CN215592846U - Dirty sour effluent disposal system - Google Patents
Dirty sour effluent disposal system Download PDFInfo
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- CN215592846U CN215592846U CN202121954798.5U CN202121954798U CN215592846U CN 215592846 U CN215592846 U CN 215592846U CN 202121954798 U CN202121954798 U CN 202121954798U CN 215592846 U CN215592846 U CN 215592846U
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Abstract
The application belongs to dirty sour field of handling, concretely relates to dirty sour effluent disposal system, include: the gas-liquid reinforced vulcanizing device is used for reacting hydrogen sulfide gas with waste acid wastewater to remove heavy metals in the waste acid wastewater; the acid concentration device is used for concentrating waste acid; the waste acid fluorine-chlorine stripping device is used for carrying out hot air stripping treatment on the concentrated waste acid to obtain product acid and fluorine-chlorine mixed acid; and the fluorine-chlorine salt separation device is used for carrying out salt separation treatment on the fluorine-chlorine mixed acid to obtain calcium fluoride and calcium chloride dihydrate. The utility model provides a dirty sour effluent disposal system, at first through the heavy metal in the hydrogen sulfide gas desorption waste acid waste water, realize heavy metal ion's recovery, the waste acid after will handling again carries out concentration, hot-blast air stripping handles to obtain sulphuric acid and fluorine chlorine mixed acid, sulphuric acid can regard as the sour export sales of product, thereby practiced thrift acid resources and cost, and finally, through dividing the salt to the fluorine chlorine mixed acid and handling, obtain calcium fluoride and calcium chloride dihydrate, realized dirty sour waste water treatment.
Description
Technical Field
The application belongs to dirty sour field of handling, concretely relates to dirty sour effluent disposal system.
Background
The polluted acid wastewater generated by the Danxia metallurgy has higher acid and heavy metal ions content and higher hazard ratio, so that the treatment of the polluted acid wastewater generated by the Danxia metallurgy is concerned and valued, and the state also develops corresponding discharge standards, such as the discharge standards of lead and zinc industrial pollutants (GB 25466-.
At present, although there are many methods for treating waste acid water, there still exist many disadvantages; taking a common neutralization treatment method as an example, the waste acid has high acid content, so that the neutralization method can cause waste of sulfuric acid resources, and the waste residue generated in the treatment still contains a large amount of low-grade heavy metal ions which are difficult to recover, thereby easily causing secondary pollution; taking the vulcanization treatment method as an example, not only the vulcanization efficiency is low and the heavy metals are difficult to recover, but also the hydrogen sulfide generated during the treatment is easy to cause secondary pollution.
SUMMERY OF THE UTILITY MODEL
In order to solve at least one technical problem in the prior art, the application provides a waste acid and wastewater treatment system.
The application provides a dirty sour effluent disposal system, includes:
the gas-liquid reinforced vulcanizing device is used for controlling the reaction of the dilute sulfuric acid solution and sodium sulfide to generate hydrogen sulfide gas, and reacting the generated hydrogen sulfide gas with the waste acid wastewater to remove heavy metals in the waste acid wastewater;
the acid concentration device is used for concentrating waste acid obtained after the treatment of the gas-liquid reinforced vulcanization device;
the waste acid fluorine-chlorine stripping device is used for carrying out hot air stripping treatment on the waste acid concentrated by the acid concentration device to obtain further concentrated product acid, hydrogen fluoride and hydrogen chloride in a gas state, and transferring the hydrogen fluoride and the hydrogen chloride in the gas state from a gas phase to a liquid phase to obtain fluorine-chlorine mixed acid;
the fluorine-chlorine salt separation device is used for carrying out salt separation treatment on the fluorine-chlorine mixed acid to obtain calcium fluoride and calcium chloride dihydrate, and specifically comprises:
the neutralizing kettle comprises a first feeding port and a second feeding port, wherein the fluo-chloro mixed acid and the calcium carbonate powder can respectively enter an inner cavity of the neutralizing kettle from the first feeding port and the second feeding port and carry out a neutralization reaction in the inner cavity;
the bin is used for containing calcium carbonate powder and is connected to a second feeding port of the neutralization kettle through a screw conveyor;
the first-stage filter press is connected with a discharge hole of the neutralization kettle and is used for separating liquid subjected to neutralization reaction in the neutralization kettle to obtain partial calcium chloride and filtrate containing calcium chloride solution and calcium chloride solution;
a filtrate collection tank for collecting the filtrate produced by the first stage filter press;
the feed inlet of the membrane box is connected to the discharge outlet of the filtrate collecting tank and used for separating filtrate into calcium fluoride and calcium chloride solutions;
the calcium chloride salt steaming equipment is connected with the liquid discharge port of the membrane box and is used for firstly treating a calcium chloride solution through a double-effect evaporation concentrator and then treating the obtained double-effect concentrated solution again through a single-effect evaporation concentrator;
and the slicer is used for cooling and crystallizing the single-effect concentrated solution obtained by the single-effect evaporation concentrator to obtain calcium chloride dihydrate.
According to at least one embodiment of the present application, the gas-liquid intensified curing apparatus includes:
the concentrated sulfuric acid storage tank is used for storing concentrated sulfuric acid;
the concentrated sulfuric acid diluter is used for diluting concentrated sulfuric acid in the concentrated sulfuric acid storage tank into a dilute sulfuric acid solution and transmitting the dilute sulfuric acid solution to the dilute sulfuric acid storage tank for storage;
the gas generation kettle is internally stored with a sodium sulfide solution which is introduced in advance, and a feeding port of the gas generation kettle is also connected with the dilute sulfuric acid storage tank, so that dilute sulfuric acid and sodium sulfide can react in the gas generation kettle, and hydrogen sulfide gas and sodium sulfate can react in the gas generation kettle;
the hydrogen sulfide gas buffer tank is connected with the gas generation kettle and is used for storing the generated hydrogen sulfide gas;
the vulcanizing reactor is provided with a wastewater feeding port and a gas feeding port, the wastewater feeding port is used for introducing waste acid wastewater, and the gas feeding port is connected with a hydrogen sulfide gas buffer tank, so that the hydrogen sulfide gas and the waste acid wastewater can react inside the vulcanizing reactor to remove heavy metals in the waste acid wastewater.
According to at least one embodiment of the present application, the gas-liquid intensified curing apparatus further includes:
the pretreatment tank is simultaneously connected with the gas generation kettle and the vulcanization reactor and is used for absorbing residual hydrogen sulfide after the reaction of the gas generation kettle and the vulcanization reactor is finished through waste acid stored in the pretreatment tank;
the sodium sulfate storage tank is connected with the pretreatment tank and is used for storing the generated sodium sulfate;
and the harm removal tower is used for treating the tail gas generated in the pretreatment tank.
According to at least one embodiment of the present application, the gas-liquid intensified curing apparatus further includes:
the post-vulcanization liquid buffer tank is used for storing liquid obtained after the vulcanization reactor finishes reaction and performing precipitation treatment;
the FBL filter is used for filtering clear liquid obtained by precipitation treatment in the vulcanized liquid buffer tank;
the waste acid clear liquid tank is used for storing clear liquid filtered by the FBL filter;
and the filter press is used for carrying out filter pressing on the bottom mud obtained by precipitation treatment in the post-vulcanization liquid buffer tank, returning the obtained filtrate to the waste acid clear liquid tank, simultaneously, carrying out filter pressing on the clear liquid in the waste acid clear liquid tank again, and returning the obtained filtrate to the waste acid clear liquid tank again.
According to at least one embodiment of the present application, the acid concentration device includes:
the triple-effect evaporator comprises an I-effect circulating pump, an I-effect evaporator, an I-effect separation chamber, a II-effect circulating pump, a II-effect evaporator, a II-effect separation chamber, a III-effect circulating pump, a III-effect evaporator, a III-effect separation chamber and a condenser which are connected;
the first-effect evaporator adopts raw steam as a heating heat source, secondary steam generated in the first-effect separation chamber serves as a heating heat source of the second-effect evaporator, and secondary steam generated in the second-effect separation chamber serves as a heating heat source of the third-effect evaporator, so that waste acid obtained after treatment of the gas-liquid intensified vulcanizing device is concentrated step by step.
According to at least one embodiment of the present application, the spent acid chlorine-fluorine stripping unit comprises:
the air stripping circulating storage tank is used for storing the sulfuric acid solution obtained by condensing and recovering the condenser of the triple-effect evaporator;
a fan for providing hot air;
the stripping tower is simultaneously connected with the stripping circulating storage tank and the fan, and when the sulfuric acid solution in the stripping circulating storage tank is conveyed into the stripping tower, the sulfuric acid solution can be in countercurrent contact with hot air conveyed by the fan so as to realize sulfuric acid concentration and obtain water vapor and hydrogen fluoride and hydrogen chloride in gaseous states;
the gas-liquid separator is used for separating the solution obtained by the stripping tower from gas;
the water absorption tower is used for transferring the hydrogen fluoride and the hydrogen chloride obtained by the separation of the gas-liquid separator from the gas phase to the liquid phase to obtain a mixed acid of fluorine and chlorine;
the acid mixing tank is connected with the water absorption tower and is used for storing the obtained mixed acid of the fluorine and the chlorine;
and the cooler is used for cooling the mixed acid of the fluorine and the chlorine stored in the acid mixing tank and then conveying the mixed acid of the fluorine and the chlorine to the fluorine and chlorine salt separation device.
According to at least one embodiment of the present application, the calcium chloride salt steaming apparatus comprises:
the raw liquid tank is used for storing the calcium chloride solution generated by the membrane box;
and the condensate water preheater is simultaneously connected with the raw liquid tank and the two-effect evaporation concentrator and is used for recovering the heat of the calcium chloride solution before the calcium chloride solution in the raw liquid tank enters the two-effect evaporation concentrator.
According to at least one embodiment of the present application, the two-effect evaporation concentrator comprises a one-effect heating chamber, a one-effect separation chamber, a one-effect axial-flow pump, a two-effect heating chamber, a two-effect separation chamber, a two-effect axial-flow pump, a two-effect condenser and a condensed water tank which are connected with each other;
the calcium chloride solution after heat recovery is subjected to a first-effect separation chamber, generated first-effect secondary steam enters a second-effect heating chamber as a heat source, the solution in the first-effect separation chamber enters the first-effect heating chamber through a first-effect axial-flow pump in a forced circulation mode to indirectly exchange heat with raw steam, then is mixed with raw water and enters the first-effect separation chamber, separated first-effect concentrated solution enters the second-effect separation chamber, second-effect secondary steam generated in the second-effect separation chamber enters a second-effect condenser to be condensed and then is collected in a condensation water tank, and the solution in the second-effect separation chamber enters the second-effect heating chamber through a second-effect axial-flow pump in a forced circulation mode to indirectly exchange heat with the first-effect secondary steam and then is mixed with the first-effect concentrated solution and enters the second-effect separation chamber.
According to at least one embodiment of the present application, the single-effect evaporative concentrator includes a single-effect axial-flow pump, a single-effect heating chamber, a single-effect separation chamber, a single-effect condenser, and a liquid storage tank connected;
the double-effect concentrated solution conveyed out of the outlet of the double-effect axial flow pump is conveyed to an outlet pipeline of the single-effect axial flow pump, mixed with the single-effect solution and then enters the single-effect heating chamber to indirectly exchange heat with raw steam, the mixed solution enters the single-effect separation chamber after being heated, single-effect secondary steam generated by the single-effect separation chamber is condensed into condensed water through the single-effect condenser and then enters a condensed water tank to be collected, and the single-effect concentrated solution generated by the single-effect separation chamber is conveyed to the liquid storage tank to be stored and then enters the slicing machine.
According to at least one embodiment of the application, the concentration of the waste acid after the concentration treatment by the acid concentration device is 30-40%; and
and the concentration of the product acid obtained after the hot air stripping treatment of the waste acid fluorine-chlorine stripping device is carried out again is more than 60%, the concentration of fluorine ions in the product acid is lower than 200mg/L, and the concentration of chlorine ions is lower than 200 mg/L.
The application has at least the following beneficial technical effects:
the utility model provides a dirty sour effluent disposal system, at first through the heavy metal in the hydrogen sulfide gas desorption waste acid waste water, realize heavy metal ion's recovery, the waste acid after will handling again carries out concentration, hot-blast air stripping handles to obtain sulphuric acid and fluorine chlorine mixed acid, sulphuric acid can regard as the sour export sales of product, thereby practiced thrift acid resources and cost, and finally, through dividing the salt to the fluorine chlorine mixed acid and handling, obtain calcium fluoride and calcium chloride dihydrate, realized dirty sour waste water treatment.
Drawings
FIG. 1 is a schematic diagram of a gas-liquid intensified sulfurization device in a waste acid and wastewater treatment system according to the present application;
FIG. 2 is a schematic diagram showing the construction of an acid concentration device and a waste acid fluorine-chlorine stripping device in the waste acid wastewater treatment system according to the present invention;
FIG. 3 is a schematic diagram showing a fluorine-chlorine salt separation apparatus in the waste acid wastewater treatment system according to the present invention.
Detailed Description
In order to make the implementation objects, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described in more detail below with reference to the drawings in the embodiments of the present application. In the drawings, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The described embodiments are a subset of the embodiments in the present application and not all embodiments in the present application. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Embodiments of the present application will be described in detail below with reference to the accompanying drawings.
The waste acid wastewater treatment system of the present application is described in further detail below with reference to fig. 1-3.
The application discloses dirty sour effluent disposal system, including gas-liquid reinforce vulcanizer, sour enrichment facility, spent acid fluorine chlorine blow off device and fluorine chlorine salt separating device.
The gas-liquid reinforced vulcanizing device is used for controlling the reaction of dilute sulfuric acid solution and sodium sulfide to generate hydrogen sulfide gas, and reacting the generated hydrogen sulfide gas with waste acid wastewater to remove heavy metals in the waste acid wastewater.
The gas-liquid reinforced vulcanizing device can adopt various known suitable devices according to the needs, or is formed by combining suitable equipment; in this embodiment, as shown in fig. 1, the gas-liquid intensified curing apparatus includes a concentrated sulfuric acid storage tank 21, a concentrated sulfuric acid diluter 22, a dilute sulfuric acid storage tank 23, a gas generation kettle 24, a hydrogen sulfide gas buffer tank 25, a curing reactor 26, a pretreatment tank 27, a sodium sulfate storage tank 28, a harm removal tower 29, a post-curing liquid buffer tank 210, an FBL filter, a contaminated acid clear liquid tank 211, and a filter press 212.
Specifically, the concentrated sulfuric acid storage tank 21 is used for storing concentrated sulfuric acid; the concentrated sulfuric acid diluter 22 is configured to dilute the concentrated sulfuric acid in the concentrated sulfuric acid storage tank 21 into a dilute sulfuric acid solution, and transmit the dilute sulfuric acid solution to the dilute sulfuric acid storage tank 23 for storage.
The inside storage of gas generation cauldron 24 has the sodium sulfide solution of leading-in advance, and the pan feeding mouth of gas generation cauldron 24 still is connected with dilute sulphuric acid storage tank 23 simultaneously for dilute sulphuric acid and sodium sulfide can be in its inside reaction, hydrogen sulfide gas and sodium sulfate.
The hydrogen sulfide gas buffer tank 25 is connected with the gas generation kettle 24 and is used for storing the generated hydrogen sulfide gas; the vulcanization reactor 26 is provided with a wastewater inlet for introducing waste acid wastewater and a gas inlet for connecting with the hydrogen sulfide gas buffer tank 25, so that the hydrogen sulfide gas and the waste acid wastewater can react inside the vulcanization reactor 26 to remove heavy metals in the waste acid wastewater.
Further, the pretreatment tank 27 is connected to the gas generation kettle 24 and the vulcanization reactor 26 at the same time, and is configured to absorb hydrogen sulfide remaining after the reaction of the gas generation kettle 24 and the vulcanization reactor 26 is completed through waste acid stored therein; a sodium sulfate storage tank 28 connected to the pretreatment 27) for storing the produced sodium sulfate; the destruction tower 29 is connected to the pretreatment tank 28 for treating the off-gas generated in the pretreatment tank 28.
Further, a post-vulcanization liquid buffer tank 210 is connected to the vulcanization reactor 27 and is used for storing the liquid obtained after the reaction in the vulcanization reactor 26 is completed and performing precipitation treatment; the FBL filter is connected with the post-vulcanization liquid buffer tank 210 and is used for filtering clear liquid obtained by precipitation treatment in the post-vulcanization liquid buffer tank 210; the dirty acid clear liquid tank 211 is connected to the FBL filter and stores clear liquid filtered by the FBL filter.
The filter press 212 is connected to the post-vulcanization liquid buffer tank 210 and the dirty acid clear liquid tank 211, and is configured to filter-press the bottom sludge obtained by the precipitation treatment in the post-vulcanization liquid buffer tank 210, and return the obtained filtrate to the dirty acid clear liquid tank 211, and at the same time, the filter press 212 is also configured to filter-press the clear liquid in the dirty acid clear liquid tank 211 again, and return the obtained filtrate to the dirty acid clear liquid tank 211 again.
It should be noted that, the connection of the devices described in the above-mentioned gas-liquid intensified-sulfurizing device generally refers to the connection through a pipeline, and during the material transportation process, the use of a transportation pump is usually involved, and the details will not be described later.
Further, the specific use flow of the gas-liquid reinforced vulcanizing device is as follows:
the purchased sodium sulfide is prepared into 30 percent aqueous solution and then is quantitatively added into the gas generating kettle 24 for standby. 98% concentrated sulfuric acid in the concentrated sulfuric acid storage tank 21 is conveyed to a concentrated sulfuric acid diluter 22 through a concentrated sulfuric acid conveying pump to preliminarily prepare a dilute sulfuric acid solution with the concentration of about 50% and enter the dilute sulfuric acid storage tank 23, and the concentrated sulfuric acid diluter 22 controls the temperature of the dilute sulfuric acid by circulating water; then quantitatively adding the dilute sulfuric acid into the gas generation kettle 24 through a dilute sulfuric acid delivery pump, reacting with sodium sulfide in the gas generation kettle 24 to generate hydrogen sulfide gas and sodium sulfate, starting stirring when the liquid level of the gas generation kettle 24 reaches a certain position along with the continuous addition of the dilute sulfuric acid to fully react with the sodium sulfide in the gas generation kettle, and quantitatively introducing the hydrogen sulfide gas generated by the reaction into a vulcanization reactor 26 after the hydrogen sulfide gas enters a gas buffer tank 25 for buffering to react with waste acid wastewater.
The spent acid wastewater from the spent acid storage tank is metered by the stock solution lift pump into the sulfidation reactor 26. Reacting hydrogen sulfide gas with waste acid in the vulcanization reactor 26 to remove heavy metals, stopping feeding hydrogen sulfide when the end point is reached, introducing nitrogen, opening a valve to the pretreatment tank 27, absorbing residual hydrogen sulfide in the vulcanization reactor 26 by waste acid in the pretreatment tank 27, closing the nitrogen and tail gas pipe valves after the pretreatment is finished, opening a normal-pressure tail gas pipe valve, and pumping the waste acid wastewater reaching the standard into the vulcanization reactor 26. And then adding the next batch of waste acid and wastewater to be treated, opening nitrogen to replace air in the vulcanization reactor 26 after the addition is finished, closing the nitrogen and a normal pressure tail gas pipe valve, and waiting for the next batch of reaction.
After the single-tank reaction in the gas generation kettle 24 is completed, residual hydrogen sulfide in the hydrogen sulfide is absorbed by waste acid in the pretreatment tank 27, after the pretreatment is completed, a nitrogen gas and tail gas pipe valve is closed, a normal-pressure tail gas pipe valve is opened, a liquid phase (a liquid-solid mixed phase containing about 40% of solid sodium sulfate) at the lower part of the pretreatment tank 27 is sent to a sodium sulfate storage tank 28 through self-retention, the pH value is adjusted by liquid alkali, and then the liquid phase is sent to a deep purification station for evaporation treatment. Then adding a sodium sulfide solution into the gas generation kettle 24, introducing nitrogen to replace the air in the gas generation kettle 24 after the addition is finished, closing the nitrogen and a normal pressure tail gas pipe valve after the replacement is finished, and waiting for the next batch of reaction.
After a certain batch of treatment, the waste acid and wastewater in the pretreatment tank 27 is returned to the vulcanization reactor 26 through a pretreatment pump, and the tail gas generated by the pretreatment tank 27 is sent to the harm removal tower 29 through a tail gas blower, so that the environmental pollution is prevented.
The post-cure buffer tank 210 produces a bottom sludge that is pumped into a microfiltration system (i.e., an FBL filter) by a pressure filtration pump, the filtered clear solution enters a dirty acid clear solution tank 211, and the concentrated solution is pumped into a filter press 212 by a pump. And pumping the filtrate in the waste acid clear liquid tank 211 into a filter press 212 through a clear liquid delivery pump, safely disposing the filter-pressed sludge, and returning the filtrate to the waste acid clear liquid tank 211.
Finally, the liquid in the dirty acid and clear liquid tank 211 (or after being filtered by a clear liquid filter) is conveyed to an acid concentration device.
Further, the acid concentration device of this application is used for carrying out the concentrated processing with the spent acid that obtains after the processing of gas-liquid reinforcement vulcanization device. Wherein, the acid concentration device adopts a triple-effect evaporator which can adopt the structure of the existing triple-effect evaporator according to the requirement; in this embodiment, as shown in fig. 2, the triple-effect evaporator includes an i-effect circulation pump 31, an i-effect evaporation 32), an i-effect separation chamber 33, an ii-effect circulation pump 34, an ii-effect evaporator 35, an ii-effect separation chamber 36, an iii-effect circulation pump 37, an iii-effect evaporator 38, an iii-effect separation chamber 39, and a condenser 310, which are connected.
Wherein, the I-effect evaporator 32 adopts raw steam as a heating heat source, the secondary steam generated in the I-effect separation chamber 33 is used as a heating heat source of the II-effect evaporator 35, and the secondary steam generated in the II-effect separation chamber 36 is used as a heating heat source of the III-effect evaporator 38, so that waste acid obtained after the treatment of the gas-liquid intensified vulcanizing device is concentrated step by step.
The vulcanized liquid is sent to the inlet of an I-effect circulating pump 31 through a feeding pump, is heated to the boiling point through an I-effect evaporator 32 and then enters an I-effect separation chamber 33, the generated secondary steam enters an II-effect evaporator 35 as a heating source, the condensate is sent to a designated liquid receiving point of a main after heat recovery is realized through heat exchange between a secondary preheater and raw water, the concentrated liquid enters the inlet of an II-effect circulating pump 34, heating to boiling point by II effect evaporator 35, entering II effect separation chamber 36, entering III effect evaporator 38 as heating source, transferring condensate to designated liquid receiving point of owner after heat recovery by first stage preheater and raw water heat exchange, entering III effect circulating pump 37 inlet, heating to boiling point by the III effect evaporator 38, then entering the III effect separation chamber 39, the generated secondary steam entering the condenser 310 for condensation and recovery, and the sulfuric acid with the concentration of 30 to 40 percent is sent to an acid fluorine-chlorine stripping device through a discharge pump.
Further, the spent acid fluorine chlorine stripping device of this application is used for carrying out hot-blast stripping treatment with the spent acid after the concentrated processing of acid enrichment facility, obtains further concentrated product acid and be gaseous state's hydrogen fluoride, hydrogen chloride to shift gaseous state's hydrogen fluoride, hydrogen chloride from the gaseous phase to the liquid phase, in order to obtain fluorine chlorine mixed acid.
Similarly, the waste acid fluorine-chlorine stripping device can adopt various currently known suitable devices according to requirements, or is formed by combining suitable equipment; in this embodiment, as shown in fig. 2, the acid fluorine-chlorine stripping device includes a stripping circulation tank 41, a blower 42, a stripping tower 43, a gas-liquid separator 44, a water absorption tower 45, an acid mixing tank 46, and a cooler 47.
Specifically, the stripping circulation storage tank 41 is used for storing the sulfuric acid solution obtained by condensing and recovering the condenser 310 of the triple-effect evaporator; the fan 42 is used to provide hot air; the stripping tower 43 is connected to the stripping circulation tank 41 and the blower 42, and when the sulfuric acid solution in the stripping circulation tank 41 is transported into the stripping tower 43, the sulfuric acid solution can be in countercurrent contact with the hot air transported by the blower 42, so as to realize sulfuric acid concentration and obtain hydrogen fluoride and hydrogen chloride in water vapor and gas states.
The gas-liquid separator 44 is used for separating the solution obtained by the stripping tower 43 from the gas; the water absorption tower 45 is used for transferring the hydrogen fluoride and the hydrogen chloride obtained by the separation of the gas-liquid separator 44 from the gas phase to the liquid phase to obtain a mixed acid of fluorine and chlorine; the acid mixing tank 46 is connected with the water absorption tower 45 and used for storing the obtained fluorine-chlorine mixed acid; the cooler 47 is used for cooling the mixed acid of fluorine and chlorine stored in the mixed acid tank 46 and then conveying the cooled mixed acid of fluorine and chlorine to the fluorine and chlorine salt separation device.
Further, the use flow of the waste acid fluorine-chlorine stripping device is as follows:
the sulfuric acid solution in the sulfuric acid stripping circulation storage tank 41 is pumped to a stripping tower 43 through a sulfuric acid circulation pump, and is in countercurrent contact with hot air sent from a fan 42 in the stripping tower 43, so that further concentration of sulfuric acid is realized, meanwhile, fluorine and chlorine components are separated from a sulfuric acid system, the sulfuric acid concentration is over 60 percent, the fluorine ion concentration in the product acid is lower than 200mg/L, the chlorine ion concentration is lower than 200mg/L, and the product acid is recycled through a product acid conveying pump outer pipe network.
The stripping hot air contains hydrogen fluoride, hydrogen chloride, water vapor and the like, and is sent into a water absorption tower 45 to be in countercurrent contact with water, so that most of the hydrogen fluoride and the hydrogen chloride are transferred from a gas phase to a liquid phase, part of the generated fluorine-chlorine mixed acid is cooled by a cooler 47 and then recycled, and part of the generated fluorine-chlorine mixed acid is sent to a fluorine-chlorine salt separation system for post-treatment. And the blow-off hot air after water absorption enters an alkali absorption tower, is contacted with 5-10% of dilute sodium hydroxide solution to realize further purification, and the gas reaching the standard is sent to a treatment system through a tail gas fan.
Further, the fluorine-chlorine salt separation device is used for carrying out salt separation treatment on the fluorine-chlorine mixed acid to obtain calcium fluoride and calcium chloride dihydrate.
Specifically, as shown in fig. 3, the fluorine-chlorine salt separating device comprises a neutralization kettle 11, a storage bin 12, a screw conveyor 13, a first-stage filter press 14, a filtrate collecting tank 15, a membrane box 16, a calcium chloride salt steaming device and a slicer 17.
The neutralizing kettle 11 comprises a first feeding port and a second feeding port, and the fluo-chloro mixed acid and the calcium carbonate powder can respectively enter an inner cavity of the neutralizing kettle 11 from the first feeding port and the second feeding port and carry out a neutralization reaction in the inner cavity; the bin 12 is used for containing calcium carbonate powder and is connected to a second feeding port of the neutralization kettle 11 through a screw conveyor 13.
The first-stage filter press 14 is connected to a discharge port of the neutralization kettle 11, and is used for separating the liquid subjected to the neutralization reaction in the neutralization kettle 11 to obtain part of calcium chloride and calcium chloride, and a filtrate containing a calcium chloride solution and a calcium chloride solution.
A feeding port of the filtrate collecting tank 15 is connected to a liquid discharging port of the first-stage filter press 14 and is used for collecting filtrate generated by the first-stage filter press 14; a feed inlet of the membrane box 16 is connected to a discharge outlet of the filtrate collecting tank 15 and used for separating the filtrate into calcium fluoride and calcium chloride solutions.
The calcium chloride salt evaporation equipment is connected with a liquid discharge port of the membrane box 16 and is used for firstly treating a calcium chloride solution through the double-effect evaporation concentrator and then treating the obtained double-effect concentrated solution again through the single-effect evaporation concentrator; and the slicer 17 is used for cooling and crystallizing the single-effect concentrated solution obtained by the single-effect evaporation concentrator to obtain calcium chloride dihydrate.
Further, the calcium chloride salt steaming device can also comprise a raw liquid tank 18 and a condensed water preheater 19.
Wherein, the raw liquid tank 18 is used for storing the calcium chloride solution generated by the membrane box 16; the condensate water preheater 19 is connected with the raw liquid tank 18 and the two-effect evaporation concentrator, and is used for recovering heat of the calcium chloride solution before the calcium chloride solution in the raw liquid tank 18 enters the two-effect evaporation concentrator.
In addition, the double-effect evaporation concentrator and the single-effect evaporation concentrator in the calcium chloride salt evaporation equipment can adopt the structures of the currently known evaporation concentrators according to requirements.
In this embodiment, as shown in fig. 3, the two-effect evaporation concentrator includes a one-effect heating chamber 110, a one-effect separation chamber 111, a one-effect axial-flow pump 112, a two-effect heating chamber 113, a two-effect separation chamber 114, a two-effect axial-flow pump 115, a two-effect condenser 116, and a condensate water tank 117, which are connected to each other. Further, the single-effect evaporation concentrator comprises a single-effect axial-flow pump 118, a single-effect heating chamber 119, a single-effect separation chamber 120, a single-effect condenser 121 and a liquid storage tank 122 which are connected with each other.
Further, the use flow of the fluorine-chlorine salt separation device is as follows:
and respectively feeding the fluorine-chlorine mixed acid solution into a neutralization kettle 11, adding calcium carbonate powder in a bin 12 into the neutralization kettle 11 through a screw conveyor 13 for neutralization reaction, and pumping the reacted solution into a first-stage filter press 14 through a first-stage filter press pump to realize the separation of calcium chloride and the calcium chloride solution. The calcium fluoride with the water content of about 60 percent can be directly bagged. The calcium chloride solution from the first stage filter press 14 is stored in a filtrate collection tank 15.
The filtrate after filter pressing is pumped into a membrane box 16 through a membrane system feeding pump, calcium fluoride and calcium chloride solution are separated through a membrane, the water produced by the membrane is relatively pure calcium chloride solution, the produced water is discharged to an evaporation stock solution tank 18 through a suction pump, and the concentrated calcium fluoride after separation returns to a neutralization kettle 11 through a sludge discharge pump.
Calcium solution after passing through the membrane is sent into a condensate water preheater 19 through a feeding pump to recover heat and then enters a first-effect separation chamber 111, generated secondary steam enters a second-effect heating chamber 113 to be used as a heating heat source, the solution in the first-effect separation chamber 111 enters a first-effect heating chamber 110 through a first-effect axial-flow pump 112 in a forced circulation mode to indirectly exchange heat with raw steam, the generated secondary steam is mixed with raw water and enters the first-effect separation chamber 111, concentrated solution enters a second-effect separation chamber 114, the generated secondary steam enters a second-effect condenser 116 to be condensed and then is collected in a condensed water tank 117, the solution in the second-effect separation chamber 114 enters the second-effect heating chamber 113 through a second-effect axial-flow pump 115 in a forced circulation mode to indirectly exchange heat with the first-effect secondary steam, the mixed solution and the first-effect concentrated solution enter the second-effect separation chamber 114, the second-effect concentrated solution at an outlet of the second-effect axial-flow pump 115 is sent into an outlet pipeline of a single-effect axial-flow pump 118 through a second-effect discharge pump, the mixed solution (provided through a single-effect drainage pipe) is mixed and then enters a single-effect heating chamber 119 to indirectly exchange heat with the raw steam And (3) heat exchange is carried out, the temperature rises, the single-effect secondary steam enters the single-effect separation chamber 120, the single-effect secondary steam becomes condensate water through the single-effect condenser 121 and enters the condensate water tank 117 for collection, the single-effect concentrated solution is pumped into the liquid storage tank 122 through the discharge pump and then enters the slicing machine 17 for cooling and crystallization, a calcium chloride dihydrate product is obtained, and the calcium chloride dihydrate product is bagged.
In conclusion, the waste acid and wastewater treatment system realizes the recovery of heavy metal ions by removing the heavy metals in the waste acid and wastewater through hydrogen sulfide gas, and then performs concentration and hot air stripping treatment on the treated waste acid to obtain sulfuric acid and a mixed acid of fluorine and chlorine, wherein the sulfuric acid can be used as a product acid for export sales, so that acid resources and cost are saved, and finally, the mixed acid of fluorine and chlorine is subjected to salt separation treatment to obtain calcium fluoride and calcium chloride dihydrate, so that the waste acid and wastewater treatment is realized.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A waste acid and wastewater treatment system is characterized by comprising:
the gas-liquid reinforced vulcanizing device is used for controlling the reaction of the dilute sulfuric acid solution and sodium sulfide to generate hydrogen sulfide gas, and reacting the generated hydrogen sulfide gas with the waste acid wastewater to remove heavy metals in the waste acid wastewater;
the acid concentration device is used for concentrating waste acid obtained after the treatment of the gas-liquid reinforced vulcanization device;
the waste acid fluorine-chlorine stripping device is used for carrying out hot air stripping treatment on the waste acid concentrated by the acid concentration device to obtain further concentrated product acid, hydrogen fluoride and hydrogen chloride in a gas state, and transferring the hydrogen fluoride and the hydrogen chloride in the gas state from a gas phase to a liquid phase to obtain fluorine-chlorine mixed acid;
the fluorine-chlorine salt separation device is used for carrying out salt separation treatment on the fluorine-chlorine mixed acid to obtain calcium fluoride and calcium chloride dihydrate, and specifically comprises:
the neutralization kettle (11) comprises a first feeding port and a second feeding port, wherein the fluo-chloro mixed acid and the calcium carbonate powder can respectively enter an inner cavity of the neutralization kettle (11) from the first feeding port and the second feeding port and carry out neutralization reaction in the inner cavity;
the bin (12) is used for containing calcium carbonate powder and is connected to a second feeding port of the neutralization kettle (11) through a screw conveyor (13);
the primary filter press (14) is connected with a discharge hole of the neutralization kettle (11) and is used for separating liquid subjected to neutralization reaction in the neutralization kettle (11) to obtain partial calcium chloride and filtrate containing calcium chloride solution and calcium chloride solution;
a filtrate collection tank (15) for collecting the filtrate produced by the one-stage filter press (14);
a feed inlet of the membrane box (16) is connected to a discharge outlet of the filtrate collecting tank (15) and used for separating filtrate into calcium fluoride and calcium chloride solutions;
the calcium chloride salt steaming equipment is connected with the liquid discharge port of the membrane box (16) and is used for firstly treating a calcium chloride solution through a double-effect evaporation concentrator and then treating the obtained double-effect concentrated solution again through a single-effect evaporation concentrator;
and the slicer (17) is used for cooling and crystallizing the single-effect concentrated solution obtained by the single-effect evaporation concentrator to obtain calcium chloride dihydrate.
2. The waste acid and wastewater treatment system according to claim 1, wherein the gas-liquid intensified curing device comprises:
the concentrated sulfuric acid storage tank (21) is used for storing concentrated sulfuric acid;
the concentrated sulfuric acid diluter (22) is used for diluting concentrated sulfuric acid in the concentrated sulfuric acid storage tank (21) into a dilute sulfuric acid solution and transmitting the dilute sulfuric acid solution to the dilute sulfuric acid storage tank (23) for storage;
the device comprises a gas generation kettle (24), wherein a sodium sulfide solution which is introduced in advance is stored in the gas generation kettle (24), and a feeding port of the gas generation kettle (24) is also connected with a dilute sulfuric acid storage tank (23) so that dilute sulfuric acid and sodium sulfide can react in the gas generation kettle, namely hydrogen sulfide gas and sodium sulfate;
the hydrogen sulfide gas buffer tank (25), the hydrogen sulfide gas buffer tank (25) is connected with the gas generation kettle (24) and is used for storing the generated hydrogen sulfide gas;
the vulcanizing reactor (26) is provided with a wastewater feeding port and a gas feeding port, the wastewater feeding port is used for introducing waste acid wastewater, and the gas feeding port is connected with a hydrogen sulfide gas buffer tank (25) so that hydrogen sulfide gas and waste acid wastewater can react inside the vulcanizing reactor (26) to remove heavy metals in the waste acid wastewater.
3. The waste acid and wastewater treatment system according to claim 2, wherein the gas-liquid intensified curing device further comprises:
the pretreatment tank (27), the pretreatment tank (27) is connected with the gas generation kettle (24) and the vulcanization reactor (26) at the same time, and is used for absorbing residual hydrogen sulfide after the reaction of the gas generation kettle (24) and the vulcanization reactor (26) is finished through waste acid stored in the pretreatment tank (27);
a sodium sulfate storage tank (28), wherein the sodium sulfate storage tank (28) is connected with the pretreatment tank (27) and is used for storing the generated sodium sulfate;
a harm removal tower (29) for treating the tail gas generated in the pretreatment tank (27).
4. The waste acid and wastewater treatment system according to claim 3, wherein the gas-liquid intensified curing device further comprises:
the post-vulcanization liquid buffer tank (210) is used for storing liquid obtained after the reaction of the vulcanization reactor (26) is finished and carrying out precipitation treatment;
an FBL filter for filtering the clear liquid obtained by the precipitation treatment in the post-vulcanization liquid buffer tank (210);
a dirty acid clear liquid tank (211) for storing clear liquid filtered by the FBL filter;
and the filter press (212) is used for carrying out filter pressing on the bottom sludge obtained by precipitation treatment in the post-vulcanization liquid buffer tank (210), returning the obtained filtrate to the clear acid and waste liquid tank (211), meanwhile, carrying out filter pressing on the clear liquid in the clear acid and waste liquid tank (211) again, and returning the obtained filtrate to the clear acid and waste liquid tank (211) again.
5. The contaminated acid wastewater treatment system according to claim 1, wherein the acid concentration device comprises:
the triple-effect evaporator comprises an I-effect circulating pump (31), an I-effect evaporator (32), an I-effect separating chamber (33), a II-effect circulating pump (34), a II-effect evaporator (35), a II-effect separating chamber (36), a III-effect circulating pump (37), a III-effect evaporator (38), a III-effect separating chamber (39) and a condenser (310) which are connected;
the first-effect evaporator (32) adopts raw steam as a heating heat source, secondary steam generated in the first-effect separation chamber (33) serves as a heating heat source of the second-effect evaporator (35), and secondary steam generated in the second-effect separation chamber (36) serves as a heating heat source of the third-effect evaporator (38), so that waste acid obtained after treatment of the gas-liquid intensified vulcanization device is concentrated step by step.
6. The waste acid wastewater treatment system according to claim 5, wherein the waste acid fluorine-chlorine stripping device comprises:
a stripping circulation storage tank (41) for storing the sulfuric acid solution obtained by condensing and recovering the condenser (310) of the triple-effect evaporator;
a fan (42), the fan (42) for providing hot air;
the stripping tower (43), the stripping tower (43) is connected with the stripping circulation storage tank (41) and the fan (42) at the same time, when the sulfuric acid solution in the stripping circulation storage tank (41) is conveyed into the stripping tower (43), the sulfuric acid solution can be in countercurrent contact with hot air conveyed by the fan (42) to realize sulfuric acid concentration, and hydrogen fluoride and hydrogen chloride in water vapor and gas states can be obtained at the same time;
a gas-liquid separator (44) for separating the solution obtained by the stripping tower (43) from the gas;
a water absorption tower (45) for transferring the hydrogen fluoride and the hydrogen chloride separated by the gas-liquid separator (44) from the gas phase to the liquid phase to obtain a mixed acid of fluorine and chlorine;
the acid mixing tank (46), the acid mixing tank (46) is connected with the water absorption tower (45) and is used for storing the obtained mixed acid of fluorine and chlorine;
and the cooler (47) is used for cooling the mixed acid of the fluorine and the chlorine stored in the acid mixing tank (46) and then conveying the mixed acid of the fluorine and the chlorine to the fluorine and chlorine salt separation device.
7. The waste acid and wastewater treatment system according to claim 1, wherein the calcium chloride salt steaming equipment comprises:
a raw liquid tank (18) for storing the calcium chloride solution generated by the membrane tank (16);
and the condensate water preheater (19) is simultaneously connected with the raw liquid tank (18) and the double-effect evaporation concentrator, and is used for recovering the heat of the calcium chloride solution before the calcium chloride solution in the raw liquid tank (18) enters the double-effect evaporation concentrator.
8. The waste acid and wastewater treatment system according to claim 7, wherein the double-effect evaporation concentrator comprises a single-effect heating chamber (110), a single-effect separation chamber (111), a single-effect axial-flow pump (112), a double-effect heating chamber (113), a double-effect separation chamber (114), a double-effect axial-flow pump (115), a double-effect condenser (116) and a condensate water tank (117) which are connected;
the calcium chloride solution after heat recovery is subjected to a first-effect separation chamber (111), generated first-effect secondary steam enters a second-effect heating chamber (113) to serve as a heat source, the solution in the first-effect separation chamber (111) is forcibly circulated by a first-effect axial-flow pump (112) to enter the first-effect heating chamber (110) to indirectly exchange heat with raw steam, then is mixed with raw water to enter the first-effect separation chamber (111), separated first-effect concentrated solution enters a second-effect separation chamber (114), the second-effect secondary steam generated by the second-effect separation chamber (114) enters a second-effect condenser (116) to be condensed and then is collected in a condensation water tank (117), and the solution in the second-effect separation chamber (114) is forcibly circulated by a second-effect axial-flow pump (115) to enter the second-effect heating chamber (113) to indirectly exchange heat with the first-effect secondary steam, and then is mixed with the first-effect concentrated solution to enter the second-effect separation chamber (114).
9. The waste acid and wastewater treatment system according to claim 8, wherein the single-effect evaporative concentrator comprises a single-effect axial flow pump (118), a single-effect heating chamber (119), a single-effect separation chamber (120), a single-effect condenser (121) and a liquid storage tank (122) which are connected;
the double-effect concentrated solution conveyed from the outlet of the double-effect axial-flow pump (115) is conveyed to an outlet pipeline of the single-effect axial-flow pump (118), mixed with the single-effect solution and then enters a single-effect heating chamber (119) to indirectly exchange heat with raw steam, the mixture enters a single-effect separation chamber (120) after being heated, single-effect secondary steam generated by the single-effect separation chamber (120) is condensed into condensed water through a single-effect condenser (121) and then enters a condensed water tank (117) to be collected, and the single-effect concentrated solution generated by the single-effect separation chamber (120) is conveyed to a liquid storage tank (122) to be stored and then enters a slicing machine (17).
10. The waste acid and wastewater treatment system according to claim 1, wherein the concentration of waste acid after the concentration treatment by the acid concentration device is 30-40%; and
and the concentration of the product acid obtained after the hot air stripping treatment of the waste acid fluorine-chlorine stripping device is carried out again is more than 60%, the concentration of fluorine ions in the product acid is lower than 200mg/L, and the concentration of chlorine ions is lower than 200 mg/L.
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| CN117923574A (en) * | 2024-03-13 | 2024-04-26 | 赛恩斯环保股份有限公司 | Sewage and acid wastewater vulcanization reaction device and vulcanization reaction end point judging method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117923574A (en) * | 2024-03-13 | 2024-04-26 | 赛恩斯环保股份有限公司 | Sewage and acid wastewater vulcanization reaction device and vulcanization reaction end point judging method |
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