CN103274539B - Method for removing fluoride in drinking water by complexation-coacervation-adsorption with defluorination adsorption material based on aluminium base composite metal oxide - Google Patents
Method for removing fluoride in drinking water by complexation-coacervation-adsorption with defluorination adsorption material based on aluminium base composite metal oxide Download PDFInfo
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Abstract
The invention relates to a method for removing fluoride in drinking water by complexation-coacervation-adsorption with defluorination adsorption material based on aluminium base composite metal oxide. Firstly free form fluorine in water is converted into complexation state fluorine by controlling appropriate pH value condition, aluminium salt form and throwing amount or the like; calcium hydrate and aluminium salt are introduced for realizing coacervation process and providing active adsorption sites with abundant surface hydroxies, thereby the dissolved state fluorine in water is converted into particulate type fluorine by coacervation and absorption effects; dissolved state fluorine is further removed after water flows though an absorption fixed bed reactor filled with defluorination adsorption material based on aluminium base composite metal oxide; finally, water flows through a filter reactor, and colloid, particle and other impurities contained in the absorption fixed bed reactor water outlet are removed. Fluorine in the drinking water is removed by using the method provided by the invention, and the processed water can reach the WHO, USEPA and other related standards and national drinking water standard (GB5749-2006).
Description
Technical field
The present invention relates to the treatment process of tap water, particularly the method for fluorochemical in complexing-cohesion-Adsorption tap water of the defluorination absorbing material based on aluminum-base composite metal oxide.
Background technology
In tap water, the pollution of fluorochemical is the problem that the many areas of China all face.Developing tendency of removal of fluoride from drinking mainly comprises activated alumina absorption, electrodialysis, bone black adsorption filtration, ion exchange resin bed filtration, aluminate coagulating method, lime-phosphoric acid salt coprecipitation method and membrane filtration etc.Various technological methods have different relative merits and working conditions, and also have difference at aspects such as running cost, simplicity of operation, long-time running reliabilities.The Rural areas lower for operation and management level, water supply scale is less, absorption method with it without the advantage such as complicated dosing process, operational management be simple and be easy to apply.But, absorption method is mainly acted on and is removed fluorochemical in water by physical adsorption, chemisorption or the ion-exchange etc. of adsorbent surface, because available surface adsorption site is very limited, therefore for water of high fluorine content, often adsorption cycle is very short, need frequent regeneration, need to extend the empty bed residence time (EBCT) if extend adsorption cycle, increase to a certain extent cost of investment.
Research discovery, complex state fluorine is more easily adsorbed on particulate matter surface compared with free state fluorine, if free state fluorine is converted into complex state fluorine, can significantly reduce the difficulty of its removal, thereby significantly improves the adsorption-defluorination effect of aluminium base composite oxides defluorination absorbing material.Fluorine in natural water body exists with the form of free state fluorine (F-) in most cases, and along with the variation of fluid chemistry and chemical constitution, the proportion relation of its occurrence patterns also may change.In the shallow ground water of neutrality or meta-alkalescence (pH7～8), the existence form of fluorine only has 10 kinds, i.e. F
-, BF (OH)
3 -, HFaq, CaF
+, MgF
+, MnF
+, AlF
2+, AlF
2 +, AlF
3and AlF
4 -, wherein with F
-, MgF
+, CaF
+three kinds of forms are main.General F
-account for F
t(total fluorine concentration) 79%～96%, be secondly MgF
+and CaF
+, be respectively F
t3.1%～19.2% and 0.3%～3.0%.If free state fluorine in water is converted into complex state fluorine in drinking water treatment process, can effectively reduce it and remove difficulty, improve fluorine removing rate; And can realize the conversion of free state fluorine to complex state fluorine by adding aluminium salt within the scope of suitable pH value, and can control easily and effectively by controlling aluminium salt form, pH value and aluminium salt throwing amount etc. the complexation process of fluorine and aluminium.
The same with free state fluorine, complex state fluorine still belongs to solubilised state fluorine, and still the filtration medium such as penetrable filter tank, filter membrane (microfiltration membrane, ultra-filtration membrane) also finally enters potable water network and user.Solubilised state fluorine is converted into particulate form fluorine, and recycling solid-liquid separation unit is removed, and this is the important technology strategy of drinking water defluorination; And condense, the process such as absorption can effectively realize the conversion of solubilised state fluorine to particulate form fluorine, and then realize the removal of fluorine.Cohesion coagulation defluorination is created on and reacts obviously difference of the upper existence such as condition of water quality, hydraulics with complex state fluorine.Traditional coagulation defluorination process is not considered the two difference at reaction conditions, system hydrochemistry condition is not adjusted to rational scope, and mainly realizes the removal of fluorine by adding the coagulating agent such as aluminium salt.Therefore, although may also there is aluminium fluorine complex reaction to a certain degree in coagulation defluorination process, complex state fluorine generates still lower and control not yet in effect of ratio, desirable thereby defluorination effect is still owed.Further, complex state fluorine is except being converted into particulate form fluorine by agglomeration process, and itself also may directly be adsorbed on solid phase particles thing surface and be removed.Design construction suitable, there is the absorption interface of enriching specific surface area, likely in said process, further improve defluorination effect.
The problem building around the absorption interface of enriching specific surface area, this case contriver has invented defluorination absorbing material and the application method (patent No. ZL200810226262.4) thereof based on aluminium base composite oxides, its technology of Fluoride Removal principle is: will have the hydrated aluminum base oxide of excellent Fluoride-Absorption Capacity, hydrated aluminum based hybroxide, hydration aluminum oxyhydroxide, the aluminium base calcium aluminate of hydration, the aluminium base magnesium aluminate of hydration, hydration hydrous iron oxide, manganese oxide hydrates etc. carry out composite, and by original position carrying method load/be entrained in carrier surface and gap, acquisition has the defluorination material that enriches activated adsorption site and surface hydroxyl, in adsorption-defluorination process, utilize material adsorption site absorption and ion exchange to realize fluorine and from water, separate and immobilization at material internal, reach absorption saturated or when going out penetration by water and reaching regeneration condition, adopt in situ regeneration method to recover the defluorination activity of adsorption layer, without regenerated liquid immersion processes such as acid/alkali lye complicated in conventional regeneration mode, thereby simplify regenerative process.Particularly, the defluorination absorbing material based on aluminium base composite oxides comprises aluminium base composite oxides and porous load matrix two portions; Wherein, the mass ratio of aluminium base composite oxides and porous load matrix is 0.25～25:100; Above-mentioned porous load matrix can be selected from quartz sand, haydite, manganese sand, hard coal, magnetite, bone black, Attapulgite, zeolite, gac, clay, diatomite, calcium phosphate powder or activated alumina etc.; Above-mentioned aluminium base composite oxides can be by aluminum oxide (Al
2o
3), hydrated aluminum oxide (Al
2o
3xH
2o), hydration aluminum oxyhydroxide (AlOOHxH
2o), hydrated aluminum based hybroxide (Al (OH)
3xH
2component and the matrix material of composition compound through chemical reaction process such as O).
The present invention is around the form transformation process of fluorine, form take aluminium and fluorine interacts as foundation, by controlling suitable pH, aluminium salt kind is with hydrochemistry conditions such as throwing amounts and react accordingly hydraulics, free state fluorine in water is converted into complex state fluorine, and further take the defluorination absorbing material adsorption-defluorination process based on aluminium base composite oxides as basis, complexing, aggregation are combined with absorption fixed-bed reactor, propose the method for the complexing-cohesion-adsorption-defluorination based on this sorbing material.Adopt method of the present invention to remove the fluorine in tap water, process water and can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006), also can effectively remove the fluorine in sewage and trade effluent.
Summary of the invention
The object of the invention is for the fluorochemical in water, especially the fluorochemical in underground drinking water source, provides that a kind of performance is efficient, economically feasible, is easy to the method for fluorochemical in complexing-cohesion-Adsorption tap water of the defluorination absorbing material based on aluminum-base composite metal oxide of large-scale application in engineering.
In complexing-cohesion-Adsorption tap water of the defluorination absorbing material based on aluminum-base composite metal oxide of the present invention, the know-why of the method for fluorochemical is, under certain pH value and well-mixed hydraulics, toward adding aluminium salt in fluorinated water, free state fluorion (F-) in water is converted into AlF
2+, [Al
2fO
2(H
2o)]
+, [AlF (OH) (H
2o)
2]
+, [Al
2fO
2(H
2o)
2]
+, [Al
3fO
3(OH) (H
2o)
2]
+, [Al
4fO
5(H
2o)
4]
+, [Al
6f
3o
7(H
2o)
3]
+, [Al
13f
2o
17(OH)]
2+, [Al
13f
6o
15(OH) (H
2o)
8]
2+etc. the complex state fluorine AlF of various forms
x(OH)
(3-
x)(wherein X is the ligancy of the single aluminium atom pairs fluorine of answering).Wherein, the complex state fluorine AlF of generation
x(OH)
(3-
x)form can control by form, kind and the throwing amount etc. of the pH value of regulation system and the aluminium salt adding.After free state fluorine is converted into complex state fluorine, then introduce respectively calcium hydroxide and aluminium salt, on the one hand pH value is adjusted to proper range and realizes the cohesion of fluorine and remove process, introducing has the W 4600 (Al (OH) that enriches surface hydroxyl on the other hand
3xH
2o) (number that wherein X is water molecules), hydrated aluminum oxide (Al
2o
3xH
2o) (number that wherein X is water molecules) and aluminium calcium complex hydroxide (Al
mca
no
3xH
2o) (wherein m is the number of Al atom; N is the number of calcium atom; X is the number of water molecules), cohesion and the adsorption process of promotion free state fluorine, complex state fluorine; Afterwards, current are further removed solubilised state fluorine through the absorption fixed-bed reactor that are filled with the defluorination absorbing material based on aluminium base composite oxides; Finally, current after filtration reactor remove the impurity such as colloid, particulate matter in absorption fixed-bed reactor water outlet.When the pH of filtration reactor water outlet value is less than 6.5 or while being greater than 8.5, by adding inorganic base aqueous solution or inorganic acid aqueous solution, pH value is adjusted in 6.5～8.5 scopes; In the time that the pH of filtration reactor water outlet value is in 6.5～8.5 scopes, does not carry out pH value and regulate.
To achieve these goals, in complexing-cohesion-Adsorption tap water of the defluorination absorbing material based on aluminum-base composite metal oxide of the present invention, the method for fluorochemical comprises the following steps:
(1) in pending fluorinated water, add aluminum saline solution, and fully reaction (time of general reaction is 0.5～60 minute) in mixing reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the throwing amount of aluminum saline solution is that to make the mol ratio of the fluorine in aluminium salt and pending fluorinated water be 0.1:1～5:1;
When the aluminium salt adding (due to the negatively charged ion of aluminium salt on effect without impact, therefore do not refer in particular in the present invention) is monomer trivalent aluminium salt (Al
3+) or when the aluminium salt polymerization degree polyaluminium salts that is 2～6, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 6～7.2; In the time that the aluminium salt adding is the aluminium salt polymerization degree polyaluminium salts that is 8～16, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 5.5～6.5; In the time that the aluminium salt adding is the aluminium salt polymerization degree polyaluminium salts that is 30, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 5～6;
(2) be suspended the aqueous solution and aluminum saline solution (calcium hydroxide is suspended the aqueous solution and aluminum saline solution is prepared respectively) to adding calcium hydroxide in the water outlet of the reacted mixing reactor of step (1), and fully reaction (time of general reaction is 1～30 minute) in mixing reactor;
Wherein: in total throwing amount that the throwing amount of aluminum saline solution is the aluminium salt in the aluminum saline solution that makes step (1) and step (2) and add and water, the mol ratio of fluorine is 2:1～15:1;
The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is determined according to following principle: in the time that the pH value of step (1) mixing reactor water outlet is less than or equal to 5.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 3:1～12:1; When the pH value of step (1) mixing reactor water outlet is greater than 5.5 and while being less than or equal to 6.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 2:1～6:1; In the time that the pH value of step (1) mixing reactor water outlet is greater than 6.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 0.25:1～3:1;
The polyaluminium salts that the polyaluminium salts that described aluminium salt is monomer trivalent aluminium salt, the aluminium salt polymerization degree polyaluminium salts that is 2～6, the aluminium salt polymerization degree is 8～16 or the aluminium salt polymerization degree are 30;
(3) water outlet of the reacted mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the defluorination absorbing material based on aluminium base composite oxides, further to remove free state fluorine and complex state fluorine in water; Preferably flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the defluorination absorbing material based on aluminium base composite oxides of the water outlet of mixing reactor is 10～120 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of filtration medium, to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH readjusts: when the pH value of step (4) filtration reactor water outlet is less than 6.5 or while being greater than 8.5, add inorganic acid aqueous solution or inorganic base aqueous solution, the pH value of the water outlet of filtration reactor is adjusted in 6.5～8.5 scopes, has obtained removing the processing water of fluorochemical; In the time that the pH of filtration reactor water outlet value is in 6.5～8.5 scopes, does not carry out pH value and regulate; Directly obtain having removed the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Described pending fluorinated water refers to the water that fluorine concentration in drinking water source is greater than 1mg/L, refers in particular to fluorine-containing and as the underground water of drinking water source.
Described mixing reactor is waterpower mixing reactor, aeration mixing reactor or mechanically mixing reactor.
The filtration medium loading in described filtration reactor is selected from one or more the combination in quartz sand, hard coal, granulated active carbon, fibrous nodules, fibrous bundle, diatomite and haydite.
The described defluorination absorbing material based on aluminium base composite oxides is the defluorination absorbing material of patent No. ZL200810226262.4, and it comprises active ingredient and porous load matrix two portions; Wherein, active ingredient is the aluminium base composite oxides being prepared from through chemical reaction by aluminum salt solution and inorganic alkali solution, aluminium base composite oxides loads on porous load matrix surface by the method for original position load, and the mass ratio of aluminium base composite oxides and porous load matrix is 0.25～25:100.Described aluminium base composite oxides can be by aluminum oxide (Al
2o
3), hydrated aluminum oxide (Al
2o
3xH
2o), hydration aluminum oxyhydroxide (AlOOHxH
2and hydrated aluminum based hybroxide (Al (OH) O)
3xH
2component and the matrix material of composition compound through chemical reaction process such as O), the number that wherein X is water molecules.The particle diameter of described porous load matrix is between 0.2mm～4mm; Can be selected from quartz sand, haydite, manganese sand, hard coal, magnetite, bone black, Attapulgite, zeolite, gac, clay, diatomite, calcium phosphate powder or activated alumina etc.
The method of described original position load is by the aluminum salt solution of water purification reactor and the entrance of inorganic alkali solution, pass into aluminum salt solution and inorganic alkali solution to being filled with in the water purification reactor of porous load body material, wherein, the mol ratio of the Al in mixed solution and OH-is 1～6:6～1; Make to react by aluminum salt solution and inorganic alkali solution the aluminium base composite oxides obtaining and be carried on porous load matrix, wherein the mass ratio of aluminium base composite oxides and porous load matrix is 0.25～25:100.
First the present invention by controlling suitable pH value condition, form and the throwing amount etc. thereof of aluminium salt, is converted into complex state fluorine by free state fluorine in water; Afterwards, further introducing calcium hydroxide and aluminium salt are realized agglomeration process and are provided and has the activated adsorption site of enriching surface hydroxyl, thereby by cohesion and adsorption, solubilised state fluorine in water (free state fluorine and complex state fluorine) are converted into particulate form fluorine (condensed state fluorine and ADSORPTION STATE fluorine); Afterwards, current are further removed solubilised state fluorine through the absorption fixed-bed reactor that are filled with the defluorination absorbing material based on aluminium base composite oxides; Finally, current after filtration reactor remove the impurity such as colloid, particulate matter comprising in absorption fixed-bed reactor water outlet.Adopt method of the present invention to remove the fluorine in tap water, process water and can reach WHO, USEPA relevant criterion and national drinking water standard (GB5749-2006).
The present invention is compared with traditional coagulation method for removing fluor, defluorination method of the present invention takes full advantage of the complex reaction of aluminium salt and fluorine and has strengthened the generation of aluminium-fluoro complex, and complex reaction is combined and significantly improved defluorination effect with cohesion, absorption reaction, reduce defluorination processing cost; Method control parameter of the present invention simple (major control pH, aluminium salt and calcium hydroxide throwing amount etc.), and be easy to realize; Method of the present invention is simple, and reactor can modularization, can design and apply according to different project scales.
The present invention is compared with simple adsorption technology, the present invention is converted into complex state fluorine by the effect such as complexing, cohesion by free state fluorine in water, thereby the absorption property that has significantly improved the follow-up defluorination absorbing material based on aluminium base composite oxides, has extended adsorption cycle, has reduced running cost.
The present invention is compared with traditional defluorination absorbing material, and the defluorination absorbing material based on aluminium base composite oxides the present invention relates to has good adsorption-defluorination performance, shows excellent defluorination ability; After material active ingredient in life-time service process is adsorbed saturated or poisoning or loss, only need simple regenerative operation can recover good adsorptive power.Defluorination absorbing material based on aluminium base composite oxides adopts the method for original position load, regeneration be prepared and regenerate, can effectively retain abundant surfactivity functional group, the specific surface area of avoiding active function groups inactivation that the processes such as sintering cause and aggregation of particles to cause such as reduces at the phenomenon.
Embodiment
Embodiment 1
Adopt the disclosed method of ZL200810226262.4 to prepare the defluorination absorbing material based on aluminium base composite oxides, concrete grammar is as follows: the haydite take grain diameter scope as 1mm～4mm is porous load matrix, is inserted in columnar water purification reactor; Compound concentration is 100Kg/m respectively
3al
2(SO
4)
3solution and 15Kg/m
3kOH alkali lye.With pump by Al
2(SO
4)
3solution pumps in water purification reactor, until will stop pumping into Al after haydite submergence
2(SO
4)
3solution, floods after 30 minutes Al
2(SO
4)
3solution is emitted; Again KOH alkali lye is pumped in water purification reactor, until will stop pumping into NaOH solution after haydite submergence, flood after 30 minutes NaOH solution is flowed out, intermittently leave standstill 15 minutes.Repeat 2 times according to aforesaid method.Make Al
2(SO
4)
3the aluminium base composite oxides original position that solution and NaOH solution are prepared from through chemical reaction loads on haydite surface, obtains based on aluminium base composite oxides defluorination absorbing material.And then clear water is pumped in purification reactor, and clear water is slowly flowed out, until in water outlet aluminum concentration and pH value lower than national drinking water quality standard.Now, the mass ratio of active ingredient aluminium base composite oxides and haydite is 2:100.The defluorination absorbing material based on aluminium base composite oxides preparing is loaded in absorption fixed-bed reactor.
(1) the pH value that first with hydrochloric acid, pending fluoro-containing concentration is greater than to the water of 1mg/L is adjusted to 5.5, then add the polymerize aluminum chloride aqueous solution that the aluminium salt polymerization degree is 8～16, and fully react 1 minute in waterpower mixing reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the mol ratio of the fluorine in polymerize aluminum chloride and pending fluorinated water that the aluminium salt polymerization degree is 8～16 is 1:1;
(2) in the water outlet of the waterpower mixing reactor that is 5.5 to the reacted pH value of step (1), add calcium hydroxide and be suspended the polymerize aluminum chloride aqueous solution that the aqueous solution and the aluminium salt polymerization degree are 8～16, and fully reaction 30 minutes in mechanically mixing reactor; Wherein: in the polymerize aluminum chloride that the aluminium salt polymerization degree adding is 8～16 and water, the mol ratio of fluorine is that the mol ratio of fluorine in total throwing amount of the 9:1(aluminium salt polymerization degree that to be step (1) add with step (2) polymerize aluminum chloride that is 8～16 and water is 10:1); The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) the aluminium salt polymerization degree polymerize aluminum chloride throwing amount that is 8～16 is 3:1;
(3) water outlet of the reacted mechanically mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the above-mentioned defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water; Flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the above-mentioned defluorination absorbing material based on aluminium base composite oxides of the water outlet of mechanically mixing reactor is 60 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of quartz sand, to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH that records the filtration reactor water outlet of step (4) is 6, therefore adds aqueous sodium hydroxide solution by the pH regulator to 7 of water outlet, has obtained removing the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Embodiment 2
Adopt the disclosed method of ZL200810226262.4 to prepare the defluorination absorbing material based on aluminium base composite oxides, concrete grammar is as follows: the bone black take grain diameter scope as 0.5mm～1mm is porous load matrix, is inserted in columnar water purification reactor; Compound concentration is 50Kg/m respectively
3polymerize aluminum chloride (PAC) solution and 4Kg/m
3naOH alkali lye.PAC solution is pumped in water purification reactor with pump, until will stop pumping into PAC solution after bone black submergence, flood and after 60 minutes, PAC solution is emitted; Again KOH alkali lye is pumped in water purification reactor, until will stop pumping into NaOH solution after bone black submergence, flood after 30 minutes NaOH solution is flowed out, intermittently leave standstill 30 minutes.Repeat 3 times according to aforesaid method.The aluminium base composite oxides original position that PAC solution and NaOH solution are prepared from through chemical reaction loads on bone black surface, obtains based on aluminium base composite oxides defluorination absorbing material.And then clear water is pumped in water purification reactor, and clear water is slowly flowed out, until in water outlet aluminum concentration and pH value lower than national drinking water quality standard.Now, the mass ratio of active ingredient aluminium base composite oxides and bone black is 6:100.The defluorination absorbing material based on aluminium base composite oxides preparing is loaded in absorption fixed-bed reactor.
(1) first with sodium hydroxide, pending fluoro-containing concentration is greater than to the water pH regulator to 7.2 of 1mg/L, then adds aluminum sulfate aqueous solution, and fully reaction 60 minutes in waterpower mixing reactor; Make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the mol ratio of the fluorine in Tai-Ace S 150 and pending fluorinated water is 0.1:1;
(2) in the water outlet of the waterpower mixing reactor that is 7.2 to the reacted pH value of step (1), add calcium hydroxide and be suspended the polyaluminum sulfate aluminum water solution that the aqueous solution and the aluminium salt polymerization degree are 8～16, and fully reaction 30 minutes in waterpower mixing reactor; Wherein: in the polyaluminium sulfate that the aluminium salt polymerization degree adding is 8～16 and water, the mol ratio of fluorine is that 1.9:1(is that the mol ratio of fluorine in total throwing amount of the aluminium salt polymerization degree that the Tai-Ace S 150 that adds of step (1) and step (2) the add polyaluminium sulfate that is 8～16 and water is 2:1); The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) the aluminium salt polymerization degree polyaluminium sulfate throwing amount that is 8～16 is 0.25:1;
(3) water outlet of the reacted waterpower mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the above-mentioned defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water; Flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the above-mentioned defluorination absorbing material based on aluminium base composite oxides of the water outlet of waterpower mixing reactor is 120 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with anthracitic filtration reactor, to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH that records the filtration reactor water outlet of step (4) is 6.9, therefore needn't carry out pH regulator to water outlet, has obtained removing the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Embodiment 3
Adopt the disclosed method of ZL200810226262.4 to prepare the defluorination absorbing material based on aluminium base composite oxides, concrete grammar is as follows: the magnetite take grain diameter scope as 0.8mm～2.0mm, as porous load matrix, is inserted in cylindrical reactor; Compound concentration is 100Kg/m respectively
3alCl
3solution and 10Kg/m
3naOH alkali lye.With pump by AlCl
3solution pumps in cylindrical reactor, until will stop pumping into AlCl after magnetite submergence
3solution, floods after 60 minutes AlCl
3solution is emitted; NaOH alkali lye is pumped in cylindrical reactor, until will stop pumping into NaOH solution after magnetite submergence, flood after 30 minutes NaOH solution is flowed out, intermittently leave standstill 30 minutes.Repeat 3 times according to aforesaid method.Make AlCl
3the aluminium base composite oxides original position that solution and NaOH solution are prepared from through chemical reaction loads on magnetite surface, obtains based on aluminium base composite oxides defluorination absorbing material.And then clear water is pumped in cylindrical reactor and clear water is slowly flowed out, until in water outlet aluminum concentration and pH value lower than national drinking water quality standard.Now, the mass ratio of active ingredient aluminium base composite oxides and magnetite is 0.8:100.The defluorination absorbing material based on aluminium base composite oxides preparing is loaded in absorption fixed-bed reactor.
(1) the pH value that first with nitric acid, pending fluoro-containing concentration is greater than to the water of 1mg/L is adjusted to 5, then add the polyaluminum sulfate aluminum water solution that the aluminium salt polymerization degree is 30, and fully react 10 minutes in aeration mixing reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the mol ratio of the fluorine in polyaluminium sulfate and pending fluorinated water that the aluminium salt polymerization degree is 30 is 1:1;
(2) in the water outlet of the aeration mixing reactor that is 5 to the reacted pH value of step (1), add calcium hydroxide and be suspended the aqueous solution and aluminum chloride aqueous solution, and fully react 30 minutes in mechanically mixing reactor; Wherein: in the aluminum chloride adding and water, the mol ratio of fluorine is that 14:1(is that the mol ratio of fluorine in total throwing amount of the aluminum chloride that adds of the aluminium salt polymerization degree that step (1) the adds polyaluminium sulfate that is 30 and step (2) and water is 15:1) to be suspended the throwing amount of the calcium hydroxide in the aqueous solution be that the mol ratio of calcium hydroxide and step (2) aluminum chloride throwing amount is 12:1 to calcium hydroxide;
(3) water outlet of the reacted mechanically mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the above-mentioned defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water; Flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the above-mentioned defluorination absorbing material based on aluminium base composite oxides of the water outlet of mechanically mixing reactor is 10 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of granulated active carbon, to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH that records the filtration reactor water outlet of step (4) is 5.3, therefore adds potassium hydroxide aqueous solution by the pH regulator to 7.4 of water outlet, has obtained removing the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Embodiment 4
Adopt the disclosed method of ZL200810226262.4 to prepare the defluorination absorbing material based on aluminium base composite oxides, concrete grammar is as follows: the diatomite take grain diameter scope as 0.2mm～0.4mm, as porous load matrix, is inserted in cylindrical reactor; Compound concentration is 50Kg/m respectively
3al
2(SO
4)
3solution and 5Kg/m
3naOH alkali lye.With pump by Al
2(SO
4)
3solution pumps in reactor, until will stop pumping into Al after diatomite submergence
2(SO
4)
3solution, floods after 30 minutes Al
2(SO
4)
3solution is emitted; NaOH alkali lye is pumped in reactor, until will stop pumping into NaOH solution after diatomite submergence, flood after 30 minutes NaOH solution is flowed out, intermittently leave standstill 30 minutes.Repeat 3 times according to aforesaid method.Make Al
2(SO
4)
3the aluminium base composite oxides original position that solution and NaOH solution are prepared from through chemical reaction loads on diatomite surface, obtains based on aluminium base composite oxides defluorination absorbing material.And then clear water is pumped in reactor and clear water is slowly flowed out, until in water outlet aluminum concentration and pH value lower than national drinking water quality standard.Now, active ingredient aluminium base composite oxides and diatomaceous mass ratio are 10:100.The defluorination absorbing material based on aluminium base composite oxides preparing is loaded in absorption fixed-bed reactor.
(1) the pH value that first with sulfuric acid, pending fluoro-containing concentration is greater than to the water of 1mg/L is adjusted to 6.5, then add the polymerize aluminum chloride aqueous solution that the aluminium salt polymerization degree is 2～6, and fully react 10 minutes in mechanically mixing reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the mol ratio of the fluorine in oligomeric state aluminium salt and pending fluorinated water is 5:1;
(2) in the water outlet of the mechanically mixing reactor that is 6.5 to the reacted pH value of step (1), add calcium hydroxide and be suspended the polymerize aluminum chloride aqueous solution that the aqueous solution and the aluminium salt polymerization degree are 30, and fully reaction 1 minute in mechanically mixing reactor; Wherein: in the polymerize aluminum chloride that the aluminium salt polymerization degree adding is 30 and water, the mol ratio of fluorine is that 5:1(is that the mol ratio of fluorine in total throwing amount of the aluminium salt polymerization degree that the aluminium salt polymerization degree that step (1) the adds polymerize aluminum chloride that is 2～6 and step (2) the add polymerize aluminum chloride that is 30 and water is 10:1); The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) the aluminium salt polymerization degree polymerize aluminum chloride throwing amount that is 30 is 3:1;
(3) water outlet of the reacted mechanically mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the above-mentioned defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water; Flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the above-mentioned defluorination absorbing material based on aluminium base composite oxides of the water outlet of mechanically mixing reactor is 20 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of fibrous nodules, to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH that records the filtration reactor water outlet of step (4) is 6, therefore adds aqueous sodium hydroxide solution by the pH regulator to 7.2 of water outlet, has obtained removing the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Embodiment 5
Adopt the disclosed method of ZL200810226262.4 to prepare the defluorination absorbing material based on aluminium base composite oxides, concrete grammar is as follows: the hard coal take grain diameter scope as 0.5mm～1.0mm is porous load matrix, is inserted in columnar water purification reactor; Compound concentration is 12Kg/m respectively
3al
2(SO
4)
3solution and 2.5Kg/m
3naOH alkali lye.With pump by Al
2(SO
4)
3solution pumps in water purification reactor, until will stop pumping into Al after hard coal submergence
2(SO
4)
3solution, floods after 15 minutes Al
2(SO
4)
3solution is emitted; Again KOH alkali lye is pumped in water purification reactor, until will stop pumping into NaOH solution after hard coal submergence, flood after 20 minutes NaOH solution is flowed out, intermittently leave standstill 60 minutes.Repeat 3 times according to aforesaid method.Make Al
2(SO
4)
3the aluminium base composite oxides original position that solution and NaOH solution are prepared from through chemical reaction loads on hard coal surface, obtains based on aluminium base composite oxides defluorination absorbing material.And then clear water is pumped in water purification reactor and clear water is slowly flowed out, until in water outlet aluminum concentration and pH value lower than national drinking water quality standard.Now, active ingredient aluminium base composite oxides and anthracitic mass ratio are 2:100.The defluorination absorbing material based on aluminium base composite oxides preparing is loaded in absorption fixed-bed reactor.
(1) the pH value that first with sodium hydroxide, pending fluoro-containing concentration is greater than to the water of 1mg/L is adjusted to 6.0, then add the polyaluminum sulfate aluminum water solution that the aluminium salt polymerization degree is 30, and fully react 2 minutes in aeration reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the mol ratio of the fluorine in polyaluminium sulfate and pending fluorinated water that the aluminium salt polymerization degree is 30 is 1:1;
(2) in the water outlet of the aeration mixing reactor that is 6.0 to the reacted pH value of step (1), add calcium hydroxide and be suspended the polyaluminum sulfate aluminum water solution that the aqueous solution and the aluminium salt polymerization degree are 30, and fully reaction 10 minutes in aeration mixing reactor; Wherein: in the polyaluminium sulfate that the aluminium salt polymerization degree adding is 30 and water, the mol ratio of fluorine is that 8:1(is that the mol ratio of fluorine in total throwing amount of the aluminium salt polymerization degree that the aluminium salt polymerization degree that step (1) the adds polyaluminium sulfate that is 30 and step (2) the add polyaluminium sulfate that is 30 and water is 9:1); The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) the aluminium salt polymerization degree polyaluminium sulfate throwing amount that is 30 is 0.25:1;
(3) water outlet of the reacted aeration mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the above-mentioned defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water; Flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the above-mentioned defluorination absorbing material based on aluminium base composite oxides of the water outlet of aeration mixing reactor is 120 minutes;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of quartz sand and hard coal combination (weight ratio is 1:1), to remove the impurity such as colloid, particulate matter comprising in the water outlet of absorption fixed-bed reactor;
(5) pH that records the filtration reactor water outlet of step (4) is 7.2, therefore needn't carry out pH regulator to water outlet, has obtained removing the processing water of fluorochemical.The processing water that gained has been removed fluorochemical can reach WHO, USEPA relevant criterion and national up-to-date drinking water standard (GB5749-2006).
Claims (7)
1. a method for fluorochemical in complexing-cohesion-Adsorption tap water of the defluorination absorbing material based on aluminum-base composite metal oxide, is characterized in that, described method comprises the following steps:
(1) in pending fluorinated water, add aluminum saline solution, and fully reaction in mixing reactor, make the free state fluorine in pending fluorinated water be converted into complex state fluorine; Wherein: the throwing amount of aluminum saline solution is that to make the mol ratio of the fluorine in aluminium salt and pending fluorinated water be 0.1:1～5:1;
In the time that the aluminium salt adding is monomer trivalent aluminium salt or the aluminium salt polymerization degree polyaluminium salts that is 2～6, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 6～7.2; In the time that the aluminium salt adding is the aluminium salt polymerization degree polyaluminium salts that is 8～16, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 5.5～6.5; In the time that the aluminium salt adding is the aluminium salt polymerization degree polyaluminium salts that is 30, first with mineral acid or mineral alkali, the pH value of pending fluorinated water is adjusted to 5～6;
(2) be suspended the aqueous solution and aluminum saline solution to adding calcium hydroxide in the water outlet of the reacted mixing reactor of step (1), and fully reaction in mixing reactor;
Wherein: in total throwing amount that the throwing amount of aluminum saline solution is the aluminium salt in the aluminum saline solution that makes step (1) and step (2) and add and water, the mol ratio of fluorine is 2:1～15:1;
The throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is determined according to following principle: in the time that the pH value of step (1) mixing reactor water outlet is less than or equal to 5.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 3:1～12:1; When the pH value of step (1) mixing reactor water outlet is greater than 5.5 and while being less than or equal to 6.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 2:1～6:1; In the time that the pH value of step (1) mixing reactor water outlet is greater than 6.5, the throwing amount that calcium hydroxide is suspended the calcium hydroxide in the aqueous solution is that the mol ratio of calcium hydroxide and step (2) aluminium salt throwing amount is 0.25:1～3:1;
The polyaluminium salts that the polyaluminium salts that described aluminium salt is monomer trivalent aluminium salt, the aluminium salt polymerization degree polyaluminium salts that is 2～6, the aluminium salt polymerization degree is 8～16 or the aluminium salt polymerization degree are 30;
(3) water outlet of the reacted mixing reactor of step (2) is flowed through and is filled with the absorption fixed-bed reactor of the defluorination absorbing material based on aluminium base composite oxides, to remove free state fluorine and complex state fluorine in water;
(4) water outlet of step (3) absorption fixed-bed reactor is flowed through and is filled with the filtration reactor of filtration medium, to remove the colloid, the particulate matter impurity that comprise in the water outlet of absorption fixed-bed reactor;
(5) when the pH value of step (4) filtration reactor water outlet is less than 6.5 or while being greater than 8.5, add inorganic acid aqueous solution or inorganic base aqueous solution, the pH value of the water outlet of filtration reactor is adjusted in 6.5～8.5 scopes, obtained removing the processing water of fluorochemical; In the time that the pH of filtration reactor water outlet value is in 6.5～8.5 scopes, does not carry out pH value and regulate; Directly obtain having removed the processing water of fluorochemical;
The described defluorination absorbing material based on aluminium base composite oxides comprises active ingredient and porous load matrix two portions; Wherein, active ingredient is the aluminium base composite oxides being prepared from through chemical reaction by aluminum salt solution and inorganic alkali solution, aluminium base composite oxides loads on porous load matrix surface by the method for original position load, and the mass ratio of aluminium base composite oxides and porous load matrix is 0.25～25:100; Described aluminium base composite oxides and the matrix material that form compound through chemical reaction process by aluminum oxide, hydrated aluminum oxide, hydration aluminum oxyhydroxide and hydrated aluminum based hybroxide component; Described porous load matrix is selected from quartz sand, haydite, manganese sand, hard coal, magnetite, bone black, Attapulgite, zeolite, gac, clay, diatomite, calcium phosphate powder or activated alumina.
2. method according to claim 1, is characterized in that: described pending fluorinated water is the water that in drinking water source, fluorine concentration is greater than 1mg/L.
3. method according to claim 1, is characterized in that: the time of the reaction described in step (1) is 0.5～60 minute.
4. method according to claim 1, is characterized in that: the time of the reaction described in step (2) is 1～30 minute.
5. method according to claim 1, is characterized in that: flow through empty bed residence time of the absorption fixed-bed reactor that are filled with the defluorination absorbing material based on aluminium base composite oxides of the water outlet of the described mixing reactor of step (3) is 10～120 minutes.
6. method according to claim 1, is characterized in that: described mixing reactor is waterpower mixing reactor, aeration mixing reactor or mechanically mixing reactor.
7. method according to claim 1, is characterized in that: the filtration medium loading in described filtration reactor is selected from one or more the combination in quartz sand, hard coal, granulated active carbon, fibrous nodules, fibrous bundle, diatomite and haydite.
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| CN108996642B (en) * | 2018-09-04 | 2021-09-10 | 中国铝业股份有限公司 | Treatment method of chlorine-containing wastewater |
| CN110885147B (en) * | 2019-12-05 | 2021-11-26 | 南京大学 | Ion exchange defluorination method for efficiently complexing fluorine-containing wastewater |
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| JP2001276815A (en) * | 2000-03-31 | 2001-10-09 | Toto Ltd | Water purifier |
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| CN1421404A (en) * | 2001-11-27 | 2003-06-04 | 中国科学院生态环境研究中心 | Drinking water defluorinating process and equipment |
| JP2004329989A (en) * | 2003-04-30 | 2004-11-25 | Shinagawa Kako Kk | Method for manufacturing fluorine adsorbing agent and waste liquid treating method |
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