CN112174416A - Treatment device and treatment method for deacidification wastewater - Google Patents
Treatment device and treatment method for deacidification wastewater Download PDFInfo
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- CN112174416A CN112174416A CN202011096593.8A CN202011096593A CN112174416A CN 112174416 A CN112174416 A CN 112174416A CN 202011096593 A CN202011096593 A CN 202011096593A CN 112174416 A CN112174416 A CN 112174416A
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- flue gas
- deacidification
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- 239000002351 wastewater Substances 0.000 title claims abstract description 246
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 85
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000003546 flue gas Substances 0.000 claims abstract description 75
- 239000000428 dust Substances 0.000 claims abstract description 52
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 27
- 239000008394 flocculating agent Substances 0.000 claims description 24
- 239000000701 coagulant Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 16
- 239000004571 lime Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000003507 refrigerant Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 abstract description 11
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000003672 processing method Methods 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 19
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 10
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004065 wastewater treatment Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 239000000378 calcium silicate Substances 0.000 description 7
- 229910052918 calcium silicate Inorganic materials 0.000 description 7
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
Abstract
The invention relates to a treatment device and a treatment method of deacidification wastewater, wherein the treatment device comprises a pre-separation unit, a dust removal unit, at least 3 stages of separation units, a heat exchange unit and a separation unit which are connected in series, which are connected in sequence; the processing method comprises the following steps: (1) pretreating deacidification wastewater to obtain pretreated wastewater; (2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and then removing heavy metal ions in the wastewater after dedusting to obtain heavy metal-removed wastewater; (3) preheating the heavy metal-removed wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and recycling the obtained condensate. The treatment method provided by the invention removes insoluble particulate matters, heavy metal ions and sodium salts in the deacidification wastewater, simultaneously purifies the flue gas, and realizes the cyclic utilization of resources.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, relates to treatment of deacidification wastewater, and particularly relates to a treatment device and a treatment method for deacidification wastewater.
Background
Wet deacidification is a common flue gas deacidification method, a washing tower form is generally adopted, flue gas enters the washing tower and then is in full contact reaction with washing liquid (usually sodium hydroxide solution with the concentration of 30-40%), and thus the aim of deacidification is achieved; however, after the washing liquid is recycled for a period of time, the salt content in the washing liquid is gradually increased, the deacidification effect is reduced, the corrosivity to deacidification equipment is also increased, and at the moment, a part of washing liquid needs to be discharged and a part of fresh alkali liquor needs to be supplemented. Deacidifying wastewater contains a large amount of salt and other pollutants, and can be discharged or recycled after being treated.
Most deacidification waste water treatment processes select a coagulating sedimentation filtration method, the method comprises three major parts, namely a waste water treatment system, a sludge dewatering system and a chemical dosing system, suspended matters, heavy metals and a small amount of salt in waste water are mainly removed, most salt substances (such as sodium salt and the like) cannot be removed, the flue gas deacidification efficiency is reduced after the treated deacidification waste water is recycled, deacidification equipment is corroded, the ecological environment is also polluted by direct discharge, and even land salinization is caused.
CN 110627146a discloses a desulfurization wastewater treatment system and a desulfurization wastewater treatment method, in the invention, firstly, desulfurization wastewater is concentrated in a concentration tower, and then the concentrated desulfurization wastewater is evaporated in an evaporator, so as to realize zero discharge of desulfurization wastewater. The method omits the chemical pretreatment of the desulfurization wastewater, saves the corresponding medicament cost, and reduces the energy consumption for treating the desulfurization wastewater by drying the desulfurization wastewater twice by using the energy discharged by the coal-fired power plant. However, the application field of the invention is narrow, the waste water with high heavy metal ion content cannot be effectively treated, a large amount of residual salt is easy to corrode the evaporator, the medicament cost is saved, and the device cleaning and maintenance cost is greatly increased.
CN 108619871A discloses a method and a device for treating flue gas and flue gas desulfurization waste water, which realize the double purposes of purifying flue gas and meeting the emission requirement and realizing zero emission of flue gas desulfurization waste liquid on the basis of fully utilizing the waste heat of the flue gas, simultaneously eliminate 'white smoke' and 'blue smoke', and reduce the comprehensive treatment cost of the flue gas desulfurization and the desulfurization waste liquid. However, the method does not remove most of sodium salt in the wastewater, and the corrosion and damage of the device can be easily caused after long-term use.
CN 108339392A discloses a wet flue gas desulfurization system and desulfurization effluent treatment plant thereof, desulfurization effluent treatment plant's design makes desulfurization water system form closed circulation, can realize desulfurization waste water's zero release, and the process flow is short, and equipment structure is simple, and area is little, investment cost and running cost are low. However, the method also does not remove most of sodium salt in the wastewater, and influences the service life of the treatment device.
Therefore, how to effectively remove a large amount of salt and other pollutants in the deacidification wastewater, especially the sodium salt which is difficult to treat, and fully recycle the treated wastewater becomes a problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a treatment device and a treatment method for deacidification wastewater, which can effectively remove heavy metal components in the deacidification wastewater, can recover sodium salt used in the treatment process, and can use the recovered condensate for cleaning a demisting device, so that the cost for cleaning the demisting device is reduced, and the economic benefit for treating the deacidification wastewater is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a deacidification wastewater treatment device, which comprises a pre-separation unit, a dust removal unit, at least 3 stages of separation units connected in series, a heat exchange unit and a separation unit, which are connected in sequence.
The pre-separation unit comprises a pre-mixing device and a pre-settling device which are connected in sequence, and a liquid outlet of the pre-settling device is connected with a liquid inlet of the dust removal unit.
The separation unit comprises a mixing device and a sedimentation device which are sequentially connected, a 1 st-stage mixing device is connected with a liquid outlet of the dust removal unit, and a last-stage sedimentation device is connected with a refrigerant inlet of the heat exchange unit.
The separation unit comprises an evaporative crystallization device, a condensing device and a condensate storage device which are connected in sequence, and the evaporative crystallization device is connected with a refrigerant outlet of the heat exchange unit.
In the present invention, the separation units connected in series are preferably 3 stages, wherein the 1 st stage separation unit is used for removing copper ions and iron ions in the wastewater within a pH range of 4 to 6, the 2 nd stage separation unit is used for removing residual iron ions and zinc ions in the wastewater after the pH is increased, and the 3 rd stage separation unit is used for adding carbonate to remove calcium ions in the wastewater.
According to the deacidification wastewater treatment device, the multistage separation units are arranged, so that the ordered separation of different heavy metal ions in the deacidification wastewater is realized, and the heavy metal ions in the deacidification wastewater are convenient to recycle; the dust removal unit not only realizes the function of purifying the flue gas, but also can increase the temperature of the deacidification wastewater by utilizing the waste heat of the flue gas, thereby reducing the solubility of calcium salt in the wastewater and improving the calcium salt removal effect; the heat exchange unit can reduce the heat required by evaporation crystallization, thereby reducing the treatment cost of deacidification wastewater.
Preferably, the heat medium outlet of the heat exchange unit is connected with the air inlet of the dust removal unit.
In the invention, the flue gas is used as a heating medium, redundant heat is firstly transmitted to the deacidification wastewater in the heat exchange unit, and then dust particles included in the deacidification wastewater are removed by mixing with the deacidification wastewater in the dedusting unit, so that the heat is recycled, and the flue gas is purified.
Preferably, the deacidification wastewater treatment device further comprises a demisting device, and an air outlet of the dust removal unit is connected with an air inlet of the demisting device.
In the invention, flue gas flows through the dust removal unit, and is mixed with a large amount of water vapor after fully contacting deacidification wastewater. According to the invention, the demisting device is arranged to remove water vapor in the flue gas, so that harmful substances in the wet flue gas are prevented from being discharged to the environment to cause pollution.
Preferably, the liquid outlet of the condensate storage device is connected with the liquid inlet of the demisting device.
In the invention, the condensate in the condensate storage device can be used for cleaning the demisting device, thereby realizing the cyclic utilization of the purified wastewater and improving the utilization rate of resources; the deacidification wastewater generated by the condensate cleaning and demisting device is circularly treated by using the treatment device for deacidification wastewater, so that the stable operation of a flue gas demisting system can be realized.
In a second aspect, the present invention provides a method for treating deacidification wastewater, comprising the following steps:
(1) pretreating deacidification wastewater to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and then removing heavy metal ions in the wastewater after dedusting to obtain heavy metal-removed wastewater;
(3) preheating the heavy metal-removed wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and recycling the obtained condensate.
In the invention, the pretreatment removes insoluble impurities in the deacidification wastewater, which is beneficial to effectively removing the following heavy metal ions; the preheating of the flue gas to the waste water and the dust removal of the flue gas by the waste water not only realize the recycling of heat and reduce the production cost, but also realize the purification of the flue gas; the sodium salt in the wastewater can be recovered through evaporative crystallization, so that the corrosion of the saline wastewater to the device and the salt blockage are prevented, the maintenance cost is reduced, and the economic benefit is improved; the condensate recycling is to wash the defogging device, has realized the cyclic utilization of waste water after the purification, has promoted the utilization ratio of resource.
Preferably, the pretreatment in step (1) is carried out by adding a flocculant and a coagulant aid to the deacidification wastewater until precipitation does not increase.
The flocculant comprises any one or a combination of at least two of aluminum sulfate, aluminum chloride, ferric sulfate, or ferric chloride, and typical but non-limiting combinations include a combination of aluminum sulfate and aluminum chloride, a combination of aluminum chloride and ferric sulfate, a combination of ferric sulfate and ferric chloride, a combination of aluminum sulfate, aluminum chloride and ferric sulfate, or a combination of aluminum chloride, ferric sulfate and ferric chloride.
The coagulant aid comprises any one or a combination of at least two of sodium silicate, calcium silicate, aluminum oxide, or silicon oxide, and typical but non-limiting combinations include combinations of sodium silicate and calcium silicate, calcium silicate and aluminum oxide, aluminum oxide and silicon oxide, sodium silicate, calcium silicate and aluminum oxide, or calcium silicate, aluminum oxide and silicon oxide.
The mass ratio of the flocculant to the coagulant aid is (10-100):1, and may be, for example, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, and is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
According to the invention, through the matching use of the flocculating agent and the coagulant aid, the removal effect of insoluble components in the deacidification wastewater is improved, and the subsequent smooth removal of heavy metal ions is ensured.
Preferably, the heavy metal ion removing step in step (2) is as follows:
a. adding a flocculating agent and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. and adding sulfide into the wastewater subjected to heavy metal removal until the precipitate is not increased any more, thereby obtaining the wastewater subjected to heavy metal removal.
According to the invention, the flocculant comprises any one or a combination of at least two of aluminum sulfate, aluminum chloride, ferric sulfate or ferric chloride, and is added with lime to generate soluble hydroxide in the wastewater, and the pH value of the wastewater is controlled within a range of 4-6, so that copper ions and iron ions in the wastewater can be converted into hydroxide precipitate with low solubility; said sulfide is Na2S or organic sulfur (TMT15) is added to remove residual iron ions and zinc ions in the wastewaterAnd (4) completely removing.
Preferably, the method also comprises the step of adding carbonate into the heavy metal removal wastewater between the step (2) and the step (3) until the precipitation is not increased.
According to the invention, the addition of the carbonate can remove calcium ions in the wastewater, so that the hardness of the wastewater is reduced, and the blockage of a device pipeline caused by calcium salt deposition is prevented, thereby saving the maintenance cost; the carbonate includes, but is not limited to, sodium carbonate.
Preferably, the flue gas obtained in the step (2) after dust removal is subjected to demisting treatment.
In the invention, the flue gas after dust removal contains a large amount of water vapor, and the water vapor contains heavy metal impurities, so that if the flue gas is discharged to the environment without being treated, ecological pollution is easily caused, and the problem can be avoided by the demisting treatment.
As a preferred technical solution of the present invention, the processing method includes the steps of:
(1) adding a flocculating agent and a coagulant aid into the deacidification wastewater until the precipitate is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding a flocculating agent and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide into the wastewater subjected to heavy metal removal until precipitation does not increase any more, so as to obtain wastewater subjected to heavy metal removal;
(3) preheating the heavy metal-removed wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and recycling the obtained condensate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the treatment method provided by the invention not only removes insoluble particulate matters and heavy metal ions in the deacidification wastewater, but also removes sodium salt which is difficult to treat, avoids corrosion and blockage of the device, reduces the cleaning and maintenance cost, and prolongs the service life of the equipment;
(2) the invention realizes the purification of the flue gas, realizes the cyclic utilization of resources and reduces the production cost by the heat exchange and dust removal treatment of the flue gas and the wastewater and the recycling of the purified wastewater.
Drawings
FIG. 1 is a schematic view of a deacidification wastewater treatment apparatus provided by the present invention.
Wherein: 11-a premixing device; 12-a pre-settling device; 13-a dust removal unit; 21-a first stage mixing device; 22-a first stage settling device; 31-a second stage mixing device; 32-a second stage settling device; 41-third stage mixing device; 42-a third stage settling device; 5-a heat exchange unit; 6-an evaporative crystallization device; 7-a condensing unit; 8-a condensate storage device; 9-demisting device.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a treatment device for deacidification wastewater as shown in figure 1, which comprises a premixing device 11, a pre-settling device 12, a dust removal unit 13, a first-stage mixing device 21, a first-stage settling device 22, a second-stage mixing device 31, a second-stage settling device 32, a third-stage mixing device 41, a third-stage settling device 42, a heat exchange unit 5, an evaporative crystallization device 6, a condensing device 7, a condensate storage device 8 and a demisting device 9 which are connected in sequence.
In the invention, a heat medium outlet of the heat exchange unit 5 is connected with an air inlet of the dust removal unit 13, and an air outlet of the dust removal unit 13 is connected with an air inlet of the demisting device 9.
The pre-mixing device 11, the first-stage mixing device 21, the second-stage mixing device 31 and the third-stage mixing device 41 are reaction tanks, the pre-settling device 12, the first-stage settling device 22, the second-stage settling device 32 and the third-stage settling device 42 are settling tanks, the dust removal unit 13 is a bubbling tank, the heat exchange unit 5 is a tubular heat exchanger, the evaporative crystallization device 6 is an MVR multi-effect evaporator, the condensing device 7 is a condenser, the condensate storage device 8 is a storage tank, and the demisting device 9 is an electric demister.
The deacidification wastewater treated by the examples and the comparative examples of the invention is simulated deacidification wastewater, and the impurity concentration and the chromaticity are shown in table 1.
TABLE 1
Example 1
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate in a mass ratio of 50:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 2
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding a flocculating agent aluminum chloride and a coagulant aid calcium silicate into the deacidified wastewater in a mass ratio of 25:1 until precipitation is not increased any more, thereby obtaining pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agents of aluminum chloride and lime into the wastewater after dust removal until precipitation is not increased any more, and obtaining the wastewater with the heavy metals removed;
b. adding a sulfide TMT15 into the wastewater from which the heavy metals are removed until the precipitation is not increased any more, thereby obtaining the wastewater from which the heavy metals are removed;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 3
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding flocculating agent ferric sulfate and coagulant aid aluminum oxide with the mass ratio of 75:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agents of ferric sulfate and lime into the wastewater after dust removal until precipitation is not increased any more, so as to obtain pre-removed heavy metal wastewater;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 4
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding a flocculating agent ferric chloride and a coagulant aid silicon oxide in a mass ratio of 10:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agents of ferric chloride and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding a sulfide TMT15 into the wastewater from which the heavy metals are removed until the precipitation is not increased any more, thereby obtaining the wastewater from which the heavy metals are removed;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 5
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding a flocculating agent and a coagulant aid in a mass ratio of 100:1 into the deacidified wastewater until the precipitate is not increased any more to obtain pretreated wastewater; the flocculating agent is a mixture of aluminum sulfate and ferric sulfate in a mass ratio of 1:1, and the coagulant aid is a mixture of sodium silicate and calcium silicate in a mass ratio of 1: 1;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding a flocculating agent and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed; the flocculating agent is a mixture of aluminum sulfate and ferric sulfate in a mass ratio of 1: 1;
b. adding a sulfide TMT15 into the wastewater from which the heavy metals are removed until the precipitation is not increased any more, thereby obtaining the wastewater from which the heavy metals are removed;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 6
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate with the mass ratio of 110:1 into the deacidification wastewater until the precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 7
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate with the mass ratio of 8:1 into the deacidification wastewater until the precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Example 8
The embodiment provides a treatment method of deacidification wastewater, which is carried out in a treatment device shown in figure 1, and comprises the following steps:
(1) adding flocculant aluminum sulfate into the deacidification wastewater until the precipitate is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
Comparative example 1
This comparative example provides a treatment method of deacidified wastewater, which was carried out in the treatment apparatus shown in FIG. 1, the treatment method comprising the steps of:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate in a mass ratio of 50:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2And S, the precipitate is not increased any more, and the wastewater for removing the heavy metals is obtained.
(3) And (3) pre-cooling the flue gas by using the heavy metal removal wastewater obtained in the step (2), and using the heavy metal removal wastewater for cleaning the demisting device 9.
Comparative example 2
This comparative example provides a treatment method of deacidified wastewater, which was carried out in the treatment apparatus shown in FIG. 1, the treatment method comprising the steps of:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate in a mass ratio of 50:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding sodium carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2And S, the precipitate is not increased any more, and the wastewater for removing the heavy metals is obtained.
(3) And (3) evaporating and crystallizing the heavy metal-removed wastewater obtained in the step (2) by using an evaporator, and using the obtained condensate for cleaning the demisting device 9.
Comparative example 3
This comparative example provides a treatment method of deacidified wastewater, which was carried out in the treatment apparatus shown in FIG. 1, the treatment method comprising the steps of:
(1) adding flocculant aluminum sulfate and coagulant aid sodium silicate in a mass ratio of 50:1 into the deacidification wastewater until precipitation is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal; the specific steps for removing heavy metal ions are as follows:
a. adding flocculating agent aluminum sulfate and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide Na into the wastewater from which heavy metals are removed2S, obtaining heavy metal-removing wastewater until the precipitate is not increased any more;
(3) preheating the heavy metal-removing wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and using the obtained condensate for cleaning the demisting device 9.
The impurity concentrations and the color degrees of the deacidified wastewater after the treatment of examples 1 to 7 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2
Wherein, the detection of the impurity concentration adopts an ion monitoring method disclosed by CN 110907620A; the chroma detection adopts a sewage chroma detector disclosed by CN 210427339U.
As shown in Table 2, the treatment methods of deacidification wastewater provided in examples 6-8 did not remove insoluble impurities in wastewater well compared to example 1, and the concentrations and chromaticities of metal ions were also higher than example 1, indicating that the ratio of flocculant and coagulant aid is important for reducing SS in wastewater, and the presence of a large amount of insoluble impurities is not beneficial to the subsequent removal of metal ions.
In addition, compared with the method for treating deacidified wastewater provided by the embodiment 1-5, sodium salt in wastewater is not removed, so that the device is easy to corrode and block in the long-term use process, and the equipment cleaning and maintenance cost is high; compared with the treatment method of deacidification wastewater provided by the comparative example 2, the heat of the flue gas is not recycled in the examples 1-5, and the heat sources for evaporating and crystallizing the wastewater are all from the heating of the evaporator, so that the production cost is increased, and the requirements of energy conservation and environmental protection are not met; compared with the treatment method of deacidification wastewater provided by the embodiment 1-5, carbonate is not added before the evaporation crystallization process to remove calcium ions in wastewater, although calcium salt can be removed in the subsequent evaporation crystallization process, the purity of sodium salt is easily reduced, the separation cost of recycling is high, and calcium salt easily causes scaling of the tube wall of an evaporator to influence the heat transfer process, so that the later maintenance cost is high.
Therefore, the treatment method provided by the invention not only removes insoluble particulate matters and heavy metal ions in the deacidification wastewater, but also removes sodium salt which is difficult to treat, avoids corrosion and blockage of the device, reduces the cleaning and maintenance cost, and prolongs the service life of the equipment; through the heat exchange and dust removal treatment of the flue gas and the wastewater and the recycling of the purified wastewater, the flue gas purification is realized, the resource recycling is realized, and the production cost is reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The treatment device for deacidification wastewater is characterized by comprising a pre-separation unit, a dedusting unit, at least 3 stages of separation units connected in series, a heat exchange unit and a separation unit which are connected in sequence;
the pre-separation unit comprises a pre-mixing device and a pre-settling device which are connected in sequence, and a liquid outlet of the pre-settling device is connected with a liquid inlet of the dust removal unit;
the separation unit comprises a mixing device and a sedimentation device which are connected in sequence, the 1 st-stage mixing device is connected with a liquid outlet of the dust removal unit, and the last-stage sedimentation device is connected with a refrigerant inlet of the heat exchange unit;
the separation unit comprises an evaporative crystallization device, a condensing device and a condensate storage device which are connected in sequence, and the evaporative crystallization device is connected with a refrigerant outlet of the heat exchange unit.
2. The treatment device according to claim 1, wherein the heat medium outlet of the heat exchange unit is connected with the air inlet of the dust removal unit.
3. The treatment apparatus according to claim 1 or 2, wherein the treatment apparatus for deacidifying wastewater further comprises a demister;
and the air outlet of the dust removal unit is connected with the air inlet of the demisting device.
4. A treatment plant as claimed in claim 3, characterized in that the liquid outlet of the condensate storage device is connected to the liquid inlet of the demister device.
5. A treatment method of deacidification wastewater is characterized by comprising the following steps:
(1) pretreating deacidification wastewater to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and then removing heavy metal ions in the wastewater after dedusting to obtain heavy metal-removed wastewater;
(3) preheating the heavy metal-removed wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and recycling the obtained condensate.
6. The treatment method according to claim 5, wherein the pretreatment in step (1) is carried out by adding a flocculant and a coagulant aid to the deacidification wastewater until precipitation does not increase.
7. The treatment method according to claim 5 or 6, wherein the heavy metal ion removal step in step (2) is as follows:
a. adding a flocculating agent and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. and adding sulfide into the wastewater subjected to heavy metal removal until the precipitate is not increased any more, thereby obtaining the wastewater subjected to heavy metal removal.
8. The treatment method according to any one of claims 5 to 7, wherein the step (2) and the step (3) further comprise adding carbonate to the heavy metal removal wastewater until precipitation does not increase.
9. The treatment method according to any one of claims 5 to 8, wherein the flue gas after dust removal obtained in the step (2) is subjected to demisting treatment.
10. A method of treatment according to any one of claims 5-9, characterized in that it comprises the steps of:
(1) adding a flocculating agent and a coagulant aid into the deacidification wastewater until the precipitate is not increased any more, so as to obtain pretreated wastewater;
(2) dedusting the flue gas by using the pretreated wastewater obtained in the step (1), and demisting the dedusted flue gas; then removing heavy metal ions in the wastewater after dust removal, and adding carbonate into the obtained heavy metal-removed wastewater until the precipitate is not increased any more; the specific steps for removing heavy metal ions are as follows:
a. adding a flocculating agent and lime into the wastewater after dust removal until the precipitation is not increased any more, so as to obtain the wastewater with the heavy metals removed;
b. adding sulfide into the wastewater subjected to heavy metal removal until precipitation does not increase any more, so as to obtain wastewater subjected to heavy metal removal;
(3) preheating the heavy metal-removed wastewater obtained in the step (2) by using flue gas, then carrying out evaporative crystallization, and recycling the obtained condensate.
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