CN104724744B - 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 PDFInfo
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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
Technical field
The present invention relates to total utilization of PCA and solid-state High-purity Polyaluminum Chloride preparation method, refer in particular to one kind with fine coal
The method that ash develops solid-state polymerization aluminum chloride flocculant for raw material.
Background technology
Flyash is the complicated multiphase solid waste that left behind after coal burns in burning boiler.Often burn one ton
Coal, will produce 250-300kg flyash.If a large amount of flyash cannot utilization effectively and reasonably, will waste substantial amounts of
Human and material resources, financial resources are stacked to it and are processed.The primary chemical composition of flyash is Al2O3、SiO2, therefore, if energy
By Al therein2O3It is used, can not only turn waste into wealth, good economic benefit, environmental benefit and society can also be produced simultaneously
Can benefit.
At present, flyash is mainly used in：Construction material, agricultural (plantation) cultivation, concrete construction, chemical and near
The fields such as a little water process growing up in year.
In water treatment procedure, the maximum product of consumption is aluminium polychlorid (PAC).PAC is AlCl3Formed through hydrolysis-polymerization
, the mixture being made up of the different various hydrolyzate of the degree of polymerization.It is generally divided into tri- kinds of polymeric species of Ala, Alb, Alc.Its
The Al of middle intermediate degree of polymerisationbIt is considered as optimal flocculation composition in flocculant, AlbWith Al13There is very big dependency, because
This, pursue Al in flocculant13Content maximizes, and becomes the common objective of domestic and international researcher.
The method producing PAC both at home and abroad has many kinds, sums up, its principle is identical：It is all to create conditions, to make
Aluminium salt constantly hydrolyzes-is polymerized to starting point, but because in preparation process influence factor numerous, prepared product is with Al13Based on other
Mixture supplemented by form, does not generally reach AlbThe maximized Expected Results of content, and product water solublity is poor, needs predissolve.
And it is considered most effective flocculation morphology in polymeric aluminum using coal ash for manufacturing is standby, there is the Al of superior water purification performance13
But have no report.Al13Because of its nano molecular size and high electric charge it is considered to be minimum and most stable of in polymeric aluminum chlorides solution
Nanometer species.However, each technical field attempts various synthesis preparation methods both at home and abroad so far, all cannot obtain with commercial Application
The high concentration being worth, high Al13The polymerization aluminum solutions of content and rafifinal 13 solid product.
Sun Zhong is in Chinese J.Struct.Chem.25 (10) within 2006：1217-1227 reports and Keggin-Al13
There are same polymeric degree, the different Al of composition structure13(OH)24(H2O)24Cl15·13H2O(P-Al13), its polycation carries
15 positive charges, number of patent application：200510064782.6 disclose under 200 DEG C of autoclave conditions, with aluminium hydroxide, crystallization
Aluminum chloride, water have prepared high-purity P-Al for raw material13, and it is proved P-Al13Under different pH value, all performance is compared
Keggin-Al13Turbid ability, broader effective flocculation is preferably gone to add the water pH value of scope and adaptation.It is indicated above that P-
Al13It is a kind of superior performance, rising efficient flocculant.To developing Huanghe water, the various waste water of process, frugally
Lower water resource is significant.
Content of the invention
The technical problem to be solved in the present invention is to provide one kind to develop solid-state polymerization chlorination aluminum flocculation with flyash for raw material
The method of agent, this method, with waste coal ash as initial feed, prepares amorphous hydroted alumina, then in normal pressure, compared with low temperature
Under the temperate condition of degree, development high-purity, the solid-state efficient flocculant Al that form is single, flocculating property is superior13(OH)24
(H2O)24Cl15·13H2O.
For solving above-mentioned technical problem, the present invention to be realized by following scheme：One kind develops solid-state with flyash for raw material
The method of flocculant of polymeric aluminium chloride it is characterised in that：With flyash as raw material, ground by intermediate product amorphous hydroted alumina
Al processed13(OH)24(H2O)24Cl15·13H2(letter is calculated as P-Al to O13), including following five steps：
1. high temperature solid state reaction：Flyash and sodium carbonate are pressed 0.8～2.0: the 1 finely ground mixing of mass ratio, in Muffle furnace
In calcination 30～150min at 750～950 DEG C, be fully ground standby after clinker cooling to room temperature；
2. acid-leaching reaction：In above-mentioned grog, add the hydrochloric acid of 3～12mol/L, every gram of grog correspondence Jia 4～20mL body
Long-pending hydrochloric acid, after being sufficiently stirred for, room temperature is filtrated to get pickle liquor after standing 5～30min；
3. the preparation reaction of amorphous hydroted alumina：Under the conditions of room temperature is to 70 DEG C, Deca concentration is more than the hydrogen of 4mol/L
Sodium hydroxide solution, to pickle liquor, is adjusted to pH=5～6.5, is precipitated as amorphous hydroted alumina, product is through filtration washing
Finely ground standby after drying；
④P-Al13Preparation reaction：By amorphous hydroted alumina under reflux conditions with 8～12mol/L hydrochloric acid reaction, instead
Answer temperature at 70～120 DEG C, condition of normal pressure issues unboiled water solution-polyreaction 2～3 hours, obtain storing solution so as to basicity
(hydroxide aluminium ratio) is 0.4～1.5, and after filtered while hot, filtrate moves into crystallizer, evaporative crystallization at room temperature～50 DEG C, waits to separate out
Al13(OH)24(H2O)24Cl15·13H2Separate after O crystal or powder, solid product is scrubbed, dry at room temperature～50 DEG C and produce
Thing, prepared solid-state efficient flocculant Al13(OH)24(H2O)24Cl15·13H2O, filtrate reusable edible；
5. Recycling Mother Solution：By P-Al13Preparation react gained mother solution be fully incorporated in the pickle liquor of acid-leaching reaction gained
Recycle, achievable aluminium ion conversion ratio maximizes, the purpose of zero-emission.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 at normal temperatures
It is insoluble in bronsted lowry acids and bases bronsted lowry.But under heating condition, can react with alkaline matter.As under the high temperature conditions, flyash and carbonic acid
Sodium can react generation nepheline.Nepheline is acid soluble material, can be decomposed by acid and generate silica gel and Al3+, that realizes sial has
Effect separates, and obtains containing aluminum solutions.
At a temperature of determining, adjust the pH value of aluminum solutions in suitable scope with sodium hydroxide solution, amorphous hydrogen can be obtained
Aluminium oxide, this aluminium hydroxide may be implemented in normal pressure, hydrolyzes-polyreaction with hydrochloric acid, when reaction reaches one under lower temperature
Can obtain containing P-Al after determining basicity13Solution.After reaching saturation, Al13(OH)24(H2O)24Cl15·13H2O analyses naturally
Go out crystallization, be filtrated to get product, and mother solution recycling capable of circulation.
High temperature solid state reaction described in this method refers to：Flyash is mixed with sodium carbonate through pyroreaction, by fine coal
Thing inversion of phases in ash is the nepheline phase being soluble in acid；Acid-leaching reaction refers to：By the salt acid dip of above-mentioned grog, silicon and aluminum is made to have
Effect separates, and obtains the liquor alumini chloridi being main foreign ion with iron ion；The preparation reaction of amorphous hydroted alumina refers to：Will
Pickle liquor sodium hydroxide adjusts pH and is obtained；P-Al13Preparation reaction refer to：With amorphous hydroted alumina for raw material in normal pressure bar
Hydrolyze with hydrochloric acid under part-polyreaction obtains storing solution, stand under room temperature, reach P-Al after saturation13Hydrochlorate will be from
So separate out crystallization, after filtration, obtain product；Recycling Mother Solution refers to：By P-Al13Preparation react gained mother solution be fully incorporated acid
Recycle in the pickle liquor of leaching reaction gained, achievable aluminium ion conversion ratio maximizes, the purpose of zero-emission.
The mass ratio of the aluminous fly-ash described in this method and sodium carbonate, and the determination of calcining heat and time is with true
Protect main thing phase mullite in flyash to react completely with sodium carbonate, and premised on not causing energy waste.
The sour consumption of the hydrochloric acid leaching grog described in this method is according to the leaching rate maximum of aluminum, loss rate in flyash
It is minimised as foundation to draw, the recyclable recycling of hydrochloric acid of excess.
The temperature that prepared by pickle liquor sodium hydroxide direct precipitation method amorphous hydroted alumina described in this method is：
, to 70 DEG C, the pH value of regulation is between 5～6.5 for room temperature.
Described in this method with amorphous hydroted alumina for raw material in 70～120 DEG C of temperature ranges, under condition of normal pressure
Hydrolyze-polyreaction 2～3 hours with hydrochloric acid, obtain storing solution.
The used in amounts of the amorphous hydroted alumina described in this method and hydrochloric acid ensures the storing solution basicity of end reaction
(hydroxide aluminium ratio) is 0.4～1.5.
The al species of the amorphous hydroted alumina described in this method can be implemented under lower temperature and condition of normal pressure with
Hydrochloric acid reaction simultaneously reaches preparation P-Al13Basicity.
Amorphous hydroted alumina described in this method and the reactant liquor of hydrochloric acid, can analyse under the conditions of room temperature～50 DEG C naturally
Go out P-Al13Crystallization, directly obtains solid-state efficient flocculant after filtration, need not any other solidification equipment and technique.
Preparation P-Al described in this method13Required raw material is only amorphous hydroted alumina and hydrochloric acid it is not necessary to other
Any catalyst or reagent, do not introduce the other any impurity ions in addition to Al (III) in preparation process.
P-Al described in this method13Hydrochloric acid salts out the remaining mother solution reusable edible after crystallization, is a kind of aluminium ion
Loss rate bottom, high conversion rate, the preparation P-Al of zero-emission13Method.
Advantages of the present invention：Amorphous hydroted alumina is prepared for raw material with aluminous fly-ash and develops efficient flocculant Al13
(OH)24(H2O)24Cl15·13H2O has the advantages that following prominent：
1. the present invention is ready for use on the efficient flocculant of water process it is achieved that turning waste into wealth using solid waste coal ash for manufacturing, with useless
The useless effect of system, is a kind of approach realizing the comprehensive utilization of flyash high added value, can produce good economic benefit, environment
Benefit and social benefit.
2. the present invention uses discarded flyash and common hydrochloric acid and sodium hydroxide reagent, therefore with low cost.
3. the P-Al of the present invention13Preparation reaction temperature is lower, and the response time is shorter, need not pressurize, process is easily operated, energy
Obtain form single, highly purified solid-state polymerization aluminum 13 Al13(OH)24(H2O)24Cl15·13H2O, and can achieve that often system must
, product quality is secure.P-Al13The aluminium ion loss rate bottom of preparation process, P-Al13High conversion rate.
4. this method can be implemented in and prepares P-Al with aluminium hydroxide for raw material under condition of normal pressure13.
5. this method makes P-Al by adjusting degree of supersaturation13Naturally separate out crystallization, obtain solid-state efficient flocculant, need not appoint
What its solidification equipment and technique.
6. this method preparation P-Al13During do not introduce other foreign ions in addition to Al (III).
7. its effectively flocculation composition P-Al of this method products therefrom13Content up to more than 91%, excellent aqueous solubility, there is no water
Insoluble matter, meets national standard (GB15892-2009) high-class product specification.
8. products obtained therefrom P-Al of the present invention13Flocculating effect is better than Keggin-Al13([AlO4Al12(OH)24(H2O)12]7+).
Contrast experiment is as shown in table 1.From table, the P-Al of present invention preparation13With Keggin-Al13Compare, no matter high concentrtion is stable
Water sample and the unstable water sample of low turbidity, all show and compare Keggin-Al13Superior flocculating effect.
Table 1, P-Al13With Keggin-Al13 aFlocculating experimentbResult
Annotationa：Keggin-Al13Preparation is using a slowly alkaline process：Under the conditions of 80 DEG C of constant temperature oil bath, strong magnetic agitation, to
AlCl3It is slowly added dropwise NaOH solution, rate of addition controls in 0.6mL/min in solution.It is cooled to room temperature after completion of dropping,
Ripening certain time must contain Keggin-Al13Polymerization PAC solution, AlbContent 80% about,27Al-NMR characterizes proves that it is main
For Keggin-Al13.Annotationb：Flocculating experiment adopts chamber test method：Instrument adopts JJ-4 type six motor stirrer, will
In 500mL simulated water sample injection beaker, start stirring, under quick stirring (rotating speed is 200r/min) to water sample in put into certain
The flocculant of amount, is changed to (rotating speed is 40r/min) stirring 15min at a slow speed, stops stirring and standing after continuing quick stirring 1min
Sedimentation 15min.Precipitation terminates to draw clarification aqueous humor at 1cm under liquid level, detects that it is remaining using 2100N type transmissometer
Turbidity.)
Brief description：
Accompanying drawing 1 is the process chart of this method.
Accompanying drawing 2 is intermediate product amorphous hydroted alumina XRD spectra.
Accompanying drawing 3 is the XRD spectra separating out product for the first time.
Accompanying drawing 4 is the XRD spectra of second precipitation product.
Accompanying drawing 5 is the XRD spectra that third time separates out product.
Specific embodiment
It is described in further detail the present invention with reference to embodiments, but not affected to the present invention any type of restriction.
1st, high-temperature fusion reaction：The flyash of Huhehaote power plant and sodium carbonate are pressed 1.2: 1 mass ratio, both generals exist
Finely ground mixing in mortar, 850 DEG C of calcination 110min in Muffle furnace.Clinker cooling is fully ground standby to room temperature.(powder
Coal ash Al2O3Content is 49.2%)
2nd, acid-leaching reaction：Take above-mentioned grog 75.2g in beaker, add 380mL concentrated hydrochloric acid and 30mL distilled water, through fully
After stirring, room temperature stands 5min, is filtrated to get pickle liquor (now the extraction ratio of aluminum is up to 95.7%).
3rd, the preparation of amorphous hydroted alumina：At ambient temperature, Deca 8mol/L sodium hydroxide solution is to above-mentioned gained
In pickle liquor, must precipitate as amorphous hydroted alumina (the XRD characterization result of product is shown in accompanying drawing 2) as pH=5, after filtration,
Product is through multiple distilled water wash, finely ground standby after drying.
4、Al13(OH)24(H2O)24Cl15·13H2The preparation of O：
(1) take amorphous hydroted alumina 42g in 500mL there-necked flask, add 53mL concentrated hydrochloric acid and 15mL under reflux conditions
Distilled water, is warming up to 70 DEG C after room temperature reaction 30min, after continuing reaction 3h, stop heated and stirred.Filter paper filtering while hot.Obtain
The basicity (hydroxide aluminium ratio) of storing solution is 1.4.Filtrate moves into crystallizer, in room temperature condition evaporative crystallization, Al to be separated out13
(OH)24(H2O)24Cl15·13H2Separate after O crystal, air-dry in room temperature after product washing with alcohol, weigh, preserve.
Product analysis result：Product gross mass：22.19g, wherein P-Al13Content is 93.2%, and aluminium ion conversion ratio is
36.87%, remaining mother solution：61.8g.The XRD characterization result of product is shown in accompanying drawing 3.
(2) the remaining mother solution taking (1) is incorporated in the pickle liquor of the 2nd step.Amorphous hydroxide is prepared using the method for step 3
Aluminum, dry, finely ground after, take 42g in 500mL there-necked flask, add 53mL concentrated hydrochloric acid and 15mL distilled water under reflux conditions.Room temperature
It is warming up to 70 DEG C after reaction 30min, after continuing reaction 3h, stop heated and stirred.Filter paper filtering while hot.Filtrate moves into crystallization and sets
Standby, in room temperature condition evaporative crystallization, Al to be separated out13(OH)24(H2O)24Cl15·13H2Separate after O crystal, product ethanol is washed
Wash and air-dry, weigh, preserve in room temperature again.
Product analysis result：Product gross mass：21.03g, wherein P-Al13Content is 91.63%, closes with front primary first-order equation
Calculating aluminium ion conversion ratio is 52.30%, remaining mother solution：63.0g.The XRD characterization result of product is shown in accompanying drawing 4.
(3) the remaining mother solution taking (2) is incorporated in the pickle liquor of the 2nd step.Deca sodium hydroxide, is adjusted to pH=5, obtains amorphous
Aluminum hydroxide precipitation.Through multiple distilled water wash, drying and finely ground after, take 42g in 500mL there-necked flask, under reflux conditions plus
Enter 53mL concentrated hydrochloric acid and 15mL distilled water.It is 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, Al to be separated out13(OH)24(H2O)24Cl15·
13H2Separate after O crystal, product washing with alcohol air-dries, weighs, preserves in room temperature again.
Product analysis result：Product gross mass：22.20g, wherein P-Al13Content is 94.09%, closes with front two secondary responses
Calculating aluminium ion conversion ratio is 62.52%, remaining mother solution：61.8g.The XRD characterization result of product is shown in accompanying drawing 5.
5th, can Theoretical Calculation be gone out according to the aluminium ion conversion ratio of first three experiment：The aluminium ion of the 4th mother liquid recycling
Conversion ratio is：69.84%；The aluminium ion conversion ratio of the 5th mother liquid recycling is：73.94%.I.e. Recycling Mother Solution number of times is got over
Many, aluminium ion conversion ratio is higher, finally can achieve aluminum ions zero-emission.Through multiple mother liquid recycling may be implemented in normal pressure,
Under the temperate condition of lower temperature, development high-purity, the solid-state efficient flocculant Al that form is single, flocculating property is superior13
(OH)24(H2O)24Cl15·13H2The purpose of O.
Claims (1)
1. a kind of method with flyash for raw material development solid-state polymerization aluminum chloride flocculant is it is characterised in that with flyash be
Raw material, develops Al by intermediate product amorphous hydroted alumina13(OH)24(H2O)24Cl15·13H2O, letter is calculated as P-Al13, including
Five steps below：
1. high temperature solid state reaction：Flyash and sodium carbonate are pressed 0.8～2.0: the 1 finely ground mixing of mass ratio, 750 in Muffle furnace
Calcination 30～150min at～950 DEG C, is fully ground standby after clinker cooling to room temperature；
2. acid-leaching reaction：In above-mentioned grog, adding the hydrochloric acid of 3～12mol/L, every gram of grog correspondence Jia 4～20mL volume
Hydrochloric acid, after being sufficiently stirred for, room temperature is filtrated to get pickle liquor after standing 5～30min；
3. the preparation reaction of amorphous hydroted alumina：Under the conditions of room temperature is to 70 DEG C, Deca concentration is more than the hydroxide of 4mol/L
Sodium solution, to pickle liquor, is adjusted to pH=5～6.5, is precipitated as amorphous hydroted alumina, product is dried through filtration washing
Finely ground standby afterwards；
④P-Al13Preparation reaction：By amorphous hydroted alumina under reflux conditions with 8～12mol/L hydrochloric acid reaction, reaction temperature
At 70～120 DEG C, condition of normal pressure issues unboiled water solution-polyreaction 2～3 hours to degree, obtains storing solution so as to basicity, i.e. hydroxyl
Aluminum ratio is 0.4～1.5, and after filtered while hot, filtrate moves into crystallizer, evaporative crystallization at room temperature～50 DEG C, Al to be separated out13
(OH)24(H2O)24Cl15·13H2Separate after O crystal or powder, solid product is scrubbed, at room temperature～50 DEG C, dry product, system
Obtain solid-state efficient flocculant Al13(OH)24(H2O)24Cl15·13H2O, filtrate reusable edible；
5. Recycling Mother Solution：By P-Al13Preparation react the mother solution of gained and be fully incorporated in the pickle liquor of acid-leaching reaction gained and circulate
Using.
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| CN1583593A (en) * | 2004-06-04 | 2005-02-23 | 刘启旺 | One step synthesis of polymerized aluminum-iron sulfurate from industrial waste slags |
| CN1718543A (en) * | 2004-07-09 | 2006-01-11 | 中国石油天然气股份有限公司 | Preparation method of polyaluminum chloride with high aluminum content |
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