CN105026320A - Method and apparatus for treating borofluoride-containing water - Google Patents
Method and apparatus for treating borofluoride-containing water Download PDFInfo
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- CN105026320A CN105026320A CN201480011099.3A CN201480011099A CN105026320A CN 105026320 A CN105026320 A CN 105026320A CN 201480011099 A CN201480011099 A CN 201480011099A CN 105026320 A CN105026320 A CN 105026320A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
Borofluoride-containing water is treated without carrying out warming so as to highly remove boron as well as fluorine therefrom. A method for treating borofluoride-containing water, which comprises: a first step of adding an aluminum compound to the borofluoride-containing water to decompose a borofluoride at pH 1 to 4; a second step of adding a calcium compound to treated water obtained in the first step to react the treated water with the calcium compound at pH 7 to 13, thereby producing an insoluble substance; and a third step of separating the insoluble substance into a solid material and a liquid material. The aluminum compound is added in such a manner that the Al/F ratio becomes 1.2 to 2.5 (by mole). The calcium compound is added in such a manner that the Ca/Al ratio becomes 2.5 to 4.0 (by mole). Each of the treatment temperature employed in the first step and the treatment temperature employed in the second step is 10 to 35 DEG C.
Description
Technical field
The present invention relates to a kind for the treatment of process and treatment unit of the water containing boron fluoride, particularly relate to and a kind of the water containing boron fluoride to be processed, thus the method for process water that significantly reduces of acquisition boron fluoride, fluorine and boron and device.
Background technology
In the past, as the treatment process of fluorine-containing water, there will be a known interpolation calcium cpd and make fluorine be precipitated with Calcium Fluoride (Fluorspan) and carry out the method for solid-liquid separation.Time in fluorine-containing water containing boron, a part for boron exists with the form of boron fluoride.Boron fluoride does not react with calcium cpd.Therefore, cannot carry out processing (non-patent literature 1) with the treatment process of the above-mentioned water containing fluorine.
There has been proposed a kind of method, it adds aluminum compound in containing the water of boron fluoride, acid and under condition of heating reaction boron fluoride is decomposed, and then interpolation calcium cpd, thus, processes (patent documentation 1,2) fluorine and boron.
A kind of method is described in patent documentation 1, it is containing in the water of boron fluoride, add aluminum compound in the mode making Al/F mol ratio become 0.3 ~ 1.05, in pH2 ~ 3, pair boron fluoride decomposes, then, add calcium cpd, generate insoluble compound in pH9 ~ 10, then, carry out solid-liquid separation, and then the mode becoming more than 5 with Al/F mol ratio in Separation of Water adds aluminum compound, generates insoluble compound and carry out solid-liquid separation in pH6 ~ 7.In the method for this patent documentation 1, in order to improve reactivity and precipitation threshold, under the condition of 50 ~ 80 DEG C, carry out these a series of operations.
Describe in patent documentation 2, containing in the water of boron fluoride, add the polyvalent metal compounds of aluminum compound etc. at below pH3, be heated to more than 35 DEG C, be preferably more than 40 DEG C, boron fluoride is decomposed, then, add slaked lime and generate insoluble compound in more than pH10, being cooled to less than 35 DEG C, then, aggegation, solid-liquid separation is carried out.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 4954131 publication;
Patent documentation 2: Japanese Patent No. 4338705 publication;
Non-patent literature
Non-patent literature 1: " environmental technology ", Vol.29, No.4 (2000) (“ Ring Jing Ji Intraoperative ", Vol.29, No.4 (2000)).
Summary of the invention
The problem that invention will solve
The treatment process of the water containing boron fluoride in the past, fully cannot carry out the removal of boron, and owing to reacting at high temperature, have the problem that operating cost is also high.
Problem of the present invention is the treatment process and the treatment unit that solve above-mentioned problem points in the past and provide a kind of water containing boron fluoride, it can process the water containing boron fluoride at low temperature (normal temperature), fluorine height not only can be made to remove boron height also can be made to remove.
In order to solve the method for problem
The present inventor etc. repeat positive self-criticism for solving above-mentioned problem, and it found that, by making the addition optimization of the addition of aluminum compound and calcium cpd and processing at normal temperature, can solve above-mentioned problem.
The present invention completes based on above-mentioned opinion, and its main contents are as follows.
[1] treatment process for the water containing boron fluoride, it has: the first operation, and this first operation adds aluminum compound in containing the water of boron fluoride, decomposes under the condition of pH 1 ~ 4 to boron fluoride; Second operation, this second operation adds calcium cpd in the process water of this first operation, reacts under the condition of pH7 ~ 13, generates insoluble compound thus; And the 3rd operation, the 3rd operation carries out solid-liquid separation to this insoluble compound,
It is characterized in that,
The addition of the aluminum compound of aforementioned first operation, counts Al/F=1.2 ~ 2.5 with the Funing tablet that Al scaled value contains the water of boron fluoride relative to this, and this ratio is mol ratio,
The addition of the calcium cpd of aforementioned second operation, counts Ca/Al=2.5 ~ 4.0 with Ca scaled value relative to the Al scaled value of this aluminum compound, and this ratio is mol ratio,
The treatment temp of aforementioned first operation and the second operation is 10 ~ 35 DEG C
The treatment process of the water containing boron fluoride [2] as described in [1], wherein,
It has:
4th operation, the 4th operation processes the Separation of Water obtained in aforementioned 3rd operation under the condition of pH 6 ~ 7, thus, generates insoluble compound; And
5th operation, the 5th operation carries out solid-liquid separation to this insoluble compound.
The treatment process of the water containing boron fluoride [3] as described in [1] or [2], wherein,
The addition of the aluminum compound of aforementioned first operation, Al/F=1.2 ~ 2.5 are counted relative to the Funing tablet of the aforementioned water containing boron fluoride with Al scaled value, and, this ratio is mol ratio, and count Al/B=2.0 ~ 4.5 with Al scaled value relative to the boron concentration of the aforementioned water containing boron fluoride, further, this ratio is mol ratio.
The treatment process of the water containing boron fluoride [4] according to any one of [1] to [3], wherein,
The aluminum concentration of the Separation of Water obtained in aforementioned 3rd operation is 30 ~ 70mg/L.
[5] containing a treatment unit for the water of boron fluoride, it has: the first reactive tank, and this first reactive tank adds aluminum compound in containing the water of boron fluoride, decomposes under the condition of pH 1 ~ 4 to boron fluoride; Second reactive tank, this second reactive tank adds calcium cpd in the process water of this first reactive tank, reacts under the condition of pH 7 ~ 13, thus, generates insoluble compound; And first solid-liquid separation device, this first solid-liquid separation device carries out solid-liquid separation to this insoluble compound,
It is characterized in that,
The addition of the aluminum compound of aforementioned first reactive tank, counts Al/F=1.2 ~ 2.5 with the Funing tablet that Al scaled value contains the water of boron fluoride relative to this, and this ratio is mol ratio,
The addition of the calcium cpd of aforementioned second reactive tank, counts Ca/Al=2.5 ~ 4.0 with Ca scaled value relative to the Al scaled value of this aluminum compound, and this ratio is mol ratio,
The treatment temp of aforementioned first reactive tank and the second reactive tank is 10 ~ 35 DEG C.
The treatment unit of the water containing boron fluoride [6] as described in [5], wherein,
It has:
3rd reactive tank, the 3rd reactive tank processes the Separation of Water obtained in aforementioned solid-liquid separation device under the condition of pH6 ~ 7, generates insoluble compound; And
Second solid-liquid separation device, this second solid-liquid separation device carries out solid-liquid separation to this insoluble compound.
The treatment unit of the water containing boron fluoride [7] as described in [5] or [6], wherein,
The addition of the aluminum compound of aforementioned first reactive tank, Al/F=1.2 ~ 2.5 are counted relative to the Funing tablet of the aforementioned water containing boron fluoride with Al scaled value, and, this ratio is mol ratio, and count Al/B=2.0 ~ 4.5 with Al scaled value relative to the boron concentration of the aforementioned water containing boron fluoride, further, this ratio is mol ratio.
The treatment unit of the water containing boron fluoride [8] according to any one of [5] to [7], wherein,
The aluminum concentration of the Separation of Water obtained in aforementioned first solid-liquid separation device is 30 ~ 70mg/L.
The effect of invention
According to the present invention, by controlling the addition of aluminum compound and the addition of calcium cpd, and processing at the normal temperature of 10 ~ 35 DEG C, not only highly can remove fluorine and also highly can remove boron.
Process of the present invention, does not substantially need to heat, therefore, can reduce operating cost.The present invention, owing to reacting at normal temperature, therefore, according to circumstances has the situation of heating time in the winter time, but owing to remaining on normal temperature in this situation, therefore, operating cost can be made more to reduce than prior art.
Also can process residual aluminum in water, by process more highly, fluorine removed to extremely low concentration.
Accompanying drawing explanation
Fig. 1 is the system diagram of the embodiment of the treatment unit representing the water containing boron fluoride of the present invention.
Fig. 2 is the BF of the process water represented in experimental example 1 ~ 4
4the chart of the relation of concentration and Ca/Al (mol ratio).
Fig. 3 is the chart of the F concentration of the process water represented in experimental example 1 ~ 4 and the relation of Ca/Al (mol ratio).
Fig. 4 is the chart of the B concentration of the process water represented in experimental example 1 ~ 4 and the relation of Ca/Al (mol ratio).
Fig. 5 is the chart of the Al concentration of the process water represented in experimental example 1 ~ 4 and the relation of Ca/Al (mol ratio).
Fig. 6 is the SO of the process water represented in experimental example 1 ~ 4
4the chart of the relation of concentration and Ca/Al (mol ratio).
Fig. 7 is the chart of the Ca concentration of the process water represented in experimental example 1 ~ 4 and the relation of Ca/Al (mol ratio).
Fig. 8 is the chart of the B concentration of the process water represented in experimental example 5,6 and the relation of Al/B (mol ratio).
Embodiment
Below, embodiments of the present invention are described in detail with reference to accompanying drawing.
Fig. 1 is the system diagram of the embodiment of the treatment unit representing the water containing boron fluoride of the present invention.
In FIG, respectively, 1 represents the first reactive tank (the 1st reactive tank), 2 represent the second reactive tank (the 2nd reactive tank), 3 represent coagulating bath, and 4 represent solid-liquid separation tank (the first solid-liquid separation device), and 5 represent the 3rd reactive tank (the 3rd reactive tank), 6 represent coagulating bath, and 7 represent solid-liquid separation tank (the second solid-liquid separation device).Former water is in the first reactive tank 1, adds aluminum compound (Al compound) and acid, makes the boron fluoride in former water carry out disaggregating treatment (the first operation) under the condition of pH1 ~ 4.
Secondly, by process water supply to the second reactive tank 2 of the first reactive tank 1, add calcium cpd (Ca compound) and alkali as required, time to process in pH7 ~ 13, generate the insoluble compounds (the second operation) such as Calcium Fluoride (Fluorspan) thus.
Then, the process water of the second reactive tank 2 is added in coagulating bath 3 after polymer coagulant carries out aggegation process, carry out solid-liquid separation (the 3rd operation) at solid-liquid separation tank 4.
The separated sludge of solid-liquid separation tank 4 is expelled to outside system, Separation of Water is supplied in the 3rd reactive tank (the 3rd reactive tank) 5, according to needing to add aluminum compound and acid, under the condition of pH6 ~ 7, carry out insoluble process (the 4th operation).
Then, by the process water of the 3rd reactive tank 5, add after polymer coagulant carries out aggegation process in coagulating bath 6, carry out solid-liquid separation (the 5th operation) at solid-liquid separation tank 7.
The separated sludge of solid-liquid separation tank 7 is expelled to outside system, Separation of Water is removed as process water.
Below, the process for former water and each operation is described.
The former water > of <
As the water (former water) containing boron fluoride processed in the present invention, the manufacture draining of glasswork, pharmaceuticals, makeup, resin, plated product can be exemplified as; The stack desulfurization draining of Coal-fired power plant; Crematorium wash cigarette draining; Nickel plating plant drainage etc.Usually, these contain in the discharge water of boron fluoride, and existing does not become BF yet
4 -but F
-, BO
3 3-form.
The water quality of these the former water processed in the present invention, usually, BF
4concentration (the BF dissolved in water
4 -ionic concn.In the present invention, " BF is recited as
4concentration ") 5 ~ 2000mg/L, the F concentration (Funing tablet dissolved in water.In the present invention, be recited as " F concentration ") 5 ~ 10000mg/L, B concentration (the boron concentration of dissolving in water.In the present invention, be recited as " B concentration ") 1 ~ 500mg/L, and pH is 0.5 ~ 11.5.
F concentration can utilize the method for regulation in 34.1 (lanthanum-ALC (lanthanum AlizarinComplexone) absorption photometrys) of JIS K0102 to measure, and B concentration can utilize the methods analyst of regulation in 47.3 (the ICP Emission Spectrophotometer methods) of JIS K0102.
< first operation >
In the first operation, in former water, add aluminum compound, by the reaction decomposes boron fluoride of following formula.
3BF
4 -+2Al
3++9H
2O→2AlF
6 3-+3H
3BO
3+9H
+
As the aluminum compound made an addition in former water, as long as dissolve the person that aluminum ion under pH condition when reacting, the one kind or two or more of such as Tai-Ace S 150, aluminum chloride, polymerize aluminum chloride (PAC), Tai-Ace S 150 etc. can be used.
As the addition of aluminum compound in former water, be configured to, Al/F (mol ratio) is counted for 1.2 ~ 2.5 relative to the F concentration in former water with the addition that Al converts, be preferably 1.5 ~ 2.5, count relative to the B concentration in former water the scope that Al/B (mol ratio) preferably becomes 2.0 ~ 4.5 with the addition that Al converts.If the addition of aluminum compound is less than above-mentioned lower limit, then fully cannot decompose boron fluoride, if more than the above-mentioned upper limit, also cannot obtain the effect matched with addition, result just increases the usage quantity of aluminum compound in rain, therefore not preferred.
The decomposition reaction of the boron fluoride undertaken by aluminum compound, is reacted in acid condition and carries out fast, and therefore, the pH of the first operation is set to 1 ~ 4, is preferably 1.5 ~ 2.5.Therefore, in former water, add acid (such as, sulfuric acid, hydrochloric acid, more preferably sulfuric acid) as required together with aluminum compound, pH is adjusted to pH 1 ~ 4, be preferably 1.5 ~ 2.5.
In the present invention, by adopting above-mentioned aluminum compound addition and pH condition, can liquid temperature 10 ~ 35 DEG C, the normal temperature being preferably 15 ~ 30 DEG C processes, and therefore, does not need to heat in the first operation.
In the reaction times of the first operation, the angle based on the resolving time of the boron fluoride guaranteed in former water is considered, is preferably set to 0.5 ~ 10 hours.
< second operation >
In the second operation, in the process water of the first operation, add calcium cpd, separate out Calcium Fluoride (Fluorspan) by the reaction of following formula and and then as described later, carry out the Adsorption of boron.
AlF
6 3-+3Ca
2++3OH
-→3CaF
2+Al(OH)
3
As calcium cpd, the one kind or two or more of such as slaked lime, calcium chloride, calcium carbonate etc. can be used.
As the addition of calcium cpd, the addition converted with Ca for Ca/Al (mol ratio) is for 2.5 ~ 4.0, preferably becomes the scope of 2.7 ~ 3.8 relative to the Al conversion gauge of the aluminum compound added in the first operation.
By being set in above-mentioned scope by the addition of calcium cpd, the Adsorption efficiency of boron can be improved.Further, by being set in above-mentioned scope by the addition of calcium cpd, the Al concentration (aluminum concentration dissolved in water residual in the process water of the second operation can be improved.In the present invention, be recited as " Al concentration "), the fluorine that can effectively utilize in the 4th operation described later is removed.
Al concentration is by the methods analyst of regulation in 58.4 (the ICP Emission Spectrophotometer methods) of JIS K0102.
In the present invention, in order to make this second operation carry out under the condition of pH 7 ~ 13, as required, in the process water of the first operation, add the acid of the alkali or sulfuric acid etc. of sodium hydroxide etc. together with calcium cpd, carry out pH adjustment.In addition, using slaked lime as calcium cpd, when becoming the pH of expectation by adding slaked lime, then not needing this pH to adjust.
Usually, the precipitation of Calcium Fluoride (Fluorspan), is preferably set to the condition of pH 4 ~ 10, but, especially, in the preferential situation removing fluorine, be then more preferably pH 9 ~ 11.This is because the key of aluminium and fluorine is easily cut off under alkaline conditions, therefore, the precipitation of Calcium Fluoride (Fluorspan) is facilitated.
In the preferential situation removing boron, be preferably pH 10 ~ 12.5.This is because under the high alkalinity condition of pH more than 10, separate out calcium aluminate (CaOAl by the reaction of following formula
2o
3), when this evolution reaction, adsorb simultaneously/remove boron.Therefore, remove the aspect of fluorine and boron at the same time, preferred pH condition is 10 ~ 12.
6Ca(OH)
2+Al
2(SO
4)
3→3CaO·Al
2O
3·3CaSO
4·6H
2O
The removal of the boron in this second operation is absorption reaction, and when liquid temperature is low, adsorptive capacity uprises, and therefore, in the present invention, the second operation is liquid temperature 10 ~ 35 DEG C, and the normal temperature being preferably 15 ~ 30 DEG C processes.Therefore, also there is no need to heat in this operation.
In the reaction times of the second operation, the aspect based on reaction times etc. of the fluorine guaranteed in former water and calcium cpd is considered, is preferably set to 0.5 ~ 4 hours.
< the 3rd operation >
In the 3rd operation, the insoluble compound separated out in the second operation (comprising the mud of Calcium Fluoride (Fluorspan) and calcium aluminate) is carried out to solid-liquid separation and obtained Separation of Water.In order to improve solid-liquid separation performance, also can, between the second operation and the 3rd operation, carry out adding the operation that polymer coagulant carries out aggegation.
As polymer coagulant, can be applicable to the polymer coagulant used in drainage sunk well, the one kind or two or more of the nonionic polymer coagulant of the negatively charged ion system polymer coagulant of the multipolymer of polyacrylamide partial hydrolystate, sodium polyacrylate, acrylamide and vinylformic acid (salt) etc. or polyacrylamide etc. can be used.The addition of polymer coagulant, though different from the water quality of the former water of handling object or polymer coagulant used, is generally about 0.1 ~ 20mg/L.
Solid-liquid separation in 3rd operation, except using the solid-liquid separation tank of settling bath etc., also can use membrane separation unit, filtration unit, water extracter etc.
In the 3rd operation, although also different from the addition etc. of the water quality of the former water of handling object, aluminum compound and calcium cpd, usually can obtain F concentration about 3 ~ 15mg/L, B concentration about 1 ~ 10mg/L, BF
4the process water of below concentration 0.1mg/L.As described later, the Al concentration of this process water is generally about 30 ~ 70mg/L.
< the 4th operation >
In the present invention, also can using the solid-liquid separation water of above-mentioned 3rd operation as process water, but also can carry out further processing this solid-liquid separation water and removing the 4th operation of fluorine.Also namely, in the second operation, fluorine is insoluble as Calcium Fluoride (Fluorspan), due to the relation of the solubleness of Calcium Fluoride (Fluorspan), although seldom still still remain fluorine in the solid-liquid separation water of the 3rd operation.Therefore, also can carry out the 4th operation, remove residual fluorine further.
In the 4th operation, according to need according to aluminum compound with acid, aluminum compound addition and add alkali and be adjusted to pH6 ~ 7, separate out aluminium hydroxide thus.Make the fluorine in water insoluble by co-precipitation when separating out this aluminium hydroxide and remove.
In the present invention, by after the first operation adds aluminum compound, add calcium cpd in the second operation with aforementioned Ca/Al (mol ratio), thus, residual about the 30 ~ 70mg/L of aluminium in the solid-liquid separation water of the 3rd operation gained can be made.Therefore, aluminum amount necessary in the 4th operation can be supplied by this residual aluminum amount, in the 4th operation, by means of only add acid with about 5 ~ 30 minutes, react under the stirring of normal temperature (10 ~ 35 DEG C), can fluorine be removed.But, according to needing, in the 4th operation, also can aluminum compound be added.As this aluminum compound, aluminum compound used in the first operation can be used as and illustrative aluminum compound.
< the 5th operation >
In the 5th operation, solid-liquid separation is carried out to the insoluble compound separated out in the 4th operation (comprising the co-precipitation mud of the fluorine of aluminium hydroxide), obtain process water.Herein, in order to improve solid-liquid separation performance, also can carry out adding polymer coagulant to carry out the operation of aggegation between the 4th operation and the 5th operation.
In this situation, as polymer coagulant, the one kind or two or more of the negatively charged ion system polymer coagulant of polyacrylamide partial hydrolystate, sodium polyacrylate, polyvinyl amidine etc. can be used.The addition of polymer coagulant, though different from the water quality of the former water of handling object or polymer coagulant used, is generally about 0.1 ~ 5mg/L.
Solid-liquid separation in 5th operation, except using the solid-liquid separation tank of settling bath etc., also can use membrane separation unit, filtration unit etc.
In 5th operation, although also different from the addition etc. of the water quality of the former water of handling object, aluminum compound and calcium cpd, usually can obtain below F concentration 1.1mg/L, B below concentration 3.5mg/L, BF
4the process water of the high water quality of below concentration 0.1mg/L, below Al concentration 1mg/L.
Other operation > of <
In the present invention, also following operation can be added further.
Former water before with the first operation process, also by carrying out solid-liquid separation to adding the insoluble compound that calcium cpd separates out in the conditioned response of pH 4 ~ 10, removes a part of fluorine in former water in advance.By additional pretreatment procedure described above, fluorine in former water is removed roughly in advance, the F concentration of the water of inflow first operation can be reduced and the addition of the aluminum compound in the first operation can be reduced.
A part of carrying out the separated sludge of solid-liquid separation gained in the 3rd operation also can be sent back to and be added into the second operation.In this situation, also the calcium cpd added in the second operation mixing can be made an addition to this mud of sending back to and upgrading is carried out to mud, this upgrading mud is made an addition in the second operation.Send back to by carrying out mud described above, and newly separate out Calcium Fluoride (Fluorspan) in this Sludge Surface.Thus, improve the dehydration property of the solid-liquid separation mud of the 3rd operation gained, the water ratio of the dewatered cake of this mud being carried out to processed gained can be reduced.
Embodiment
Below, enumerate the experimental example representing the present invention's example and comparative example, the present invention is further illustrated.
In addition, below, as former water, use the former water of following water quality.
< raw water quality >
F concentration: 600mg/L (31.6 mmoles/L)
B concentration: 200mg-B/L (18.5 mmoles/L)
BF
4concentration: 250mg/L
Tai-Ace S 150 (8 % by weight, Al are used as aluminum compound
2o
3), use slaked lime (Ca (OH) as calcium cpd
2).Use the negatively charged ion system polymer coagulant " Network リ フ ァ ー system (registered trademark) PA823 " of Kurita Water Industries Ltd as polymer coagulant, its addition is set to 10mg/L.
[experimental example 1 ~ 4]
In former water, add Tai-Ace S 150 with the amount shown in following table 1 respectively, after being adjusted to pH 2 with sulfuric acid, react 4 hours.Then, add slaked lime, react 1 hour under the condition of pH 10.Slaked lime in the scope that the Ca/Al (mol ratio) calculated with Tai-Ace S 150 addition and slaked lime addition is 1 ~ 6, carries out various change add.
When making pH not become 10 because adding slaked lime, then the suitable acid (sulfuric acid) of interpolation or alkali (sodium hydroxide) are adjusted to pH 10.
Table 1
Then, add polymer coagulant and carry out aggegation process in 5 minutes, solid-liquid separation is carried out to aggegation process water.
Above-mentioned a succession of process is all carried out liquid temperature 20 DEG C.
Analyze the water quality of the process water (solid-liquid separation water) obtained, the relation of investigation and Ca/Al mol ratio, result is shown in Fig. 2 ~ 7.
As shown in Figure 2, if Al/F (mol ratio) is more than 1.5, then boron fluoride (the BF in former water
4) can decompose completely.
From Fig. 3,4, if Al/F (mol ratio) is more than 1.5, Ca/Al (mol ratio) is the scope of 2.5 ~ 4.0, then the clearance of fluorine and boron is high, especially can improve the removal efficiency of boron.
As shown in Figure 5, if Ca/Al (mol ratio) is the scope of 2.5 ~ 4.0, then the residual Al quantitative change processed in water is many, and then can effectively utilize the process in fluorine.
As shown in Figure 6, if Ca/Al (mol ratio) is the scope of 2.5 ~ 4.0, then process the SO in water
4concentration (SO
4 2-ionic concn) low, can the CaSO of alleviator back segment (process water pipe arrangement etc.)
4fouling is perplexed.
As shown in Figure 7, if Ca/Al (mol ratio) is the scope of 2.5 ~ 4.0, then process the Ca concentration (Ca in water
2+ionic concn) low, can the CaSO of alleviator back segment (process water pipe arrangement etc.)
4fouling is perplexed.
[experimental example 5,6]
In former water, add the Tai-Ace S 150 of specified amount, after being adjusted to pH 2 with sulfuric acid, react 4 hours.Then, add slaked lime, react 1 hour under the condition of pH 10.Slaked lime is that the mode becoming 2.5 at the Ca/Al (mol ratio) calculated with Tai-Ace S 150 addition and slaked lime addition is added.
When making pH not become 10 because adding slaked lime, then the suitable acid (sulfuric acid) of interpolation or alkali (sodium hydroxide) are adjusted to pH 10.
Then, add polymer coagulant and carry out aggegation process in 5 minutes, solid-liquid separation is carried out to aggegation process water.
Tai-Ace S 150 is that the addition converted in Al carries out various change for the boron in former water with Al/B (mol ratio) and adds.Funing tablet in former water is about 1.7 times of boron concentration, and therefore, if Al/B (mol ratio) is the scope of about 2.0 ~ 4.0, then Al/F (mol ratio) becomes 1.2 ~ 2.5.
Above-mentioned a succession of process, experimental example 5 carries out liquid temperature 20 DEG C, and experimental example 6 carries out liquid temperature 60 DEG C.
Analyze the B concentration of the process water (solid-liquid separation water) obtained, be shown in Fig. 8 with the relation of Al/B mol ratio.
As shown in Figure 8, be the situation of 60 DEG C compared to treatment temp, treatment temp is the situation of 20 DEG C, and boron clearance is especially high.If Al/B (mol ratio) is the scope of 2.0 ~ 4.5, then boron removal effect is excellent.
[experimental example 7]
In experimental example 3, solid-liquid separation water (F concentration=the 9mg/L obtained when adding Tai-Ace S 150 in the mode of Al/F (mol ratio)=1.5, Al/B (mol ratio)=2.5, Ca/Al (mol ratio)=3.3, B concentration=3.5mg/L, BF
4concentration <0.1mg/L, Al concentration=61mg/L) in, add sulfuric acid and make into pH 6.5, stir 15 minutes, insoluble compound is separated out.
Then, add polymer coagulant and carry out aggegation process in 5 minutes, solid-liquid separation is carried out to aggegation process water.
The process water (solid-liquid separation water) obtained is F concentration=1.1mg/L, B concentration=3.5mg/L, BF
4the process water of the high water quality of concentration <0.1mg/L, Al concentration <1mg/L.
Although employ specific scheme to invention has been detailed description, those skilled in the art can understand, are not departing under the intent of the present invention and scope and can carry out various change.
The application be based on February 28th, 2013 propose Japanese patent application laid is willing to No. 2013-039193 and propose, its full text be applied at by way of reference in the application.
Claims (8)
1. a treatment process for the water containing boron fluoride, it has: the first operation, and this first operation adds aluminum compound in containing the water of boron fluoride, decomposes under the condition of pH 1 ~ 4 to boron fluoride; Second operation, this second operation adds calcium cpd in the process water of this first operation, reacts under the condition of pH7 ~ 13, generates insoluble compound thus; And the 3rd operation, the 3rd operation carries out solid-liquid separation to this insoluble compound,
It is characterized in that,
The addition of the aluminum compound of aforementioned first operation, counts Al/F=1.2 ~ 2.5 with the Funing tablet that Al scaled value contains the water of boron fluoride relative to this, and this ratio is mol ratio,
The addition of the calcium cpd of aforementioned second operation, counts Ca/Al=2.5 ~ 4.0 with Ca scaled value relative to the Al scaled value of this aluminum compound, and this ratio is mol ratio,
The treatment temp of aforementioned first operation and the second operation is 10 ~ 35 DEG C.
2. the treatment process of the water containing boron fluoride as claimed in claim 1, wherein,
It has:
4th operation, the 4th operation processes the Separation of Water obtained in aforementioned 3rd operation under the condition of pH 6 ~ 7, thus, generates insoluble compound; And
5th operation, the 5th operation carries out solid-liquid separation to this insoluble compound.
3. the treatment process of the water containing boron fluoride as claimed in claim 1 or 2, wherein,
The addition of the aluminum compound of aforementioned first operation, Al/F=1.2 ~ 2.5 are counted relative to the Funing tablet of the aforementioned water containing boron fluoride with Al scaled value, and, this ratio is mol ratio, and count Al/B=2.0 ~ 4.5 with Al scaled value relative to the boron concentration of the aforementioned water containing boron fluoride, further, this ratio is mol ratio.
4. the treatment process of the water as claimed any one in claims 1 to 3 containing boron fluoride, wherein,
The aluminum concentration of the Separation of Water obtained in aforementioned 3rd operation is 30 ~ 70mg/L.
5. a treatment unit for the water containing boron fluoride, it has: the first reactive tank, and this first reactive tank adds aluminum compound in containing the water of boron fluoride, decomposes under the condition of pH 1 ~ 4 to boron fluoride; Second reactive tank, this second reactive tank adds calcium cpd in the process water of this first reactive tank, reacts under the condition of pH 7 ~ 13, thus, generates insoluble compound; And first solid-liquid separation device, this first solid-liquid separation device carries out solid-liquid separation to this insoluble compound,
It is characterized in that,
The addition of the aluminum compound of aforementioned first reactive tank, counts Al/F=1.2 ~ 2.5 with the Funing tablet that Al scaled value contains the water of boron fluoride relative to this, and this ratio is mol ratio,
The addition of the calcium cpd of aforementioned second reactive tank, counts Ca/Al=2.5 ~ 4.0 with Ca scaled value relative to the Al scaled value of this aluminum compound, and this ratio is mol ratio,
The treatment temp of aforementioned first reactive tank and the second reactive tank is 10 ~ 35 DEG C.
6. the treatment unit of the water containing boron fluoride as claimed in claim 5, wherein,
It has:
3rd reactive tank, the 3rd reactive tank processes the Separation of Water obtained in aforementioned solid-liquid separation device under the condition of pH6 ~ 7, generates insoluble compound; And
Second solid-liquid separation device, this second solid-liquid separation device carries out solid-liquid separation to this insoluble compound.
7. the treatment process of the water containing boron fluoride as described in claim 5 or 6, wherein,
The addition of the aluminum compound of aforementioned first reactive tank, Al/F=1.2 ~ 2.5 are counted relative to the Funing tablet of the aforementioned water containing boron fluoride with Al scaled value, and, this ratio is mol ratio, and count Al/B=2.0 ~ 4.5 with Al scaled value relative to the boron concentration of the aforementioned water containing boron fluoride, further, this ratio is mol ratio.
8. the treatment unit of the water containing boron fluoride according to any one of claim 5 to 7, wherein,
The aluminum concentration of the Separation of Water obtained in aforementioned first solid-liquid separation device is 30 ~ 70mg/L.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-039193 | 2013-02-28 | ||
| JP2013039193 | 2013-02-28 | ||
| PCT/JP2014/054155 WO2014132887A1 (en) | 2013-02-28 | 2014-02-21 | Method and apparatus for treating borofluoride-containing water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105026320A true CN105026320A (en) | 2015-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480011099.3A Pending CN105026320A (en) | 2013-02-28 | 2014-02-21 | Method and apparatus for treating borofluoride-containing water |
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| Country | Link |
|---|---|
| JP (1) | JP6269651B2 (en) |
| KR (1) | KR101990179B1 (en) |
| CN (1) | CN105026320A (en) |
| SG (2) | SG11201506360QA (en) |
| TW (1) | TWI588096B (en) |
| WO (1) | WO2014132887A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590013A (en) * | 2019-09-15 | 2019-12-20 | 北京航天国环技术有限公司 | Method and system for treating fluorine-containing waste sulfuric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6396827B2 (en) * | 2015-03-06 | 2018-09-26 | 株式会社Ｎｓｃ | Method and system for treating wastewater containing borofluoride |
| JP6485290B2 (en) * | 2015-08-31 | 2019-03-20 | 住友金属鉱山株式会社 | Fluorine separation method from fluorine-containing wastewater |
| JP7089345B2 (en) * | 2017-05-25 | 2022-06-22 | 株式会社 イージーエス | Water treatment method and water treatment equipment |
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- 2014-02-21 SG SG10201706798UA patent/SG10201706798UA/en unknown
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| Publication number | Publication date |
|---|---|
| JP6269651B2 (en) | 2018-01-31 |
| KR101990179B1 (en) | 2019-09-30 |
| KR20150120971A (en) | 2015-10-28 |
| SG11201506360QA (en) | 2015-09-29 |
| TW201500297A (en) | 2015-01-01 |
| TWI588096B (en) | 2017-06-21 |
| JPWO2014132887A1 (en) | 2017-02-02 |
| SG10201706798UA (en) | 2017-09-28 |
| WO2014132887A1 (en) | 2014-09-04 |
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