CN110563177A - Chromium-containing wastewater online circulating treatment device and method - Google Patents
Chromium-containing wastewater online circulating treatment device and method Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 142
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 112
- 239000002351 wastewater Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 121
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 88
- 238000003795 desorption Methods 0.000 claims description 71
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 24
- 239000010802 sludge Substances 0.000 claims description 18
- 229920001429 chelating resin Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000013522 chelant Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 14
- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000012528 membrane Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000009388 chemical precipitation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001994 activation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides an online cyclic treatment device for chromium-containing wastewater, which comprises a deslagging device, a filtering device and an adsorption device which are sequentially connected through pipelines, wherein the deslagging device is used for removing precipitates and suspended matters in the chromium-containing wastewater; the filtering device is used for removing particulate matters in the chromium-containing wastewater; the adsorption device is used for adsorbing chromium metal ions. And a method for carrying out online cyclic treatment on the chromium-containing wastewater by using the device. The device and the method have high treatment efficiency, low cost and simple operation, simultaneously realize the separation and purification of chromium metal ions, and are the chromium electroplating wastewater treatment method with the most application prospect at present. By the design and optimization of the technical route, the near zero discharge of waste water and the recovery and cyclic utilization of metal resources can be realized.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an online cyclic treatment device and method for chromium-containing wastewater.
Background
The main techniques for treating the chromium-containing wastewater at present comprise a chemical precipitation method, an adsorption method, an electrolysis method, a membrane separation method, a biodegradation method, a solvent extraction method and the like.
the chemical precipitation method is the earliest developed method for treating the chromium electroplating wastewater. It mainly utilizes chemical precipitant to make electricityHeavy metals such as Cr (VI) in the chromium plating wastewater form precipitates to be separated from a water phase, so that the residual wastewater can be discharged. The early precipitation method is to add BaCl into the waste water containing Cr (VI)2barium chromate precipitate is formed, and the treated wastewater is directly discharged; the generated sludge containing barium chromate sediment is cured by sodium silicate cement or lime fly ash and then discarded. The treatment method is easy to cause Cr (VI) to enter the water body, thereby causing threats to human health, ecological environment safety and the like. Further, the method has been developed in which Cr (VI) is reduced to Cr (III) by using a chemical reducing agent and then Cr (OH) is added3the chemical precipitation process, in which the precipitate leaves the aqueous phase, significantly reduces the environmental hazard. However, these chemical precipitation treatment methods still produce solid wastes such as sludge, and the chromium resources are not reused.
The adsorption method is to make Cr (VI) be separated from water phase by utilizing adsorbent to adsorb Cr (VI) ions in the chromium electroplating wastewater, so that the treated wastewater can be discharged. The common adsorbent is activated carbon, and the adsorption capacity of the adsorbent for adsorbing Cr (VI) can reach 101 mg/g. The newly developed biological adsorbent is produced from agricultural wastes, is low in price, has high Cr (VI) adsorption efficiency, and remarkably reduces sludge generated during regeneration. However, the biological adsorbent has its own dissolution, which increases the indexes of Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD), and Total Organic Carbon (TOC) of the treated wastewater, and thus limits its further development and application. Industrial wastes such as blast furnace slag and red mud are also used as an adsorbent for adsorbing Cr (VI) in wastewater, and are not widely used because of their limited adsorption efficiency. Whichever adsorbent, after adsorbing Cr (VI) in the wastewater, it needs to be regenerated for recycling. During regeneration of the adsorbent, a large amount of solid wastes such as sludge and the like can be generated to pollute the environment after being accumulated and buried; and the chromium resource is not reused.
The electrolysis method can remove Cr (VI) in the wastewater by controlling the oxidation-reduction potential to reduce the soluble Cr (VI) in the wastewater into insoluble matters such as Cr (OH)3, and can be divided into a membrane electrolysis method and an electrochemical precipitation method. The method has the Cr (VI) removing rate of over 99 percent, and is suitable for treating wastewater which is difficult to biodegrade and has higher physical and chemical treatment cost. Although the method can reduce the production amount of waste sludge and recover chromic acid in the electrolytic bath to be returned and applied to the electroplating bath, the method has high energy consumption and difficult control of process conditions, and is not widely applied.
the membrane separation method utilizes a filter membrane to separate Cr (VI) ions in the wastewater by principles of physical adsorption, ion exchange, extraction dissolution and the like. Commonly used separation membranes can be classified into inorganic membranes (e.g., porous ceramics), polymeric membranes, and liquid membranes (e.g., emulsion membranes, immobilized liquid membranes). Although these membrane separation methods have high selectivity, they are only in the pilot stage due to their relatively low removal efficiency, and thus have not been industrially applied. Electrodialysis is a newly developed membrane separation method that uses potential difference as a driving force to realize the separation of ions in an aqueous solution. The method can realize the recycling of water and the recovery of heavy metal elements. However, the core component of the electrodialysis method is an ion exchange membrane, which is expensive and has a short service life in high-salt wastewater, resulting in high operation cost of the electrodialysis method and being not suitable for popularization and application.
The biodegradation method is to utilize microorganisms or plants to absorb Cr (VI) in the wastewater and enrich the Cr (VI) in biological tissues, or reduce the Cr (VI) into Cr (III) to form Cr (OH)3 precipitates so as to realize the treatment of removing the Cr (VI) from the wastewater. Including bioadsorption methods, plant extraction methods, and the like. Although biodegradation has been widely studied as early as 90 s in the last century, the method has not been widely applied due to limited reduction capability of microorganisms on Cr (VI) and few kinds of plants capable of realizing Cr (VI) extraction.
the solvent extraction method utilizes an organic extractant to be complexed with Cr (VI) to form a hydrophobic organic complex, so that the Cr (VI) enters an organic phase from a water phase, and the Cr (VI) in the wastewater is removed. By adopting a proper water phase, Cr (VI) can be back-extracted into a new water phase to realize the recovery of chromium resources. However, the current efficient organic extracting agent aiming at Cr (VI) has few types, and the extraction rate of the current extracting agent is relatively low, so that the method cannot be widely applied. In addition, although the organic solvent and the organic extracting agent can be recycled, more wastewater is introduced when the method is used for recovering chromium resources, and the wastewater discharge amount is increased.
At present, the existing miniaturized online electroplating chromium-containing wastewater treatment devices at home and abroad adopt the traditional chemical precipitation method, the yield of sludge (solid waste) is large, the energy consumption is high, only chromium resources in the sludge (solid waste) can be recovered, zero emission of the electroplating chromium wastewater and cyclic utilization of the chromium resources and water resources in the electroplating chromium wastewater cannot be realized, and the development trend of electroplating wastewater treatment technology and equipment and the urgent requirements of electroplating enterprises cannot be met.
Disclosure of Invention
The invention aims to provide a chromium-containing wastewater online circulating treatment device and method, and provides a brand-new solution and thought aiming at the current situations that the existing electroplating chromium-containing wastewater treatment method is high in byproduct treatment difficulty and treatment cost, cannot realize the recycling of heavy metal ions and is difficult to realize the online circulating treatment of wastewater. The aims of online cyclic treatment of the electroplating chromium-containing wastewater and cyclic recycling of heavy metals are fulfilled; the problems of large sludge yield, high sludge treatment cost and incapability of effectively realizing the recovery and cyclic utilization of heavy metals in the traditional process are solved. The device and the method have high treatment efficiency, low cost and simple operation, simultaneously realize the separation and purification of chromium metal ions, and are the chromium electroplating wastewater treatment method with the most application prospect at present. By the design and optimization of the technical route, the near zero discharge of waste water and the recovery and cyclic utilization of metal resources can be realized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an on-line circulating treatment device for chromium-containing wastewater, which comprises a deslagging device, a filtering device and an adsorption device which are connected in sequence through pipelines,
the deslagging device is used for removing sediments and suspended matters in the chromium-containing wastewater;
the filtering device is used for removing particulate matters in the chromium-containing wastewater;
The adsorption device is used for adsorbing chromium metal ions.
On the basis of the technical scheme, the invention can further have the following specific selection or optimized selection.
Specifically, the adsorption device comprises a trivalent chromium adsorption device and a hexavalent chromium adsorption device which are sequentially connected through a pipeline, the trivalent chromium adsorption device comprises a vertically arranged trivalent chromium adsorption column, the hexavalent chromium adsorption device comprises a vertically arranged hexavalent chromium adsorption column, inner cavities of the trivalent chromium adsorption column and the hexavalent chromium adsorption column are respectively provided with a water distribution area, a reaction area and a water outlet area from bottom to top in sequence, positions on the trivalent chromium adsorption column and the hexavalent chromium adsorption column corresponding to the water outlet area are provided with water outlets communicated with the water outlets, the reaction area is filled with chelate resin, a water distributor is arranged in the water distribution area, water inlets communicated with the water distributor are arranged on the trivalent chromium adsorption column and the hexavalent chromium adsorption column, a water inlet of the trivalent chromium adsorption column is communicated with a water outlet of the filtering device through a pipeline, a water outlet of the trivalent chromium adsorption column is communicated with a water inlet of the hexavalent chromium adsorption column through a pipeline, and the water outlet of the hexavalent chromium adsorption column is communicated with a purified water collecting device through a pipeline. The purified water collecting device can collect the treated water reaching the standard and can directly recycle the treated water to the electroplating production line.
Specifically, in the hexavalent chromium adsorption column, the chelate resin is a chlorine-type wet spherical strong base anion exchange resin, and the diameter of the chelate resin is 0.4-0.7 mm. In the trivalent chromium adsorption column, the chelating resin is a hydrogen wet spherical strong acid type cation exchange resin, and the diameter of the chelating resin is 0.4-0.6 mm. The chelating resin is favorable for forming a fluid state with the chromium-containing wastewater in the adsorption column, so that the contact area is increased to the maximum extent, and the adsorption efficiency is improved.
Specifically, hexavalent chromium adsorption equipment includes many the hexavalent chromium adsorption column, through the pipeline interconnect who takes the valve between the hexavalent chromium adsorption column, first the water inlet of hexavalent chromium adsorption column pass through the pipeline with the delivery port intercommunication of trivalent chromium adsorption column, last the delivery port of hexavalent chromium adsorption column passes through pipeline and purified water collection device intercommunication.
Specifically, dross removal mechanism includes pipe chute sedimentation tank and clean water basin, pipe chute sedimentation tank lateral wall lower part is equipped with the water inlet with contain chromium wastewater discharge pipe intercommunication, pipe chute sedimentation tank bottom is equipped with hourglass hopper-shaped sludge bucket, sludge bucket top is equipped with the pipe chute and subsides the layer, be located on the pipe chute sedimentation tank lateral wall the position of pipe chute subsides the layer top be equipped with the delivery port of clean water basin intercommunication, the clean water basin bottom also is equipped with hourglass hopper-shaped sludge bucket, just the delivery port of clean water basin with the filter equipment intercommunication.
Specifically, still be equipped with the elevator pump on the pipeline between dross removal mechanism with filter equipment, the water inlet of elevator pump with clean water basin intercommunication, the delivery port of elevator pump with filter equipment's water inlet intercommunication, the water inlet department of elevator pump is equipped with check valve and gauze.
the desorption device comprises a first desorption loop and a second desorption loop, the first desorption loop comprises a first desorption groove filled with first desorption liquid, the upper part of the trivalent chromium adsorption column is provided with a first desorption liquid inlet communicated with the inner cavity of the trivalent chromium adsorption column, the lower end of the trivalent chromium adsorption column is provided with a first desorption liquid outlet communicated with the inner cavity of the trivalent chromium adsorption column, the water outlet of the first desorption groove is communicated with the first desorption liquid inlet through a pipeline, and the water inlet of the first desorption groove is communicated with the first desorption liquid outlet through a pipeline; the second desorption return circuit is including being equipped with the second desorption groove that the second detached liquid, every hexavalent chromium adsorption column upper portion is equipped with the second detached liquid entry of intercommunication its inner chamber, and its lower extreme is equipped with the second detached liquid export of intercommunication its inner chamber, the delivery port of second desorption groove pass through the pipeline with the second detached liquid entry intercommunication, the water inlet of second desorption groove pass through the pipeline with the second detached liquid export intercommunication.
In addition, the invention also provides an online circulating treatment method of the chromium-containing wastewater by using the online circulating treatment device of the chromium-containing wastewater, which comprises the following steps:
1) Introducing the chromium-containing wastewater into the deslagging device to remove sediments and suspended matters in the chromium-containing wastewater;
2) introducing the chromium-containing wastewater treated in the step 1) into the filtering device to remove particulate matters in the chromium-containing wastewater;
3) Introducing the chromium-containing wastewater treated in the step 2) into the adsorption device to adsorb chromium metal ions;
Wherein, the total chromium content in the water treated in the step 3) is below 0.5mg/L, and the hexavalent chromium content is below 0.1 mg/L.
On the basis of the technical scheme, the invention can further have the following specific selection or optimized selection.
specifically, the method further comprises a desorption step, wherein hydrochloric acid solution with the mass fraction of 2-5% is used as first desorption liquid to desorb the trivalent chromium adsorption column from top to bottom, and the first desorption tank filled with the first desorption liquid and the trivalent chromium adsorption form a first desorption loop through a pipeline; and desorbing the hexavalent chromium adsorption column from top to bottom by using an industrial salt solution with the mass fraction of 10-15% as a second desorption solution, wherein the second desorption tank filled with the second desorption solution and the divalent chromium are adsorbed to form a second desorption loop through a pipeline.
Specifically, in the hexavalent chromium adsorption column, the chelate resin is crosslinked polystyrene having an ammonium functional group; in the trivalent chromium adsorption column, the chelating resin is a styrene copolymer with a nucleon sulfonic acid functional group.
Compared with the prior art, the invention has the beneficial effects that:
1. because above-mentioned device directly sets up beside the production line, as single metal ion's treatment facility, the pertinence is higher, and adsorption efficiency is stronger. Therefore, the problem that different heavy metal wastewater must be collected and discharged in different pipes does not exist. And the type of the waste water generated by the fixed production line belongs to a fixed state, and the pollution of other heavy metals does not exist.
2. The invention is an on-line circulation treatment, has compact integral structure, is arranged beside a production line, realizes an on-line circulation treatment mode of production and treatment, can directly discharge the effluent as the treatment reclaimed water, and can directly recycle the desorption solution to the activation working section of the production line after being concentrated and concentrated for a plurality of times by carrying out rear end arrangement.
3. The hexavalent chromium adsorption column adopts a multi-purpose one-standby mode, and can realize simultaneous operation and desorption.
4. The whole system generates a small amount of precipitate in the pretreatment stage, and the rest components do not generate secondary pollutants. Compared with the traditional method, a large amount of sludge containing heavy metals is generated, and the treatment cost of the sludge is high and is limited by related policies.
5. All valves in the whole system can adopt electric valves, and the valves are connected into a PLC (programmable logic controller) through a circuit, so that the programming control and the higher automation degree can be realized.
Drawings
FIG. 1 is a process flow diagram of the chromium-containing wastewater on-line circulating treatment device provided by the invention.
in the figure: 1-a deslagging device, 2-a filtering device, 3-an adsorption device, 4-a desorption device, 5-a lifting pump device and 6-a production line.
Detailed Description
For a better understanding of the present invention, the following further illustrates the present invention with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples.
Example (b):
as shown in figure 1, the invention provides a process flow diagram of an online cyclic treatment device for chromium-containing wastewater, wherein the wastewater is lifted into a deslagging device 1 with a special structure through a water pump, the deslagging device 1 comprises an inclined tube sedimentation tank and a clean water tank, and impurities and suspended particulate matters in the wastewater are intercepted and precipitated by the inclined tube sedimentation tank so as to reduce the load of a subsequent treatment unit. Funnel-shaped mud hoppers are arranged at the bottoms of the inclined tube sedimentation tank and the clean water tank; a UPVC sludge discharge valve is arranged at the corresponding height outside the equipment. The wastewater entering the deslagging device 1 flows into the inclined tube settling zone from bottom to top through a gap arranged at the bottom of the clapboard of the inclined tube settling tank. Impurities and flocs in the wastewater are deposited into a funnel-shaped mud bucket positioned right below the inclined pipe under the action of the inclined pipe, and are discharged outside through an external valve for disposal. And the wastewater passing through the inclined pipe area overflows from the top of the baffle plate of the inclined pipe to enter the clean water tank.
the deslagging device 1 is communicated with the filtering device 2 through an external self-suction type corrosion-resistant pump, and a water inlet pipe of the pump is arranged in the clean water tank; the pipe orifice is provided with a check valve and a gauze. Pumping the water in the clean water tank into a fine filter at high pressure, wherein a 5-10 micron filter element is arranged in the fine filter. The wastewater is conveyed by the high pressure of the lifting pump 5, and the particles beyond the particle size range are intercepted on the surface of the filter element, so that 90 percent of the particles can be removed.
the adsorption device 3 consists of two parts, namely a hexavalent chromium and a trivalent chromium adsorption device. The chromium-containing wastewater passes through a precision filter and then enters a trivalent chromium adsorption device, and then enters a hexavalent chromium adsorption device, so that hexavalent chromium and trivalent chromium are removed.
The filtering device 2 is connected with the adsorption column through a UPVC pipeline. The adsorption column is made of glass fiber reinforced plastic and is vertically arranged in a cylindrical shape on the whole. The interior of the adsorption column is divided into three sections. The adsorption column comprises a hemispherical water distribution area at the lower part of the adsorption column, a reaction area at the middle part and a hemispherical water outlet area at the upper part. The middle part of the adsorption column is filled with chelating resin. And the wastewater enters the water distribution area through a water inlet arranged at the bottom of the adsorption column after passing through the filtering device 2. The water distribution area is provided with a special stainless steel water distributor which can uniformly distribute the waste water in the reaction area of the adsorption column. In a proper pressure interval, the chelating resin filled in the middle part of the reaction tower is in a completely fluidized state and can be fully contacted with the waste water to form a homogeneous reaction state.
The adsorption column is trivalent chromium adsorption column and hexavalent chromium adsorption column and establishes ties, and wherein the hexavalent chromium adsorption column is for multi-purpose one is equipped with, comprises many adsorption columns promptly, connects into through UPVC pipeline and electric valve between each adsorption column and can make up many adsorption columns at will and establish ties, the mode that an adsorption column was reserve. Each electric valve is connected with a master control PLC program through a signal wire, and the opening and closing of each valve are realized through the programming of the PLC program so as to realize the serial operation of a plurality of adsorption columns. When the adsorption columns connected in series normally operate, the standby adsorption columns are backwashed simultaneously. Namely, the effect of simultaneous operation of operation and desorption is realized.
The chelate resin for adsorbing hexavalent chromium is strong base type anion exchange resin. The resin is in a chlorine-type wet spherical shape. The main structure is crosslinked polystyrene, and a special ammonium functional group is combined on the structure of the crosslinked polystyrene. The chelating resin for adsorbing trivalent chromium is strong acid cation exchange resin. The resin is in a hydrogen form wet spherical shape. The main structure is macroporous styrene cross-linked copolymer, which is combined with iminodiacetic acid functional group. The method has higher adsorption efficiency aiming at hexavalent chromium and trivalent chromium ions in the electroplating wastewater, and the exchange adsorption capacity can reach 40 g/L. Compared with the conventional resin, the modified resin has the advantages of large adsorption capacity, large specific surface area, difficult breakage, long service life (about 5 years), and the like.
After the two chelating resins are saturated, the two chelating resins need to be regenerated to recover the adsorption activity. Aiming at the hexavalent chromium adsorption resin, 10-15% of industrial salt solution is used as a desorption agent, and the desorption agent is stored in a desorption tank. And pumping the desorption agent into the reaction tower from the UPVC pipeline at the upper part of the middle part of the reaction tower from top to bottom through a pump. And desorbing the hexavalent chromium adsorbed on the chelate resin group through full contact reaction with the chelate resin in the reaction tower. And sodium ions in the desorption agent to form sodium chromate. The desorption time is adjusted according to the adsorption amount. Preparing a desorption agent once, and desorbing four to five reaction columns at most. After repeated use for many times, the content of hexavalent chromium in the desorption agent can be accumulated to a greater extent. When the content of hexavalent chromium in the desorption agent reaches more than 20g/L, the hexavalent chromium can be recycled to the activation process section of the production line 6.
aiming at the trivalent chromium adsorption resin, 2-5% hydrochloric acid solution is adopted as a desorption agent, and the desorption agent is stored in a desorption tank. And pumping the desorption agent into the reaction tower from the UPVC pipeline at the upper part of the middle part of the reaction tower from top to bottom through a pump. And (3) fully contacting and reacting with the chelating resin in the reaction tower, and desorbing the trivalent chromium adsorbed on the chelating resin group. Forming chromium chloride with chloride ions in the desorbent. The desorption time is adjusted according to the adsorption amount. Preparing a desorption agent for one time, and desorbing the reaction column for two to three times at most. After repeated use for many times, the content of trivalent chromium in the desorption agent can be accumulated to a large extent. When the content of hexavalent chromium in the desorption agent reaches more than 20g/L, the hexavalent chromium can be recycled to the production line 6.
After the wastewater is treated by the system, the total chromium content can reach below 0.5mg/L, and the hexavalent chromium content can reach below 0.1 mg/L.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An online circulating treatment device for chromium-containing wastewater is characterized by comprising a deslagging device (1), a filtering device (2) and an adsorption device (3) which are sequentially connected through pipelines,
The deslagging device (1) is used for removing precipitates and suspended matters in the chromium-containing wastewater;
The filtering device (2) is used for removing particulate matters in the chromium-containing wastewater;
The adsorption device (3) is used for adsorbing chromium metal ions.
2. The on-line circulating treatment device for chromium-containing wastewater according to claim 1, characterized in that: dross removal mechanism (1) includes pipe chute sedimentation tank and clean water basin, pipe chute sedimentation tank lateral wall lower part be equipped with contain the water inlet of chromium wastewater discharge pipe intercommunication, pipe chute sedimentation tank bottom is equipped with leaks hopper-shaped sludge bucket, the sludge bucket top is equipped with the pipe chute and subsides the layer, be located on the pipe chute sedimentation tank lateral wall the position of pipe chute subsides the layer top be equipped with the delivery port of clean water basin intercommunication, the clean water basin bottom also is equipped with leaks hopper-shaped sludge bucket, just the delivery port of clean water basin with filter equipment (2) intercommunication.
3. The on-line circulating treatment device for chromium-containing wastewater according to claim 1, characterized in that: still be equipped with elevator pump (5) on the pipeline between dross removal mechanism (1) and filter equipment (2), the water inlet of elevator pump (5) with the clean water basin intercommunication, the delivery port of elevator pump (5) with the water inlet intercommunication of filter equipment (2), the water inlet department of elevator pump (5) is equipped with check valve and gauze.
4. the on-line recycling treatment device for chromium-containing wastewater according to any one of claims 1 to 3, characterized in that: the adsorption device (3) comprises a trivalent chromium adsorption device and a hexavalent chromium adsorption device which are sequentially connected through a pipeline, the trivalent chromium adsorption device comprises a vertically-arranged trivalent chromium adsorption column, the hexavalent chromium adsorption device comprises a vertically-arranged hexavalent chromium adsorption column, inner cavities of the trivalent chromium adsorption column and the hexavalent chromium adsorption column are respectively provided with a water distribution area, a reaction area and a water outlet area from bottom to top in sequence, positions on the trivalent chromium adsorption column and the hexavalent chromium adsorption column corresponding to the water outlet area are provided with water outlets communicated with the water outlet area, the reaction area is filled with chelate resin, a water distributor is arranged in the water distribution area, water inlets communicated with the water distributor are arranged on the trivalent chromium adsorption column and the hexavalent chromium adsorption column, a water inlet of the trivalent chromium adsorption column is communicated with a water outlet of the filtering device (2) through a pipeline, a water outlet of the trivalent chromium adsorption column is communicated with a water inlet of the hexavalent chromium adsorption column through a pipeline, and the water outlet of the hexavalent chromium adsorption column is communicated with a purified water collecting device through a pipeline.
5. the on-line recycling treatment device for chromium-containing wastewater according to claim 4, characterized in that: in the hexavalent chromium adsorption column, the chelating resin is a strong alkali anion exchange resin in a chlorine wet spherical shape, and the diameter of the chelating resin is 0.4-0.7 mm; in the trivalent chromium adsorption column, the chelating resin is a hydrogen wet spherical strong acid type cation exchange resin, and the diameter of the chelating resin is 0.4-0.6 mm.
6. The on-line recycling treatment device for chromium-containing wastewater according to claim 4, characterized in that: hexavalent chromium adsorption equipment includes many the hexavalent chromium adsorption column, connect gradually through the pipeline of taking the valve between the hexavalent chromium adsorption column, first the water inlet of hexavalent chromium adsorption column pass through the pipeline with the delivery port intercommunication of trivalent chromium adsorption column, last the delivery port of hexavalent chromium adsorption column passes through pipeline and purified water collection device intercommunication.
7. the on-line recycling treatment device for chromium-containing wastewater according to claim 6, characterized in that: the desorption device comprises a first desorption loop and a second desorption loop, the first desorption loop comprises a first desorption groove filled with first desorption liquid, the upper part of the trivalent chromium adsorption column is provided with a first desorption liquid inlet communicated with the inner cavity of the trivalent chromium adsorption column, the lower end of the trivalent chromium adsorption column is provided with a first desorption liquid outlet communicated with the inner cavity of the trivalent chromium adsorption column, the water outlet of the first desorption groove is communicated with the first desorption liquid inlet through a pipeline, and the water inlet of the first desorption groove is communicated with the first desorption liquid outlet through a pipeline; the second desorption return circuit is including being equipped with the second desorption groove that the second detached liquid, every hexavalent chromium adsorption column upper portion is equipped with the second detached liquid entry of intercommunication its inner chamber, and its lower extreme is equipped with the second detached liquid export of intercommunication its inner chamber, the delivery port of second desorption groove pass through the pipeline with the second detached liquid entry intercommunication, the water inlet of second desorption groove pass through the pipeline with the second detached liquid export intercommunication.
8. an online circulating treatment method of chromium-containing wastewater by using the online circulating treatment device of chromium-containing wastewater according to any one of claims 1 to 6, which is characterized by comprising the following steps:
1) Introducing the chromium-containing wastewater into the deslagging device (1) to remove precipitates and suspended matters in the chromium-containing wastewater;
2) Introducing the chromium-containing wastewater treated in the step 1) into the filtering device (2) to remove particulate matters in the chromium-containing wastewater;
3) Introducing the chromium-containing wastewater treated in the step 2) into the adsorption device (3) to adsorb chromium metal ions;
Wherein, the total chromium content in the water treated in the step 3) is below 0.5mg/L, and the hexavalent chromium content is below 0.1 mg/L.
9. The chromium-containing wastewater online circulation treatment method by using the chromium-containing wastewater online circulation treatment device of claim 7 is characterized by comprising the following steps:
1) Introducing the chromium-containing wastewater into the deslagging device (1) to remove precipitates and suspended matters in the chromium-containing wastewater;
2) Introducing the chromium-containing wastewater treated in the step 1) into the filtering device (2) to remove particulate matters in the chromium-containing wastewater;
3) Introducing the chromium-containing wastewater treated in the step 2) into the adsorption device (3) to adsorb chromium metal ions;
4) A desorption step, wherein hydrochloric acid solution with the mass fraction of 2-5% is used as first desorption solution to desorb the trivalent chromium adsorption column from top to bottom, and the first desorption tank filled with the first desorption solution and the trivalent chromium adsorption form a first desorption loop through a pipeline; taking an industrial salt solution with the mass fraction of 10-15% as a second desorption solution to desorb the hexavalent chromium adsorption column from top to bottom, and forming a second desorption loop by adsorbing the divalent chromium and the second desorption tank filled with the second desorption solution through a pipeline;
Wherein, the total chromium content in the water treated in the step 3) is below 0.5mg/L, and the hexavalent chromium content is below 0.1 mg/L.
10. The method of claim 9, wherein in the hexavalent chromium adsorption column, the chelating resin is crosslinked polystyrene having ammonium functional groups; in the trivalent chromium adsorption column, the chelating resin is a styrene copolymer with a nucleon sulfonic acid functional group.
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| CN201910882573.4A CN110563177A (en) | 2019-09-18 | 2019-09-18 | Chromium-containing wastewater online circulating treatment device and method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299602A (en) * | 2020-10-14 | 2021-02-02 | 广东益诺欧环保股份有限公司 | Purification system and method for separating nickel and chromium in water |
| CN112857933A (en) * | 2020-09-08 | 2021-05-28 | 山东大学 | Seawater heavy metal element multi-unit cooperative online enrichment and self-cleaning method |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112857933A (en) * | 2020-09-08 | 2021-05-28 | 山东大学 | Seawater heavy metal element multi-unit cooperative online enrichment and self-cleaning method |
| CN112299602A (en) * | 2020-10-14 | 2021-02-02 | 广东益诺欧环保股份有限公司 | Purification system and method for separating nickel and chromium in water |
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Application publication date: 20191213 |