CN111115938A - Activated carbon regeneration gas washing acidic wastewater treatment device and method - Google Patents
Activated carbon regeneration gas washing acidic wastewater treatment device and method Download PDFInfo
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- CN111115938A CN111115938A CN202010063383.2A CN202010063383A CN111115938A CN 111115938 A CN111115938 A CN 111115938A CN 202010063383 A CN202010063383 A CN 202010063383A CN 111115938 A CN111115938 A CN 111115938A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000005406 washing Methods 0.000 title claims abstract description 43
- 230000008929 regeneration Effects 0.000 title claims abstract description 34
- 238000011069 regeneration method Methods 0.000 title claims abstract description 34
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 12
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 146
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 75
- 230000003647 oxidation Effects 0.000 claims abstract description 64
- 239000012266 salt solution Substances 0.000 claims abstract description 63
- 238000005189 flocculation Methods 0.000 claims abstract description 60
- 230000016615 flocculation Effects 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 239000002351 wastewater Substances 0.000 claims abstract description 46
- 238000001704 evaporation Methods 0.000 claims abstract description 39
- 230000008020 evaporation Effects 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008394 flocculating agent Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
- 239000010802 sludge Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 238000005352 clarification Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000006115 defluorination reaction Methods 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 208000028659 discharge Diseases 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/5281—Installations for water purification using chemical agents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to an active carbon regeneration gas washing acidic wastewater treatment device and method, wherein the device comprises a reaction tank, a flocculation tank, an oxidation tank, an evaporation crystallizer, a centrifugal machine and a drying machine, the reaction tank is connected with the flocculation tank, the flocculation tank is connected with the oxidation tank, the oxidation tank is connected with the evaporation crystallizer, a crystal outlet of the evaporation crystallizer is connected with a feed inlet of the centrifugal machine, a mother liquor port and a crystal outlet are arranged below the centrifugal machine, the mother liquor port is connected with the evaporation crystallizer, and the crystal outlet is connected with the drying machine. The method comprises the following steps: firstly, acidic wastewater enters a reaction tank to be added with ammonia, the acidic wastewater is neutralized into a first ammonium salt solution, clear liquid is sent into an oxidation tank after sedimentation to obtain a second ammonium salt solution, the second ammonium salt solution is sent into an evaporation crystallizer to form ammonium salt crystals through evaporation crystallization, finally, the ammonium salt crystals are sent to centrifugal separation, and the ammonium salt crystals are dried and packaged to form bagged products. The method realizes the treatment of the acidic wastewater generated by washing the regenerated activated carbon gas, and obtains the ammonium salt with economic value.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method and a device for treating acidic wastewater from washing of regenerated activated carbon gas.
Background
The dry active carbon fume desulfurizing and denitrating technology is one engineering treating process with active carbon and simultaneous desulfurizing and denitrating, and the treating process is carried out in one reactor to reach the desulfurizing and denitrating effect2NOx and can additionally remove various pollutants such as dioxin, heavy metal, dust and the like, and SO as a byproduct2Can be processed into various sulfate, sulfite or sulfuric acid products, and has been successfully applied to the industries of chemical industry, power plants, coking coke ovens, nonferrous smelting, steel sintering and pelletizing at present.
The activated carbon dry flue gas desulfurization and denitrification device adopts the activated carbon which is recycled, and is generally provided with a set of activated carbon regeneration system for adsorbing SO2The activated carbon is delivered to a regeneration tower and heated to release SO with high concentration at high temperature2Is called activated carbon regeneration gas.
The active carbon regeneration gas has complex components except for containing high-concentration SO2In addition, it usually contains NH3、HCl、HF、SO3Dust (mainly carbon powder) and active carbon regeneration gas are usually purified by a water washing process to remove NH in the flue gas3、HCl、HF、SO3Carbon powder is washed off, and wastewater is discharged periodically, because the discharged wastewater is usually acidic, COD and ammonia nitrogen contentExtremely high, which causes great difficulty in subsequent processing.
Therefore, there is a need to develop a method and a device for treating acidic wastewater from washing of activated carbon regeneration gas, which can realize zero discharge, and has the advantages of low cost, simple process, safety and reliability.
Disclosure of Invention
The invention aims to solve the technical problem of providing the device for treating the acidic wastewater generated by washing the activated carbon regeneration gas, which has a compact structure, realizes zero emission treatment on the acidic wastewater generated by washing the activated carbon regeneration gas, and has a safe and reliable technological process.
In order to solve the technical problems, the invention adopts the technical scheme that: this acidic effluent treatment plant of active carbon regeneration gas washing, including retort, flocculation jar, oxidation tank, evaporation crystallizer, centrifuge and desiccator, the retort is equipped with acid waste water entry and neutralizer entry, the retort with the flocculation jar links to each other, the flocculation jar with the oxidation tank links to each other, the oxidation tank with evaporation crystallizer links to each other, evaporation crystallizer's crystal export with centrifuge pan feeding mouth links to each other, centrifuge's below is equipped with mother liquor mouth and goes out the brilliant mouth, the mother liquor mouth with evaporation crystallizer links to each other just go out the brilliant mouth with the desiccator links to each other.
By adopting the technical scheme, the acidic wastewater contains sulfuric acid, hydrochloric acid, sulfurous acid, sulfur dioxide, fluoride and acid salt, and the wastewater is strongly acidic, so that the acidic wastewater is firstly introduced into a reaction tank for neutralization reaction to obtain ammonium sulfite and ammonium chloride solution, then the ammonium sulfite and ammonium chloride solution is settled and filtered to remove suspended matters, and then clear liquid is sent into an oxidation tank to oxidize the ammonium sulfite into ammonium sulfate, so as to prepare ammonium salt solution containing the ammonium sulfate and the ammonium chloride; evaporating and crystallizing the ammonium salt solution containing ammonium sulfate and ammonium chloride by an evaporation crystallizer, and then centrifugally drying; wherein the evaporation crystallizer is in circulating connection with the centrifuge, so that the centrifuged mother liquor returns to the evaporation crystallizer again for recrystallization, and the arrangement can improve the yield and realize zero emission.
As a preferable technical scheme of the invention, a clarifier and a filter are communicated between the flocculation tank and the oxidation tank, a flocculation liquid outlet of the flocculation tank is connected with a flocculation liquid inlet of the clarifier, a sludge outlet at the bottom of the clarifier is connected with a sludge inlet of the filter, a filtering liquid outlet at the lower part of the filter is connected with the clarifier, and the clarifier and the filter form a circulation loop; and a mud bucket is arranged at the lower part of the filter and used for discharging filter residues. Wherein clarifier and filter circulation intercommunication for the flowing back after the filtration reentries the clarifier through the leakage fluid dram, and circulation like this can improve the decontamination rate of clear liquid, improves the utilization ratio of first ammonium salt solution simultaneously.
As a preferable technical scheme of the invention, the reaction tank is provided with a stirrer and a pH value detection instrument, and the reaction tank is also provided with a defluorinating agent inlet. Adding a fluorine removal agent through a fluorine removal agent inlet so as to selectively remove fluoride in the acidic wastewater; the stirrer is arranged in the reaction tank, so that the speed of neutralization reaction can be increased, the reaction rate is increased, the pH value in the reaction tank is monitored by the pH value detection instrument, and the amount of the neutralizer is added according to the monitored real-time pH value. A first stirrer is arranged in the flocculation tank.
As a preferred technical scheme of the invention, the evaporative crystallizer is also provided with a condensate outlet for feeding the condensate generated in the evaporative crystallization process of the evaporative crystallizer back to the activated carbon regeneration gas washing device. Such an arrangement can achieve zero emissions.
In a preferred embodiment of the present invention, the outlet of the dryer is connected to a packaging machine for packaging the dried ammonium salt solid.
As a preferred technical scheme of the invention, the oxidation tank is connected with the evaporative crystallizer through a brine discharge pump; the bottom of the oxidation tank is also provided with a blower used for introducing air into the oxidation tank; the clarifier is connected with the filter through a sludge pump. The bottom of clarifier is decurrent cone, and the clarifier is equipped with in the inside of cone department and scrapes the ware, scrapes the ware and include the rotation axis with the barrel coaxial line of clarifier and the scraper blade that links to each other and set up along the cone direction with the rotation axis, the one end that the scraper blade was kept away from to the rotation axis extends to the barrel external connection has the motor.
As a preferred technical scheme of the invention, the evaporative crystallizer adopts a multi-effect evaporator or a Mechanical Vapor Recompression (MVR) evaporator; the centrifuge is in a horizontal piston pusher centrifuge or a horizontal spiral filtering centrifuge; the dryer adopts an air flow dryer or a vibration fluidized bed dryer.
The invention also aims to solve the technical problem of providing a method for treating the acidic wastewater generated by washing the regenerated activated carbon gas, which realizes zero emission treatment of the acidic wastewater generated by washing the regenerated activated carbon gas and has safe and reliable technological process.
In order to solve the technical problems, the invention adopts the technical scheme that: the method for treating the acidic wastewater generated by washing the regenerated gas with the activated carbon comprises the following steps:
(1) preparation of ammonium salt: introducing acidic wastewater generated by washing activated carbon regenerated gas into a reaction tank, adding a neutralizing agent to perform a neutralization reaction on the acidic wastewater to generate a first ammonium salt solution, and then sending clear liquid obtained by settling the first ammonium salt solution into an oxidation tank to perform an oxidation reaction to generate a second ammonium salt solution;
(2) evaporating and crystallizing the ammonium salt solution: feeding the second ammonium salt solution generated in the step (1) into an evaporative crystallizer, and carrying out evaporative crystallization to form ammonium salt crystals;
(3) drying of ammonium salt: and (3) conveying the ammonium salt crystals generated in the step (2) into a centrifugal machine for centrifugal separation to obtain ammonium salt crystals.
By adopting the technical scheme, the acidic wastewater contains sulfuric acid, hydrochloric acid, sulfurous acid, sulfur dioxide, fluoride and acid salt, the wastewater is strongly acidic, the reaction tank is provided with an acidic wastewater inlet, a neutralizer inlet and a defluorinating agent inlet, and the reaction tank is provided with a stirrer and a pH value detection instrument; the rotating speed of a stirrer of the reaction tank is 30-60 r/min; the liquid outlet of the reaction tank is connected with the feed inlet of the flocculation tank; the liquid outlet of the flocculation tank is connected with the liquid inlet of the clarifier, sludge is discharged from the bottom of the clarifier, the sludge is pumped to the filter, filter residues are discharged from a mud bucket at the lower part of the filter, the liquid outlet of the filter is connected with the liquid inlet of the clarifier, clear liquid is discharged from the upper part of the clarifier, and the clear liquid enters the oxidation tank; the oxidation tank is connected with a blower, and air is blown in from the bottom of the oxidation tank; the bottom of the oxidation tank is also connected with a brine discharge pump, and the oxidized solution is pumped to an evaporation crystallizer; concentrating the ammonium salt solution to supersaturation by an evaporation crystallizer to generate ammonium salt crystals; discharging ammonium salt crystals from the evaporation crystallizer and conveying the ammonium salt crystals to a centrifugal machine, wherein the centrifugal machine is sequentially connected with a drying machine and a packaging machine, the ammonium salt crystals are firstly dehydrated by the centrifugal machine, the water content of the ammonium salt crystals after centrifugal dehydration is less than or equal to 10%, and then the ammonium salt crystals are dried by the drying machine, and the water content of the ammonium salt crystals is less than or equal to 1; the discharge port of the dryer is connected with a packaging machine, and the ammonium salt solid powder is packaged into a bagged product; the invention realizes that the acidic wastewater is treated by lower amount, the resources are recovered, and the obtained ammonium salt can be used as a raw material, has economic value and is easy to store; the method realizes zero discharge treatment of the acidic wastewater generated by washing the activated carbon regeneration gas, and the process is safe and reliable.
The invention is further improved in that the process of settling the first ammonium salt solution in the step (1) comprises the following steps: feeding the first ammonium salt solution into a flocculation tank for flocculation to obtain a flocculation liquid, and feeding the flocculation liquid into a clarifier for clarification to obtain the clear liquid; wherein the first ammonium salt solution comprises an ammonium sulfite solution and an ammonium chloride solution; the second ammonium salt solution comprises an ammonium salt solution comprising ammonium sulfate and ammonium chloride.
The invention is further improved in that the mother liquor obtained by centrifuging the ammonium salt crystals in the step (3) by the centrifuge is sent back to the evaporation crystallizer, the ammonium salt crystals obtained after centrifugation are sent to a dryer to be dried to obtain ammonium salt solid, and the ammonium salt solid is packaged to form a bagged product; and (3) sending the condensate generated in the evaporative crystallization process of the evaporative crystallizer in the step (2) back to the activated carbon regeneration gas washing device.
The invention is further improved in that in the step (1), the sludge at the bottom after being clarified by the clarifier is sent to a filter for filtration, the filtered filter residue is discharged from the bottom of the filter, the filtered filtrate is sent to the clarifier again through a liquid discharge port of the filter, the filter and the clarifier form a circulation loop, so that the flocculated liquid is clarified and filtered for multiple times, and the clear liquid is discharged from the upper part of the clarifier and sent to the oxidation tank.
As a preferable technical solution of the present invention, a fluorine removal agent for removing fluoride is added to the reaction tank in the step (1); the defluorinating agent is one or two or more of calcium hydroxide, calcium chloride and calcium sulfate; the defluorination reaction is carried out for 5-30 min, the reaction temperature is 40-80 ℃, the molar ratio is 1.01-1.5, the pH value is 5.0-9.0, and the total removal rate is 99%; the neutralizing agent in the step (1) is an ammonia-containing compound, and the ammonia-containing compound is one or a combination of ammonia water, liquid ammonia and ammonia gas; the temperature of the neutralization reaction is 40-80 ℃, and the reaction residence time is 10-30 min; the pH value of the reaction end point is 5.0-9.0; in the step (1), oxidizing reaction is carried out on the first ammonium salt solution in the oxidation tank in an air blowing forced oxidation mode, the oxidizing air quantity is 3-10 times of the air quantity required by the reaction, the oxidizing reaction temperature is 40-60 ℃, and the slurry stays for 1-6 hours; the oxidation rate of the sulfite is controlled to be more than or equal to 98 percent. The defluorinating agent is added, and the principle that calcium ions and fluoride ions are combined to form stable calcium fluoride is utilized, so that the total fluorine removal rate is 99%.
As a preferred technical scheme of the invention, a flocculating agent is arranged in the flocculation tank, the flocculating agent is an organic flocculating agent, the organic flocculating agent is PAC or/and PAM, the addition amount of the flocculating agent is 0.2-1.0%, the temperature of the flocculation reaction is 40-80 ℃, the reaction retention time is 5-30 min, and the pH value is 5.0-9.0.
As a preferred technical scheme of the invention, the rotating speed of the centrifugal machine during centrifugal separation is 1500-3500 r/min, and the water content of the separated material is controlled to be less than or equal to 10%; the air inlet temperature of the dryer is 100-180 ℃, the drying air outlet temperature is 70-120 ℃, the drying retention time is more than 1s, and the water content of the dried ammonium salt solid is controlled to be less than or equal to 1%.
As a preferred technical scheme of the invention, the evaporative crystallizer is operated under negative pressure, the evaporation temperature is controlled to be 50-80 ℃, and the residence time of the second ammonium salt solution is 10-30 min. Such a process is advantageous for ammonium salt crystallization.
The principle of the invention is as follows: the method comprises the steps of adopting ammonia as a neutralizing agent, neutralizing the acid to convert the acid into ammonium salt and ammonium sulfite, adding a defluorinating agent to form stable calcium fluoride, removing suspended matters and the calcium fluoride by adopting a settling and filtering method to obtain ammonium sulfite, forcibly oxidizing the ammonium salt into stable ammonium salt, crystallizing the ammonium salt by adopting an evaporation crystallizer, and finally separating crystals and drying to obtain solid ammonium salt. The invention realizes the low treatment of the acid wastewater, recycles resources, simultaneously the obtained ammonium salt can be used as waste material, is easy to store, has safe and reliable process and environment-friendly property, and simultaneously the process device system can be well connected with the original device. The method relates to the following reaction processes:
and (3) a neutralization process:
and (3) an oxidation process:
fluoride removal process: ca2++2F-＝CaF2↓
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a relatively economic and low-cost treatment process for acidic wastewater washed by regenerated activated carbon gas;
2) according to the invention, an economical amino neutralizer is adopted, ammonium salt generated after neutralization is subjected to evaporative crystallization, centrifugal separation and drying to form solid ammonium salt, the recovered ammonium salt can be used as an external chemical fertilizer, and an ammonium salt solution evaporation condensate is reused in a front-stage activated carbon washing device, so that zero discharge of wastewater is realized;
3) the process is novel, safe, reliable and environment-friendly;
4) the device adopted by the invention has simple structure and convenient maintenance and can be well connected with the original device.
Drawings
The technical scheme of the invention is further described by combining the accompanying drawings as follows:
FIG. 1 is a schematic diagram of the construction of an activated carbon regeneration gas scrubbing acid wastewater treatment plant according to the present invention;
wherein: 101-an acidic wastewater inlet; 102-a neutralizer inlet; 103-sludge outlet; 104-a condensate outlet; a 105-ammonium salt solid outlet; 1-a reaction tank; 2-a flocculation tank; 3-an oxidation tank and 4-an evaporative crystallizer; 5-a centrifuge; 6-a dryer and 7-a packaging machine; 8-a filter; 9-a sludge pump; 10-a clarifier; 11-a blower; 12-brine discharge pump.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1: the device for treating acidic wastewater from washing of the activated carbon regenerated gas comprises a reaction tank 1, a flocculation tank 2, an oxidation tank 3, an evaporative crystallizer 4, a centrifuge 5 and a dryer 6, wherein the reaction tank 1 is provided with an acidic wastewater inlet 101 and a neutralizing agent inlet 102, the reaction tank 1 is connected with the flocculation tank 2, the flocculation tank 2 is connected with the oxidation tank 3, the oxidation tank 3 is connected with the evaporative crystallizer 4, a crystal outlet of the evaporative crystallizer 4 is connected with a feeding port of the centrifuge 5, a mother liquor port and a crystal outlet port are arranged below the centrifuge 5, the mother liquor port is connected with the evaporative crystallizer 4, and the crystal outlet port is connected with the dryer 6; a clarifier 10 and a filter 8 are communicated between the flocculation tank 2 and the oxidation tank 3, a flocculation liquid outlet of the flocculation tank 2 is connected with a flocculation liquid inlet of the clarifier 10, a sludge outlet at the bottom of the clarifier 10 is connected with a sludge inlet of the filter 8, a filtering liquid discharge port at the lower part of the filter 8 is connected with the clarifier 10, and the clarifier 10 and the filter 8 form a circulation loop; a mud bucket is also arranged at the lower part of the filter 8 and used for discharging filter residues; the reaction tank 1 is provided with a stirrer and a pH value detection instrument, and the reaction tank is also provided with a defluorination agent inlet; a condensate outlet is also formed in the evaporative crystallizer 4 and is used for sending condensate generated in the evaporative crystallization process of the evaporative crystallizer 4 back to the activated carbon regeneration gas washing device; the outlet of the dryer 6 is communicated with a packaging machine 7 for packaging the dried ammonium salt solid; the oxidation tank 1 is connected with the evaporative crystallizer 4 through a brine discharge pump 12; the bottom of the oxidation tank 1 is also provided with a blower 11 for introducing air into the oxidation tank 1; the clarifier 10 is connected with the filter 8 through a sludge pump 9; the evaporative crystallizer 4 adopts a multi-effect evaporator or a Mechanical Vapor Recompression (MVR) evaporator; the type of the centrifuge 5 adopts a horizontal piston pusher centrifuge or a horizontal spiral filtering centrifuge; the dryer 6 adopts an air flow dryer or a vibration fluidized bed dryer.
Example 2: the treatment method of the activated carbon regeneration gas washing acidic wastewater treatment device in the embodiment 1 comprises the following steps:
(1) preparation of ammonium salt: introducing acidic wastewater generated by washing activated carbon regenerated gas into a reaction tank 1, adding ammonia water serving as a neutralizing agent to perform a neutralization reaction on the acidic wastewater to generate a first ammonium salt solution, and then sending clear liquid obtained by settling the first ammonium salt solution into an oxidation tank 3 to perform an oxidation reaction to generate a second ammonium salt solution; feeding the first ammonium salt solution into a flocculation tank 2 for flocculation to obtain a flocculation liquid, and feeding the flocculation liquid into a clarifier 10 for clarification to obtain the clear liquid; the sludge at the bottom after clarification is sent into a filter 8 for filtration, the filtered filter residue is discharged from the bottom of the filter 8, the filtered filtrate is sent into the clarifier 10 through a liquid discharge port of the filter 8, the filter 8 and the clarifier 10 form a circulation loop, so that the flocculated liquid is clarified and filtered for multiple times, and the clear liquid is discharged from the upper part of the clarifier 10 and sent into the oxidation tank 3; the first ammonium salt solution comprises an ammonium sulfite solution and an ammonium chloride solution; the second ammonium salt solution comprises an ammonium salt solution comprising ammonium sulfate and ammonium chloride;
a fluorine removal agent is added into the reaction tank 1 in the step (1) and is used for removing fluoride; the defluorinating agent is calcium hydroxide; the reaction residence time of the defluorination reaction is 30min, the pH value is 5.0-9.0, the reaction temperature is 40 ℃, the molar ratio is 1.01, and the total removal rate is 99%;
the reaction tank 1 is provided with a stirrer and a pH value detection instrument; the rotating speed of a stirrer of the reaction tank 1 is 60 r/min; the neutralizing agent in the step (1) is ammonia water, the temperature of the neutralization reaction is 40 ℃, and the reaction retention time is 30 min; the pH value of the reaction end point is 5.0-9.0;
a flocculating agent is arranged in the flocculation tank 2, the flocculating agent is an organic flocculating agent, the organic flocculating agent is PAC or/and PAM, the addition amount of the flocculating agent is 0.2%, the temperature of flocculation reaction is 40 ℃, the reaction retention time is 30min, and the pH value is 5.0-9.0;
in the step (1), the first ammonium salt solution is subjected to oxidation reaction in the oxidation tank 3 in a forced air blowing oxidation mode, wherein the oxidation air volume is 3 times of the air volume required by the reaction, the oxidation reaction temperature is 40 ℃, and the slurry stays for 6 hours; controlling the oxidation rate of the sulfite to be more than or equal to 98 percent;
(2) evaporating and crystallizing the ammonium salt solution: feeding the second ammonium salt solution generated in the step (1) into an evaporative crystallizer 4, wherein the evaporative crystallizer 4 is operated under negative pressure, the evaporation temperature is controlled at 50 ℃, and the retention time is 30 min; evaporating and crystallizing to form ammonium salt crystals; in the step (2), the condensate generated in the evaporative crystallization process of the evaporative crystallizer 4 is sent back to the activated carbon regeneration gas washing device;
(3) drying of ammonium salt: sending the ammonium salt crystals generated in the step (2) into a centrifuge 5 for centrifugal separation to obtain ammonium salt crystals; the mother liquor obtained after the ammonium salt crystals are centrifuged by the centrifuge 5 is sent back to the evaporation crystallizer 4, the ammonium salt crystals obtained after centrifugation are sent to a dryer 6 to be dried to obtain ammonium salt solid, and the ammonium salt solid is packaged to form a bagged product; the rotating speed of the centrifugal machine 5 during centrifugal separation is 1500r/min, and the water content of the separated material is controlled to be less than or equal to 10%; the air inlet temperature of the dryer 6 is 100 ℃, the drying air outlet temperature is 70 ℃, the drying retention time is 15s, and the solid water content of the dried ammonium salt is controlled to be less than or equal to 1%.
Example 3: the treatment method of the activated carbon regeneration gas washing acidic wastewater treatment device in the embodiment 1 is different from the treatment method in the embodiment 2 in the reaction conditions, and specifically comprises the following steps:
(1) preparation of ammonium salt: introducing acidic wastewater generated by washing activated carbon regenerated gas into a reaction tank 1, adding ammonia water serving as a neutralizing agent to perform a neutralization reaction on the acidic wastewater to generate a first ammonium salt solution, and then sending clear liquid obtained by settling the first ammonium salt solution into an oxidation tank 3 to perform an oxidation reaction to generate a second ammonium salt solution; feeding the first ammonium salt solution into a flocculation tank 2 for flocculation to obtain a flocculation liquid, and feeding the flocculation liquid into a clarifier 10 for clarification to obtain the clear liquid; the sludge at the bottom after clarification is sent into a filter 8 for filtration, the filtered filter residue is discharged from the bottom of the filter 8, the filtered filtrate is sent into the clarifier 10 through a liquid discharge port of the filter 8, the filter 8 and the clarifier 10 form a circulation loop, so that the flocculated liquid is clarified and filtered for multiple times, and the clear liquid is discharged from the upper part of the clarifier 10 and sent into the oxidation tank 3; the first ammonium salt solution comprises an ammonium sulfite solution and an ammonium chloride solution; the second ammonium salt solution comprises an ammonium salt solution comprising ammonium sulfate and ammonium chloride;
a fluorine removal agent is added into the reaction tank 1 in the step (1) and is used for removing fluoride; the defluorinating agent is calcium hydroxide; the reaction residence time of the defluorination reaction is 20min, the pH value is 5.0-9.0, the reaction temperature is 60 ℃, the molar ratio is 1.25, and the total removal rate is 99%;
the reaction tank 1 is provided with a stirrer and a pH value detection instrument; the rotating speed of a stirrer of the reaction tank 1 is 45 r/min; the neutralizer in the step (1) is ammonia water; the temperature of the neutralization reaction is 60 ℃, and the reaction retention time is 20 min; the pH value of the reaction end point is 5.0-9.0;
a flocculating agent is arranged in the flocculation tank 2, the flocculating agent is an organic flocculating agent, the organic flocculating agent is PAC or/and PAM, the addition amount of the flocculating agent is 0.6%, the temperature of flocculation reaction is 60 ℃, the reaction retention time is 20min, and the pH value is 5.0-9.0;
in the step (1), the first ammonium salt solution is subjected to oxidation reaction in the oxidation tank 3 in a forced air blowing oxidation mode, wherein the oxidation air volume is 6 times of the air volume required by the reaction, the oxidation reaction temperature is 50 ℃, and the slurry stays for 3 hours; controlling the oxidation rate of the sulfite to be more than or equal to 98 percent;
(2) evaporating and crystallizing the ammonium salt solution: feeding the second ammonium salt solution generated in the step (1) into an evaporative crystallizer 4, wherein the evaporative crystallizer 4 is operated under negative pressure, the evaporation temperature is controlled to be 65 ℃, and the retention time is 20 min; evaporating and crystallizing to form ammonium salt crystals; in the step (2), the condensate generated in the evaporative crystallization process of the evaporative crystallizer 4 is sent back to the activated carbon regeneration gas washing device;
(3) drying of ammonium salt: sending the ammonium salt crystals generated in the step (2) into a centrifuge 5 for centrifugal separation to obtain ammonium salt crystals; the mother liquor obtained after the ammonium salt crystals are centrifuged by the centrifuge 5 is sent back to the evaporation crystallizer 4, the ammonium salt crystals obtained after centrifugation are sent to a dryer 6 to be dried to obtain ammonium salt solid, and the ammonium salt solid is packaged to form a bagged product; the rotation speed of the centrifugal machine 5 during centrifugal separation is 2300r/min, and the water content of the separated material is controlled to be less than or equal to 10 percent; the air inlet temperature of the dryer 6 is 140 ℃, the drying air outlet temperature is 100 ℃, the drying retention time is 10s, and the solid water content of the dried ammonium salt is controlled to be less than or equal to 1%.
Example 4: the treatment method of the activated carbon regeneration gas washing acidic wastewater treatment device in the embodiment 1 is different from the treatment method in the embodiment 2 in the reaction conditions, and specifically comprises the following steps:
(1) preparation of ammonium salt: introducing acidic wastewater generated by washing activated carbon regenerated gas into a reaction tank 1, adding ammonia water serving as a neutralizing agent to perform a neutralization reaction on the acidic wastewater to generate a first ammonium salt solution, and then sending clear liquid obtained by settling the first ammonium salt solution into an oxidation tank 3 to perform an oxidation reaction to generate a second ammonium salt solution; feeding the first ammonium salt solution into a flocculation tank 2 for flocculation to obtain a flocculation liquid, and feeding the flocculation liquid into a clarifier 10 for clarification to obtain the clear liquid; the sludge at the bottom after clarification is sent into a filter 8 for filtration, the filtered filter residue is discharged from the bottom of the filter 8, the filtered filtrate is sent into the clarifier 10 through a liquid discharge port of the filter 8, the filter 8 and the clarifier 10 form a circulation loop, so that the flocculated liquid is clarified and filtered for multiple times, and the clear liquid is discharged from the upper part of the clarifier 10 and sent into the oxidation tank 3; the first ammonium salt solution comprises an ammonium sulfite solution and an ammonium chloride solution; the second ammonium salt solution comprises an ammonium salt solution comprising ammonium sulfate and ammonium chloride;
a fluorine removal agent is added into the reaction tank 1 in the step (1) and is used for removing fluoride; the defluorinating agent is one or two or more of calcium hydroxide, calcium chloride and calcium sulfate; the reaction residence time of the defluorination reaction is 6min, the pH value is 5.0-9.0, the reaction temperature is 80 ℃, the molar ratio is 1.5, and the total removal rate is 99%; the reaction tank 1 is provided with a stirrer and a pH value detection instrument; the rotating speed of a stirrer of the reaction tank 1 is 60 r/min; the neutralizing agent in the step (1) is ammonia water, the temperature of the neutralization reaction is 80 ℃, and the reaction residence time is 10 min; the pH value of the reaction end point is 5.0-9.0;
a flocculating agent is arranged in the flocculation tank 2, the flocculating agent is an organic flocculating agent, the organic flocculating agent is PAC or/and PAM, the addition amount of the flocculating agent is 1.0%, the temperature of flocculation reaction is 40-80 ℃, the reaction retention time is 5min, and the pH value is 5.0-9.0;
in the step (1), the first ammonium salt solution is subjected to oxidation reaction in the oxidation tank 3 in a forced air blowing oxidation mode, wherein the oxidation air volume is 10 times of the air volume required by the reaction, the oxidation reaction temperature is 60 ℃, and the slurry stays for 1 h; controlling the oxidation rate of the sulfite to be more than or equal to 98 percent;
(2) evaporating and crystallizing the ammonium salt solution: feeding the second ammonium salt solution generated in the step (1) into an evaporative crystallizer 4, wherein the evaporative crystallizer 4 is operated under negative pressure, the evaporation temperature is controlled to be 80 ℃, and the retention time is 10 min; evaporating and crystallizing to form ammonium salt crystals; in the step (2), the condensate generated in the evaporative crystallization process of the evaporative crystallizer 4 is sent back to the activated carbon regeneration gas washing device;
(3) drying of ammonium salt: sending the ammonium salt crystals generated in the step (2) into a centrifuge 5 for centrifugal separation to obtain ammonium salt crystals; the mother liquor obtained after the ammonium salt crystals are centrifuged by the centrifuge 5 is sent back to the evaporation crystallizer 4, the ammonium salt crystals obtained after centrifugation are sent to a dryer 6 to be dried to obtain ammonium salt solid, and the ammonium salt solid is packaged to form a bagged product; the rotating speed of the centrifugal machine 5 during centrifugal separation is 3500r/min, and the water content of the separated material is controlled to be less than or equal to 10 percent; the air inlet temperature of the dryer 6 is 180 ℃, the drying air outlet temperature is 120 ℃, the drying retention time is 5s, and the solid water content of the dried ammonium salt is controlled to be less than or equal to 1%.
The working principle is as follows: the liquid outlet of the reaction tank 1 is connected with the feed inlet of the flocculation tank 2; a liquid outlet of the flocculation tank 2 is connected with a liquid inlet of the clarifier 10, sludge is discharged from the bottom of the clarifier 10 and is sent to the filter 8 through a sludge pump 9, filter residues are discharged from a hopper at the lower part of the filter 8, a liquid outlet of the filter 8 is connected with a feed inlet of the clarifier 10 to form a circulation loop, clear liquid is discharged from the upper part of the clarifier 10, and the clear liquid enters the oxidation tank 3; the bottom of the oxidation tank 3 is connected with an air blower 11, and air is blown in from the bottom of the oxidation tank 3; the bottom of the oxidation tank 3 is also connected with a brine discharge pump 12, and the oxidized second ammonium salt solution is sent to the evaporative crystallizer 4 through the brine discharge pump 12; the evaporative crystallizer 4 concentrates the second ammonium salt solution to supersaturation to produce ammonium salt crystals; discharging ammonium salt crystals from the evaporative crystallizer 4 and conveying the ammonium salt crystals to a centrifuge 5, wherein the centrifuge 5 is sequentially connected with a dryer 6 and a packing machine 7, the ammonium salt crystals are firstly dehydrated by the centrifuge 5, the water content of the ammonium salt crystals after centrifugal dehydration is less than or equal to 10 percent, and then the ammonium salt crystals are dried by the dryer 6, and the water content of the ammonium salt crystals is less than or equal to 1 percent; the discharge port of the dryer 6 is connected with the packing machine 7, and the ammonium salt solid powder is packed into a bagged product.
It is obvious to those skilled in the art that the present invention is not limited to the above embodiments, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical scheme of the present invention, or to directly apply the concept and technical scheme of the present invention to other occasions without modification.
Claims (14)
1. The utility model provides an active carbon regeneration gas washing acid effluent treatment plant, its characterized in that, includes retort, flocculation jar, oxidation tank, evaporation crystallizer, centrifuge and desiccator, the retort is equipped with acid waste water entry and neutralizer entry, the retort with the flocculation jar links to each other, the flocculation jar with the oxidation tank links to each other, the oxidation tank with evaporation crystallizer links to each other, evaporation crystallizer's crystal export with centrifuge pan feeding mouth links to each other, centrifuge's below is equipped with mother liquor mouth and goes out the crystal mouth, the mother liquor mouth with evaporation crystallizer links to each other just go out the crystal mouth with the desiccator links to each other.
2. The activated carbon regeneration gas washing acidic wastewater treatment device as claimed in claim 1, wherein a clarifier and a filter are further communicated between the flocculation tank and the oxidation tank, a flocculation liquid outlet of the flocculation tank is connected with a flocculation liquid inlet of the clarifier, a sludge outlet at the bottom of the clarifier is connected with a sludge inlet of the filter, a filtering liquid discharge port at the lower part of the filter is connected with the clarifier, and the clarifier and the filter form a circulation loop; and a mud bucket is arranged at the lower part of the filter and used for discharging filter residues.
3. The apparatus of claim 2, wherein the reaction tank is provided with a stirrer and a pH value detection instrument, and the reaction tank is further provided with a fluorine removal agent inlet.
4. The activated carbon regeneration gas washing acidic wastewater treatment device as claimed in claim 2, wherein a condensate outlet is further provided on the evaporative crystallizer for returning condensate generated in the evaporative crystallization process of the evaporative crystallizer to the activated carbon regeneration gas washing device.
5. The activated carbon regeneration gas washing acidic wastewater treatment device as claimed in claim 3 or 4, wherein the outlet of the dryer is communicated with a packaging machine for packaging the dried ammonium salt solid.
6. The activated carbon regeneration gas scrubbing acidic wastewater treatment plant of claim 5, wherein said oxidation tank is connected to said evaporative crystallizer by a brine discharge pump; the bottom of the oxidation tank is also provided with a blower used for introducing air into the oxidation tank; the clarifier is connected with the filter through a sludge pump.
7. The activated carbon regeneration gas washing acidic wastewater treatment device of claim 5, wherein the evaporative crystallizer employs a multiple-effect evaporator or a Mechanical Vapor Recompression (MVR) evaporator; the centrifuge is in a horizontal piston pusher centrifuge or a horizontal spiral filtering centrifuge; the dryer adopts an air flow dryer or a vibration fluidized bed dryer.
8. The method for treating acidic wastewater generated by washing regenerated activated carbon gas is characterized by comprising the following steps:
(1) preparation of ammonium salt: introducing acidic wastewater generated by washing activated carbon regenerated gas into a reaction tank, adding a neutralizing agent to perform a neutralization reaction on the acidic wastewater to generate a first ammonium salt solution, and then sending clear liquid obtained by settling the first ammonium salt solution into an oxidation tank to perform an oxidation reaction to generate a second ammonium salt solution;
(2) evaporating and crystallizing the ammonium salt solution: feeding the second ammonium salt solution generated in the step (1) into an evaporative crystallizer, and carrying out evaporative crystallization to form ammonium salt crystals;
(3) drying of ammonium salt: and (3) conveying the ammonium salt crystals generated in the step (2) into a centrifugal machine for centrifugal separation to obtain ammonium salt crystals.
9. The method for treating acidic wastewater generated by washing activated carbon regeneration gas according to claim 8, wherein the first ammonium salt solution is settled in step (1) by: feeding the first ammonium salt solution into a flocculation tank for flocculation to obtain a flocculation liquid, and feeding the flocculation liquid into a clarifier for clarification to obtain the clear liquid; wherein the first ammonium salt solution comprises an ammonium sulfite solution and an ammonium chloride solution; the second ammonium salt solution comprises an ammonium salt solution comprising ammonium sulfate and ammonium chloride.
10. The method for treating acidic wastewater from washing of regenerated activated carbon gas according to claim 9, wherein the mother liquor obtained by centrifuging the ammonium salt crystals in step (3) by the centrifuge is returned to the evaporative crystallizer, and the ammonium salt crystals obtained by centrifuging are sent to a dryer to be dried to obtain ammonium salt solids, which are then packaged to form bagged products; and (3) sending the condensate generated in the evaporative crystallization process of the evaporative crystallizer in the step (2) back to the activated carbon regeneration gas washing device.
11. The method for treating acidic wastewater washed by regenerated activated carbon gas as claimed in claim 9, wherein in the step (1), the sludge at the bottom of the clarifier is filtered by a filter, the filtered filter residue is discharged from the bottom of the filter, the filtered filtrate is fed into the clarifier again through a liquid discharge port of the filter, the filter and the clarifier form a circulation loop, the flocculated liquid is clarified and filtered for multiple times, and the clear liquid is discharged from the upper part of the clarifier and fed into the oxidation tank.
12. The method for treating acidic wastewater generated by washing activated carbon regeneration gas according to claim 9, wherein a fluorine removal agent is added into the reaction tank in the step (1) for removing fluoride; the defluorinating agent is one or two or more of calcium hydroxide, calcium chloride and calcium sulfate; the defluorination reaction is carried out for 5-30 min, the reaction temperature is 40-80 ℃, the molar ratio is 1.01-1.5, the pH value is 5.0-9.0, and the total removal rate is 99%; the neutralizing agent in the step (1) is an ammonia-containing compound, and the ammonia-containing compound is one or a combination of ammonia water, liquid ammonia and ammonia gas; the temperature of the neutralization reaction is 40-80 ℃, and the reaction residence time is 10-30 min; the pH value of the reaction end point is 5.0-9.0; in the step (1), oxidizing reaction is carried out on the first ammonium salt solution in the oxidation tank in an air blowing forced oxidation mode, the oxidizing air quantity is 3-10 times of the air quantity required by the reaction, the oxidizing reaction temperature is 40-60 ℃, and the slurry stays for 1-6 hours; the oxidation rate of the sulfite is controlled to be more than or equal to 98 percent.
13. The method for treating acidic wastewater generated by washing with activated carbon regeneration gas according to claim 9, wherein a flocculating agent is arranged in the flocculation tank, the flocculating agent is an organic flocculating agent, the organic flocculating agent is PAC or/and PAM, the addition amount of the flocculating agent is 0.2-1.0%, the temperature of flocculation reaction is 40-80 ℃, the reaction residence time is 5-30 min, and the pH value is 5.0-9.0.
14. The method for treating acidic wastewater generated by washing regenerated activated carbon gas according to claim 9, wherein the rotation speed of the centrifugal machine during centrifugal separation is 1500-3500 r/min, and the water content of the separated material is controlled to be less than or equal to 10%; the air inlet temperature of the dryer is 100-180 ℃, the drying air outlet temperature is 70-120 ℃, the drying retention time is more than 1s, and the water content of the dried ammonium salt solid is controlled to be less than or equal to 1%.
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