 8mol/L sodium hydroxide solution to above-mentioned gained pickling liquor, must precipitate as pH=5 and be amorphous hydroted alumina (the XRD characterization result of product is shown in accompanying drawing 2), after filtration, product is through repeatedly distilled water wash, and after drying, porphyrize is for subsequent use.
4, Al 13(OH) 24(H 2o) 24cl 1513H 2the preparation of O:
(1) get amorphous hydroted alumina 42g in 500mL there-necked flask, under reflux conditions add 53mL concentrated hydrochloric acid and 15mL distilled water, after room temperature reaction 30min, be warming up to 70 DEG C, after continuing reaction 3h, stop heated and stirred.Filter paper filtering while hot.The basicity (hydroxide aluminium ratio) obtaining storing solution is 1.4.Filtrate moves into crystallizer, in room temperature condition evaporative crystallization, waits to separate out Al 13(OH) 24(H 2o) 24cl 1513H 2be separated after O crystal, air-dry in room temperature after product washing with alcohol, weigh, preserve.
Product analyses: product total mass: 22.19g, wherein P-Al 13content is 93.2%, and aluminum ion transformation efficiency is 36.87%, residue mother liquor: 61.8g.The XRD characterization result of product is shown in accompanying drawing 3.
(2) the residue mother liquor getting (1) is incorporated in the pickling liquor of the 2nd step.Adopt the method for step 3 to prepare amorphous hydroted alumina, after oven dry, porphyrize, get 42g in 500mL there-necked flask, under reflux conditions add 53mL concentrated hydrochloric acid and 15mL distilled water.Be warming up to 70 DEG C after room temperature reaction 30min, after continuing reaction 3h, stop heated and stirred.Filter paper filtering while hot.Filtrate moves into crystallizer, in room temperature condition evaporative crystallization, waits to separate out Al 13(OH) 24(H 2o) 24cl 1513H 2be separated after O crystal, product washing with alcohol more air-dry in room temperature, weigh, preserve.
Product analyses: product total mass: 21.03g, wherein P-Al 13content is 91.63%, is 52.30% with the worthwhile aluminum ion transformation efficiency of front primary first-order equation, residue mother liquor: 63.0g.The XRD characterization result of product is shown in accompanying drawing 4.
(3) the residue mother liquor getting (2) is incorporated in the pickling liquor of the 2nd step.Drip sodium hydroxide, be adjusted to pH=5, obtain amorphous hydroted alumina precipitation.After repeatedly distilled water wash, oven dry and porphyrize, get 42g in 500mL there-necked flask, under reflux conditions add 53mL concentrated hydrochloric acid and 15mL distilled water.Be warming up to 70 DEG C after room temperature reaction 30min, after continuing reaction 3h, stop heated and stirred.Filter paper filtering while hot.Filtrate moves into crystallizer, in room temperature condition evaporative crystallization, waits to separate out Al 13(OH) 24(H 2o) 24cl 1513H 2be separated after O crystal, product washing with alcohol more air-dry in room temperature, weigh, preserve.
Product analyses: product total mass: 22.20g, wherein P-Al 13content is 94.09%, is 62.52% with the worthwhile aluminum ion transformation efficiency of front two secondary response, residue mother liquor: 61.8g.The XRD characterization result of product is shown in accompanying drawing 5.
5, can Theoretical Calculation go out according to the aluminum ion transformation efficiency of first three experiment: the aluminum ion transformation efficiency of the 4th mother liquid recycling is: 69.84%; The aluminum ion transformation efficiency of the 5th mother liquid recycling is: 73.94%.Namely Recycling Mother Solution number of times is more, and aluminum ion transformation efficiency is higher, finally can realize aluminum ions zero release.Can realize under the mild conditions of normal pressure, lesser temps through repeatedly mother liquid recycling, development high purity, the solid-state efficient flocculant Al that form is single, flocculating property is superior 13(OH) 24(H 2o) 24cl 1513H 2the object of O.

Claims (1)

1. be a method for raw material development solid-state polymerization aluminum chloride flocculant with flyash, it is characterized in that, take flyash as raw material, by intermediate product amorphous hydroted alumina development Al 13(OH) 24(H 2o) 24cl 1513H 2(P-Al is counted in letter to O 13), comprise following five steps:
1. high temperature solid state reaction: by flyash and sodium carbonate by 0.8 ~ 2.0: 1 quality mix than porphyrize, calcination 30 ~ 150min at 750 ~ 950 DEG C in retort furnace, after clinker cooling to room temperature, fully grinding is for subsequent use;
2. acid-leaching reaction: in above-mentioned grog, adds the hydrochloric acid of 3 ~ 12mol/L, and every gram of grog correspondence adds the hydrochloric acid of 4 ~ 20mL volume, after fully stirring, filters and obtain pickling liquor after room temperature leaves standstill 5 ~ 30min;
3. the preparation feedback of amorphous hydroted alumina: under room temperature to 70 DEG C condition, drip concentration and be greater than the sodium hydroxide solution of 4mol/L in pickling liquor, be adjusted to pH=5 ~ 6.5, be precipitated and be amorphous hydroted alumina, product after filtration after washing and drying porphyrize for subsequent use;
4. P-Al 13preparation feedback: by amorphous hydroted alumina under reflux conditions with 8 ~ 12mol/L hydrochloric acid reaction, temperature of reaction is at 70 ~ 120 DEG C, condition of normal pressure issues unboiled water solution-polyreaction 2 ~ 3 hours, obtain storing solution, its basicity (hydroxide aluminium ratio) is made to be 0.4 ~ 1.5, after filtered while hot, filtrate moves into crystallizer, evaporative crystallization at room temperature ~ 50 DEG C, waits to separate out Al 13(OH) 24(H 2o) 24cl 1513H 2be separated after O crystal or powder, solid product, through washing, dries product at room temperature ~ 50 DEG C, obtained solid-state efficient flocculant Al 13(OH) 24(H 2o) 24cl 1513H 2o, filtrate reusable edible;
5. Recycling Mother Solution: by P-Al 13the mother liquor of preparation feedback gained be all incorporated to recycle in the pickling liquor of acid-leaching reaction gained.
CN201510026718.2A 2015-01-15 2015-01-15 Method for preparing solid-state polyaluminium chloride flocculating agent by utilizing fly ash as raw material Expired - Fee Related CN104724744B (en)

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