CN103402917A - Method and device for recovering boric acid - Google Patents

Method and device for recovering boric acid Download PDF

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Publication number
CN103402917A
CN103402917A CN2012800100210A CN201280010021A CN103402917A CN 103402917 A CN103402917 A CN 103402917A CN 2012800100210 A CN2012800100210 A CN 2012800100210A CN 201280010021 A CN201280010021 A CN 201280010021A CN 103402917 A CN103402917 A CN 103402917A
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Prior art keywords
boric acid
processed liquid
crystallization
regulator
alkali metal
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Inventor
田中俊幸
上原雅夫
菊地真太郎
山田兼士
佐佐木道人
末续克也
赤木亮介
向田民人
藤原义浩
土肥诚子
西村靖史
西山蓝
岸靖也
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Sasakura Engineering Co Ltd
AGC Inc
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Asahi Glass Co Ltd
Sasakura Engineering Co Ltd
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Publication of CN103402917A publication Critical patent/CN103402917A/en
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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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1045—Oxyacids
    • C01B35/1054—Orthoboric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1045—Oxyacids
    • C01B35/1054—Orthoboric acid
    • C01B35/109—Purification; Separation; Concentration
    • 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
    • C02F1/22—Treatment of water, waste water, or sewage by freezing
    • 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
    • C02F2101/108—Boron compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The present invention relates to a method for recovering boric acid from a liquid to be treated containing either waste water or solid waste comprising boron compounds and alkali metal compounds, wherein the liquid to be treated is concentrated after an acid is added to the liquid to be treated and the pH is adjusted to less than 4, or an acid is added to the liquid to be treated and the pH is adjusted to less than 4 after the liquid to be treated is concentrated, the concentrated and pH-adjusted liquid to be treated not containing insoluble materials is cooled to form an aqueous solution in which boric acid crystals are precipitated, the boric acid crystals are separated from the aqueous solution in which boric acid crystals are precipitated, 50-90 mass% of the filtrate after separating the boric acid crystals is added to the liquid to be treated before concentration and pH-adjustment, a liquid to be treated for recrystallization which is formed by adding a boric acid aqueous solution or water to the separated boric acid crystals is heated to dissolve the boric acid crystals, the heated liquid to be treated for recrystallization in which the boric acid crystals are dissolved is cooled to form an aqueous solution in which boric acid crystals are reprecipitated, the boric acid crystals are separated from the aqueous solution in which boric acid crystals are reprecipitated, and at least a part of the filtrate after separating the reprecipitated boric acid crystals is added to the liquid to be treated before concentration and pH-adjustment.

Description

The recovery method of boric acid and retrieving arrangement
Technical field
The present invention relates to, recovery method boric acid boric acid from reclaiming the waste water that contains organic boron compound and alkali metal compound and solid waste and retrieving arrangement.
Background technology
Contain in the manufacture of glass of boron component, the waste gas of discharging from glass-melting furnace, with higher concentration, contain the various materials such as boric acid and sulphur.
Therefore, this waste gas can't be directly released in atmosphere, for example, with alkali such as sodium hydroxide, processes, and after removing harmful material, discharges into the atmosphere.
The waste water of association and solid waste are processed as industrial waste mostly in such waste-gas cleaning.
But, in these waste water and solid waste, contain in a large number the useful materials such as organic boron compound and alkali metal compound.Particularly the price of boric acid is high, if can reclaim and recycle its waste water after processing waste gas etc., can reduce the manufacturing cost of the glass that contains boron component.In addition, from the viewpoint of environmental problem, also preferred from waste water and solid waste, reclaiming as far as possible useful material.
Therefore, be not limited to contain the waste water of association in the off gas treatment in the manufacture of glass of boron component, proposed various from the waste water that comprises boron compound and solid waste, reclaiming the method for boric acid etc.
For example, in patent documentation 1, put down in writing following method: the waste gas that produces in the time of will be to glass melting purifies and the waste water that obtains neutralizes, and is then dry, as the raw material of glass, uses.
Particularly, make with water, to contact and purify spray tower from the waste gas that glass-melting furnace is discharged, or, after purifying, the exhaust gas utilization wet type electric vacuum cleaner after further water being purified discharges into the atmosphere.At this moment, will with white lime, neutralize from the waste water of spray-drier or the discharge of wet type electric vacuum cleaner, then dry, the solids component that obtains is recycled in frit.
In addition, in patent documentation 2, put down in writing and by the waste gas that contains boric acid etc. to from discharges such as glass-melting furnaces, undertaken coolingly, together with the purification of waste gas, reclaimed boric acid.
Particularly, by water spray formula cooling way and air mixed formula cooling way and the method such as use waste gas is cooled to below 70 ℃, thus, gaseous state boric acid in waste gas is separated out with solid form, then, utilize the dry type electric vacuum cleaner to reclaim boric acid, and waste gas is purified.
In addition, in patent documentation 3, put down in writing the waste water of the nickel plating bath from becoming waste liquid or aluminium surface treatment liquid, the boracics such as waste water of discharging glass manufacture is processed and the method that reclaims boric acid the ion exchange resin of boron arranged from absorption.
In the method, sulfuric acid is passed through from absorption has the ion exchange resin of boron, obtain the boron elutriant.After interpolation sodium hydroxide neutralized in this boron elutriant, heating was concentrated, thus, sodium sulfate is separated out, and separate.After residual mother liquor is cooled to 35～40 ℃, adds sulfuric acid and by pH regulator to 4～6, boric acid is separated out, utilize separating centrifuge etc. to separate boric acid, reclaim thus boric acid.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-238236 communique
Patent documentation 2: TOHKEMY 2003-305331 communique
Patent documentation 3: TOHKEMY 2002-29732 communique
Summary of the invention
Invent problem to be solved
By utilizing these methods, can be from the waste water that contains organic boron compound etc. and solid waste etc., reclaiming boric acid and recycle.
At this, the waste gas from discharges such as glass-melting furnaces, not only contain the composition that melts in stove, but also contain the combustion exhaust composition of the fuel that uses to some extent.
Therefore, in the method for patent documentation 1 record, using heavy oil as the situation of the fuel of glass-melting furnace etc. in the situation that in waste gas, contain sulphur compound, the sulphur compounds such as vitriol also drop in glass-melting furnace as the frit of recirculation.Like this, while in frit, containing the sulphur compound such as sulfuric acid, from raw material bring into beyond the sulphur composition be concentrated, produce the problems such as quality reduction of glass.
Therefore, in the method, only can process the waste water that uses in fact association in the not purification of the waste gas of the fuel of sulfur-bearing etc.
Similarly as the method for record in patent documentation 2, even in the method for boric acid being separated out with solid form/being reclaimed by cooling exhaust, in the situation that in waste gas, contain sulphur, when waste gas is cooled to the temperature that boric acid separates out with solid form, the temperature of waste gas reaches below acid dew point, and sulfuric acid also can be separated out.If sulfuric acid is separated out, the corrosion of generating unit etc., in addition, obtain also containing the result of sulfuric acid in the boric acid that reclaims.
Therefore, in the method, also only can process using in fact the not waste gas of the fuel of sulfur-bearing.
With respect to this, if the method for record in patent documentation 3, as the situation of using heavy oil as the fuel of glass-melting furnace, can process and recovery boric acid the waste water of association etc. from the waste gas to containing the sulphur composition.
But, in the method, due to the processing of the waste water that has carried out utilizing ion exchange resin, therefore need to be from ion exchange resin, making the step of boron wash-out, in the situation that waste strength is high, there is the very large problem of the required Di of wastewater treatment.In addition, in the situation that the boron elutriant contains boric acid many kinds of substance in addition, can't reclaim the sufficiently high boric acid of purity.
The object of the invention is to solve the problem of above-mentioned prior art, recovery method and the retrieving arrangement of boric acid are provided, it can be processed the waste gas that contains the sulphur composition is processed and waste water of association etc. contains the liquid or solid thing of sulphur composition, in addition, can also be from the liquid of high density, contain the liquid or solid thing of the various materials beyond organic boron compound and reclaim highly purified boric acid.
For the method for dealing with problems
To achieve these goals, the invention provides a kind of recovery method (1) of boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, wherein,
To adding acid in described processed liquid by pH regulator to after 4, concentrating, or after described processed liquid is concentrated, add acid and by pH regulator to lower than 4,
The described processed liquid that has carried out concentrated and pH regulator and do not contained insolubles is carried out cooling, obtains separating out the aqueous solution that the boric acid crystallization is arranged,
From the described aqueous solution of separating out the boric acid crystallization, isolating this boric acid crystallization,
50～90 quality % that isolate the filtrate after this boric acid crystallization are added in the processed liquid before described concentrated and pH regulator,
The recrystallization that adds boric acid aqueous solution or water in the described isolated boric acid crystallization of subtend and obtain heats with processed liquid and makes the boric acid dissolving crystallized, this is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling with processed liquid, obtain separating out again the aqueous solution that the boric acid crystallization is arranged, from the described aqueous solution of separating out again the boric acid crystallization, isolating this boric acid crystallization
At least a portion of isolating the filtrate after this boric acid crystallization of separating out is again added in the processed liquid before described concentrated and pH regulator.
In addition, the invention provides a kind of recovery method (2) of boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, wherein,
To adding acid in described processed liquid by pH regulator to after 4, concentrating, an alkali metal salt is separated out, by an alkali metal salt from the described processed liquid of separating out an alkali metal salt, removing,
Perhaps described processed liquid is concentrated and an alkali metal salt is separated out, by an alkali metal salt after the described processed liquid of separating out an alkali metal salt, removing, add acid by pH regulator to lower than 4,
To described, carried out concentrated and pH regulator and removed in the processed liquid of described an alkali metal salt, adding water and diluting,
Processed liquid after this dilution is carried out cooling, obtains separating out the aqueous solution that the boric acid crystallization is arranged,
From the described aqueous solution of separating out the boric acid crystallization, isolating this boric acid crystallization,
By in the processed liquid of isolating before filtrate after this boric acid crystallization is added described concentrated and pH regulator to,
The recrystallization that adds boric acid aqueous solution or water in the described isolated boric acid crystallization of subtend and obtain heats with processed liquid and makes the boric acid dissolving crystallized, this is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling with processed liquid, obtain separating out again the aqueous solution that the boric acid crystallization is arranged, from the described aqueous solution of separating out again the boric acid crystallization, isolating this boric acid crystallization
At least a portion of isolating the filtrate after this boric acid crystallization of separating out is again added in the processed liquid before described concentrated and pH regulator.
In addition, the invention provides a kind of retrieving arrangement (1) of boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, and described retrieving arrangement possesses:
The concentrating unit that described processed liquid is concentrated;
Add acid by the pH regulator of processed liquid to the pH regulator device lower than 4;
The described processed liquid that has carried out pH regulator and do not contained insolubles is carried out cooling and obtains separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out;
50～90 quality % of the filtrate after this boric acid crystallization of Separation and Recovery are delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator;
The recrystallization that adds boric acid aqueous solution or water in the boric acid crystallization of the described Separation and Recovery of subtend and obtain heats with processed liquid and makes the heating for dissolving device of boric acid dissolving crystallized;
This is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged again with processed liquid;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out again; With
At least a portion of filtrate after the boric acid crystallization that this is separated out again by Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator.
In addition, the invention provides a kind of retrieving arrangement (2) of boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, and described retrieving arrangement possesses:
Described processed liquid is concentrated and concentrating unit that an alkali metal salt is separated out;
By the remove device of an alkali metal salt from removing processed liquid of separating out;
Add acid by the pH regulator of processed liquid to the pH regulator device lower than 4;
To utilizing, describedly remove processed liquid that device removed an alkali metal salt and utilized described pH regulator device to carry out pH regulator and carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out;
Filtrate after this boric acid crystallization of Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator;
The recrystallization that adds boric acid aqueous solution or water in the boric acid crystallization of the described Separation and Recovery of subtend and obtain heats with processed liquid and makes the heating for dissolving device of boric acid dissolving crystallized;
This is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged again with processed liquid;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out again; With
At least a portion of filtrate after the boric acid crystallization that this is separated out again by Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator.
The invention effect
According to the present invention, can be by easy operation from the waste water of association and solid waste etc. contain in the waste water of organic boron compound and alkali metal compound and solid waste and reclaim highly purified boric acid by purifying from the waste gas that contains boric acid of discharging the manufacturing process of pyrex.
The accompanying drawing explanation
Fig. 1 is the schema that describes for the example to boron recovery method of the present invention (the first mode).
Fig. 2 is the schema that describes for the example to boron recovery method of the present invention (the second mode).
Fig. 3 is the concept map that the example for the processed liquid to processing by boron recovery method of the present invention describes.
Embodiment
Below, with reference to the recovery method of accompanying drawing to boric acid of the present invention, at length describe.
The schema of one example of the recovery method (the first mode) of boric acid of the present invention has been shown in Fig. 1, the schema of an example of the recovery method (the second mode) of boric acid of the present invention has been shown in Fig. 2.
As shown in Figure 1 and Figure 2, the recovery method of boric acid of the present invention (below, also referred to as recovery method) be to utilize logical overcooled crystallization (crystallization/crystallization) from processed liquid, reclaiming the method for boric acid.Below, in the situation that special instruction is not the first mode or the second mode, as the common content of the first mode and the second mode, describe.
Waste water in the present invention and solid waste all contain organic boron compound and alkali metal compound.In the present invention, boron compound and alkali metal compound are distinguished, in case of no particular description, the compound that Sodium Tetraborate etc. is contained to boron atom and alkali metal atom is considered as boron compound.Therefore, in case of no particular description, alkali metal compound is the alkali metal compound that does not contain the boron atom.In addition, boron compound is not limited to contain basic metal, also can contain various Constitution Elements.Alkali metal compound similarly also can contain the various Constitution Elements beyond boron.
Waste water in the present invention comprises the water that contains organic boron compound and alkali metal compound, and the solid waste in the present invention comprises the solid (powder etc.) that contains organic boron compound and alkali metal compound.These waste water and solid waste can contain the compound beyond organic boron compound and alkali metal compound.
These waste water and solid waste are to discharge from the industrial processes of processing boron compound and alkali metal compound, be particularly preferably waste water or the solid waste of from the off gas treatment operation, discharging, in described off gas treatment operation, make to contact with the alkali metal compound aqueous solution of alkalescence from the waste gas of discharging the manufacturing process of pyrex described later.
Processed liquid in the present invention is at least a processed liquid that comprises in above-mentioned waste water and solid waste, as shown in Figure 1 or 2, in the situation of above-mentioned waste water, can be waste water itself, also can be the water diluent that adds water to obtain in waste water.In the situation of above-mentioned solid waste, be in solid waste, to add water and the aqueous solution that obtains.In addition, as shown in Figure 1 or 2, as the water that adds, can use above-mentioned waste water in solid waste, in addition, also the mixture water of solid waste and waste water can be diluted, as the processed liquid in the present invention.
In addition, also can use boric acid crystallization described later and isolate this crystallization after the aqueous solution that contains boric acid (filtrate etc.) as at least a portion of dilution water.
In addition, these processed liquid can be also mix wherein more than 2 kinds and the aqueous solution that obtains.
As the waste water in the present invention and solid waste, as an example, can illustration: waste water and the solid waste of association when in the manufacture of FPD (flat-panel monitor, Flat Panel Display) with the pyrex that uses in glass, used for solar batteries glass etc., the waste gas from discharges such as glass-melting furnace, melten glass forming furnaces being purified.
In the manufacture of pyrex, because boron oxide has volatility, therefore, boron oxide is from volatilizing in the frit of the high temperature melting process, melten glass, be blended in the Exhaust Gas such as combustion exhaust, as the waste gas that contains boron oxide from the manufacturing process of pyrex, discharging.Therefore, to need to purify this waste gas, in order effectively purifying, in most cases to use the aqueous solution of basic cpd or powder to purify.As basic cpd, use alkali metal compound, particularly sodium compound.As concrete alkali metal compound, can enumerate: the water miscible alkaline sodium compounds such as sodium hydroxide, sodium bicarbonate, sodium carbonate.
In Fig. 3, conceptually show an example of the purification process of this waste gas.
In purification process shown in Figure 3, at first, will cooling tower, utilize water or aqueous sodium hydroxide solution to be cooled to approximately 200 ℃ from the waste gas that the glass-melting furnace for the manufacture of pyrex is discharged.At this moment, as required, as the reagent of removing the evil, add sodium hydroxide, sodium bicarbonate (only expressing aqueous sodium hydroxide solution in Fig. 3).
Then, in completing cooling waste gas, add as required sodium bicarbonate powder etc., utilize deep bed filter to purify.In addition, the waste gas after purifying with deep bed filter is processed with sodium hydroxide etc. in Venturi scrubber, purifies, and as the waste gas that completes purification, discharges into the atmosphere.In addition, the alkali metal compounds such as sodium hydroxide that add in the purification process of this waste gas can add with the form of solid, also can add with the form of the aqueous solution, or can add solid and the aqueous solution.
In this purification process, the refuse of the solid of being caught by deep bed filter, from comprising various boron compounds and the alkali metal compounds such as boric acid, boron oxide, Sodium Tetraborate, sodium hydroxide, sodium-chlor, Sodium Fluoride, sodium sulfate, SODIUMNITRATE the waste liquid that Venturi scrubber is discharged.
Therefore, in recovery method of the present invention, can be using the solid waste disposal of solid waste in the present invention of being caught by deep bed filter in this purification process, in addition, the waste liquid that can discharge from Venturi scrubber is as the liquid waste disposal the present invention.In addition, below, also these waste liquids, solid waste are called to waste water, solid waste.
That is, in the recovery method of boric acid of the present invention, in the situation that the by product that the purification process of the waste gas by shown in Figure 3 is generated processes, the waste water that will discharge from Venturi scrubber is as the waste water that contains organic boron compound and alkali metal compound.In addition, the solid waste that will be caught by deep bed filter is as the solid waste that contains organic boron compound and alkali metal compound.Therefore, the processed liquid in the invention described above uses these waste water, solid waste and obtains.
In addition, in the purification process of waste gas shown in Figure 3, from in the situation of also discharging the solid waste contain organic boron compound and alkali metal compound or waste liquid cooling tower, the waste water that they are also discharged with the solid waste of being caught by deep bed filter or from Venturi scrubber is same, can be used as the waste water and the solid waste disposal that contain organic boron compound and alkali metal compound.
In addition, in recovery method of the present invention, as the waste water that contains organic boron compound and alkali metal compound and solid waste, be not limited to waste water and the solid waste of association in the purification of the waste gas in above-mentioned pyrex manufacturing process, can illustration contain various waste water and the solid waste of organic boron compound and alkali metal compound.
Solid waste in the present invention and waste water all, except containing organic boron compound and alkali metal compound, can also contain sulphur compound, chlorine compound, fluorine cpd etc.These compositions beyond boron compound and alkali metal compound, as shown in above-mentioned definition, are any one compounds as Constitution Elements that does not contain in boron and basic metal.Therefore, for example, above-mentioned sodium-chlor, Sodium Fluoride, sodium sulfate, SODIUMNITRATE etc. are the alkali metal compound in the present invention.Solid waste in the present invention and waste water all can contain sulphur compound, chlorine compound, fluorine cpd on a small quantity, but preferably do not contain in fact.
The boron compound that comprises in solid waste in the present invention and waste water preferably is mainly boric acid and Sodium Tetraborate.The alkali metal compound that comprises in solid waste in the present invention and waste water preferably is mainly sodium sulfate and sodium-chlor, in addition to these, can contain more a small amount of Sodium Fluoride, SODIUMNITRATE etc.
Than (mass ratio), so that boron amount (quality) is made as to 1 relative ratio, the preferred as alkali amount is 0.6～13 as the Constitution Elements of the compound that comprises in the solid waste in the present invention and waste water, sulfur content be 0～6 and chlorine dose be 0～6.In addition, sulphur, the chlorine in this Constitution Elements ratio is mainly the element in the alkali metal compounds such as sodium sulfate, sodium-chlor.
As the solid waste and the waste water that comprise the various compounds with such Constitution Elements ratio, take the waste water of association the purification of the waste gas of discharging from pyrex manufacturing process and solid waste as representative.The present invention can be from reclaiming highly purified boric acid such waste water and solid waste.
Concentration as each Constitution Elements that contains in the processed liquid at least a the present invention who comprises in above-mentioned waste water and solid waste, preferred boron concentration is 10～40g/L, na concn is 20～400g/L, and sulphur concentration is 0～200g/L, and cl concn is 0～200g/L.In addition, sulphur and the chlorine in this each Constitution Elements concentration is mainly the Constitution Elements in alkali metal compound.
Think in addition, the most generation of the compound in processed liquid ionization.Can think, in processed liquid, have such as borate ion, sodium ion, sulfate ion, chloride ion, fluoride ion, nitrate ion etc.
In addition, processed liquid does not preferably contain insoluble composition.But, so long as heating, obtain the stage of heating water solution, do not contain insoluble composition, also can contain the insoluble composition that dissolves by heating.As required, also can the processed liquid before heating, by filtration, wait and remove insoluble composition.
In recovery method of the present invention, as preferred mode, as shown in Figure 1, so processed liquid is heated, obtain heating water solution.This heating water solution need to not contain the heating water solution of insolubles.In the situation that also have insolubles as heating water solution, by filtration, wait and remove insoluble composition.
The Heating temperature of heating water solution is not particularly limited, and is preferably more than 50 ℃.The Heating temperature of heating water solution is during lower than 50 ℃, and the rate of recovery of boric acid is low, and in addition, the boric acid crystallization of separating out can not grown fully, therefore, the unfavorable condition of separation performance variation occurs.
The Heating temperature of heating water solution is preferably below 100 ℃, further preferred 70 ℃～80 ℃.
Thus, can improve the rate of recovery and the separation performance of boric acid crystallization.
In recovery method of the present invention, as mentioned above, the heating of this processed liquid is carried out as preferred mode, not necessarily operation.
Then, at heating water solution, (while not heating, be processed liquid.Below, by processed liquid and heating water solution also referred to as processed liquid) in add acid and by pH regulator to lower than 4.
In the present invention, by utilizing like this pH regulator device (pH regulator pond), the pH of processed liquid is regulated so that it (makes the pH of processed liquid lower than pH4 at pH under heating condition lower than 4 when not heating.Lower same), can reclaim the boric acid crystallization that purity is high.In addition, by before cooling crystallization, regulating pH, carry out cooling operation after can the alkali metal borate in making the aqueous solution changing into boric acid, thereby easily control particle shape and the particle diameter of boric acid crystallization.In addition, also can improve thus the purity of boric acid.
In addition, the pH that has carried out the processed liquid of pH regulator is 4 when above, in the high situation of the solid component concentration of processed liquid, can't reclaim the sufficiently high boric acid of purity.The boric acid that the amount of the impurity such as alkali metal borate is many is difficult to the raw materials such as the pyrex recycling as the alkali-free metal ingredient.In addition, even in the situation that resulting boric acid is further carried out to purifying with recrystallization method, also be difficult to obtain highly purified boric acid.
Carried out the pH of processed liquid of pH regulator lower than 4, be preferably below 3.5, more preferably less than 3.5, more preferably 1～3.
Thus, can reclaim more highly purified boric acid crystallization.
The acid of using in the pH regulator of processed liquid is not particularly limited, and can utilize the various mineral acids such as sulfuric acid, hydrochloric acid, nitric acid.As such acid, preferably sulfuric acid.
While the purification of the waste gas of discharging from the glass-melting furnace from pyrex, in the waste water of association etc., reclaiming boric acid, in most cases in this waste water etc., contain sulfate ion.Therefore, by in pH regulator, using sulfuric acid, can suppress to add unnecessary composition in processed liquid.
In addition, while in pH regulator, using hydrochloric acid, chloride ion likely becomes the reason of corrosion crystallization device, more preferably uses sulfuric acid.
In addition, in recovery method of the present invention, pH regulator is not limited to carry out after the processed liquid of heating.
That is, the pH regulator of processed liquid, as shown in phantom in Figure 1, can carry out before the heating of carrying out above-mentioned processed liquid, or also can described laterly carry out after concentrated carrying out.
The processed liquid that has carried out pH regulator preferably frontly concentrates with concentrating unit cooling, the processed liquid after being concentrated.By concentrating, can improve the rate of recovery of boric acid.
As concentrating unit, can use such as the surface to a plurality of heat-transfer pipes that make the heating fluid such as internal circulation steam in post-decompression condensing crystal tank, from nozzle and scatter processed liquid and make the known evaporation concentration device etc. of its heating evaporation.In this concentrating unit, the interior processed liquid of condensing crystal tank is utilized in the nozzle of recycle pump in being dispersed in a plurality of heat-transfer pipes and circulate.
The steam that produces in concentrating unit is condensed, and imports in condensate water pot, and the utilization of condensed water of this condensate water pot is in diluting water, the rinse water of each device or the rinse water of the crystallization in recovery process etc.
In recovery method of the present invention, according to the concentration of the boron in processed liquid and sodium (Na), apply or select any one in the first mode and the second mode described later.
In the situation that processed liquid is concentrated and pH regulator until do not separate out Na salt, preferred the first mode while being suitable for the boron concentration of crystallization.In the situation that when processed liquid is concentrated into to the boron concentration that is suitable for crystallization or processed liquid concentrate and pH regulator until separate out Na salt, preferably the second mode described later while being suitable for the boron concentration of crystallization.
Particularly, according to the mass ratio (Na/B) of the sodium (Na) that contains in the processed liquid before concentrated and pH regulator with boron (B), apply or select any one in the first mode and the second mode described later.
At processed liquid, contain Na 2SO 4In the situation of NaCl, mass ratio (Na/B) is 3.6 when following, preferred the first mode, and mass ratio (Na/B) is greater than 3.6 o'clock, preferred the second mode.
At processed liquid, contain NaCl and do not contain Na 2SO 4Situation under, mass ratio (Na/B) is 3.9 when following, preferred the first mode, mass ratio (Na/B) is greater than 3.9 o'clock, preferred the second mode.
At processed liquid, contain Na 2SO 4And do not contain in the situation of NaCl, mass ratio (Na/B) is 3.1 when following, preferred the first mode, and mass ratio (Na/B) is greater than 3.1 o'clock, preferred the second mode.
In the first mode, the concentrated degree of not separating out insolubles that proceeds to.In addition, at this said insolubles, be to concentrate with pH regulator, result to make to contain the crystalline solid that composition is separated out over saturation solubility.
In addition, in the second mode, concentrate an alkali metal salt that makes as insolubles and separate out.Making an alkali metal salt that contains in processed liquid is Na salt, for example sodium sulfate (Na 2SO 4), sodium-chlor (NaCl) etc. separates out as impurity.
In the first mode, the second mode, in order to improve the rate of recovery of boric acid, more than preferably by the concentrated solid component concentration that makes the processed liquid after pH regulator, reaching 15 quality %.In other words, preferably concentrate until more than the solid component concentration of processed liquid reaches 15 quality %.
On the other hand, deteriorated due to the difficulty of operation, the crystalline quality that caused by inadequate stirring, therefore, the solid component concentration of preferred processed liquid after concentrated is below 30 quality %.
Thickening temperature is not particularly limited, preferred 50 ℃～100 ℃.By the temperature by concentrated, be made as above-mentioned scope, can improve the rate of recovery of boric acid.When the temperature in the time of should be concentrated can be manufactured from processed liquid or the temperature of the processed liquid during pH regulator different.Usually with pH regulator after processed liquid phase with the temperature of degree or at than the high temperature of this temperature, concentrate.In addition, in concentrating under reduced pressure etc., also can be below the temperature for the processed liquid after pH regulator.Decompression is at preferred 10000Pa～80000Pa, more preferably carry out under 20000Pa～70000Pa.The temperature of the heating water solution after concentrated and the temperature of the processed liquid after above-mentioned heating are same, are preferably 50 ℃～100 ℃, particularly preferably 70 ℃～80 ℃.
But, in the first mode, all can be due to the concentrated insolubles that generates, therefore preferably while under any condition, concentrating.
In addition, in the second mode, while considering machine utilization, an alkali metal salt of separating out with respect to the liquid after concentrated preferably is no more than 10 quality %.
In the situation that the second mode, the tip speed of the turbine of the recycle pump by regulating concentrating unit, the particle diameter of the Na salt that control will be separated out, optionally remove Na salt in removing operation.
Particularly, make the tip speed of the turbine of recycle pump be 10～18m/ for example second, thus, the particle diameter that makes sodium-chlor, sodium sulfate as the Na salt that will separate out is about 100 μ m～300 μ m.At this moment, the particle diameter of not expecting the boric acid crystallization of separating out is 20～50 μ m, and the cyclonic separator after utilizing, can be from isolating the Na salt as impurity the concentrated solution that contains boric acid.
In addition, as equipment for separating liquid from solid, be not limited to cyclonic separator, also can use the separation of the large particle diameter crystallization that utilizes horizontal continuous centrifuge, the classification that utilizes fluidised bed or the settlement separate method of intermittent type etc.
In the second mode, at this, before enrichment process, carry out the pH regulator operation of adding acid in processed liquid, therefore, concentrate after in advance the alkali metal borate in processed liquid being changed into to boric acid and an alkali metal salt, thereby, can also comprise an alkali metal salt that produces by this conversion, in enrichment process, make the crystalline growth of an alkali metal salt, thus, in removing operation, can effectively remove an alkali metal salt.
In the situation that the second mode, utilize cyclonic separator to remove the processed liquid that obtains as the crystallization of the Na salt of impurity and import in the crystallization original fluid container as crystallization stoste.In the crystallization original fluid container, add diluting water and dilute processed liquid (being called the dilution operation).Like this, processed liquid is diluted with diluting water, therefore, after the crystallization operation in, can suppress the separating out of impurity beyond the boric acid crystallization.
In addition, as mentioned above, in recovery method of the present invention, be not limited to process according to as shown in Figure 1 or 2, order " (heating of processed liquid →) pH regulator → concentrated " (below, be called embodiment 1).
namely, other embodiments as the first mode and the second mode, after being heated to processed liquid more than 50 ℃ (wherein, at this also as mentioned above, heating is not necessarily) concentrate, complete concentrated processed liquid (in the situation of the second mode, concentrate after the Na salt crystallization that makes as impurity and utilize cyclonic separator to remove the crystallization of Na salt and the processed liquid that obtains) can obtain under the state more than 50 ℃, add the acid such as sulfuric acid to carry out pH regulator and by pH regulator to lower than 4, preferred below 3.5, more preferably less than 3.5, further after preferred 1～3 complete concentrated carrying out the processed liquid of pH regulator (below, be called embodiment 2).
In addition, at this moment, for above-mentioned same reason, also preferably complete concentrated carrying out the solid component concentration of processed liquid of pH regulator be more than 15 quality %, and be preferably below 30 quality %.
In embodiment 1, utilize concentrating unit to heat the strong processed liquid of acidity after interpolation sulphur acid for adjusting pH concentrated, therefore, concentrating unit need to use the material of uncorruptible costliness.On the other hand, in embodiment 2, after utilizing the enrichment process of concentrating unit, carry out the pH regulator operation, therefore, with embodiment 1, compare, concentrating unit, without using expensive material, can reduce costs.
In addition, other embodiments as the second mode, can be listed below embodiment.
(embodiment 3 of the second mode)
In the embodiment 2 of the second mode, the pH regulator operation is set removing between operation and crystallization operation, but in this situation, in processed liquid after removing operation (saturated solution that is equivalent to an alkali metal salt), add an alkali metal salt of following the conversion of alkali metal borate to produce by pH regulator, as a result, regenerate sometimes the crystallization of an alkali metal salt.In this situation, an alkali metal salt crystallization all is supplied in the crystallization original fluid container, and therefore, the amount that is blended into the diluting water of crystallization operation for the crystallization that suppresses an alkali metal salt increases sometimes.Thus, the boric acid concentration in dilution crystallization stoste also reduces, and the amount of the boric acid crystallization of separating out in the crystallization operation reduces sometimes.
In this situation, as the different mode of embodiment 1,2 from the second mode, at enrichment process and remove between operation pH regulator operation (not shown) also can be set.
In this embodiment, at least a portion of crystallization by removing an alkali metal salt that operation will regenerate by pH regulator is removed, thus, with compare removing the situation that the pH regulator operation is set between operation and crystallization operation, can reduce the amount of diluting water, can increase the amount of the boric acid that can reclaim in the crystallization operation.But, in this situation, remove operation and carry out under the state of low pH, therefore, in the situation that alleviate the acid proof load in removing operation, preferably the pH regulator operation is set removing between operation and crystallization operation.In addition, by adding sulfuric acid, an alkali metal salt crystallization of separating out easily becomes crystallite, therefore, in the situation that utilize the crystallization of the separation an alkali metal salts such as cyclonic separator, the crystallization that also likely can't effectively remove an alkali metal salt, preferably carry out the sulfuric acid interpolation before enrichment process in this situation.
(embodiment 4 of the second mode)
Before enrichment process, the mode that changes into boric acid and an alkali metal salt with at least a portion of the alkali metal borate in processed liquid is carried out pH regulator (preferred pH4～6, more preferably pH4～5.5, further preferred pH4～5), in addition, after removing operation, in order to improve boric acid purity, also can carry out pH regulator (preferred pH lower than 4, more preferably pH1～3) (not shown).
In this embodiment, utilize the pH of the liquid that concentrating unit processes higher, therefore, the use of expensive material is controlled, can reduce costs, and by at least a portion that makes alkali metal borate before enrichment process, transform, an alkali metal salt that thereupon produces is grown to the particle diameter of the size that is suitable for removing in enrichment process, therefore, in removing operation, can effectively remove, as a result, diluting water measure control, can be increased in the amount of the boric acid crystallization of separating out in the crystallization operation.
Then, the processed liquid (preferably completed concentrated carrying out the processed liquid of pH regulator) that will carry out pH regulator is cooled to certain temperature, makes the boric acid crystallization.That is, utilize crystallization device (crystallizer), by the so-called cooling crystallization (cooling crystallization) that utilizes, make the boric acid crystallization.In cooling crystallization, along with the temperature reduction of the aqueous solution in cooling operation, the solubleness of boric acid crystallization reduces, result, boric acid crystallization.Below, the temperature of the terminal of this cooling operation is called to cooling temperature.
In the present invention, by utilizing crystallization, can be from the processed liquid that contains organic boron compound and alkali metal compound, optionally reclaiming boric acid.In addition, by crystallization, can optionally reclaim boric acid, therefore, also can be from the waste-gas cleaning that will contain the sulphur composition and reclaim boric acid the waste water of association and solid waste.In addition, as mentioned above, after with acid, heating water solution being carried out to pH regulator, cooling, by crystallization, separate out the boric acid crystallization, thus, easily control particle shape and the particle diameter of boric acid crystallization.Can further improve the purity of the boric acid crystallization of recovery.
Particularly in the situation that the second mode, before cooling crystallization, using processed liquid is concentrated, make to separate out and be removed as an alkali metal salt of impurity, therefore, even the high processed liquid of the concentration of an alkali metal salt also can reclaim the boric acid that purity is high.
In addition, as shown in patent documentation 3, the processed liquid to containing boric acid (boron compound) carry out cooling after, add sulfuric acid etc. and by pH regulator to the method for the acidity of regulation, also can make the crystallization of boric acid and reclaim boric acid.
But, in the method, because the crystallization moment that makes boric acid by pH regulator separates out, therefore, in the boric acid crystallization, easily sneak into the impurity such as Na salt, in addition, owing to being crystallite, therefore, the adhesion amount that is attached to the water that contains the impurity such as Na salt of crystal surface increases, therefore, in processed liquid, mix while having various compound, can't obtain highly purified boric acid crystallization.
In addition, with this processing sequence, boric acid crystallization moment separates out, and therefore, produces the unfavorable condition of the shape distortion of boric acid crystallization.
Above-mentioned cooling temperature is not particularly limited, and is preferably more than 30 ℃ and lower than 50 ℃.Cooling temperature is more than 50 ℃ the time, can not separate out fully the boric acid crystallization, produces the unfavorable condition of rate of recovery variation.
On the contrary, cooling temperature is during lower than 30 ℃, produces the unfavorable condition that the crystallization of the alkali metal compounds such as sodium sulfate is separated out with the mixed crystal form.
In addition, the carrying out before cooling the temperature of processed liquid of pH regulator and the difference of cooling temperature be to be suitable for more than 10 ℃, be preferably more than 20 ℃.Particularly preferably more than 30 ℃.By increasing this temperature head, can improve the rate of recovery of boric acid crystallization.
Thus, sneaking into of impurity can be suppressed to bottom line, thereby can further improve the rate of recovery of boric acid crystallization.
In addition, by the processed liquid to having carried out pH regulator, undertaken cooling and separating out preferably of boric acid crystallization that cause under reduced pressure carried out.
By under reduced pressure cooling, carry out separating out of boric acid crystallization, can be suppressed at while adopting the jacket cooling mode rust on heat-transfer surface that worry can occur and generate, the maintenance of device becomes easily, and the loss of boric acid crystallization reduces, thus, can improve the rate of recovery of boric acid.
In addition, the discharge head of this moment is not particularly limited, during cooling beginning preferably with 10000Pa～70000Pa, more preferably with 20000Pa～60000Pa, reduce pressure, during cooling end preferably with 1000Pa～15000Pa, more preferably with 2000Pa～8000Pa, reduce pressure.
Processed liquid by having carried out pH regulator cooling utilizes retrieving arrangement (separating centrifuge) from the aqueous solution, isolating the crystallization of separating out, thereby reclaims the crystallization of boric acid after making the crystallization of boric acid in recovery process.At this moment, the temperature that preferably contains the aqueous solution of crystallization remains on above-mentioned cooling temperature, preferably more than 30 ℃ and under 50 ℃, carries out lock out operation.
The separation method of boric acid crystallization is not particularly limited, and can utilize various filtrations, centrifugation, sedimentation etc. for from liquid, isolating the known separation method of solids component.
At this, in the filtrate after isolating the boric acid crystallization, contain the boric acid of not separating out.
Therefore, preferably utilize liquid feeding device that this filtrate being delivered to is contained at least a processed liquid in waste water and solid waste, as the raw material of above-mentioned processed liquid recycling (below, also referred to as in above-mentioned processed liquid, adding filtrate).That is, preferably use this filtrate as dilution water of above-mentioned waste liquid or solid waste etc.For example the mixture of above-mentioned solid waste of being caught by deep bed filter and this filtrate can be added in above-mentioned processed liquid and use (or using as processed liquid), in addition, also can in the mixture of solid waste and filtrate, add water as required and obtain above-mentioned processed liquid.Thus, can further improve from above-mentioned waste liquid or solid waste, reclaiming the rate of recovery of boric acid.
At this, in going out the residual filtrate of boric acid crystallization, initial separation contains a large amount of boric acid, on the other hand, also contain impurity.Therefore, in the first mode, when the usage quantity of this filtrate in processed liquid was too much, impurity was concentrated gradually, and the impurity concentration in processed liquid reaches high density, likely can't carry out suitable processing.
Therefore, add in processed liquid and the filtrate of recycling is preferably the part of filtrate.The filtrate of particularly, adding in processed liquid is preferably 50 quality %～90 quality % with respect to the filtrate integral body of isolating after the boric acid crystallization.Thus, prevent from causing detrimentally affect because the impurity in processed liquid increases, and can suitably improve the rate of recovery of boric acid.
In addition, in the second mode, utilize concentrating unit to make the Na as impurity that comprises in processed liquid salt concentrate and separate out, utilize as the cyclonic separator of removing device and remove, therefore, even in the situation that the processed liquid that alkali metal salt concentration is high concentrates, also can access and contain hardly alkali-metal crystallization, the liquid after concentrated.Therefore, add in processed liquid and the filtrate of recycling can be at least a portion of filtrate, be preferably all.Thus, can suitably improve the rate of recovery of boric acid.
In the first mode and the second mode, the part that all will reclaim the processing water after the boric acid crystallization is discarded, remainder is back to above-mentioned interpolation operation, therefore, by adjusting, process the discarded amount of water, that is, the alkali metal salt concentration of processed liquid is high, to enrichment process with while removing the operation applying load, can increase the discarded amount of processing water, easily carry out enrichment process, remove operation.On the other hand, when enrichment process is little with the load of removing operation, can reduce the discarded amount of processing water, improve the rate of recovery of boric acid.
Like this, the boric acid crystallization of reclaiming in recovery method of the present invention is the sufficiently high material of purity, also can be directly as the uses such as raw material of pyrex.
But according to purposes etc., the boric acid crystallization of recovery is not enough clean, and the purity of boric acid crystallization does not reach the value of expectation sometimes yet.In this situation, utilize boric acid aqueous solution or the water of alkali-free metal ingredient, can clean the boric acid crystallization of reclaiming.In addition, the cleaning of boric acid crystallization gets final product by known method.In addition, the boric acid aqueous solution of alkali-free metal ingredient refers to, certainly do not contain alkali metal compound nor contains the boric acid aqueous solution of boron compound that Sodium Tetraborate etc. comprises alkali metal atom, the compound that comprises alkali metal atom beyond these compounds, alkalimetal ion etc.
In addition, according to purposes etc., the purity of the boric acid crystallization of recovery is sometimes also enough high.In this situation, preferably by again carrying out crystallization (recrystallization processing), further improve the purity of boric acid crystallization.The recrystallization that can carry out as required more than 2 times is processed, but usually by 1 recrystallization, processes and can access the sufficiently high boric acid crystallization of purity.
In recrystallization is processed, as shown in Figure 1 or 2, in the boric acid crystallization of reclaiming, add water (or the boric acid aqueous solution of alkali-free metal ingredient.Perhaps the filtrate after recrystallization described later is boric acid aqueous solution.Below, by them also referred to as boric acid aqueous solution), obtain the processed liquid of recrystallization, utilize the heating for dissolving device to heat, make thus the boric acid dissolving crystallized.
For the preparation of recrystallization, with the water of processed liquid or the addition of boric acid aqueous solution, be not particularly limited, according to suitable settings the such as amount of boric acid crystallization, get final product.In addition, Heating temperature also is not particularly limited, so long as can dissolve the temperature of boric acid crystallization, gets final product, and is preferably 50 ℃～100 ℃, more preferably 70 ℃～80 ℃.
Then, with processed liquid, be cooled to more than 30 ℃ recrystallization and lower than 50 ℃, the boric acid crystallization separated out again.That is, by the cooling crystallization that utilizes crystallization device (crystallizer), the boric acid crystallization is separated out again.Recrystallization is to be suitable for more than 10 ℃ with the cooling front temperature of processed liquid and the difference of cooled temperature, and is preferred more than 20 ℃.Particularly preferably more than 30 ℃.By increasing this temperature head, can improve the rate of recovery of the boric acid crystallization in the recrystallization processing.
Same when the restriction reason of cooling temperature scope and crystallization before.In addition, for the reason with same before, utilize separating out again preferably of cooling boric acid crystallization to carry out under the decompression with same before.
Like this, after by cooling crystallization, the crystallization of boric acid being separated out again, with above-mentioned, similarly by known method, utilize retrieving arrangement (separating centrifuge) from the aqueous solution that contains the boric acid crystallization, again isolating the boric acid crystallization, the boric acid crystallization after the recrystallization processing is carried out in recovery.
The boric acid crystallization that obtains by the purifying that utilizes this recrystallization to process for the impurity such as alkali metal compound still less, boric acid crystallization that purity is higher.
At this, in the filtrate again isolate the boric acid crystallization in this recrystallization is processed after (below, be called the filtrate after recrystallization), also contain the boric acid of not separating out.
Therefore, as shown in Figure 1 or 2, filtrate after this recrystallization also with above-mentioned boric acid Crystallization Separation after filtrate same, preferably utilize liquid feeding device at least a portion to be delivered at least a processed liquid that contains in waste water and solid waste, as the raw material of above-mentioned processed liquid recycling (below, also referred to as in above-mentioned processed liquid, adding filtrate).Thus, can further improve from the rate of recovery of recovery boric acid processed liquid and the rate of recovery in the recrystallization processing.
In addition, at this moment, also can with interpolation/blended solid refuse in this filtrate similarly before, and add (or can be used as processed liquid) in processed liquid to.
By above-mentionedly isolating 5～100 quality %, preferred 10～75 quality % of the filtrate after the boric acid crystallization of separating out again, more preferably 15～50 quality % add in the processed liquid before above-mentioned concentrated and pH regulator, and preferred by 0～95 quality % of this filtrate, preferred 25～90 quality %, more preferably 50～85 quality % add above-mentioned recrystallization to in processed liquid.
At this, in the filtrate after this recrystallization, also contain the impurity such as alkali metal compound.But the impurity that comprises in the filtrate after recrystallization is adhere to once or be blended into the impurity in the boric acid crystallization that goes out by crystallizing and separating, on amount, be micro-.
Therefore, in order to improve the rate of recovery of boric acid, the filtrate after recrystallization is as the raw material recycling of above-mentioned processed liquid, and it is favourable adding to as much as possible in processed liquid, particularly preferably it is all measured to add in processed liquid to recycle.
Alkali metal content (being converted into the amount of alkali metal atom) in the boric acid that obtains by recovery method of the present invention is preferably below 0.5 quality %, more preferably below 1000ppm.More preferably below 500ppm.In recovery method of the present invention, can make alkali metal content in the boric acid before recrystallization is processed is below 0.5 quality %.In addition, by carrying out 1 recrystallization, process, can make alkali metal content is below 500ppm.
Waste water in the present invention and solid waste all are preferably waste water or the solid waste of discharging from the off gas treatment operation, in described off gas treatment operation, make to contact with the alkali metal compound aqueous solution of alkalescence from the waste gas of discharging the manufacturing process of pyrex.
As pyrex, be preferably alkali metal component (the alkali-metal oxide compounds such as sodium, potassium) less or (being alkali-free) pyrex of alkali-free metal ingredient in fact.
As pyrex, in the mass percent based on oxide compound, the pyrex of preferred following composition (1), the more preferably pyrex of following composition (2).Wherein, following R represents basic metal.Following metal oxide (the Fe in addition that can contain in addition, a small amount of (be preferably below 3 quality % in total amount, more preferably below 2 quality %, further preferred 1 quality % is following) 2O 3, SnO 2Deng), nonmetal oxide (oxysulfide (SO 3) etc.), halogen (Cl, F) etc.
SiO 2: 40～85 quality %, Al 2O 3: 1～22 quality %, B 2O 3: 2～20 quality %, MgO:0～8 quality %, CaO:0～14.5 quality %, SrO:0～24 quality %, BaO:0～30 quality %, R 2O:0～10 quality %... (1).
Contain SiO 2: 58～66 quality %, Al 2O 3: 15～22 quality %, B 2O 3: the non-alkali glass of 5～12 quality %, MgO:0～8 quality %, CaO:0～9 quality %, SrO:3～12.5 quality %, BaO:0～2 quality %, MgO+CaO+SrO+BaO:9～18 quality % ... (2).
Thermally resistant container or Physicochemical are with the pyrex that comprises alkali metal component that uses in utensil etc. alkali metal component (R in above-mentioned composition (1) normally 2O) contain the proportional pyrex of 10 quality % of about 2 quality %～approximately that is.
On the other hand, the pyrex as the substrate as liquid crystal display device uses, use the few pyrex of alkali metal component, more preferably uses and be called as the pyrex alkali-free pyrex, that alkali metal component is few.The pyrex that is called as alkali-free pyrex (non-alkali glass) is alkali metal component (R in above-mentioned composition (1) 2O) to contain proportional be the following pyrex of 0.1 quality %, be in above-mentioned composition (2) except as inevitably impurity contains, do not contain in fact the pyrex of alkalimetal oxide (for example, alkalimetal oxide is that 0.1 quality % is following).
As the pyrex in the manufacturing process of the pyrex in the discharge source of the waste water in the present invention and solid waste, be preferably the pyrex of above-mentioned alkali metal component few (namely lower than 2 quality %), more preferably alkali metal component is the following pyrex of 1 quality %.Particularly preferably above-mentionedly be called as the pyrex alkali-free pyrex, alkali metal component few (namely below 0.1 quality %).
The amount of the alkali metal component in above-mentioned pyrex is the condition that restricts the application target of the boric acid that reclaims according to the present invention.According to the amount of the alkali metal component as impurity in the boric acid that reclaims, the kind of the pyrex that can use as the pyrex raw material is restricted.When the amount of the alkali metal component in the boric acid that reclaims was many, this boric acid was difficult to use as the raw material of the few pyrex of alkali metal component, particularly likely can't use as the raw material of alkali-free pyrex.
Therefore, as mentioned above, the alkali metal content (being converted into the amount of alkali metal atom) in the boric acid that obtains by recovery method of the present invention is preferably below 0.5 quality %, more preferably below 1000ppm.Below further preferred 500ppm.The raw material that the boric acid that such purity is high can be used as the alkali-free pyrex uses.
Therefore, can be using from for example raw material recycling from the boric acid that reclaims in the waste liquid of association in the processing of the waste gas of discharging the manufacturing process of alkali-free pyrex or solid waste as this alkali-free pyrex (alkali metal content is lower than the pyrex of 2 quality %).
Above, the recovery method of boric acid of the present invention at length is illustrated, but the invention is not restricted to above-mentioned example, in the scope that does not break away from purport of the present invention, can carry out various improvement and change, this is self-evident.
Embodiment
Below, enumerate specific embodiments of the invention the present invention is described in more detail.It should be noted that, the present invention is not limited to following embodiment certainly.
The<the first mode >
[embodiment 1]
By purification process shown in Figure 3, the waste gas that the glass-melting furnace from for the manufacture of pyrex is discharged purifies.In this purification process, the waste water of discharging from Venturi scrubber, dissolve the solid waste of being caught by deep bed filter, thus, the liquid of preparation conduct processing object (below, this liquid is called to the mother liquor body).
Get this mother liquor body 1000mL, at first, be heated to 75 ℃, obtain heating water solution.Then, in heating water solution, add sulfuric acid and by pH regulator to 2.
Then, the heating water solution that this has been carried out to pH regulator concentrates until solid namely will be separated out under 75 ℃.In heating water solution (completing pH regulator) after this is concentrated, contain respectively boron 32g/L, sodium 60g/L, sulfate ion 61g/L.
Heating water solution (completing pH regulator) after concentrated is cooled to 35 ℃ from 75 ℃, makes the boric acid crystallization.
By separating out the processed liquid that the boric acid crystallization is arranged, under 35 ℃, filter, reclaim the boric acid crystallization.
By ion chromatography, the purity of the boric acid of recovery is measured, result, the impurity concentration in the boric acid crystallization of recovery is: sulfate ion is 0.7 quality %, sodium is 0.4 quality %.
[embodiment 2]
In the boric acid crystallization of reclaiming, add the water that the aqueous solution that makes 75 ℃ becomes the amount of saturated aqueous solution in embodiment 1, obtain the processed liquid of recrystallization.This recrystallization is heated to 75 ℃ with processed liquid, the boric acid crystallization is all dissolved, manufacture saturated aqueous solution.
Then, the saturated aqueous solutions of above-mentioned 75 ℃ are cooled to 35 ℃, the boric acid crystallization is separated out again.
By separating out again the aqueous solution that the boric acid crystallization is arranged, under 35 ℃, filter, reclaim the boric acid crystallization.
Similarly to Example 1 the purity of the boric acid that reclaims is measured, result, the impurity in the boric acid crystallization, sodium ion, sulfate ion, chlorion, fluorion are all below 100ppm.
[comparative example 1]
The addition of the sulfuric acid of pH regulator is carried out in adjusting to heating water solution, making the pH of the heating water solution after pH regulator is 4, and in addition, operation similarly to Example 1, reclaim the boric acid crystallization.
Similarly to Example 1 the purity of the boric acid crystallization of reclaiming is measured, result, the impurity concentration in the boric acid crystallization of recovery is: sulfate ion is that 1.7 quality %, sodium are 1.0 quality %.
[comparative example 2]
Get mother liquor body 1000mL similarly to Example 1, be heated to 75 ℃.This heating water solution is cooled to 35 ℃, the borate of sodium is separated out, then, in completing the cooling aqueous solution, add sulfuric acid and, by pH regulator to 2, make it change into the boric acid crystallization.
The boric acid crystallization of separating out is filtered similarly to Example 1 and reclaimed.
Similarly to Example 1 the purity of the boric acid crystallization of reclaiming is measured, result, impurity concentration is: sulfate ion is that 2.4 quality %, sodium are 1.8 quality %.
According to above result, effect of the present invention is clear and definite.
The<the second mode >
[embodiment 3]
By purification process shown in Figure 3, the waste gas that the glass-melting furnace from for the manufacture of pyrex is discharged purifies.In this purification process, use the waste water of discharging from Venturi scrubber as stoste.In the second mode, in processed liquid, contain a large amount of an alkali metal salts.In order to reappear the processed liquid in this technique, to obtain making processed liquid that alkali metal salt concentration improves as purpose, preparation is added with the liquid (below, this liquid is called to the mother liquor body) of sodium sulfate, sodium-chlor the stoste of discharging from washer.
Get this mother liquor body 1440mL, add sulfuric acid and by pH regulator to 2.
Then, this liquid that has carried out pH regulator is concentrated under 75 ℃, solids component is separated out.Then, use filter paper, by filtering separation, become solids component and supernatant liquor.Solids component is 69g.Water of condensation while concentrating in addition, is 430g.
By ion chromatography, this solids component is analyzed, result contains sodium 36.2 quality %, sulfate ion 44.4 quality %, chloride ion 17.8 quality %, boron 0.9 quality %.Therefore, can think that this solids component is mainly the mixed crystal of sodium sulfate and sodium-chlor.
In this supernatant liquor, add the pure water of 5 % by weight, then be cooled to 35 ℃ from 75 ℃, make the boric acid crystallization.By separating out the processed liquid that the boric acid crystallization is arranged, under 35 ℃, filter, reclaim the boric acid crystallization.
By ion chromatography, the purity of the boric acid crystallization of recovery is measured, result, the impurity concentration in the boric acid crystallization of recovery is: sulfate ion is that 0.4 quality %, chloride ion are 0.7 quality %.
[embodiment 4]
In the supernatant liquor that the operation by similarly to Example 3 obtains, add the pure water of 10 % by weight, then be cooled to 35 ℃ from 75 ℃, make the boric acid crystallization.By separating out the processed liquid that the boric acid crystallization is arranged, under 35 ℃, filter, reclaim the boric acid crystallization.
By ion chromatography, the purity of the boric acid crystallization of recovery is measured, result, the impurity concentration in the boric acid crystallization of recovery is: sulfate ion is that 0.4 quality %, chloride ion are 0.8 quality %.
[comparative example 3]
In the supernatant liquor that the operation by similarly to Example 3 obtains, do not add pure water, be cooled to 35 ℃ from 75 ℃, make the boric acid crystallization.By separating out the processed liquid that the boric acid crystallization is arranged, under 35 ℃, filter, reclaim the boric acid crystallization.
By ion chromatography, the purity of the boric acid crystallization of recovery is measured, result, the impurity concentration in the boric acid crystallization of recovery is: sulfate ion is that 0.5 quality %, chloride ion are 6.7 quality %.
In addition, with reference to specific embodiment, the present invention at length is illustrated, but it is obvious to the skilled person that without departing from the scope and spirit of the present invention and can carry out various modifications and changes.
The application, based on the Japanese patent application 2011-209254 of the Japanese patent application 2011-035896 that proposed on February 22nd, 2011 and proposition on September 26th, 2011, is incorporated to its content in this specification sheets as a reference.
Utilizability on industry
Can contain in the waste water of organic boron compound and alkali metal compound and solid waste and reclaim the boric acid that can use as the pyrex raw material from the waste water of discharging the manufacturing process of pyrex and solid waste etc.

Claims (12)

1. the recovery method of a boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, wherein,
To adding acid in described processed liquid by pH regulator to after 4, concentrating, or after described processed liquid is concentrated, add acid and by pH regulator to lower than 4,
The described processed liquid that has carried out concentrated and pH regulator and do not contained insolubles is carried out cooling, obtains separating out the aqueous solution that the boric acid crystallization is arranged,
From the described aqueous solution of separating out the boric acid crystallization, isolating this boric acid crystallization,
50～90 quality % that isolate the filtrate after this boric acid crystallization are added in the processed liquid before described concentrated and pH regulator,
The recrystallization that adds boric acid aqueous solution or water in the described isolated boric acid crystallization of subtend and obtain heats with processed liquid and makes the boric acid dissolving crystallized, this is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling with processed liquid, obtain separating out again the aqueous solution that the boric acid crystallization is arranged, from the described aqueous solution of separating out again the boric acid crystallization, isolating this boric acid crystallization
At least a portion of isolating the filtrate after this boric acid crystallization of separating out is again added in the processed liquid before described concentrated and pH regulator.
2. the recovery method of boric acid as claimed in claim 1, wherein,
The described concentrated front processed liquid of pH regulator that reaches contains Na 2SO 4During with NaCl, the sodium (Na) that contains in this processed liquid is below 3.6 with the mass ratio (Na/B) of boron (B),
This processed liquid contains NaCl and does not contain Na 2SO 4The time, described mass ratio (Na/B) is below 3.9,
This processed liquid contains Na 2SO 4And while not containing NaCl, described mass ratio (Na/B) is below 3.1.
3. the recovery method of a boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, wherein,
To adding acid in described processed liquid by pH regulator to after 4, concentrating, an alkali metal salt is separated out, by an alkali metal salt from the described processed liquid of separating out an alkali metal salt, removing,
Perhaps described processed liquid is concentrated and an alkali metal salt is separated out, by an alkali metal salt after the described processed liquid of separating out an alkali metal salt, removing, add acid by pH regulator to lower than 4,
To described, carried out concentrated and pH regulator and removed in the processed liquid of described an alkali metal salt, adding water and diluting,
Processed liquid after this dilution is carried out cooling, obtains separating out the aqueous solution that the boric acid crystallization is arranged,
From the described aqueous solution of separating out the boric acid crystallization, isolating this boric acid crystallization,
At least a portion of isolating the filtrate after this boric acid crystallization is added in the processed liquid before described concentrated and pH regulator,
The recrystallization that adds boric acid aqueous solution or water in the described isolated boric acid crystallization of subtend and obtain heats with processed liquid and makes the boric acid dissolving crystallized, this is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling with processed liquid, obtain separating out again the aqueous solution that the boric acid crystallization is arranged, from the described aqueous solution of separating out again the boric acid crystallization, isolating this boric acid crystallization
At least a portion of isolating the filtrate after this boric acid crystallization of separating out is again added in the processed liquid before described concentrated and pH regulator.
4. the recovery method of boric acid as claimed in claim 3, wherein,
The described concentrated front processed liquid of pH regulator that reaches contains Na 2SO 4During with NaCl, the sodium (Na) that contains in this processed liquid and the mass ratio (Na/B) of boron (B) be greater than 3.6,
This processed liquid contains NaCl and does not contain Na 2SO 4The time, described mass ratio (Na/B) is greater than 3.9,
This processed liquid contains Na 2SO 4And while not containing NaCl, described mass ratio (Na/B) is greater than 3.1.
5. as the recovery method of claim 3 or 4 described boric acid, wherein, in described processed liquid concentrated, the particle diameter of the described an alkali metal salt that separate out is controlled and an alkali metal salt is optionally removed.
6. as the recovery method of the described boric acid of any one in claim 1～5, wherein, described 5～100 quality % that isolate the filtrate after the boric acid crystallization of separating out are again added in the processed liquid before described concentrated and pH regulator, and add 0～95 quality % of this filtrate to described recrystallization with in processed liquid.
7. as the recovery method of the described boric acid of any one in claim 1～6, wherein, the solids component of described waste water and described solid waste contain boron, basic metal, sulphur and chlorine at least as element, boron is made as at 1 o'clock, and the mass ratio of this element is that basic metal is 0.6～13, sulphur is below 6 and chlorine is below 6.
8. as the recovery method of the described boric acid of any one in claim 1～7, wherein, the alkali metal component in the boric acid that is recovered is below 0.5 quality %.
9. as the recovery method of the described boric acid of any one in claim 1～8, wherein, described waste water and solid waste are waste water or the solid waste of discharging from the off gas treatment operation, in described off gas treatment operation, make from least a contact the in the solid of the waste gas of discharging the manufacturing process of pyrex and alkali metal compound and the alkali metal compound aqueous solution.
10. the recovery method of boric acid as claimed in claim 9, wherein, the alkali metal content of described pyrex in the quality percentage based on oxide compound lower than 2 quality %.
11. the retrieving arrangement of a boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, and described retrieving arrangement possesses:
The concentrating unit that described processed liquid is concentrated;
Add acid by the pH regulator of processed liquid to the pH regulator device lower than 4;
The described processed liquid that has carried out pH regulator and do not contained insolubles is carried out cooling and obtains separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out;
50～90 quality % of the filtrate after this boric acid crystallization of Separation and Recovery are delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator;
The recrystallization that adds boric acid aqueous solution or water in the boric acid crystallization of the described Separation and Recovery of subtend and obtain heats with processed liquid and makes the heating for dissolving device of boric acid dissolving crystallized;
This is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged again with processed liquid;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out again; With
At least a portion of filtrate after the boric acid crystallization that this is separated out again by Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator.
12. the retrieving arrangement of a boric acid, for from processed liquid, reclaiming boric acid, described processed liquid comprises at least a in the waste water that contains organic boron compound and alkali metal compound and solid waste, and described retrieving arrangement possesses:
Described processed liquid is concentrated and concentrating unit that an alkali metal salt is separated out;
By the remove device of an alkali metal salt from removing processed liquid of separating out;
Add acid by the pH regulator of processed liquid to the pH regulator device lower than 4;
To utilizing, describedly remove processed liquid that device removed an alkali metal salt and utilized described pH regulator device to carry out pH regulator and carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out;
Filtrate after this boric acid crystallization of Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator;
The recrystallization that adds boric acid aqueous solution or water in the boric acid crystallization of the described Separation and Recovery of subtend and obtain heats with processed liquid and makes the heating for dissolving device of boric acid dissolving crystallized;
This is heated and makes the recrystallization after the boric acid dissolving crystallized carry out cooling and obtain separating out the crystallization device of the aqueous solution that the boric acid crystallization is arranged again with processed liquid;
From the described aqueous solution, separating and reclaim the retrieving arrangement of the boric acid crystallization of separating out again; With
At least a portion of filtrate after the boric acid crystallization that this is separated out again by Separation and Recovery is delivered to the liquid feeding device of the processed liquid before described concentrated and pH regulator.
CN2012800100210A 2011-02-22 2012-02-16 Method and device for recovering boric acid Pending CN103402917A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236439A (en) * 2015-09-07 2016-01-13 成都程德化工科技有限责任公司 Large-granular boric acid, continuously cooling recrystallization preparation process and continuously cooling recrystallization preparation method thereof
CN108083528A (en) * 2016-11-21 2018-05-29 江苏同禾药业有限公司 A kind of method that waste water containing boron is handled in 6- hydroxyl -8- Lipase Catalyzed Resolution of Racemic Ethyl preparation process
CN108689544A (en) * 2018-07-24 2018-10-23 苏州方舟环保科技有限公司 A kind of the waste water containing boron processing unit and method of zero-emission
CN108946752A (en) * 2018-08-21 2018-12-07 苏州福赛思生物科技有限公司 A kind of method that high efficiente callback utilizes the catalyst in lactulose preparation system
CN109678167A (en) * 2019-03-05 2019-04-26 李洪岭 A method of boric acid is produced from lithium borate waste solution is mentioned
CN115569401A (en) * 2022-11-04 2023-01-06 武汉宏达丰源分离技术有限公司 Boric acid production method and device for boron-containing brine
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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003305331A (en) * 2002-04-12 2003-10-28 Cottrell Kogyo Kk Recovery method and recovery apparatus for specific component in exhaust gas
JP2004298738A (en) * 2003-03-31 2004-10-28 Sumitomo Metal Mining Co Ltd Boron-containing water treatment method
JP2010069399A (en) * 2008-09-17 2010-04-02 Toshiba Corp Boron separation system

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59173182A (en) * 1983-03-18 1984-10-01 Kurita Water Ind Ltd Treatment of boron-containing water
JPH10310421A (en) * 1997-05-01 1998-11-24 Nittetsu Mining Co Ltd Treatment of waste dilute hydrochloric acid used in glass cleaning

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003305331A (en) * 2002-04-12 2003-10-28 Cottrell Kogyo Kk Recovery method and recovery apparatus for specific component in exhaust gas
JP2004298738A (en) * 2003-03-31 2004-10-28 Sumitomo Metal Mining Co Ltd Boron-containing water treatment method
JP2010069399A (en) * 2008-09-17 2010-04-02 Toshiba Corp Boron separation system

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236439A (en) * 2015-09-07 2016-01-13 成都程德化工科技有限责任公司 Large-granular boric acid, continuously cooling recrystallization preparation process and continuously cooling recrystallization preparation method thereof
CN108083528A (en) * 2016-11-21 2018-05-29 江苏同禾药业有限公司 A kind of method that waste water containing boron is handled in 6- hydroxyl -8- Lipase Catalyzed Resolution of Racemic Ethyl preparation process
CN108689544A (en) * 2018-07-24 2018-10-23 苏州方舟环保科技有限公司 A kind of the waste water containing boron processing unit and method of zero-emission
CN108946752A (en) * 2018-08-21 2018-12-07 苏州福赛思生物科技有限公司 A kind of method that high efficiente callback utilizes the catalyst in lactulose preparation system
CN109678167A (en) * 2019-03-05 2019-04-26 李洪岭 A method of boric acid is produced from lithium borate waste solution is mentioned
TWI805426B (en) * 2022-06-29 2023-06-11 暟豐實業有限公司 Boron resource recovery system for waste liquid
CN115569401A (en) * 2022-11-04 2023-01-06 武汉宏达丰源分离技术有限公司 Boric acid production method and device for boron-containing brine

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