CN115626731B - System and method for reducing hardness of high-salt wastewater by three-stage reaction - Google Patents
System and method for reducing hardness of high-salt wastewater by three-stage reaction Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000007788 liquid Substances 0.000 claims abstract description 151
- 238000005406 washing Methods 0.000 claims abstract description 120
- 239000010881 fly ash Substances 0.000 claims abstract description 79
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000006722 reduction reaction Methods 0.000 claims abstract description 22
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
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- 229910001425 magnesium ion Inorganic materials 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000001095 magnesium carbonate Substances 0.000 claims description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims description 10
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- 239000002956 ash Substances 0.000 claims description 5
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 24
- 238000000746 purification Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
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- -1 CaCO 3 Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of high-salt wastewater water quality purification treatment, and relates to a system and a method for reducing the hardness of high-salt wastewater by utilizing three-stage reaction. The hardness of fly ash washing liquid is reduced through three-level hardness reduction reaction of CO 2-Na2SO4-Na2CO3. Firstly, CO 2 is utilized to reduce 10-40% of total hardness of the fly ash water washing liquid; secondly, reducing the hardness of the original fly ash washing liquid by 60-90% by adding Na 2SO4; and then, the hardness of the fly ash water washing liquid is reduced to the standard required to be reached by utilizing Na 2CO3, so that the recycling of CO 2 can be realized, and raw materials such as Ca (OH) 2、NaOH、Na2CO3 and the like can be replaced by CO 2、Na2SO4, the pH of the fly ash water washing liquid is reduced, and the purification cost of the fly ash water washing liquid is reduced.
Description
Technical Field
The invention belongs to the technical field of high-salt wastewater water quality purification treatment, and relates to a system and a method for reducing the hardness of high-salt wastewater by utilizing three-stage reaction.
Background
In recent years, global warming has become increasingly serious. To address the problem of climate warming, there is a need to reduce greenhouse gas emissions, the core of which is to reduce carbon dioxide emissions.
Therefore, the content of calcium and magnesium ions in the fly ash water washing liquid is reduced by utilizing carbon dioxide, and the purpose of reducing the pH value is achieved, so that the fly ash water washing liquid meets the requirement of subsequent evaporation salt making treatment. The technology is used as one of links of recycling treatment of dangerous wastes, and can effectively utilize carbon dioxide generated in an industrial production process.
Fly ash is a powder material with light volume weight and small particle size generated in the incineration process of garbage, and the total amount of the fly ash accounts for about 3-5% of the treatment capacity of biological garbage. At present, the harmless, the reduction and the recycling treatment of the fly ash can be realized greatly by utilizing the fly ash washing technology to treat the fly ash and then utilizing the fly ash. However, in the process of washing the fly ash, cl -、Na+、K+、Ca2+、Mg2+, heavy metal ions and the like can enter the washing liquid to form high-hardness high-salt wastewater, so that the temporary hardness and the permanent hardness of the washing liquid are increased, and the difficulty and the cost of water quality purification of the washing liquid are increased, so that how to reduce the hardness of the fly ash washing liquid with low cost becomes a great difficulty for restricting the development of the fly ash washing technology and the washing liquid purification technology.
The method for reducing the hardness in the water treatment process mainly comprises a double-alkali method, an electrochemical method, an ion exchange method, a membrane separation method and the like, and the methods can reduce the hardness of the water body, but have the defects of high cost, easiness in causing secondary pollution and the like, for example, the double-alkali method reduces the hardness of the water body through the reaction of lime, na 2CO3, CO 3 2-、SO4 2-、Ca2+、Mg2+ and the like in the water body to form CaCO 3、MgCO3、Ca(OH)2、 CaSO4、MgSO4 and the like, but can raise the pH of the water body, and hydrochloric acid or sulfuric acid needs to be added to adjust the pH of the water body at the later stage and the like.
In the prior art, china patent No. 202111253789.8 discloses a process for reducing the hardness of a fly ash water washing liquid by coupling CO 2 with alkali metal hydroxide, which mainly adds CO 2 purified by kiln tail smoke and alkali metal hydroxide into the fly ash water washing liquid, improves the concentration of CO 3 2- in the water washing liquid to form a large amount of calcium carbonate precipitate, reduces the hardness of the fly ash water washing liquid, simultaneously can recycle CO 2, and combines with NaOH to replace Na 2CO3, thereby reducing the treatment cost of the fly ash water washing liquid.
The Na 2O、K2 O, caO and other substances in the fly ash can generate NaOH, KOH, ca (OH) 2 and other alkali metal hydroxides in the water washing liquid, so that the water washing liquid has higher pH, the pH of the fly ash water washing liquid can be reduced after a certain amount of CO 2 is introduced, and the subsequent dissolution of CO 2 is restrained, so that NaOH is sequentially or simultaneously added to maintain the pH of the fly ash water washing liquid, however, the process needs to carry out multiple cyclic treatments according to the hardness of the fly ash water washing liquid until the hardness is less than 200, a large amount of NaOH is consumed to maintain the dissolution of CO 2, the fly ash water washing liquid has higher pH, and the treatment cost of the fly ash water washing liquid in the later process is increased.
The invention of China patent 2015100001918.2 discloses a device for removing hardness and reducing pH of ash water washing liquid generated by waste incineration, which mainly comprises a stirring tank, a centrifugal machine and a bubbling reactor, wherein a large amount of CO 2 is introduced into the water washing liquid to reduce the hardness and pH value of the water washing liquid, the stirring tank is provided with an ash water washing liquid inlet and an alkali liquid inlet which are communicated with each other, a liquid outlet of the centrifugal machine is communicated with a spraying port at the upper end of the bubbling reactor, and a gas carbon dioxide inlet is arranged at the bottom of the bubbling reactor. Also discloses a method for removing hardness and reducing pH value of the waste incineration fly ash washing liquid. The invention uses a large amount of CO 2 generated at the tail of the cement kiln to reduce the hardness and the pH value, thereby reducing the carbon emission and lowering the cost. By setting the pH value, the system can automatically adjust the amount of CO 2, and has high control precision and stable operation.
The method comprises the steps of adding NaOH solution to adjust the hardness to 800-1200mg/L, leading CO 2 to a pH of 7-9, and then leading the CO 2 to a hardness of less than 50mg/L, wherein a large amount of alkali liquor is consumed to adjust the hardness of the fly ash washing liquid, and the difficulty of reducing the residual hardness by using CO 2 is gradually increased along with the dissolution of a large amount of CO 2 into the fly ash washing liquid, so that excessive CO 2 is wasted, and the method is inaccurate only by taking the pH value as a reference.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a system and a method for reducing the hardness of high-salt wastewater by utilizing three-stage reaction.
The technical scheme of the invention is as follows: the system for reducing the hardness of the high-salt wastewater by utilizing the three-stage reaction comprises a CO 2 first-stage reaction system, a Na 2SO4 second-stage reaction system and a Na 2CO3 third-stage reaction system.
The CO 2 first-stage reaction system comprises a water quality online measuring device 1, a CO 2 storage device, a first-stage reactor, a sludge collecting device and a water quality online measuring device 2. The gas outlet of the CO 2 storage device is connected with the gas inlet of the primary reactor, the liquid phase inlet of the primary reactor is the fly ash washing liquid inlet, and the liquid phase outlet of the primary reactor is connected with the inlet of the secondary reactor; and the inlet of the sludge collecting device is connected with the solid phase outlet of the primary reactor.
Further, an air outlet of the CO 2 storage device is connected with an air inlet of the primary reactor;
Further, the outlet of the sludge collecting device is connected with the fly ash washing unit;
further, the water quality online measuring device 1 is positioned at the water inlet of the primary reactor and is used for collecting data such as flow, pH, hardness and the like in the fly ash water washing liquid; the water quality online measuring device 2 is connected with the primary reactor and is used for collecting data such as pH, hardness and the like of ash flying water washing liquid in the primary reactor.
The Na 2SO4 secondary reaction system comprises a Na 2SO4 pre-dissolving device, a secondary reactor, a solid-liquid separation device and a water quality on-line measuring device 3. The Na 2SO4 is connected with a feed inlet of the Na 2SO4 pre-dissolving device; the outlet of the Na 2SO4 pre-dissolving device is connected with the Na 2SO4 solution inlet of the secondary reactor; and the liquid phase outlet of the secondary reactor is connected with the inlet of the solid-liquid separation device.
The solid-liquid separation device liquid phase outlet is connected with the third-stage reactor inlet, and the second-stage reactor solid phase outlet and the solid-liquid separation device solid phase outlet are both connected with the sludge collection device; the water quality on-line measuring device 3 is connected with the secondary reactor.
The Na 2CO3 three-stage reaction system comprises a Na 2CO3 pre-dissolving device, a three-stage reactor, a membrane filtering device, a softening water tank, a water quality online measuring device 4 and a water quality online measuring device 5.
The Na 2CO3 medicament is connected with a feed inlet of a Na 2CO3 pre-dissolving device, and an outlet of the Na 2CO3 pre-dissolving device is connected with a Na 2CO3 solution inlet of the three-stage reactor; the liquid phase outlet of the three-stage reactor is connected with the inlet of the membrane filtering device; the liquid phase outlet of the membrane filtering device is connected with the inlet of the softening water tank through a pipeline, and the concentrated solution outlet is connected with the sludge collecting device; the liquid phase outlet of the membrane filtering device is connected with the water inlet of the softening water tank; the liquid phase outlet 1 of the softening water tank enters the subsequent process through a pipeline, and the outlet 2 is connected with the liquid phase inlets of the Na 2SO4 pre-dissolving device and the Na 2CO3 pre-dissolving device; the soft water tank emptying port is connected with the sludge collecting device; the water quality on-line measuring device 4 is connected with the three-stage reactor; the water quality on-line measuring device 5 is connected with a softening water tank.
The second technical scheme of the invention is a method for reducing the hardness of high-salt wastewater by utilizing three-stage reaction, which comprises the following steps:
The method comprises the steps of (1) measuring data such as initial flow, pH, hardness and the like of fly ash washing liquid entering a primary reactor through a water quality online measuring device 1, and calculating the dosage of CO 2 aeration quantity, na 2SO4 and Na 2CO3 solution which can meet the water quality requirement according to the data; the actual total addition mass of CO 2-Na2SO4-Na2CO3 is 1.0-1.5 times of the theoretical value, and the addition mass proportion of CO 2-Na2SO4- Na2CO3 is (10% -40%): (60% -90%): (10% -40%).
Introducing CO 2 in a CO 2 storage device into a first-stage reactor according to set aeration quantity, temperature and pressure, dissolving CO 2 by a gas distribution device and a stirring device in the first-stage reactor, fully reacting with Ca 2+、Mg2+ and the like in water washing liquid, returning the residual gas into the CO 2 storage device through a gas outlet for reuse, and introducing the fly ash water washing liquid into a second-stage reactor after primary hardness reduction reaction; solid precipitates such as CaCO 3、MgCO3 and the like are collected by a sludge collecting device; the pH and hardness change of fly ash water washing liquid in the first-level hardness reduction reaction process is measured by the water quality on-line measuring device 2.
Principle of CO 2 to reduce hardness and pH: the calcium in the high-salt wastewater mainly exists in the form of Ca (OH) 2、CaSO4, according to the solution precipitation balance under certain temperature and pressure, ca 2+ concentration is further reduced, ca 2+ can be converted into CaCO 3 for removal, Under alkaline condition, CO 2 gas is introduced to react with Ca 2+ to generate insoluble Ca 2+ precipitate, and the precipitate is filtered to reduce the hardness of the water washing liquid. CO 2 is easy to dissolve in water to form carbonic acid (H 2CO3), the carbonic acid is weak acid, H +、HCO3 - and CO 3 2-,H+ can be ionized in water to neutralize OH － in alkaline water to play a role in regulating the pH of water, The CO 3 2- reacts with Ca 2+、Mg2+ ions in water to form a precipitate, which acts to reduce hardness. When the pH of the water washing liquid is reduced to a certain degree, the hardness reducing efficiency of CO 2 is obviously reduced, and the hardness reducing effect of CO 2 is fully exerted by controlling the water inlet flow, CO 2 aeration and the like in the primary reactor, and then the water washing liquid is introduced into the secondary reactor, The tertiary reactor continues to reduce hardness with Na 2SO4、Na2CO3.
And (3) adding a certain amount of Na 2SO4 solution into the secondary reactor, adjusting the adding mode, the dosage, the stirring mode and the like of the Na 2SO4 solution in real time according to the data of the water quality online measuring devices 1, 2 and 3, wherein the Na 2SO4 solution is intermittently added for 10-50 minutes, and a stirrer is arranged in the secondary reactor for fully mixing and reacting Na 2SO4 with Ca 2+ in the water washing liquid, and the stirring speed is 30-80 revolutions per minute.
Principle of Na 2SO4 to reduce hardness: and the SO 4 2- and the Ca 2+ are utilized to form CaSO 4 sediment, the concentration of the Ca 2+ in the water washing liquid is reduced, SO that the effect of reducing the hardness is achieved, the supersaturation degree in the reactor is gradually increased and controlled by intermittently adding the Na 2SO4, SO that the SO 4 2- and the Ca 2+ fully form sediment, and excessive SO 4 2- can be avoided. Depending on the nature of CaSO 4、MgSO4, the water wash entering the tertiary reactor still contains a small amount of Ca 2+、Mg2+, which can be further reduced in hardness by Na 2CO3.
Step (4), introducing the mixed solution obtained in the step (3) into a solid-liquid separation device to obtain sludge and water washing liquid, and enabling the sludge to enter a sludge collecting device in the step (2) through a pipeline; the water washing liquid enters a three-stage reactor to carry out a three-stage hardness reduction reaction.
And (5) adding a certain amount of Na 2CO3 solution into the three-stage reactor, adjusting the adding mode, the dosage, the stirring mode and the like of the Na 2CO3 solution in real time according to the data of the water quality on-line measuring devices 1, 2, 3 and 4, wherein the Na 2CO3 solution is intermittently added for 10-50 minutes, and a stirrer is arranged in the three-stage reactor for fully mixing and reacting Na 2CO3 with Ca 2+ in the water washing liquid, and the stirring rotating speed is 30-80 revolutions per minute.
Principle of Na 2CO3 to reduce hardness: the CO 3 2- in Na 2CO3 and Ca 2+、Mg2+ in the three-stage reactor are utilized to form CaCO 3、MgCO3 precipitate, the hardness of the water washing liquid is reduced again, and the CO 3 2- and Ca 2+、Mg2+ are fully formed into the precipitate by gradually increasing and controlling the supersaturation degree in the reactor by intermittently adding Na 2CO3 and utilizing the water-insoluble property of CaCO 3、 MgCO3.
Step (6), filtering the mixed solution obtained in the step (5) by using a membrane filtering device, and simultaneously filtering excessive SO 4 2-、CO3 2- in the water washing liquid; the clear liquid passing through the membrane filtering device is connected into a softening water tank through a pipeline, and the concentrated liquid enters the sludge collecting device in the step (2) through a pipeline;
the water quality of the softened water is measured through a water quality online measuring device 5, and after the softened water meets the requirement of a later process on the water quality, the softened water can be subjected to subsequent treatment, wherein part of the softened water flows back to a Na 2SO4 pre-dissolving device, a Na 2CO3 pre-dissolving device, a solid-liquid separation device, a membrane filtering device through a pipeline for recycling, device flushing and the like;
And (8) comparing and analyzing data acquired by the online water quality measuring device in the system, establishing a real-time database of three-level CO 2-Na2SO4-Na2CO3 hardness reduction reaction, utilizing the database to simulate a mode of combining with the real-time data of the online water quality measuring devices 1,2, 3, 4 and 5, controlling the dosage, proportion, adding mode and the like of CO 2、Na2SO4 and Na 2CO3, and adjusting the pH, hardness and other parameters of the fly ash washing liquid in different reaction stages, so that the fly ash washing liquid can finally meet the requirements of the subsequent process.
1. The hardness of fly ash washing liquid is reduced through three-level hardness reduction reaction of CO 2-Na2SO4-Na2CO3:
firstly, CO 2 is utilized to reduce 10-40% of total hardness of the fly ash water washing liquid;
secondly, reducing the hardness of the original fly ash washing liquid by 60-90% by adding Na 2SO4;
Then Na 2CO3 is utilized to reduce the hardness of the fly ash water washing liquid to the standard required to be reached, so that the recycling of CO 2 can be realized,
CO 2、Na2SO4 can be used for replacing Ca (OH) 2、NaOH、Na2CO3 and other raw materials, so that the pH value of the fly ash washing liquid is reduced, and the purification cost of the fly ash washing liquid is reduced;
2. a hardness adjusting system of fly ash washing liquid is established, the required dosage and proportion of CO 2、 Na2SO4 and Na 2CO3 are adjusted in real time according to the pH, hardness and other data of the washing liquid, chemical properties of CO 2、Na2SO4、Na2CO3 are fully utilized to stabilize the hardness, pH and other indexes of the washing liquid, dynamic hardness adjustment is achieved, the dosage of medicaments is saved, excessive medicaments are avoided, and the cost of a later process is reduced.
Advantageous effects
Compared with the prior art, the invention has the following technical effects:
1. the hardness of the water washing liquid can be greatly reduced by utilizing the three-level hardness reduction reaction of CO 2-Na2SO4-Na2CO3, and the water quality requirement of the subsequent process on the fly ash water washing liquid is met.
2. The low-cost CO 2、Na2SO4 is utilized to replace Ca (OH) 2、NaOH、Na2CO3 and other raw materials, so that the effective utilization of CO 2 is realized, the cost of purifying the water quality of the fly ash water washing liquid is reduced, the pH rise of the water washing liquid caused by adding alkaline substances is avoided, and the treatment difficulty and cost of the subsequent process to the fly ash water washing liquid are reduced.
3. The required dosage, proportion and the like of the CO 2、Na2SO4 and the Na 2CO3 are calculated in real time according to the hardness condition of the water washing liquid, the properties of the fly ash water washing liquid and the CO 2、Na2SO4、Na2CO3 are fully utilized, the dynamic regulation of the hardness is realized, and meanwhile, the excessive medicament can be avoided, so that the medicament cost in the purification process of the fly ash water washing liquid is reduced.
Drawings
FIG. 1 is a flow chart of a method.
Fig. 2 is a process flow diagram.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
As shown in fig. 1 and 2, in the step (1), the data such as initial flow, pH, hardness and the like of the fly ash washing liquid entering the primary reactor are measured by the water quality online measuring device 1, theoretical values of the aeration quantity of the CO 2, the dosages of the Na 2SO4 and Na 2CO3 solutions and the hardness in each reaction stage which can meet the requirement of the water quality of the later process are calculated according to the data, the actual total addition mass of the CO 2-Na2SO4- Na2CO3 is 1.2 times of the theoretical values, and the addition mass proportion of the CO 2-Na2SO4-Na2CO3 is 10%:80%:10%;
Step (2) introducing CO 2 in a CO 2 storage device into a primary reactor according to a dosage of 10% of the total hardness, fully dissolving CO 2 by a gas distribution device and a stirring device in the primary reactor, and reacting with Ca 2+、Mg2+ and the like in water washing liquid; solid precipitates such as CaCO 3、MgCO3 and the like are collected by a sludge collecting device and then sent to a washing unit; the fly ash washing liquid is introduced into a secondary reactor after the primary hardness reduction reaction; the change condition of the data such as pH, hardness and the like of the fly ash washing liquid in the first-stage hardness reduction reaction process is measured by the water quality online measuring device 2.
Step (2-1), using a CO 2 gas distribution device to fully contact and react CO 2 with the fly ash water washing liquid;
introducing CO 2 gas with sufficient aeration quantity into 4 porous pipes which are deep under the liquid level in a continuous or intermittent mode, promoting the CO 2 to be fully dissolved into fly ash washing liquid by controlling gas pressure, CO 2 aeration quantity, stirring rotation speed and the like, and returning the residual gas to a CO 2 storage device through a gas outlet of the primary reactor for reuse;
In the step (2-2), in the reaction process of the primary hardness reduction, the online water quality measuring device 2 is utilized to collect data such as pH, hardness and the like in real time, and the introducing mode, pressure, aeration quantity, stirring rotation speed and the like of the CO 2 are adjusted according to the data, and when the pH in the primary reactor is lower than 11, fly ash water washing liquid can be introduced into the secondary reactor to carry out the secondary hardness reduction reaction;
Step (2-3) is that CO 3 2- in step (2) reacts with Ca 2+、Mg2+ in the washing liquid to generate CaCO 3、MgCO3 solid precipitate, the CaCO 3、MgCO3 solid precipitate enters a sludge collecting device and is discharged to a washing unit through a pipeline, so that the recycling of CaCO 3、MgCO3 can be realized;
Adding Na 2SO4 solution capable of removing 80% of the total hardness into the secondary reactor in an intermittent feeding mode, and fully reacting SO 4 2- with Ca 2+ through a stirring device in the secondary reactor;
Step (3-1) preparing Na 2SO4 solution with concentration of 10% in a Na 2SO4 pre-dissolving device by using Na 2SO4 and softened water;
The Na 2SO4 solution in the step (3-2) is added into a secondary reactor through four porous pipes which extend into the position below the liquid level, SO 4 2- in the Na 2SO4 solution fully reacts with Ca 2+ and the like in the ash flying washing liquid under the stirring effect of 60 revolutions per minute, SO that the problems of insufficient medicament utilization rate, insufficient reaction and the like caused by uneven local concentration of Na 2SO4 are avoided;
The dosage and the adding mode of Na 2SO4 solution are adjusted in real time according to the data of the water quality on-line measuring devices 1, 2 and 3, and the adding mode also comprises one-time adding, equal-quantity multiple adding, equal-quantity continuous adding and the like; when the data of the online measuring device 3 approaches to a theoretical value, the fly ash washing liquid can be introduced into the solid-liquid separation device;
The solid sediment of CaSO 4 at the bottom of the secondary reactor in the step (3-4) is discharged into the sludge collecting device in the step (2) through a pipeline;
step (4) utilizing a solid-liquid separation device to carry out solid-liquid separation on the mixed solution in the step (3); the sludge enters the collecting device in the step (2) through a pipeline; and introducing the water washing liquid after centrifugation into a three-stage reactor to perform a three-stage hardness reduction reaction.
Adding Na 2CO3 solution capable of removing residual total hardness into the three-stage reactor in an intermittent feeding mode, and fully reacting CO 3 2- with Ca 2+、Mg2+ and the like through a water distribution device and a stirring device in the three-stage reactor;
Step (5-1) preparing a 10% Na 2CO3 solution in a Na 2CO3 pre-dissolving device by using Na 2CO3 and softened water;
Adding the Na 2CO3 solution in the step (5-2) into a three-stage reactor through 4 porous pipes penetrating into the position below the liquid level, and fully reacting CO 3 2- in the Na 2CO3 solution with Ca 2+、Mg2+ and the like under the stirring effect of 60 revolutions per minute, so that the problems of insufficient medicament utilization rate, uneven reaction and the like caused by uneven local concentration of Na 2CO3 are avoided;
The dosage and the adding mode of Na 2CO3 solution are adjusted in real time according to the data of the water quality on-line measuring devices 1,2, 3 and 4, and the adding mode also comprises one-time adding, equal-quantity multiple adding, equal-quantity continuous adding and the like; when the data of the water quality on-line measuring device 4 meets the requirement of the subsequent process on the water quality, the fly ash water washing liquid can be introduced into the membrane filtering device for filtering;
Solid precipitates such as CaCO 3、MgCO3 and the like at the bottom of the three-stage reactor in the step (5-4) are discharged into the sludge collecting device in the step (2) through a pipeline;
Step (6), introducing the mixed solution obtained in the step (5) into a membrane filtration device for filtration, removing excessive SO 4 2-、CO3 2- by the membrane filtration device, introducing clear liquid passing through the membrane filtration device into a softening water tank through a pipeline, and introducing concentrated liquid into a sludge collection device in the step (2) through the pipeline;
Step (7) measuring data such as pH, hardness and the like of the softened water in the softened water tank through the water quality online measuring device 5, and accessing a subsequent process after the hardness of the softened water meets the requirement of the subsequent process, otherwise, refluxing the softened water to the primary reactor through a pipeline to continuously perform hardness reduction treatment until the water quality hardness meets the requirement of the subsequent process;
Part of softened water in the softened water quality in the step (7-1) flows back to a Na 2SO4 pre-dissolving device, a Na 2CO3 pre-dissolving device, a solid-liquid separation device, a membrane filtration device through a pipeline for recycling, device flushing and the like;
And (8) comparing and analyzing data acquired by the online water quality measuring device in the system, establishing a real-time database of three-level CO 2-Na2SO4-Na2CO3 hardness reduction reaction, utilizing the database to simulate a mode of combining with the real-time data of the online water quality measuring devices 1,2, 3, 4 and 5, controlling the dosage, proportion, adding mode and the like of CO 2、Na2SO4 and Na 2CO3, and adjusting the pH, hardness and other parameters of the fly ash washing liquid in different reaction stages, so that the fly ash washing liquid can finally meet the requirements of the subsequent process.
Examples 2 to 4
Examples 2-4 the procedure is as in example 1 except that the main process parameters of examples 2-4 are varied as shown in the following table.
Examples 2 to 4 main process parameters
Firstly, the hardness of the water washing liquid is reduced for the first time through CO 2, so that the recycling of CO 2 is realized, and meanwhile, the pH of the water washing liquid can be reduced by utilizing CO 2; secondly, the hardness of the fly ash washing liquid is reduced secondarily by using Na 2SO4 solution with a certain concentration, and the hardness of the washing liquid can be greatly reduced in the process; thirdly, the Na 2CO3 solution with a certain concentration is utilized to reduce the residual hardness of the water washing liquid, the pH, hardness and other data of the water quality are measured in real time through the online water quality measuring device in the system, and the dosage of CO 2、Na2SO4 and Na 2CO3 is intelligently regulated to enable the water quality detection indexes such as SO 4 2-, hardness and the like in the water washing liquid to meet the requirements required by the subsequent process. The invention utilizes the three-level hardness reduction mode of CO 2-Na2SO4-Na2CO3 to promote the effective utilization of CO 2, can also utilize low-cost raw materials such as CO 2、Na2SO4 to replace 80-90% of alkali and Na 2CO3, reduces the hardness of the fly ash water washing liquid and also reduces the pH of the fly ash water washing liquid, thereby achieving the purpose of reducing the treatment cost of the fly ash water washing liquid.
Claims (9)
1. A system for reducing the hardness of high-salt wastewater by utilizing three-stage reaction is characterized by comprising a CO 2 first-stage reaction system, a Na 2SO4 second-stage reaction system and a Na 2CO3 third-stage reaction system;
The CO 2 first-stage reaction system comprises a water quality online measuring device 1, a first-stage reactor, a CO 2 collecting device, a sludge collecting device and a water quality online measuring device 2 which are connected with the first-stage reactor; the gas outlet of the CO 2 collecting device is connected with the gas inlet of the primary reactor, the liquid phase inlet of the primary reactor is the fly ash washing liquid inlet, and the liquid phase outlet of the primary reactor is connected with the inlet of the secondary reactor; the inlet of the sludge collection device is connected with the solid phase outlet of the primary reactor;
The Na 2SO4 secondary reaction system comprises a secondary reactor, a Na 2SO4 pre-dissolving device, a solid-liquid separation device and a water quality on-line measuring device 3 which are connected with the secondary reactor, wherein Na 2SO4 is connected with a feeding port of the Na 2SO4 pre-dissolving device, an outlet of the Na 2SO4 pre-dissolving device is connected with a Na 2SO4 solution inlet of the secondary reactor, a liquid phase outlet of the secondary reactor is connected with an inlet of the solid-liquid separation device, a liquid phase outlet of the solid-liquid separation device is connected with an inlet of the tertiary reactor, and a solid phase outlet of the secondary reactor and a solid phase outlet of the solid-liquid separation device are both connected with the sludge collecting device;
The Na 2CO3 three-stage reaction system comprises a three-stage reactor, and a Na 2CO3 pre-dissolving device, a membrane filtering device, a softening pond, an online water quality measuring device 4 and an online water quality measuring device 5 which are connected with the three-stage reactor, wherein a Na 2CO3 medicament is connected with a feeding port of the Na 2CO3 pre-dissolving device, an outlet of the Na 2CO3 pre-dissolving device is connected with a Na 2CO3 solution inlet of the three-stage reactor, a liquid phase outlet of the three-stage reactor is connected with an inlet of the membrane filtering device, a liquid phase outlet of the membrane filtering device is connected with an inlet of the softening pond through a pipeline, a concentrated liquid outlet of the membrane filtering device is connected with a water inlet of the softening pond, a liquid phase outlet of the softening pond is connected with a water inlet of the Na 2SO4 pre-dissolving device, a Na 2CO3 pre-dissolving device, a flushing port of the solid-liquid separating device and a water inlet of a back flushing port of the membrane filtering device through a pipeline, an emptying port of the softening pond is connected with a sludge collecting device, and the online water quality measuring device 5 is connected with the softening pond.
2. The system of claim 1, wherein the sludge collection device outlet is connected to a fly ash washing unit.
3. The system according to claim 1, wherein the water quality online measuring device 1 is positioned at the water inlet of the primary reactor, and is used for collecting flow, pH and hardness data in the fly ash water washing liquid.
4. The system according to claim 1, wherein the water quality online measuring device 2 is connected with the primary reactor and is used for collecting the pH and hardness data of the fly ash washing liquid in the primary reactor.
5. A method for reducing hardness of high salt wastewater using the system according to any one of claims 1 to 4, comprising the steps of:
1) The method comprises the steps of measuring initial flow, pH and hardness data of ash flying washing liquid entering a primary reactor through a water quality online measuring device 1, and calculating the dosage of CO 2 aeration quantity, na 2SO4 and Na 2CO3 solution which can meet the water quality requirement according to the data; the actual total addition mass of CO 2-Na2SO4-Na2CO3 is 1.0-1.5 times of the theoretical value, and the addition mass proportion of CO 2-Na2SO4-Na2CO3 is (10% -40%): (60% -90%): (10% -40%);
2) Introducing CO 2 in the CO 2 collecting device into the first-stage reactor according to set aeration quantity, temperature and pressure, dissolving CO 2 by using a gas distribution device and a stirring device in the first-stage reactor, fully reacting with Ca 2+、Mg2+ in the water washing liquid, returning the residual gas to the CO 2 collecting device through a gas outlet for reuse, and introducing the fly ash water washing liquid into the second-stage reactor after primary hardness reduction reaction; the CaCO 3、MgCO3 solid precipitate is collected by a sludge collecting device; the pH and hardness change condition of fly ash washing liquid in the primary hardness reduction reaction process is measured by a water quality online measuring device 2;
3) Adding a certain dosage of Na 2SO4 solution into the secondary reactor, and adjusting the adding mode, dosage and stirring mode of the Na 2SO4 solution in real time according to the data of the water quality online measuring devices 1, 2 and 3, wherein the Na 2SO4 solution adopts an intermittent adding mode, the interval is 10-50 minutes, and in order to fully mix and react Na 2SO4 with Ca 2+ in the water washing liquid, a stirrer is arranged in the secondary reactor, and the stirring rotating speed is 30-80 revolutions per minute;
4) Introducing the mixed solution obtained in the step 3) into a solid-liquid separation device to obtain sludge and water washing liquid, and introducing the sludge into a sludge collection device in the step 2) through a pipeline; the washing liquid enters a three-stage reactor to carry out a three-stage hardness reduction reaction;
5) Adding a certain dosage of Na 2CO3 solution into the three-stage reactor, and adjusting the adding mode, dosage and stirring mode of the Na 2CO3 solution in real time according to the data of the water quality on-line measuring devices 1,2,3 and 4, wherein the Na 2CO3 solution adopts an intermittent adding mode, the interval is 10-50 minutes, and in order to fully mix and react Na 2CO3 with Ca 2+ in the water washing liquid, a stirrer is arranged in the three-stage reactor, and the stirring rotating speed is 30-80 revolutions per minute;
6) Filtering the mixed solution obtained in the step 5) by using a membrane filtering device, and filtering excessive SO 4 2-、CO3 2- in the water washing liquid; the clear liquid passing through the membrane filtering device is connected into a softening water tank through a pipeline, and the concentrated liquid enters the sludge collecting device in the step 2) through a pipeline;
7) The water quality of the softened water is measured by the water quality online measuring device 5, and the softened water can be subjected to subsequent treatment after meeting the requirement of a later process on the water quality, wherein part of the softened water flows back to the Na 2SO4 pre-dissolving device, the Na 2CO3 pre-dissolving device, the solid-liquid separation device and the membrane filtering device through pipelines for recycling and device flushing;
8) The method comprises the steps of comparing and analyzing data acquired by a water quality online measuring device in a system, establishing a real-time database of three-level CO 2-Na2SO4-Na2CO3 hardness reduction reaction, simulating a mode of combining real-time data of the water quality online measuring devices 1, 2, 3, 4 and 5 by using the database, controlling the dosage, proportion and adding mode of CO 2、Na2SO4 and Na 2CO3, and regulating pH and hardness parameters of the fly ash washing liquid in different reaction stages, so that the fly ash washing liquid can finally meet the requirements of subsequent processes.
6. The method according to claim 5, wherein the CO 2 collecting device is used for collecting and concentrating CO 2 in the air, kiln tail waste gas and residual gas after the primary reaction to obtain 20-99% concentration CO 2 gas;
The CO 2 gas enters a first-stage reactor and fully reacts with the water washing liquid through a gas distribution device and a stirring device, and then the total hardness of the fly ash water washing liquid is reduced by 10-40%;
The gas distribution device consists of a plurality of vertical pipes with different apertures and a horizontal annular pipe, is arranged below the liquid level of the primary reactor, and promotes the dissolution of CO 2 into the fly ash water washing liquid by adjusting the length of the porous pipe, the CO 2 gas pressure, the aeration quantity and the stirring mode.
7. The method according to claim 5, wherein the Na 2SO4 agent is added into the secondary reactor, and the total hardness is reduced by 60-90% after stirring and solid-liquid separation;
The Na 2SO4 solution adding pipe consists of a plurality of porous pipes with different pore diameters, the device is arranged below the liquid level of the secondary reactor, and the hardness of the fly ash water washing liquid can be reduced by adjusting the distance between the bottom of the porous pipe and the liquid level, the concentration, the dosage, the adding mode and the stirring rotation speed of the Na 2SO4 solution to promote SO 4 2-;
Adding Na 2CO3 reagent into the three-stage reactor, stirring and membrane filtering to remove the residual total hardness;
the Na 2CO3 solution adding pipe is composed of a plurality of porous pipes with different pore diameters, the device is arranged below the liquid level of the three-stage reactor, and the hardness of the fly ash water washing liquid can be reduced by adjusting the distance between the bottom of the porous pipe and the liquid level, the concentration, the dosage, the adding mode and the stirring rotation speed of the Na 2CO3 solution to promote CO 3 2-.
8. The method according to claim 5, wherein the adjusting modes of the gas distribution device, the Na 2SO4 solution adding pipe and the porous pipe in the Na 2CO3 solution adding pipe comprise:
① And (3) movement adjustment: adjusting the distance of the porous pipe extending below the liquid level by moving the porous pipe;
② And (3) hole opening adjustment: the pore diameter of the porous pipe is regulated by using a method of opening holes, shifting sheets and sleeves, and the pore diameter of the porous pipe of the CO 2 gas distribution device is increased along with the increase of the liquid level height in the vertical direction; increasing in the horizontal direction with increasing distance from the riser; the Na 2SO4 and Na 2CO3 solution adding pipes are provided with round holes with different diameters at the upper part and the lower part in the vertical direction.
9. The method of claim 5, wherein the hardness of the fly ash water washing liquid is reduced by adopting a three-stage CO 2-Na2SO4-Na2CO3 hardness reduction reaction, and the hardness of the fly ash water washing liquid after softening can meet the requirement of the subsequent process on the hardness of water quality;
the softened water flows back to the Na 2SO4 pre-dissolving device, the Na 2CO3 pre-dissolving device, the solid-liquid separation device for flushing and the membrane filtration device for back flushing through pipelines; 1. and the CaCO 3、CaSO4、MgCO3 solid precipitate generated in the second-stage and third-stage hardness reduction reaction, solid-liquid separation device and membrane filtration device is summarized to a sludge collection device through a pipeline and then enters a fly ash washing unit for utilization.
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