WO2013153587A1 - 坑井からの随伴水処理方法および装置 - Google Patents
坑井からの随伴水処理方法および装置 Download PDFInfo
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- WO2013153587A1 WO2013153587A1 PCT/JP2012/007552 JP2012007552W WO2013153587A1 WO 2013153587 A1 WO2013153587 A1 WO 2013153587A1 JP 2012007552 W JP2012007552 W JP 2012007552W WO 2013153587 A1 WO2013153587 A1 WO 2013153587A1
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2311/08—Specific process operations in the concentrate stream
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- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/263—Chemical reaction
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- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2642—Aggregation, sedimentation, flocculation, precipitation or coagulation
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- B01D2311/2673—Evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- 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
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- 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
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- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
- C02F2001/5218—Crystallization
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- C02F2101/10—Inorganic compounds
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- C02F2101/101—Sulfur compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Definitions
- the present invention relates to a method for treating associated water produced when mining natural gas or crude oil from a well such as shale gas, oil sand, CBM (coal bed methane), or oil.
- an aqueous chemical solution may be injected as drilling water or steam to increase the amount of natural gas or crude oil.
- the crude oil extracted from the oil reservoir contains these chemical aqueous solutions and groundwater containing inorganic ions in the formation as associated water, and the associated water is separated from the mined natural gas and crude oil. Since the separated associated water contains salt, organic matter, suspension, etc., if it is discharged as it is, it causes environmental pollution problems and needs to be purified.
- Patent Document 1 discloses that after separating the oil from the accompanying water, a magnesium salt and caustic soda are added to adjust the pH of the accompanying water within the range of 9 to 11. Then, the soluble silica contained in the accompanying water is insolubilized and precipitated, and then the precipitated silica is filtered and separated using a ceramic membrane, and then the membrane filtered water from which the precipitated silica is removed is reverse osmosis ( RO) membrane treatment is thus disclosed, in which residual salts are removed from the accompanying water, recovered as fresh water, steamed and reused.
- RO reverse osmosis
- Patent Document 2 a treatment agent containing at least one compound selected from iron salt, aluminum salt, and magnesium salt is added to water to be treated, and a condensate is precipitated under alkaline pH 7.5-12. And a method for treating waste water containing silica, characterized in that the agglomerates are separated to reduce the silica concentration.
- the soluble silica contained in the accompanying water is insolubilized and precipitated, and the precipitated silica is removed, thereby preventing the RO membrane from being blocked by the precipitated silica in the RO membrane treatment step. Therefore, it is possible to improve the recovery rate of fresh water from the accompanying water.
- the removal rate is about 70% even when a silica removal agent having a molar ratio of 5 times or more with respect to the silica concentration in the water to be treated is added, the chemical cost increases, and the amount of sludge generated increases.
- the silica removal mechanism of aluminum and iron-based chemicals is due to the aggregation of polymerized silica and the adsorption of ionic silica, and the amount of adsorption depends on the specific surface area.
- magnesium-based chemicals form a compound such as MgSiO 3 to remove silica, and there is a problem that the compound is not generated unless the alkali is high.
- calcium carbonate may be deposited to block the RO membrane.
- the object of the present invention is to efficiently remove soluble silica from the accompanying water containing calcium ions and soluble silica produced from the well and to block the reverse osmosis membrane in the subsequent reverse osmosis membrane treatment step. It is to provide a method and apparatus that does not.
- the present invention has been made in order to solve the above-mentioned problems, and calcium remains in the associated water adjusted in the range from pH 9 to pH 11 in order to remove silica, while the pH is reduced. This is based on the finding that if the range of 5 to 9 and the Langelia index are set to a negative range, the precipitation of calcium carbonate is suppressed and the reverse osmosis membrane is not blocked.
- magnesium salt is added to admixed water produced from a well and containing calcium ions, soluble silica, and sulfate ions under alkaline conditions by the addition of caustic soda.
- Silica is insolubilized and precipitated.
- the reaction solution is filtered through a microfiltration (MF) membrane to separate and remove the precipitated silica.
- MF microfiltration
- sulfate ions react with calcium ions to precipitate as gypsum (CaSO 4 ), and are separated and removed together with silica.
- most of the calcium ions pass through the MF membrane and remain in the MF filtered water. Thereafter, the MF membrane filtrate is subjected to RO membrane treatment.
- the calcium salt contained in the MF membrane filtrate is not precipitated, and the greatest feature of the present invention is that hydrochloric acid is added to the MF membrane filtrate. Is added to maintain the pH value of the MF membrane filtered water within the range of 5 to 9 and the Langeria index in the negative range. Then, the reaction solution is subjected to RO membrane treatment to concentrate dissolved salts and collect fresh water.
- magnesium salt is added to and mixed with water accompanying calcium ions, soluble silica, and sulfate ions produced from a well under alkaline conditions to produce insoluble silica and calcium sulfate.
- An acid is added to and mixed with the filtered water obtained in step 1 to obtain the pH value of the filtered water within the range of 5 to 9 and the Langerian index within the negative range, and the acid adding step.
- a reverse osmosis membrane treatment step of obtaining fresh water and membrane concentrated water by subjecting the obtained second reaction solution to a reverse osmosis membrane treatment.
- the present invention also includes an inflow means for accompanying water containing calcium ions, soluble silica, and sulfate ions produced from a well, a means for adding a chemical agent of an alkali agent and a magnesium salt, and an outflow means for the liquid in the tank.
- a first reaction tank a precision membrane filtration device installed on the downstream side of the first reaction tank; an inflow means for filtered water flowing out from the precision membrane filtration apparatus; an acid addition means; and an outflow of liquid in the tank PH value of the reaction liquid which flows out of the said 2nd reaction tank,
- Comprising water treatment apparatus which has the 2nd reaction tank which has a means, and the reverse osmosis membrane apparatus installed in the downstream of the said 2nd reaction tank Is provided, and an associated water treatment apparatus is provided which is provided with an adjusting means for adjusting the Langelia index within a negative range.
- hydrotalcite-like bulky hydroxylation can be obtained by adding water-soluble magnesium salt and water-soluble aluminum salt in a specific ratio to the accompanying water containing calcium ions and water-soluble organic matter produced from the well.
- a precipitate of the product is formed, and the hydrotalcite-like precipitate includes a lot of hydration water and has a property of adsorbing various anions in its three-dimensional structure. It has been found that this property is used to improve the removability of silica. It was also found that the concentration of adsorbed silica was increased by reducing the carbonate ion concentration in water.
- the present invention provides a water-soluble magnesium salt and a water-soluble aluminum salt (Mg + Al) / SiO 2 (molar ratio) to the accompanying water containing calcium ions, soluble silica, and water-soluble organic matter produced from the well. Is added so that the Mg / Al (molar ratio) is 1 to 4, and an alkali is added to adjust the pH value in the range of 10.5 to 11, thereby generating insoluble silica.
- Mg + Al water-soluble aluminum salt
- An acid is added to and mixed in the solid-liquid separation step and the separation water obtained in the solid-liquid separation step, so that the pH value of the separation water is in the range of 5 to 9, and the Langeria index is in the negative range.
- Acid addition step and the acid addition The second reaction liquid obtained in extent by treating the reverse osmosis membrane, there is provided a produced water treatment method characterized in that it comprises a reverse osmosis membrane treatment to obtain fresh water and membrane retentate.
- the present invention also provides the accompanying water treatment method, wherein the silica precipitation treatment step is performed in a nitrogen atmosphere.
- the present invention further includes an inflow means for accompanying water containing calcium ions, soluble silica and water-soluble organic substances produced from a well, and means for adding a water-soluble magnesium salt and a water-soluble aluminum salt in a predetermined blending amount.
- a first reaction tank having an alkali addition means, an outflow means for the liquid in the tank, a coagulation tank having a first reaction liquid inflow means and a polymer flocculant addition means in the first reaction tank, and the coagulation tank
- An adjoining water treatment device having a reverse osmosis membrane device installed on the downstream side of the tank, wherein the first adjusting means adjusts the pH value of the liquid in the first reaction tank to a range of 10.5 to 11 And the second reaction liquid flowing out of the second reaction tank Within the scope of the H values from 5 9, and is intended to provide an associated water treatment apparatus characterized in that a second adjusting means for adjusting the Langelier index in the negative range.
- the accompanying water treatment is characterized in that the first reaction tank has a means for replacing a gas phase portion in the tank with nitrogen or a means for aeration of nitrogen in a liquid in the tank.
- a device is also provided.
- the soluble silica is efficiently removed from the accompanying water containing calcium ions and the soluble silica to solve the silica precipitation problem in the apparatus and piping for treating the accompanying water, and further the precipitation of calcium carbonate. Can also prevent fresh water efficiently and treat the accompanying water.
- FIG. 1 is a diagram showing a schematic configuration of an associated water treatment apparatus according to an embodiment of the present invention.
- FIG. 2 is a diagram showing a schematic configuration of an accompanying water treatment apparatus which is another embodiment of the present invention. It is a figure which shows another example of the 1st reaction tank in FIG. It is a graph which shows the relationship between the pH value of membrane filtration water, and Ca ion concentration. It is a graph which shows the relationship between the pH value of membrane filtration water, and the residual ion concentration of Ca and Si. It is a graph showing the relationship between the SiO 2 concentration after treatment with aluminum mini um compounding ratio. (Mg + Al) SiO 2 is a graph showing the relationship between drug costs per removal SiO 2 and aluminum mixing ratio for the case where the 2 1. It is a graph which shows the relationship between the existence rate according to Si form, and PH. It is a graph which shows the relationship between the alkali consumption and sludge generation amount in each pH.
- Wells to which the present invention is applied are not particularly limited as long as they discharge associated water, but are wells that mine shale gas, oil sand, CBM (coal bed methane), oil, and the like.
- evaporation residues mainly Na + , K + , Ca 2+ , Cl ⁇ , SO 4 2 ⁇ , etc.
- organic substances oil and And the like in the range of 10 mg / L to 1,000 mg / L as the TOC and the suspended substance in the range of 100 to 10,000 mg / L.
- Si is 40 mg / L to 1000 mg / L, usually 40 mg / L to 200 mg / L
- Ca 2+ is 50 mg / L to 10,000 mg / L, usually 100 mg / L to 5000 mg / L
- the carbonic acid concentration is 10 mg / L to 1000 mg / L, usually 10 mg / L to 100 mg / L.
- magnesium salt is added and mixed under alkaline conditions to the accompanying water containing calcium ions, soluble silica, and sulfate ions produced from this well, to form insoluble silica.
- a magnesium salt addition step for producing calcium sulfate a precision membrane filtration step for filtering and separating insolubilized silica and calcium sulfate by subjecting the first reaction liquid obtained in the magnesium salt addition step to a precision membrane filtration, Acid added to the filtered water obtained in the precision membrane filtration treatment step, mixed, and the pH value of the filtered water is in the range of 5 to 9, and the Langerian index is in the negative range
- the second reaction liquid obtained in the acid addition step is subjected to a reverse osmosis membrane treatment to have a reverse osmosis membrane treatment step for obtaining fresh water and membrane concentrated water.
- Magnesium salt addition step The magnesium salt is preferably soluble in an alkaline aqueous solution, and magnesium chloride, magnesium oxide, magnesium carbonate and the like can be used.
- the amount of magnesium added is about 1 to 4, preferably about 1 to 2, in terms of the molar ratio to silica.
- the addition form may be any form such as an aqueous solution, slurry, and powder.
- the reaction is carried out under alkaline conditions, in order to make the silica insoluble.
- the pH is about 7 to 8 before addition of the magnesium salt, and about 10.5 to 11 is appropriate for the supernatant in which the insoluble silica and calcium sulfate are precipitated. It is.
- the alkali to be added may be any alkali that can be adjusted to a predetermined pH, and sodium hydroxide is preferable. When sodium carbonate is used, a large amount of calcium carbonate precipitates at the same time, which is not preferable because separation and disposal become a burden.
- reaction for forming insoluble silica is completed in about 10 minutes to 1 hour.
- separates the insoluble silica and calcium sulfate which were produced
- a microfiltration membrane a normal membrane can be used.
- a ceramic membrane or a porous glass membrane can also be used.
- the preferred pore size of the microfiltration membrane is not particularly specified, but is preferably 0.1 ⁇ m or less.
- filtered water that has passed through the precision filtration membrane is obtained, and suspended substances including insoluble silica and calcium sulfate trapped in the precision filtration membrane are discharged by regular backwashing. Suspended substances in the backwash water are reduced in volume through a solid-liquid separation process such as a sedimentation tank and discarded, and the supernatant water is returned to the raw water.
- FIG. 4 is a graph showing the relationship between the pH value of the filtered water and the Ca ion concentration
- FIG. 5 is a graph showing the relationship between the pH value of the filtered water and the residual ion concentrations of Ca and Si.
- the carbonate ions contained in the raw water are precipitated and separated as calcium carbonate in the Si removal step, and the carbonate ion concentration can be reduced to 1 mg / L or less. Precipitation of calcium carbonate can be suppressed.
- the pH is set to 5 or more.
- a preferred pH range is pH 6 to 8, particularly preferably pH 6.5 to 7.5.
- hydrochloric acid As the acid, hydrochloric acid, sulfuric acid or the like can be used.
- the Langelia index (Langeliar Saturation Index. LSI) is mainly used as an index for evaluating the corrosion tendency and scale tendency of water in a water supply system as disclosed in Japanese Patent Application Laid-Open No. 2011-147899. It is represented by (1).
- pH-pHs pH-pHs (1) pH is the actual pH value of water, and pHs is the theoretical pH value when in an equilibrium state where calcium carbonate does not dissolve or precipitate in water.
- Total alkalinity is an index of alkali content such as bicarbonate, carbonate or hydroxide contained in water.
- the total alkalinity in natural water is mainly composed of carbonates or bicarbonates, and when the total alkalinity is high, there are many substances that combine with the hardness components of Ca and Mg to produce precipitates. Show.
- Total alkalinity (mg / L) is acid consumption up to pH 4.8 and can be analyzed by titration with hydrochloric acid or sulfuric acid.
- the Langellia index is preferably in the range of ⁇ 0.5 to less than 0 so as to be negative.
- the scale component is deposited, and the reverse osmosis membrane is likely to be clogged.
- the Langeria index is too lower than ⁇ 0.5, it is assumed that the pH of the reverse osmosis membrane treatment water is lower than 6 and it is necessary to inject an alkaline agent such as caustic soda into the RO membrane treatment water. .
- the Langeria index can be adjusted to decrease by increasing the amount of the acidic agent added by the pH adjuster adding device.
- Reverse Osmosis Membrane Treatment Step The second reaction solution obtained by adding acid in the acid addition step is treated with a reverse osmosis membrane device to obtain fresh water and membrane concentrated water.
- a reverse osmosis membrane a normal membrane may be used, and various materials such as cellulose acetate, polysulfone, aliphatic polyamide, and aromatic polyamide can be used.
- a commercially available reverse osmosis membrane apparatus can also be used as the apparatus.
- the obtained fresh water can be used for various purposes, but can be reused as well water for excavation of the well, thereby reducing the amount of water discharged outside the system.
- the membrane concentrated water contains a high concentration of salts, and can be effectively used as it is or can be injected into a waste well, but is preferably further processed.
- a treatment method there is a method of heating and further concentrating to crystallize salts.
- the membrane concentrated water is concentrated by heating. Concentration may be carried out at normal pressure or reduced pressure. Although the steam obtained by the concentration may be released, it can be condensed using a heat exchanger or the like to obtain fresh water, which can be reused for drilling water or the like.
- the concentrated water obtained in the evaporation step can be further heated and concentrated to separate and separate the salts.
- the generated steam is condensed using a heat exchanger or the like to obtain fresh water, which can be reused for drilling water or the like.
- salts are crystallized in the remaining concentrated liquid to form a slurry. This slurry is subjected to solid-liquid separation, the mother liquor is discarded, and the crystal can be used as a snow melting agent or the like if it contains almost no environmental pollution component.
- Such a first aspect includes an inflow means for accompanying water containing calcium ions, soluble silica, and sulfate ions produced from a well, an agent addition means for an alkali agent and a magnesium salt, and an outflow of liquid in the tank.
- a first reaction tank having a means; a precision membrane filtration device installed on the downstream side of the first reaction tank; an inflow means of filtered water flowing out from the precision membrane filtration apparatus; an acid addition means;
- An associated water treatment apparatus having a second reaction tank having a liquid outflow means and a reverse osmosis membrane device installed on the downstream side of the second reaction tank, the reaction liquid flowing out from the second reaction tank This can be carried out using an accompanying water treatment apparatus characterized in that an adjusting means is provided for adjusting the pH value of 5 to 9 and adjusting the Langelia index to a negative range.
- 1 is a 1st reaction tank which has the outflow means 4 of the liquid in a tank.
- the 1st reaction tank 1 the accompanying water which is produced from a well and contains calcium ion, soluble silica, and sulfate ion flows in by the inflow means 2.
- the reaction tank may be of a normal type such as a cylindrical shape or a box shape, and is preferably provided with a stirrer, a pH meter and the like.
- the inflow means 2 includes a pipe, a pump, a flow rate adjustment valve, a water level gauge, and the like.
- the chemical addition means 3 is a means for adding an alkali such as NaOH and a magnesium salt such as MgCl 2 to the accompanying water in the first reaction tank 1, and contains a tank, a pipe, a flow rate adjustment valve, a stirrer, It consists of a water level gauge.
- the tank liquid outflow means 4 includes a pipe, an on-off valve, and the like.
- the first reaction liquid flowing out from the first reaction tank 1 by the outflow means 4 enters the precision membrane filtration device 5, where insoluble silica and calcium sulfate generated in the first reaction tank 1 are separated by filtration.
- the filtered water separated by the precision membrane filtration device 5 flows into the second reaction tank 7 through the inflow means 6.
- the inflow means includes a pipe, an on-off valve, a pump, and the like.
- the second reaction tank 7 may be a commonly used reaction tank such as a cylindrical shape or a box shape, and a stirrer, a pH meter, or the like is appropriately provided.
- the second reaction tank 7 is provided with acid addition means 8.
- the acid addition means 8 includes a tank for storing an acid such as HCl, a pipe, and a water level gauge.
- Adjustment means 9 is attached to the acid addition means 8.
- the adjusting means 9 includes a flow tube adjusting valve, a pH meter and the like.
- the second reaction liquid obtained by the reaction in the second reaction tank 7 is sent to the reverse osmosis membrane device 11 through the outflow means 10 for the liquid in the tank.
- the tank outflow means includes a pipe, an on-off valve, a (pump), and the like.
- the membrane concentrated water is sent to the evaporator 12 and further concentrated.
- the evaporator 12 may be a normal evaporator, that is, a single can, a multi-effect can, a vapor compression evaporator, a multistage flash evaporator, or the like. Evaporation may be performed at normal pressure or reduced pressure depending on the heat source. Steam generated by the evaporation is condensed through heat exchange, and the obtained fresh water is sent to the well as drilling water.
- the concentrated water remaining after evaporation is sent to the crystallizer 13, where it is further evaporated and concentrated to crystallize the contained salts.
- the steam generated at this time is condensed, and the obtained fresh water is sent to the well as drilling water.
- the remaining slurry is subjected to solid-liquid separation by solid-liquid separation means such as centrifugation, and then discarded or used as a snow melting agent.
- a silica precipitating agent in which water-soluble magnesium and water-soluble aluminum coexist is added to waste water containing calcium, soluble silica, and water-soluble organic matter, and the pH is made alkaline by making the pH alkaline.
- Silica is removed by forming aluminum composite hydroxide (hydrotalcite-like substance). That is, in this embodiment, water-soluble magnesium salt and water-soluble aluminum salt are added to the accompanying water containing calcium ions, soluble silica, and water-soluble organic matter produced from the well (Mg + Al) / SiO 2 (molar ratio).
- the water-soluble magnesium salt is magnesium chloride, magnesium nitrate or the like
- the water-soluble aluminum salt is aluminum chloride, aluminum nitrate or polyaluminum chloride.
- the addition amount is suitably about 1 to 2 in terms of a molar ratio of (Mg + Al) / SiO 2 .
- the molar ratio is less than 1, the silica removal performance is insufficient.
- it exceeds 2 the unreacted Mg and Al are dissolved to increase the drug cost and the salt concentration increases.
- a load is applied to the treatment process and the evaporation process.
- a suitable Mg / Al molar ratio is 1 to 4.
- the initial concentration of silicic acid is 120 mg / L, and magnesium chloride and polyaluminum chloride are added with (Mg + Al) / SiO 2 in the case of 1 and 2 in different proportions of Al and reacted at pH 10.5.
- the results of measuring the residual concentration of SiO 2 are shown in FIG.
- dissolved silica is molecular silica, it is desirable to treat Al alone, but as shown in FIG. 8, there is a problem that the amount of sludge generated increases and sludge disposal costs increase.
- the results of calculating the amount of drug per removed SiO 2 with aluminum (Al in polyaluminum chloride) being 760 yen / kg and magnesium (Mg in magnesium chloride hexahydrate) being 590 yen / kg are shown in FIG. From FIG. 7 shown in FIG. 7, the Al ratio may be 0.2 to 0.8, that is, 4/1 to 1/4 for Mg / Al. However, if there is a large amount of Al, the amount of sludge tends to increase. Al is preferably 1 to 4.
- the above molar ratio is a molar ratio in which both magnesium and aluminum are one compound.
- the form of addition may be any form such as an aqueous solution, slurry, powder, etc., and the order of addition may be either first or simultaneously.
- the reaction is carried out by adding magnesium salt and aluminum salt and adding alkali to adjust the pH value within the range of 10.5 to 11. This is because the reaction between magnesium and Si occurs selectively between divalent SiO 4 ions, but as shown in FIG. 8, SiO 4 2 ⁇ appears at a pH of 10 or more, and at a pH of less than 10.5, magnesium appears.
- the hydrotalcite-like substance is not formed sufficiently, and when the pH exceeds 11, the removal effect of aluminum hydroxide is reduced because aluminum hydroxide is dissolved as a hydroxide complex ion. by.
- the results of calculating the alkali consumption and sludge generation amount (wet weight) for making 100 mg / L of SiO 2 40 mg / L or less are shown in FIG.
- ⁇ indicates alkali consumption
- ⁇ indicates sludge generation.
- Al is added alone, but the amount of sludge generated is increased instead of the alkali consumption being small.
- the amount of sludge generated can be reduced by adding Mg alone, but the alkali consumption increases.
- pH 10.5 and (Mg + Al) / Si 1, the sum of cost and alkali consumption and sludge generation is minimized, and this condition is the most economical.
- reaction of adding magnesium salt and aluminum salt to the accompanying water to form insoluble silica is completed in about 10 minutes to 1 hour. Furthermore, the reaction vessel is completely sealed and the gas phase is replaced with nitrogen, or nitrogen aerated. It is preferable to reduce the carbon dioxide dissolution from the atmosphere by performing the above. Since hydrotalcite-like substances preferentially take up carbonate ions, it is desirable that the concentration of carbonate ions in water to inhibit the uptake of other anions including silica is as low as possible.
- An aggregating agent preferably a polymer aggregating agent, is added to the first treatment liquid obtained in the silica precipitation treatment step to agglomerate the precipitated silica.
- a polymer flocculant a polyacrylamide type anionic flocculant or the like can be used, and the addition amount is suitably about 1 mg / L to 2 mg / L.
- the addition is performed after silica precipitation.
- the aggregation treatment time may be about 15 minutes to 1 hour after silica deposition.
- Solid-liquid separation step When the precipitated silica is agglomerated, the agglomerates are separated.
- the separation means precipitation separation, centrifugation, filtration and the like can be used.
- the acid addition step may be performed in the same manner as in the first aspect. Further, it may be carried out after the precipitation separation and before the precision membrane filtration treatment.
- Reverse osmosis membrane treatment step The reverse osmosis membrane treatment step may be performed in the same manner as in the first embodiment.
- forward osmosis membrane treatment can be performed instead of reverse osmosis membrane treatment.
- the second reaction solution obtained in the acid addition step is brought into contact with a higher osmotic pressure induction solution through a semipermeable membrane, and water in the second treatment solution is passed through the semipermeable membrane.
- This is a method of transferring to an induction solution, and a semipermeable membrane device is used.
- the induction solution is an aqueous solution having an osmotic pressure higher than that of the membrane filtrate, for example, an aqueous ammonium carbonate solution formed by dissolving a predetermined amount of ammonia and carbon dioxide in water.
- the predetermined amount is an amount that makes the water in the membrane filtrate pass through the semipermeable membrane and move to the induction solution, so that the osmotic pressure of the induction solution is higher than the osmotic pressure of the membrane filtration water.
- the upper limit of the concentration is determined so that a salt of ammonia and carbon dioxide, that is, ammonium carbonate, ammonium hydrogen carbonate, ammonium carbamate, etc.
- the molar ratio of ammonia to carbon dioxide is about 1.5-3. This molar ratio is also taken into consideration so that the salt of ammonia and carbon dioxide does not precipitate on the semipermeable membrane surface or in the evaporator.
- solute of the induction solution in addition, a high solubility and high osmotic pressure can be obtained, and a low boiling point, high volatility, and low toxicity can be used.
- alcohols such as ethyl alcohol and butyl alcohol can be used.
- ketones such as acetone can also be used.
- the semipermeable membrane is preferably one that can selectively permeate water and is preferably a forward osmosis membrane, but a reverse osmosis membrane can also be used.
- the material is not particularly limited, and examples thereof include cellulose acetate-based, polyamide-based, polyethyleneimine-based, polysulfone-based, and polybenzimidazole-based materials.
- the form of the semipermeable membrane is not particularly limited and may be any of a flat membrane, a tubular membrane, a hollow fiber, and the like.
- the apparatus to which this semipermeable membrane is attached usually has a semipermeable membrane installed in a cylindrical or box-shaped container, and the second reaction liquid flows into one chamber partitioned by the semipermeable membrane, and the other chamber
- a known semipermeable membrane device can be used, and a commercially available product can be used.
- Evaporation process, crystallization process The evaporation process and the crystallization process may be performed in the same manner as in the first embodiment.
- the inflow means for the accompanying water containing calcium ions, soluble silica, and water-soluble organic matter produced from the well, water-soluble magnesium salt and water-soluble aluminum salt in a predetermined blending amount Means for adding; alkali adding means; first reaction tank having tank outflow means; first reaction liquid inflow means in said first reaction tank; and coagulation tank having polymer flocculant adding means; A solid-liquid separation means for the coagulated liquid flowing out from the coagulation tank, an inflow means for separated water flowing out from the solid-liquid separation means, an acid addition means, a second reaction tank having an outflow means for liquid in the tank, An adjoining water treatment apparatus having a reverse osmosis membrane apparatus installed on the downstream side of the second reaction tank, wherein the pH value of the liquid in the first reaction tank is adjusted to a range of 10.5 to 11. 1 adjusting means and a second flow out of the second reaction tank The pH value of the reaction solution in the range from 5 to 9, and can be carried out using the produced water
- 1 is a 1st reaction tank
- medical agent addition means is water-soluble magnesium
- the first reaction tank 1 is the same as the first reaction tank of FIG. 2 except that a nitrogen gas supply pipe is connected to the bottom of the reaction tank and an air diffusion hole 15 for aeration of the inside is provided.
- the inflow means 16 includes a pipe, an on-off valve, a pump, and the like.
- the agglomeration tank 17 is provided with a stirrer, a tank for accommodating the polymer flocculant, a pipe, a flow rate adjusting valve, a constant flow pump, and the like as the polymer flocculant addition means 18.
- the outlet side of the coagulation tank 17 is connected to solid-liquid separation means 19.
- This solid-liquid separation means 19 is a coagulation sedimentation tank and a microfiltration membrane treatment.
- the outlet side of the solid-liquid separation means 19 is connected to the second reaction tank 7, and the subsequent steps are the same as in the first mode.
- a 5N sodium hydroxide aqueous solution was added to 100 L of adjoining water containing 5000 mg / L of calcium ions, 120 mg / L of soluble silica and 300 mg / L of sulfate ions produced from a well to obtain a pH of 10.5.
- the mixture was added (Mg added amount: 10 g), and slowly stirred at room temperature for 30 minutes to precipitate insoluble silica and calcium sulfate.
- the obtained first reaction solution was filtered through a microfiltration membrane having a pore size of 0.1 ⁇ m to obtain 90 L of filtered water having a pH of 10.4 containing 4900 mg / L of calcium ions.
- the resulting second reaction solution having a Langelia index of -0.6 was treated with a reverse osmosis membrane to obtain 45 L of fresh water and 45 L of membrane concentrated water.
- This solution was able to operate stably for a long time without precipitation of calcium carbonate on the reverse osmosis membrane surface.
- the second reaction liquid with a Langeriaria index of +0.5 calcium carbonate was deposited on the reverse osmosis membrane surface, and the water flow rate decreased with the start of operation, and eventually no permeate was obtained.
- the membrane concentrated water obtained by the reverse osmosis membrane treatment was further concentrated by an evaporator and condensed to obtain 30 L of fresh water and 15 L of concentrated water.
- the concentrated water was further concentrated in a crystallizer, and 14.5 L of fresh water obtained by condensation was obtained.
- the residual liquid was 0.5 L, and a large amount of salts were precipitated.
- the second reaction solution thus obtained was subjected to reverse osmosis membrane treatment to obtain 45 L of fresh water and 45 L of membrane concentrated water. This solution was able to operate stably for a long time without precipitation of calcium carbonate on the reverse osmosis membrane surface.
- the membrane concentrated water obtained by the reverse osmosis membrane treatment was further concentrated by an evaporator and condensed to obtain 30 L of fresh water and 15 L of concentrated water.
- the concentrated water was further concentrated in a crystallizer, and 14.5 L of fresh water obtained by condensation was obtained.
- the residual liquid was 0.5 L, and a large amount of salts were precipitated.
- the present invention can be widely used in a method of obtaining fresh water by treating accompanying water because silica is efficiently separated from the accompanying water produced from the well and there is no clogging in the membrane filtration process due to precipitation of calcium carbonate.
- Second reaction tank 8 Acid addition means 9: Adjustment means 10: Outflow means 11: Reverse osmosis membrane treatment means 12: Evaporation apparatus 13: Crystallization apparatus 14: Nitrogen gas replacement means 15: Air diffuser 16: Inflow means 17: Coagulation tank 18: Polymer flocculant addition means 19: Solid-liquid separation means
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Abstract
Description
また、水中の炭酸イオン濃度を減らすことで、吸着するシリカ濃度を増やすことも見出した。
マグネシウム塩はアルカリ性水溶液に可溶なものがよく、塩化マグネシウム、酸化マグネシウム、炭酸マグネシウムなどを使用できる。マグネシウムの添加量は、シリカに対するモル比で1~4程度、好ましくは1~2程度が適当である。添加形態は水溶液、スラリー、粉体などいずれの形態でもよい。
得られた第1反応液は、精密ろ過膜でろ過して生成した不溶性シリカと硫酸カルシウムを分離する。精密ろ過膜は通常の膜を使用することができ、例えば、酢酸セルロース、ポリテトラフルオロエチレン、ポリスルホン、ポリ塩化ビニルなどの外、セラミック製の膜や多孔質ガラス製の膜なども利用できる。精密ろ過膜の好ましい孔径は特に指定しないが,0.1μm以下であることが望ましい。精密膜ろ過処理では、精密ろ過膜を通過したろ過水が得られ,精密ろ過膜に捕捉された不溶性シリカや硫酸カルシウムを含む懸濁物質は定期的に行われる逆流洗浄により排出される。逆流洗浄水中の懸濁物質は沈殿槽などの固液分離工程を経て減容化して廃棄すると共に,上澄み水は原水に返送する。
本発明では、精密膜ろ過工程で分離されたろ過水中にカルシウムが高濃度で残存していることを見出した。
pHは水の実際のpH値であり、pHsは水中に炭酸カルシウムが溶解も析出もしない平衡状態にあるときの理論上のpH値である。
Ca2+(meq/L) … Ca2+(mg/L)÷(40.1÷2)
A(総アルカリ度)(meq/L) … 総アルカリ度(mg/L)÷(100÷2)
総アルカリ度とは水中に含まれる炭酸水素塩、炭酸塩または水酸化物等のアルカリ分の指標。自然水中の総アルカリ度は炭酸塩または炭酸水素塩が主体をなすことが多く、総アルカリ度が高い場合には、CaやMgの硬度成分と結合して析出物を生成する物質が多いことをあらわす。総アルカリ度(mg/L)は、pH4.8までの酸消費量であり、塩酸または硫酸で滴定することによって分析できる。
本発明では、ランゲリア指数がマイナスになるように、好ましくは、-0.5~0未満の範囲になるようにする。ランゲリア指数が正の場合には、スケール成分が析出するため逆浸透膜の目詰まりが発生しやすくなる。一方、ランゲリア指数が-0.5より低すぎる場合には、逆浸透膜の処理水pHが6より低くなり、RO膜処理水に苛性ソーダ等のアルカリ剤の注入が必要になることが想定される。
酸添加工程で酸を添加して得られた第2反応液は逆浸透膜装置で処理して淡水と膜濃縮水を得る。逆浸透膜は通常の膜を使用すればよく、例えば、酢酸セルロース、ポリスルホン、脂肪族ポリアミド、芳香族ポリアミドなど各種の材料のものを用いることができる。装置も市販の逆浸透膜装置を用いることができる。
膜濃縮水を加熱濃縮してさらに濃縮する。濃縮は常圧で行っても減圧で行ってもよい。濃縮によって得られた蒸気は放出してもよいが、熱交換器などを用いて凝縮させて淡水を得、これを掘削用水などに再利用することができる。
蒸発工程で得られた濃縮水は、さらに加熱濃縮して、塩類を晶析分離することができる。その際、発生する蒸気は熱交換器などを用いて凝縮させて淡水を得、これを掘削用水などに再利用することができる。一方、残った濃縮液には塩類が晶析されてスラリーとなっている。このスラリーは固液分離して、母液は廃棄処理し、結晶は環境汚染成分をほとんど含んでいなければ融雪剤などに利用することもできる。
水溶性マグネシウム塩は、塩化マグネシウム、硝酸マグネシウムなどであり、水溶性アルミニウム塩は、塩化アルミニウム、硝酸アルミニウム、ポリ塩化アルミニウムなどである。添加量は、(Mg+Al)/SiO2のモル比で、1から2程度が適当である。モル比で1未満になるとシリカ除去性能が不十分であり、一方、2を超えると未反応のMg、Alが溶存して薬剤費が嵩むとともに、塩濃度が上昇するため、後段の逆浸透膜処理工程や蒸発工程などに負荷がかかる。Mg/Alのモル比では1から4になる程度が適当である。ケイ酸の初期濃度を120mg/Lとし、これに塩化マグネシウムとポリ塩化アルミニウムを(Mg+Al)/SiO2が1の場合と2の場合について、Alの割合を変えて添加1、pH10.5で反応させてSiO2の残存濃度を測定した結果を図6に示す。溶存シリカが分子状のシリカの場合はAl単独処理が望ましいが,図8に示すように汚泥発生量が多くなり,汚泥処分費が嵩むという問題が生じる。また、アルミニウム(ポリ塩化アルミニウム中のAl)を760円/kg、マグネシウム(塩化マグネシウム6水和物中のMg)を590円/kgとして、除去したSiO2あたりの薬剤量を計算した結果を図7に示す図7からはAl割合が0.2~0.8すなわちMg/Alでは4/1~1/4でも良いが、Alが多いと汚泥発生量が増加する傾向があるため、Mg/Alは1から4が好ましい。上記モル比は、マグネシウムとアルミニウムがいずれも1個の化合物としたモル比である。添加形態は、水溶液、スラリー、粉体などいずれの形態でもよく、添加順序もいずれが先でもあるいは同時でもよい。
さらに、反応槽を完全密封し、気相部を窒素置換すること、または窒素曝気を行うことで、大気からの二酸化炭素溶解を少なくすることが好ましい。ハイドロタルサイト様物質は炭酸イオンを優先的に取り込むため、シリカを含む他の陰イオンの取り込みを阻害する水中の炭酸イオン濃度はなるべく低いことがのぞましい。
上記シリカ析出処理工程で得られた第1処理液に凝集剤、好ましくは高分子凝集剤を加えて析出したシリカを凝集させる。高分子凝集剤には、ポリアクリルアミド系のアニオン凝集剤などを用いることができ、添加量は1mg/L~2mg/L程度が適当である。添加はシリカ析出後に行う。凝集処理の時間はシリカ析出後15分~1時間程度でよい。
析出したシリカの凝集処理が終ったら凝集物の分離を行う。分離手段は、沈殿分離、遠心分離、ろ過などを利用することができる。
酸添加工程は第1の態様と同様に行えばよい。また,沈殿分離後,精密膜ろ過処理前に行ってもよい。
逆浸透膜処理工程も第1の態様と同様に行えばよい。
蒸発工程と晶析工程は第1の態様と同様に行えばよい。
2:流入手段
3:薬剤添加手段
4:流出手段
5:MF膜ろ過装置
6:流入手段
7:第2反応槽
8:酸添加手段
9:調整手段
10:流出手段
11:逆浸透膜処理手段
12:蒸発装置
13:晶析装置
14:窒素ガス置換手段
15:散気孔
16:流入手段
17:凝集槽
18:高分子凝集剤添加手段
19:固液分離手段
Claims (20)
- 坑井から産出された、カルシウムイオン、溶解性シリカ、硫酸イオンを含む随伴水にアルカリ性の条件下でマグネシウム塩を添加、混合して、不溶性のシリカと硫酸カルシウムを生成させるマグネシウム塩添加工程と、前記マグネシウム塩添加工程で得られた第1反応液を精密膜ろ過処理して、不溶化したシリカおよび硫酸カルシウムをろ過分離する精密膜ろ過処理工程と、前記精密膜ろ過処理工程で得られたろ過水に酸を添加、混合して、前記ろ過水のpH値を5から9の範囲内、かつ、ランゲリア指数を負の範囲とする酸添加工程と、前記酸添加工程で得られた第2反応液を逆浸透膜処理して、淡水と膜濃縮水を得る逆浸透膜処理工程とを有することを特徴とする随伴水処理方法。
- 前記膜濃縮水を加熱し、発生した蒸気を凝縮させて淡水を得ると共に、さらなる濃縮水を得る蒸発工程を有することを特徴とする、請求項1に記載の随伴水処理方法。
- 前記濃縮水を加熱して、含有する塩類を晶析分離すると共に、発生した蒸気を凝縮させて淡水を得る晶析工程を有することを特徴とする、請求項2に記載の随伴水処理方法。
- 得られた淡水の少なくとも一部を前記坑井の掘削用水として再利用することを特徴とする、請求項1から3の何れか1つに記載の随伴水処理方法。
- 坑井から産出された、カルシウムイオン、溶解性シリカ、硫酸イオンを含む随伴水の流入手段と、アルカリ剤とマグネシウム塩の薬剤添加手段と、槽内液の流出手段を有する第1反応槽と、前記第1反応槽の後流側に設置された精密膜ろ過装置と、前記精密膜ろ過装置から流出するろ過水の流入手段と、酸添加手段と、槽内液の流出手段を有する第2反応槽と、前記第2反応槽の後流側に設置された逆浸透膜装置とを有する随伴水処理装置であって、前記第2反応槽から流出する反応液のpH値を5から9の範囲内、かつ、ランゲリア指数を負の範囲内に調整する調整手段を設けたことを特徴とする随伴水処理装置。
- 前記逆浸透膜装置の後流側に、前記逆浸透膜装置から流出する膜濃縮水を加熱し、発生した蒸気を冷却し、凝縮させて淡水を得ると共に、さらなる濃縮水を得る蒸発装置を有することを特徴とする、請求項5に記載の随伴水処理装置。
- 前記蒸発装置の後流側に、前記蒸発装置から流出する濃縮水を加熱し、含有する塩類を晶析分離すると共に、発生した蒸気を冷却し、凝縮させて淡水を得る晶析装置を有することを特徴とする、請求項6に記載の随伴水処理装置。
- 坑井から産出された、カルシウムイオン、溶解性シリカ、水溶性有機物を含む随伴水に、水溶性マグネシウム塩と水溶性アルミニウム塩とを(Mg+Al)/SiO2(モル比)が1から2、かつ、Mg/Al(モル比)が1から4となるよう添加するとともに、アルカリを添加し、pH値を10.5から11の範囲に調整し、不溶性のシリカを生成させるシリカ析出処理工程と、前記シリカ析出処理工程で得られた第1反応液に凝集剤を添加し、混合する凝集処理工程と、前記凝集処理工程で得られた処理液を固液分離する固液分離工程と、前記固液分離工程で得られた分離水に酸を添加、混合して、前記分離水のpH値を5から9の範囲内、かつ、ランゲリア指数を負の範囲とする酸添加工程と、前記酸添加工程で得られた第2反応液を逆浸透膜処理して、淡水と膜濃縮水を得る逆浸透膜処理工程とを有することを特徴とする随伴水処理方法。
- 前記シリカ析出処理工程が窒素雰囲気下で行なわれることを特徴とする請求項8に記載の随伴水処理方法。
- 前記逆浸透膜処理に替えて正浸透膜処理を行なうことを特徴とする請求項8又は請求項9に記載の随伴水処理方法。
- 前記膜濃縮水を加熱し、発生した蒸気を凝縮させて淡水を得ると共に、さらなる濃縮水を得る蒸発工程を有することを特徴とする、請求項8乃至請求項10のいずれか1項に記載の随伴水処理方法。
- 前記濃縮水を加熱して、含有する塩類を晶析分離すると共に、発生した蒸気を凝縮させて淡水を得る晶析工程を有することを特徴とする、請求項11に記載の随伴水処理方法。
- 前記淡水を前記坑井の掘削用水として再利用することを特徴とする、請求項8乃至請求項12のいずれか1項に記載の随伴水処理方法。
- 坑井から産出された、カルシウムイオン、溶解性シリカ、水溶性有機物を含む随伴水の流入手段と、水溶性マグネシウム塩と水溶性アルミニウム塩を所定の配合量で添加する手段と、アルカリ添加手段と、槽内液の流出手段を有する第1反応槽と、前記第1反応槽における第1反応液の流入手段と凝集剤添加手段を有する凝集槽と、前記凝集槽から流出した凝集液の固液分離手段と、前記固液分離手段から流出する分離水の流入手段と、酸添加手段と、槽内液の流出手段を有する第2反応槽と、前記第2反応槽の後流側に設置された逆浸透膜装置とを有する随伴水処理装置であって、前記第1反応槽内の液のpH値を10.5から11の範囲に調整する第1調整手段と、前記第2反応槽から流出する第2反応液のpH値を5から9の範囲内、かつ、ランゲリア指数を負の範囲内に調整する第2調整手段を設けたことを特徴とする随伴水処理装置。
- 前記第1反応槽が、該槽内の気相部分を窒素に置換する手段あるいは該槽内の液に窒素を曝気する手段を有することを特徴とする請求項14に記載の随伴水処理装置。
- 前記逆浸透膜装置に替えて、正浸透膜装置を備えたことを特徴とする請求項14又は請求項15に記載の随伴水処理装置。
- 前記逆浸透膜装置の後流側に、前記逆浸透膜装置から流出する膜濃縮水を加熱し、発生した蒸気を冷却し、凝縮させて淡水を得ると共に、さらなる濃縮水を得る蒸発装置を有することを特徴とする、請求項14または請求項15に記載の随伴水処理装置。
- 前記蒸発装置の後流側に、前記蒸発装置から流出する濃縮水を加熱し、含有する塩類を晶析分離すると共に、発生した蒸気を冷却し、凝縮させて淡水を得る晶析装置を有することを特徴とする、請求項17に記載の随伴水処理装置。
- 前記正浸透膜装置の後流側に、前記正浸透膜装置から流出する膜濃縮水を加熱し、発生した蒸気を冷却し、凝縮させて淡水を得ると共に、さらなる濃縮水を得る蒸発装置を有することを特徴とする、請求項16に記載の随伴水処理装置。
- 請求項19に記載の発明において、前記蒸発装置の後段に、前記蒸発装置から流出する濃縮水を加熱し、含有する塩類を晶析分離すると共に、発生した蒸気を冷却し、凝縮させて淡水を得る晶析装置を有することを特徴とする、請求項19に記載の随伴水処理装置。
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