CN210313821U - Ferrous ion-containing acidic wastewater resource recovery system - Google Patents
Ferrous ion-containing acidic wastewater resource recovery system Download PDFInfo
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- CN210313821U CN210313821U CN201921072645.0U CN201921072645U CN210313821U CN 210313821 U CN210313821 U CN 210313821U CN 201921072645 U CN201921072645 U CN 201921072645U CN 210313821 U CN210313821 U CN 210313821U
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Abstract
The utility model provides a resource recovery system for ferrous ion-containing acidic wastewater, belonging to the field of environmental engineering; the utility model is used for treating acid pickling wastewater in metallurgical industry, and the ferrous ion-containing acidic wastewater resource recovery system comprises a vulcanization reaction device, a solid waste reduction device, an iron phosphate preparation device, a waste gas absorption device and the like; the utility model provides a complete set of solution for treating the pickling wastewater in the metallurgical industry, reduces the treatment process flow equipment and simplifies the operation flow; other heavy metal impurity ions can be effectively stabilized, and the stabilization of hazardous waste is realized; recycling ferrous chloride ions in the pickling wastewater to prepare iron phosphate; in addition, the heavy metal vulcanized sludge is reduced to the maximum extent by using methods such as acid leaching and the like.
Description
Technical Field
The utility model belongs to the technical field of environmental engineering, concretely relates to contain ferrous ion acid waste water resource recovery system.
Background
Since the second industrial revolution, the socioeconomic development is remarkable, and the construction of the economic society 7 is more and more independent of the support of steel. Before stainless steel or other alloy materials are made into finished products, a process called pickling is carried out; a method for removing oxide skin and rust on the surface of steel by using an acid solution is a method for cleaning the surface of metal. In addition, acidic waste liquid is generated in the electroplating process, mainly because the electroplating solution is strongly acidic, heavy metal ions cover the surface of iron metal under the action of an electric field, and a large amount of waste liquid is generated in the process, and contains metal ions and chloride ions.
In the prior art, the treatment method of heavy metal sludge generated by acidic wastewater is mainly treated in a landfill mode after high-temperature incineration, a flocculation precipitation membrane filtration mode and the like, so that the cost is high, and the problem of secondary pollution is easily caused; and aiming at the traditional treatment process system, the recycling of acid wastewater resources and the reduction and stabilization of sludge can not be effectively realized.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a contain ferrous ion acid waste water resource recovery system to there is with high costs, easily brings secondary pollution in the processing method who solves among the prior art acid waste water and produce heavy metal mud, and can't realize the problem of recycle, the mud minimizing and the stabilization of acid waste water resource.
The utility model provides a following technical scheme:
a resource recovery system for ferrous ion-containing acidic wastewater comprises a vulcanization reaction device, a solid waste reduction device and an iron phosphate preparation device which are sequentially arranged on a steel frame structure; the vulcanization reaction device comprises a vulcanization reaction kettle, a first plate-and-frame filter press and a first regulation and control device; the vulcanization reaction kettle is respectively provided with a first feeding device, a first feeding port, a first exhaust port and a discharge port; the discharge hole of the vulcanization reaction kettle is connected with the feed inlet of the first plate-and-frame filter press through a pipeline; the liquid outlet of the first plate-and-frame filter press is connected with the liquid inlet of the first regulating and controlling device through a liquid pipeline; the solid waste reduction device comprises an acid liquor dosing device, an acid leaching sludge reduction reaction kettle, a second plate-and-frame filter press and a second regulation and control device; an acid liquor feeding hole, a second exhaust hole and a discharge hole are formed in the acid leaching sludge reduction reaction kettle respectively, and the acid liquor dosing device is connected with the acid liquor feeding hole of the acid leaching sludge reduction reaction kettle through a liquid pipeline; the discharge hole of the acid leaching sludge reduction reaction kettle is connected with the feed hole of the second plate-and-frame filter press through a liquid pipeline; the liquid outlet of the second plate-and-frame filter press is connected with the liquid inlet of the second regulating device through a liquid pipeline; the first regulating device and the second regulating device have the same structure and are funnel-shaped; the first regulating device and the second regulating device are respectively provided with a first liquid outlet and a second liquid outlet; each first liquid outlet is respectively positioned at the bottom of the first regulating device and the bottom of the second regulating device, and each first liquid outlet is connected with a first charging hole of the vulcanization reaction kettle through a liquid pipeline; each second liquid outlet is respectively positioned at the top of the first regulating device and the second regulating device; the iron phosphate preparation device comprises a water pumping device and an iron phosphate preparation reaction kettle, wherein the water pumping device comprises a water pump and a liquid collecting barrel; a second feeder, a solution discharge port and two feed ports are arranged on the iron phosphate preparation reaction kettle; and second liquid outlets of the first regulating device and the second regulating device are respectively connected with two feed inlets of the iron phosphate preparation reaction kettle through liquid pipelines.
Further, the ferrous ion-containing acidic wastewater resource recovery system also comprises a waste gas absorption device; the waste gas absorption device comprises an alkali liquor dosing device and a waste gas absorption device main body; the waste gas absorption device main body is respectively provided with an alkali liquor feeding hole, a waste gas inlet, a waste gas exhaust hole and a discharge hole; the discharge hole of the alkali liquor dosing device is connected with the alkali liquor feeding hole of the waste gas absorption device main body through a liquid pipeline; and the first exhaust port of the vulcanization reaction kettle and the second exhaust port of the acid leaching sludge reduction reaction kettle are connected with the waste gas inlet through gas pipelines.
Further, the waste gas absorbing device main part is the ring channel of perpendicular placing, and alkali lye feed inlet and waste gas air inlet all are located pipeline upper portion, and the alkali lye feed inlet is located waste gas air inlet below, and the waste gas air inlet is central symmetry with the waste gas vent and sets up on the ring channel.
Further, the alkali liquor dosing device and the acid liquor dosing device have the same structure, and the liquid pipelines connected with the discharge ports of the alkali liquor dosing device and the acid liquor dosing device are respectively provided with a dosing pump; the acid liquor dosing device and the alkali liquor dosing device are respectively provided with a water inlet, are connected with a water outlet of a tap water pipeline through the water inlet, and are provided with control valves at the connection positions.
Further, stirring devices are arranged inside the vulcanization reaction kettle, the acid leaching sludge reduction reaction kettle and the iron phosphate preparation reaction kettle.
Further, a chemical pump and a control valve are arranged at the discharge port of the vulcanization reaction kettle, the discharge port of the acid leaching sludge reduction reaction kettle, the liquid outlet of the first plate-and-frame filter press, the liquid outlet of the second plate-and-frame filter press, the first liquid outlet and the second liquid outlet of the first regulation and control device and the second liquid outlet of the iron phosphate preparation reaction kettle.
Furthermore, the first plate-and-frame filter press, the second plate-and-frame filter press, the first regulation and control device and the second regulation and control device are fixedly arranged on a steel frame structure and sequentially correspond to the positions below the vulcanization reaction device, the solid waste reduction device, the waste gas absorption device and the iron phosphate preparation device.
The utility model has the advantages that:
1. the utility model stabilizes heavy metal ions in the acidic wastewater through the vulcanization reaction of the vulcanization reaction device; solid waste is reduced through acid leaching reaction; the ferrous ions are recycled through the redox reaction, and the iron phosphate is recycled, so that a whole set of working system is formed, the cost is reduced, and the resource recycling process is simplified.
2. The utility model discloses sludge amount and pickling waste liquid volume that can handle as required can guarantee the safety in pollutant serialization processing and the production life process, and the useless process treatment of danger can realize the stabilization, the requirement of minimizing to retrieve the ferrous ion in the acid waste liquid, make the iron phosphate product, realized handling gauge modulization.
3. The utility model discloses a set up waste gas absorbing device, can be with the whole absorptions of harmful gas such as hydrogen sulfide that the reaction formed and neutralization dissolve, realized waste gas "zero release".
4. The utility model simplifies the whole process system equipment, has simple operation, saves labor and time, greatly reduces the cost, realizes the precipitation stabilization and immobilization treatment of hazardous waste (acid wastewater), and improves the resource utilization of ferrous chloride; the process system realizes the large-scale treatment of the acidic wastewater containing ferrous ions; the controllability of pollutant discharge amount and iron phosphate quality in the whole process system is effectively realized.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention, and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a process flow diagram of the present invention.
The reference signs are: 1. 21, a vulcanization reaction kettle, 211, a first feeder, 212, a first charging port, 213, a first exhaust port, 214, a discharge port A, 215, a perspective window, 22, a first plate-and-frame filter press, 221, a feed port A, 222, a liquid outlet A, 23, a first regulation device, 231, a liquid inlet A, 232, a first liquid outlet A, 233, a second liquid outlet A, 31, an acid solution dosing device, 311, a discharge port, 312, a dosing pump, 313, a tap water pipeline, 32, an acid leaching sludge reduction reaction kettle, 321, an acid solution feed port, 322, a second charging port, 323, a second exhaust port, 324, a discharge port B, 33, a second plate-and-frame filter press, 331, a feed port B, 332, a liquid outlet B, 34, a second regulation device, 341, a liquid inlet B, 342, a first iron phosphate outlet B, 343, a second liquid outlet B, 41, a water pumping device, 42, a preparation reaction kettle, 421. the second feeder, 422, a solution discharge port, 43, a spare water pumping device, 44, an iron phosphate product, 51, an alkali liquor dosing device, 52, a waste gas absorption device main body, 521, an alkali liquor feeding port, 522, a waste gas inlet, 523, a waste gas exhaust port, 524, a gas leakage early warning device, 6, a stirring device, 7, a liquid pipeline, 71, a chemical pump, 72, a control valve and 8, a gas pipeline.
Detailed Description
As shown in fig. 1-2, a system and a method for resource recovery of acidic wastewater containing ferrous ions comprise a vulcanization reaction device, a solid waste reduction device and an iron phosphate preparation device which are sequentially arranged on a steel frame structure 1; the vulcanization reaction device comprises a vulcanization reaction kettle 21, a first plate-and-frame filter press 22 and a first regulation and control device 23; the vulcanization reaction kettle 21 is respectively provided with a first feeding device 211, a first feeding port 212, a first exhaust port 213 and a discharge port A214; the discharge hole A214 of the vulcanization reaction kettle 21 is connected with the feed hole A221 of the first plate-and-frame filter press 22 through a pipeline; the liquid outlet A222 of the first plate-and-frame filter press 22 is connected with the liquid inlet A231 of the first regulating and controlling device 23 through a liquid pipeline 7; the solid waste reduction device comprises an acid liquor dosing device 31, an acid leaching sludge reduction reaction kettle 32, a second plate-and-frame filter press 33 and a second regulation and control device 34; the acid leaching sludge reduction reaction kettle 32 is respectively provided with an acid liquor feeding hole 321, a second feeding hole 322, a second exhaust hole 323 and a discharge hole B324, and the acid liquor dosing device 31 is connected with the acid liquor feeding hole 321 of the acid leaching sludge reduction reaction kettle 32 through a liquid pipeline 7; a discharge hole B324 of the acid leaching sludge reduction reaction kettle 32 is connected with a feed hole B331 of the second plate-and-frame filter press 33 through a liquid pipeline 7; the liquid outlet B332 of the second plate-and-frame filter press 33 is connected with the liquid inlet B341 of the second regulating and controlling device 34 through a liquid pipeline 7; the first regulating device 23 and the second regulating device 34 have the same structure and are funnel-shaped; the first regulating device 23 is provided with a first liquid outlet A232 and a second liquid outlet A233, and the second regulating device 34 is provided with a first liquid outlet B342 and a second liquid outlet B343; the first liquid outlet a232 and the first liquid outlet B342 are respectively located at the bottom of the first regulating device 23 and the bottom of the second regulating device 34, and the first liquid outlet a232 and the first liquid outlet B342 are connected with the first charging port 212 of the vulcanization reaction kettle 21 through liquid pipelines; the second liquid outlet A233 and the second liquid outlet B343 are respectively positioned at the top of the first regulating device 23 and the second regulating device 34; the iron phosphate preparation device comprises a water pumping device 41 and an iron phosphate preparation reaction kettle 42, wherein the water pumping device 41 comprises a water pump and a liquid collecting barrel; the iron phosphate preparation reaction kettle 42 is provided with a second feeder 421, a solution discharge port 422 and two feed ports; the second liquid outlet a233 of the first regulating and controlling device 23 and the second liquid outlet B343 of the second regulating and controlling device 34 are respectively connected with two feed inlets of the iron phosphate preparation reaction kettle 42 through a liquid pipeline 7.
As shown in fig. 1-2, the ferrous ion-containing acidic wastewater resource recovery system further comprises a waste gas absorption device; the waste gas absorption device comprises an alkali liquor dosing device 51 and a waste gas absorption device main body 52; the waste gas absorption device main body 52 is respectively provided with an alkali liquor feeding hole 521, a waste gas inlet 522, a waste gas outlet 523 and a discharge hole; the discharge hole of the alkali liquor dosing device is connected with an alkali liquor feed hole 521 of the waste gas absorption device main body 52 through a liquid pipeline 7; the first exhaust port 213 of the vulcanization reaction kettle 21 and the second exhaust port 323 of the acid leaching sludge reduction reaction kettle 32 are connected with an exhaust gas inlet 522 through a gas pipeline 8; the waste gas absorption device main body 52 is a vertically arranged annular pipeline, the alkali liquor feeding port 521 and the waste gas inlet 522 are both positioned at the upper part of the pipeline, the alkali liquor feeding port 521 is positioned below the waste gas inlet 522, and the waste gas inlet 522 and the waste gas outlet 523 are arranged on the annular pipeline in a centrosymmetric manner; the alkali liquor dosing device 521 and the acid liquor dosing device 31 have the same structure, and the liquid pipelines 7 connected with the discharge port 311 are provided with dosing pumps 312; the acid liquor dosing device 31 and the alkali liquor dosing device 521 are respectively provided with a water inlet, connected with the water outlet of the tap water pipeline 313 through the water inlet, and the connection position is provided with a control valve 72; stirring devices 6 are arranged in the vulcanization reaction kettle 21, the acid leaching sludge reduction reaction kettle 32 and the iron phosphate preparation reaction kettle 42; a chemical pump 71 and a control valve 72 are arranged at a discharge port A214 of the vulcanization reaction kettle 21, a discharge port B324 of the acid leaching sludge reduction reaction kettle 32, a discharge port A222 of the first plate-and-frame filter press 22, a discharge port B332 of the second plate-and-frame filter press 33, a first discharge port A232 and a second discharge port A233 of the first regulating device 23, a first discharge port B342 and a second discharge port B343 of the second regulating device 34, and a solution discharge port 422 of the iron phosphate preparation reaction kettle 42; the first plate-and-frame filter press 22, the second plate-and-frame filter press 33, the first regulation and control device 23 and the second regulation and control device 34 are fixedly arranged on the steel frame structure 1 and sequentially correspond to the positions below the vulcanization reaction device, the solid waste reduction device, the waste gas absorption device and the iron phosphate preparation device; the material of the vulcanization reaction kettle 21, the acid leaching sludge reduction reaction kettle 32, the first regulation and control device 23, the second process regulation and control device 34 and the iron phosphate preparation reaction kettle 42 is enamel material.
As shown in fig. 1-2, a recycling method of a ferrous ion-containing acidic wastewater resource recycling system comprises the following specific steps:
s1, treating acidic wastewater: adding the acidic wastewater into the vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring device 6 in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater;
s2, vulcanization reaction: under a sealed state, adding sodium sulfide powder solid into a vulcanization reaction kettle 21 through a first adding device 211 on the vulcanization reaction kettle 21, wherein the molar ratio of heavy metal iron zinc to sodium sulfide is 1:2-3, and stirring by adopting a stirring device 6 in the vulcanization reaction kettle 21 to ensure that ionic iron and heavy metal ions fully undergo a vulcanization reaction and form sulfide precipitate;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 through the power of a chemical pump 71, and realizing solid-liquid separation through the first plate-and-frame filter press 22; opening a control valve 72 on the liquid pipeline 7 of the first plate-and-frame filter press 22 close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into the first regulating and controlling device 23 by the power of a chemical pump 71;
s4, acid leaching reaction: adding the sulfide solid compressed by the first plate-and-frame filter press 22 in the step S3 into the reduction reaction kettle 32 for acid leaching sludge through the second feed inlet 322; in a sealed state, conveying a hydrochloric acid solution with pH of 3-5 in the acid solution dosing device 31 to an acid solution feed port 321 through a liquid pipeline 7 by a dosing pump 312 through power, and feeding the hydrochloric acid solution into an acid leaching sludge reduction reaction kettle 32; stirring by adopting a stirring device 6 in the acid leaching sludge reduction reaction kettle 32, so that unstable heavy metal impurity ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71; sending the solid precipitate obtained by pressure filtration for disposal; opening a control valve 72 on the liquid pipeline 7 of the second plate-and-frame filter press 33 close to the liquid outlet B332, and conveying the separated mixed solution containing ferrous chloride and heavy metals into the second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: the mixed solution containing ferrous chloride and heavy metal and conveyed to the second regulating and controlling device 34 from the step S5 is sampled and detected to detect the concentrations of heavy metal zinc and iron ions; if the concentration of the heavy metal ions exceeds the standard by more than 10%, respectively opening the control valves 72 on the liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 which are respectively close to the first liquid outlet a232 and the first liquid outlet B342, re-conveying the mixed solution containing the ferrous chloride and the heavy metal obtained by the separation in the step S5 to the vulcanization reaction kettle 21 through the chemical pump 71 and the first charging hole 212, carrying out the vulcanization reaction again, and repeating the process flow; if the content of the heavy metal exceeds the standard by 10%, the concentration of the heavy metal ions reaches the standard by adding water into the second regulating and controlling device 34 for dilution;
s7, preparing iron phosphate: respectively opening control valves 72 on the liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, and dynamically conveying the mixed solution containing ferrous chloride and heavy metals, which is detected to reach the standard in the step S6, and the ferrous chloride solution obtained in the step S3 to the iron phosphate preparation reaction kettle 42 through a chemical pump 71; and putting the sodium phosphate powdery solid into the iron phosphate preparation reaction kettle 42 through the second adder 421, wherein the molar ratio of the ferrous ions to the phosphate radicals is 1: 1-3; stirring by adopting a stirring device 6 in the iron phosphate preparation reaction kettle 42 to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metal which reaches the standard in detection and sodium phosphate fully react to form iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; and then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing.
As shown in fig. 1-2, harmful gases such as hydrogen sulfide generated during the reaction in steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 by negative pressure of air draft, and are conveyed into the exhaust gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is dynamically conveyed to the alkaline solution feed port 521 through the liquid pipeline 7 by the dosing pump 312, and enters the whole exhaust gas absorption device main body 52, so that the hydrogen sulfide gas is sufficiently neutralized and dissolved; the plate-frame spacing of the first plate-frame filter press 22 and the second plate-frame filter press 33 is 0.1mm-1 mm.
Example 1
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 1t of acidic wastewater (generated in a galvanizing process) containing ferrous ions into a vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; sampling to determine that the molar concentration of the iron is 0.4mol/L and the molar concentration of other heavy metal zinc is 0.1 mol/L;
s2, vulcanization reaction: 62.43kg of sodium sulfide powdery solid was charged into the vulcanization reaction kettle 21 through a first feeder 211 on the vulcanization reaction kettle 21 under a sealed condition, and the molar ratio of heavy metals iron, zinc and sodium sulfide was 1: 2; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable ionic iron and zinc to perform a vulcanization reaction and form sulfide precipitate;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 110.65kg (manually conveyed or conveyed by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through a second feed inlet 322; in a sealed state, 331.95kg of hydrochloric acid solution with the pH value of 4 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:4 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for pickling sludge, so that unstable heavy metal zinc ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 83.35kg of solid precipitate (mainly stable sulfide precipitate) obtained by pressure filtration are sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals obtained by pressure filtration in the step S5 into a second regulating device 34 for sampling detection, and detecting the concentration of the heavy metal zinc ions to reach the standard (the detection standard: national surface water standard GB 3838-2002);
s7, preparing iron phosphate: respectively opening control valves 72 on liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, and dynamically conveying the mixed solution containing ferrous chloride and heavy metals detected in the step S6 and the ferrous chloride solution obtained in the step S3 to an iron phosphate preparation reaction kettle 42 by a chemical pump 71, wherein the total volume is 1400L, and the concentration of ferrous ions is measured by sampling and is 0.2 mol/L; 30.62kg of sodium phosphate powdery solid is added into the iron phosphate preparation reaction kettle 42 through the second adding device 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 1; stirring by using a stirring paddle in a ferric phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metals which reach the standard in detection and sodium phosphate fully react to form 17.44kg of ferric phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
Example 2
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 1t of acidic wastewater (generated in a galvanizing process) containing ferrous ions into a vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; sampling to determine that the molar concentration of the iron is 0.4mol/L and the molar concentration of other heavy metal zinc is 0.15 mol/L;
s2, vulcanization reaction: 128.77kg of sodium sulfide powdery solid was charged into the vulcanization reaction kettle 21 through a first feeder 211 on the vulcanization reaction kettle 21 under a sealed condition, and the molar ratio of heavy metals iron, zinc and sodium sulfide was 1: 3; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable ionic iron and zinc to perform a vulcanization reaction and form sulfide precipitate;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 156.22kg (manually conveyed or conveyed by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through a second feed inlet 322; in a sealed state, 624.88kg of hydrochloric acid solution with the pH value of 4 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:4 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for pickling sludge, so that unstable heavy metal zinc ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 134.11kg of solid precipitate (mainly stable sulfide precipitate) obtained by pressure filtration are sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals obtained by pressure filtration in the step S5 into a second regulating device 34 for sampling detection, and detecting the concentration of the heavy metal zinc ions to reach the standard (the detection standard: national surface water standard GB 3838-2002);
s7, preparing iron phosphate: respectively opening control valves 72 on liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, dynamically conveying the mixed solution containing ferrous chloride and heavy metal detected in the step S6 and the ferrous chloride solution obtained in the step S3 to an iron phosphate preparation reaction kettle 42 through a chemical pump 71, wherein the total volume is 1600L, and sampling to determine that the concentration of ferrous ions is 0.125 mol/L; 15.31kg of sodium phosphate powdery solid is put into the iron phosphate preparation reaction kettle 42 through the second adder 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 2; stirring by using a stirring paddle in the iron phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metals which reach the detection standard and sodium phosphate fully react to form 21.87kg of iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
Example 3
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 1t of acidic wastewater (generated in a galvanizing process) containing ferrous ions into a vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; sampling and determining that the molar concentration of iron is 0.43mol/L, and the molar concentration of other heavy metal zinc is 0.12 mol/L;
s2, vulcanization reaction: under sealed conditions, 64.38kg of sodium sulfide powdery solid is added into the vulcanization reaction kettle 21 through a first feeder 211 on the vulcanization reaction kettle 21, and the molar ratio of heavy metals of iron, zinc and sodium sulfide is 1: 1.5; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable ionic iron and zinc to perform a vulcanization reaction and form sulfide precipitate;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 62.36kg (manually conveyed or conveyed by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through a second feed inlet 322; in a sealed state, 187.08kg of hydrochloric acid solution with the pH of 3 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:3 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for pickling sludge, so that unstable heavy metal zinc ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 39.43kg of solid precipitate (mainly stable sulfide precipitate) obtained by pressure filtration is sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of zinc ions) containing ferrous chloride and heavy metals obtained by pressure filtration in the step S5 into a second regulating and controlling device 34 for sampling detection, wherein the concentration of the heavy metal zinc ions is detected to be 2.5mg/L and exceeds 25% (the detection standard: the national surface water standard GB 3838-2002); the second regulating device 34 is opened to close to the control valve 72 on the first liquid outlet, the mixed solution containing ferrous chloride and heavy metal (containing ferrous ions and a very small amount of zinc ions) is refluxed to the vulcanization reaction kettle 21 through the liquid pipeline 7, and the next batch of acidic wastewater is subjected to the process flow;
s7, preparing iron phosphate: opening a control valve 72 on the liquid pipeline 7 of the first regulating device 23 close to the second liquid outlet, conveying the ferrous chloride solution obtained in the step S3 to the iron phosphate preparation reaction kettle 42 through a chemical pump 71 for 1200L in total, and sampling to determine that the ferrous ion concentration is 0.24 mol/L; 35.86kg of sodium phosphate powdery solid is added into the iron phosphate preparation reaction kettle 42 through the second adding device 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 2; stirring by using a stirring paddle in the iron phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that the ferrous chloride solution and the sodium phosphate fully react to form 20.43kg of iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
Example 4
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 2t of acidic wastewater (generated by pickling alloy) containing ferrous ions into the vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; sampling to determine that the molar concentration of the iron is 0.4mol/L, the iron is mainly ferrous ions, and the molar concentration of the nickel which is a heavy metal existing in the iron is 0.05 mol/L;
s2, vulcanization reaction: under a sealed condition, 21170.24kg of sodium sulfide powder solid is added into the vulcanization reaction kettle 21 through a first adding device on the vulcanization reaction kettle 21, and the molar ratio of heavy metal iron to sodium sulfide is 1: 1; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable iron and nickel in ionic states to perform a vulcanization reaction and form sulfide precipitates;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 70.22kg (manually conveyed or conveyed by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through a second feed inlet 322; in a sealed state, 210.66kg of hydrochloric acid solution with the pH of 3 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:3 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for acid leaching sludge, so that unstable heavy metal nickel ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 50.24kg of solid precipitate (mainly stable sulfide precipitate) obtained by pressure filtration is sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals obtained by filter pressing in the step S5 into a second regulating device 34 for sampling detection, and detecting the concentration of the heavy metal nickel ions to reach the standard (the detection standard: the national surface water standard GB 3838-2002);
s7, preparing iron phosphate: respectively opening control valves 72 on liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, dynamically conveying the mixed solution containing ferrous chloride and heavy metals detected in the step S6 and the ferrous chloride solution obtained in the step S3 to an iron phosphate preparation reaction kettle 42 through a chemical pump 71, wherein the total volume is 2400L, and sampling to determine that the ferrous ion concentration is 0.21 mol/L; 61.63kg of sodium phosphate powdery solid is put into the iron phosphate preparation reaction kettle 42 through the second adder 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 2; stirring by using a stirring paddle in the iron phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metals which reach the detection standard and sodium phosphate fully react to form 35.13kg of iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
And (4) experimental conclusion: according to the acid wastewater resource recovery system and method in the embodiment, ferrous ions in 62.56% acid wastewater can be effectively recovered, and the stabilization and reduction of sludge are realized while the resource recovery of ferrous chloride solution is realized.
Example 5
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 2t of acidic wastewater (generated by pickling alloy) containing ferrous ions into the vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; the molar concentration of iron is 0.45mol/L, and the molar concentration of iron is mainly ferrous ions, and the molar concentration of nickel which is a heavy metal is 0.03 mol/L.
S2, vulcanization reaction: under a sealed condition, 21173.36kg of sodium sulfide powder solid is added into the vulcanization reaction kettle 21 through a first adding device on the vulcanization reaction kettle 21, and the molar ratio of heavy metal iron to sodium sulfide is 1: 2; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable iron and nickel in ionic states to perform a vulcanization reaction and form sulfide precipitates;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 68.51kg (manually conveyed or conveyed by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through a second feed inlet 322; in a sealed state, 274.04kg of hydrochloric acid solution with the pH of 3 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:4 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for acid leaching sludge, so that unstable heavy metal nickel ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 42.88kg (mainly stable sulfide precipitate) of solid precipitate obtained by pressure filtration is sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals obtained by filter pressing in the step S5 into a second regulating device 34 for sampling detection, and detecting the concentration of the heavy metal nickel ions to reach the standard (the detection standard: the national surface water standard GB 3838-2002);
s7, preparing iron phosphate: respectively opening control valves 72 on liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, and dynamically conveying the mixed solution containing ferrous chloride and heavy metal detected in the step S6 and the ferrous chloride solution obtained in the step S3 to the iron phosphate preparation reaction kettle 42 through a chemical pump 71, wherein the total volume is 2620L, and the concentration of ferrous ions is measured to be 0.26mol/L by sampling; 74.48kg of sodium phosphate powdery solid is put into the iron phosphate preparation reaction kettle 42 through the second adder 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 2; stirring by using a stirring paddle in the iron phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metals which reach the detection standard and sodium phosphate fully react to form 42.43kg of iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
And (4) experimental conclusion: according to the acid wastewater resource recovery system and method in the embodiment, ferrous ions in 75.68% acid wastewater can be effectively recovered, and the stabilization and reduction of sludge are realized while the resource recovery of ferrous chloride solution is realized.
Example 6
A recovery method of a ferrous ion-containing acidic wastewater resource recovery system comprises the following specific steps:
s1, treating acidic wastewater: adding 2t of acidic wastewater (generated by pickling alloy) containing ferrous ions into the vulcanization reaction kettle 21 through a first feeding port 212 on the vulcanization reaction kettle 21, and stirring by using a stirring paddle in the vulcanization reaction kettle 21 to uniformly mix the acidic wastewater; sampling to determine that the molar concentration of the iron is 0.35mol/L, the iron is mainly ferrous ions, and the molar concentration of the other heavy metal nickel is 0.12 mol/L;
s2, vulcanization reaction: under a sealed condition, 211110.04kg of sodium sulfide powder solid is added into the vulcanization reaction kettle 21 through a first adding device on the vulcanization reaction kettle 21, and the molar ratio of heavy metal iron to sodium sulfide is 1: 1.5; stirring by adopting a stirring paddle in the vulcanization reaction kettle 21 to enable iron and nickel in ionic states to perform a vulcanization reaction and form sulfide precipitates;
s3, primary solid-liquid separation: opening a control valve 72 on the liquid pipeline 7 of the vulcanization reaction kettle 21 close to the discharge port A214, conveying the solid-liquid mixture formed by the reaction in the step S2 to the first plate-and-frame filter press 22 of 1mm level by the power of a chemical pump 71, and realizing solid-liquid separation by the first plate-and-frame filter press 22 of 1mm level; opening a control valve 72 on a liquid pipeline 7 of the first plate-and-frame filter press 22 of 1mm grade close to the liquid outlet A222, and conveying the ferrous chloride solution obtained by filter pressing into a first regulation and control device 23 by power of a chemical pump 71;
s4, acid leaching reaction: 86.51kg (in a mode of manual carrying or conveying by a conveyor belt) of sulfide solid compressed by the first plate-and-frame filter press 22 of the 1mm level in the step S3 is added into the reduction reaction kettle 32 of the acid leaching sludge through the second feed opening 322; in a sealed state, 258.53kg of hydrochloric acid solution with the pH value of 5 in the acid solution dosing device 31 is dynamically conveyed to an acid solution feeding port 321 through a liquid pipeline 7 by a dosing pump 312 and enters an acid leaching sludge reduction reaction kettle 32, wherein the acid leaching solid-liquid ratio of sulfide solid to hydrochloric acid solution is 1:3 g/L; stirring by using a stirring paddle in the reduction reaction kettle 32 for acid leaching sludge, so that unstable heavy metal nickel ions are dissolved out while ferrous ions are recovered;
s5, secondary solid-liquid separation: opening a control valve 72 on a liquid pipeline 7 of the acid leaching sludge reduction reaction kettle 32 close to a discharge hole, and conveying the solid-liquid mixture subjected to acid leaching in the step S4 to a 0.1 mm-level second plate-and-frame filter press 33 for solid-liquid separation through a chemical pump 71 for power; 62.88kg of solid precipitate (mainly stable sulfide precipitate) obtained by pressure filtration is sent out for disposal; opening a control valve 72 on a liquid pipeline 7 of the 0.1 mm-grade second plate-and-frame filter press 33 close to a liquid outlet, and conveying the separated mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals into a second regulating and controlling device 34 by the power of a chemical pump 71;
s6, sampling and detecting: conveying the mixed solution (containing ferrous ions and a very small amount of nickel ions) containing ferrous chloride and heavy metals obtained by filter pressing in the step S5 into a second regulating device 34 for sampling detection, and detecting the concentration of the heavy metal nickel ions to reach the standard (the detection standard: the national surface water standard GB 3838-2002);
s7, preparing iron phosphate: respectively opening control valves 72 on liquid pipelines 7 of the first regulating device 23 and the second regulating device 34 close to the second liquid outlet A233 and the second liquid outlet B343, and dynamically conveying the mixed solution containing ferrous chloride and heavy metals, which is detected to reach the standard in the step S6, and the ferrous chloride solution obtained in the step S3 to a ferric phosphate preparation reaction kettle 42 through a chemical pump 71, wherein the total volume is 2200L, and the ferrous ion concentration is measured by sampling and is 0.21 mol/L; 50.51kg of sodium phosphate powdery solid is put into the iron phosphate preparation reaction kettle 42 through the second adder 421, and the molar ratio of ferrous ions to phosphate radicals is 1: 1.5; stirring by using a stirring paddle in the iron phosphate preparation reaction kettle 42, and standing for 2 hours to ensure that a ferrous chloride solution, a mixed solution containing ferrous chloride and heavy metals which reach the detection standard and sodium phosphate fully react to form 28.78kg of iron phosphate precipitate;
s8, iron phosphate finished product: starting a water pump in the water pumping device 41, and pumping the upper water body of the iron phosphate preparation reaction kettle 42 into the liquid collecting barrel; then opening a control valve 72 on the liquid pipeline 7 at the bottom of the iron phosphate preparation reaction kettle 42 close to the solution discharge port 422, outputting and finally barreling the iron phosphate precipitate obtained in the step S7 into an iron phosphate product 44, and then sending the iron phosphate product into an iron phosphate microbial fuel cell system for further processing;
s9, waste gas recovery: harmful gases such as hydrogen sulfide generated in the reaction processes of the steps S2 and S4 are exhausted from the first exhaust port 213 and the second exhaust port 323 through the suction negative pressure and are conveyed into the waste gas absorption device main body 52 through the gas pipeline 8, and the alkaline solution in the alkaline solution dosing device 51 is conveyed to the alkaline solution feed port 521 through the power of the liquid pipeline 7 by the dosing pump 312 and enters the whole waste gas absorption device main body 52, so that the hydrogen sulfide gas is fully neutralized and dissolved.
And (4) experimental conclusion: according to the acid wastewater resource recovery system and method in the embodiment, ferrous ions in 65.03% acid wastewater can be effectively recovered, and the stabilization and reduction of sludge are realized while the resource recovery of ferrous chloride solution is realized.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The utility model provides a contain ferrous ion acid waste water resource recovery system which characterized in that: comprises a vulcanization reaction device, a solid waste reduction device and an iron phosphate preparation device which are arranged on a steel frame structure in sequence;
the vulcanization reaction device comprises a vulcanization reaction kettle, a first plate-and-frame filter press and a first regulation and control device; the vulcanization reaction kettle is respectively provided with a first feeding device, a first feeding port, a first exhaust port and a discharge port; the discharge hole of the vulcanization reaction kettle is connected with the feed inlet of the first plate-and-frame filter press through a pipeline; the liquid outlet of the first plate-and-frame filter press is connected with the liquid inlet of the first regulating and controlling device through a liquid pipeline;
the solid waste reduction device comprises an acid liquor dosing device, an acid leaching sludge reduction reaction kettle, a second plate-and-frame filter press and a second regulation and control device; an acid liquor feeding hole, a second exhaust hole and a discharge hole are formed in the acid leaching sludge reduction reaction kettle respectively, and the acid liquor dosing device is connected with the acid liquor feeding hole of the acid leaching sludge reduction reaction kettle through a liquid pipeline; the discharge hole of the acid leaching sludge reduction reaction kettle is connected with the feed hole of the second plate-and-frame filter press through a liquid pipeline; the liquid outlet of the second plate-and-frame filter press is connected with the liquid inlet of the second regulating device through a liquid pipeline;
the first regulating device and the second regulating device have the same structure and are funnel-shaped; the first regulating device and the second regulating device are respectively provided with a first liquid outlet and a second liquid outlet; each first liquid outlet is respectively positioned at the bottom of the first regulating device and the bottom of the second regulating device, and each first liquid outlet is connected with a first charging hole of the vulcanization reaction kettle through a liquid pipeline; each second liquid outlet is respectively positioned at the top of the first regulating device and the second regulating device;
the iron phosphate preparation device comprises a water pumping device and an iron phosphate preparation reaction kettle, wherein the water pumping device comprises a water pump and a liquid collecting barrel; a second feeder, a solution discharge port and two feed ports are arranged on the iron phosphate preparation reaction kettle; and second liquid outlets of the first regulating device and the second regulating device are respectively connected with two feed inlets of the iron phosphate preparation reaction kettle through liquid pipelines.
2. The resource recovery system for acidic wastewater containing ferrous ions according to claim 1, characterized in that: the ferrous ion-containing acidic wastewater resource recovery system also comprises a waste gas absorption device; the waste gas absorption device comprises an alkali liquor dosing device and a waste gas absorption device main body; the waste gas absorption device main body is respectively provided with an alkali liquor feeding hole, a waste gas inlet, a waste gas exhaust hole and a discharge hole; the discharge hole of the alkali liquor dosing device is connected with the alkali liquor feeding hole of the waste gas absorption device main body through a liquid pipeline; and the first exhaust port of the vulcanization reaction kettle and the second exhaust port of the acid leaching sludge reduction reaction kettle are connected with the waste gas inlet through gas pipelines.
3. The resource recovery system for acidic wastewater containing ferrous ions according to claim 2, characterized in that: the waste gas absorbing device main part is the annular duct of perpendicular placing, and alkali lye feed inlet and waste gas air inlet all are located pipeline upper portion, and the alkali lye feed inlet is located waste gas air inlet below, and the waste gas air inlet is central symmetry with the waste gas vent and sets up on the annular duct.
4. The resource recovery system for acidic wastewater containing ferrous ions according to claim 2, characterized in that: the structure of the alkali liquor dosing device is the same as that of the acid liquor dosing device, and dosing pumps are arranged on liquid pipelines connected with the discharge ports of the alkali liquor dosing device and the acid liquor dosing device; the acid liquor dosing device and the alkali liquor dosing device are respectively provided with a water inlet, are connected with a water outlet of a tap water pipeline through the water inlet, and are provided with control valves at the connection positions.
5. The resource recovery system for acidic wastewater containing ferrous ions according to claim 1, characterized in that: stirring devices are arranged in the vulcanization reaction kettle, the acid leaching sludge reduction reaction kettle and the iron phosphate preparation reaction kettle.
6. The resource recovery system for acidic wastewater containing ferrous ions according to claim 1, characterized in that: and a chemical pump and a control valve are arranged at the discharge port of the vulcanization reaction kettle, the discharge port of the acid leaching sludge reduction reaction kettle, the liquid outlet of the first plate-and-frame filter press, the liquid outlet of the second plate-and-frame filter press, the first liquid outlet and the second liquid outlet of the first regulation and control device and the solution discharge port of the iron phosphate preparation reaction kettle.
7. The resource recovery system for acidic wastewater containing ferrous ions according to claim 1, characterized in that: the first plate frame filter press, the second plate frame filter press, the first regulation and control device and the second regulation and control device are fixedly arranged on a steel frame structure and sequentially correspond to the positions below the vulcanization reaction device, the solid waste reduction device, the waste gas absorption device and the iron phosphate preparation device.
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