CN106495356A - The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor - Google Patents
The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor Download PDFInfo
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- CN106495356A CN106495356A CN201610869339.4A CN201610869339A CN106495356A CN 106495356 A CN106495356 A CN 106495356A CN 201610869339 A CN201610869339 A CN 201610869339A CN 106495356 A CN106495356 A CN 106495356A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The process recovery method of nitric hydrofluoric acid mixed acid pickle liquor and its system, acid solution obtained in bipolar membrane electrodialysis equipment is used for steel and iron industry pickling lines is used for pickling steel, saves cost of material；And go to process nitric hydrofluoric acid mixing acid waste liquid using the alkali liquor of bipolar membrane electrodialysis equipment.And by the way of reaction water tank bottom aeration it is more fully mixed reactant liquor, and the oxygen of abundance is constantly provided into mixed solution, greatly shorten the response time.And mixed solution after reaction is filtered with bag filter, supernatant and precipitate are carried out solid-liquid separation.After reaction, nitrate anion and fluorion in nitric hydrofluoric acid mixing acid waste liquid are replaced out, the Fe in nitric hydrofluoric acid mixing acid waste liquid2+Form Precipitation.Supernatant after being filtered by bag filter can return to bipolar membrane electrodialysis equipment antacid alkaline again, and precipitate can be reclaimed after drying, and greatly reduce raw material input cost.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of steel industry nitric hydrofluoric acid mixing acid waste liquid
Process recovery method and its system.
Background technology
Rustless steel, alloy steel surface in steel and iron industry, produces one layer of oxide in process, typically uses
Mixed acid is removed and is gone.How domestic and international manufacturer, removed using nitrate acid and hydrofluoric acid mixed acid and deoxygenate compound at present.Using nitric acid,
Fluohydric acid. mixed acid pickling, fast with pickling speed, it is difficult overpickling a little, and keeps just now good table after pickling
Face.This three is that other pickling institutes are inaccessiable.Through multiple pickling, the metal ion in pickle increases to finite concentration,
Acid content drops to certain percentage, that is, lose pickling ability and become waste liquid, but the total acidity in this waste liquid or at a relatively high
, and be highly corrosive agents containing salt, nitric acid, Fluohydric acid .s such as substantial amounts of metallic iron, nickel, chromium, chromium is extremely toxic substance, is such as allowed to outer
Row, will cause severe contamination to environment, so must refrain from pickle liquor arranging without process is arbitrarily outer.Additionally, nitric acid, fluoric acid
Cost price is more expensive, and the nitric acid, fluoric acid in spent acid liquid does not have reuse directly to discharge the waste for yet causing significantly resource.
Mainly there are chemical method, reduction vaporization method, ion exchange to the processing method of nitric acid, hydrofluoric acid waste liquid both at home and abroad at present
Method and solvent extraction.
Chemical method：Process is neutralized to which using Calx, carbide slag or Caustic soda typically, makes pH value reach country's discharge mark
Discharge after standard.Which has the disadvantage to neutralize medicament high cost, and expensive, spent acid treating capacity is restricted, and in pickle liquor
HNO3, the resource such as HF and slaine is not utilized effectively.Sludge quantity is big, and remaining salt residue treatment is difficult, and equipment is rotten
Erosion is serious.
Reduction vaporization method：Reduction vaporization method its principle be toward acid pickle in add sulphuric acid, make the nitre in sulfate radical and waste liquid
Acid group and fluorion displacement, form the sulfate of metal, under negative pressure, using sulphuric acid and nitric acid, Fluohydric acid. equilibrium temperature not
With heating evaporation goes out gaseous nitric acid and Fluohydric acid., condensed, that is, obtain the mixed acid for regenerating, be re-used for pickling.In residual liquid
Slaine and sulphuric acid containing sulphuric acid, through supercooling, sulfate formation is crystallized, through solid-liquid separation, containing certain density sulphuric acid
Liquid can be recycled.Solid metallic sulfate sediment otherwise processed, can reclaim the metals such as nickel therein, chromium.The method
Acid recovering rate is high, but one-time investment is big, and maintenance of equipment is difficult, and the residual acid amount of bottoms is larger.
Ion exchange：Commutative group in using ion-exchanger and various interionic ion exchange energy in solution
The difference of power is carrying out a kind of detached method.Its shortcoming the method has a certain limitation, high equipment cost, the ferrum in water from
The materials such as son, aluminium ion meeting contaminated ion exchanger resin, affects resin work exchange capacity, causes resin poison to fail.
Solvent extraction：Its principle is to be passed through sulphuric acid in waste liquid, and the metallic salt in sulphuric acid and waste liquid occurs double decomposition
Reaction, the slaine in waste liquid changes into the sulfate of metal, nitric acid and Fluohydric acid. separate out, with tbp (TBP)
Make extractant, nitric acid and Fluohydric acid. are transferred in extractant, in back extraction tower, then use water back extraction, that is, obtain nitric acid, hydrogen fluorine
The mixed acid of acid, is re-used for pickling.The method advantage less energy consumption, equipment and materials are easily selected, but the response rate of acid is low.
In this context, with membrane technology as relying on, spent acid equipment for reclaiming has been developed successfully, it is with being easily achieved
Technological transformation, rate of return on investment are high, easily operated, easy to maintain, operating cost is low, high degree of automation the features such as.Spent acid is returned
Spent acid reuse can be processed with equipment, changed harmful to treasure, be that enterprise solves high economic benefit also to be brought while environmental issue, make
Very considerable with prospect with field, it is worth with huge investment repayment.
Content of the invention
In order to overcome the problems of the prior art, the technical problem to be solved in the present invention to be to provide a kind of energy-saving and environmental protection
And in steel and iron industry nitric hydrofluoric acid mixed acid liquid waste disposal technique, can achieve no pollution during acid washing rolled steel, comply fully with
The steel nitric hydrofluoric acid mixed acid liquid waste processing and the method and its system of recovery of environmental requirement.
The technical scheme that adopted for achieving the above object of the present invention is：A kind of steel industry nitric hydrofluoric acid mixed acid acid
The process recovery system of waste liquid is washed, including single filter unit, reaction member and cascade filtration unit, acid pickle entrance is by pipe
Road is connected to the filter inlet on single filter unit top, the filter outlet of single filter unit bottom through water pump and valve
Reaction member upper entrance is connected to by pipeline, as nitric hydrofluoric acid mixed acid has volatility, so the reaction is single
First top is sealed construction, and is provided with seal gasket on the gap of pipeline with being placed at the top of reaction member, reaction member bottom
The reactant liquor outlet in portion is connected to the filter inlet on cascade filtration unit top, cascade filtration by pipeline through water pump and valve
The filter outlet of unit bottom is connected to circulating and recovering mouth by pipeline through valve, and the system also includes bipolar membrane electrodialysis
Equipment, the bipolar membrane electrodialysis equipment include alkali liquor circulating box, saline solution circulating box, acid cycle case and pole water circulation case, institute
The entrance that circulating and recovering mouth is connected to saline solution circulating box by pipeline is stated, as the mixed liquor of nitric acid and Fluohydric acid. does not only volatilize
Property, and see that light easily decomposes, so the casing of the acid cycle case is made up of light tight material and is also set in its water tank upper
Closure is equipped with, the outlet of the alkali liquor circulating box is connected to reaction member upper entrance, the reaction member chamber by pipeline
Inner bottom part is additionally provided with evenly distributed aeration head, and the aeration head is connected to the air inlet of reaction member bottom by pipeline,
Aerator is additionally provided with the air inlet, the outlet of the acid cycle case is connected to pickling lines, the pickling production
The leakage fluid dram connection acid pickle entrance of line.
Further, system also includes control module, described be additionally provided with PH value detector before valve pipeline, pH value is examined
Survey instrument to electrically connect with control module, the PH value detector is connected to floss hole by pipeline via valve, the valve and valve
Door is electric control valve and is electrically connected with control module.
Further, the single filter unit and cascade filtration unit are bag filter.
Further, the application also provides a kind of application said system is used for steel industry nitric hydrofluoric acid mixed acid pickling
The process recovery method of waste liquid, methods described comprise the steps：
Step one, the NaCl solution of prescribed concentration is placed in the salt chamber circulating water groove of bipolar membrane electrodialysis equipment, is started bipolar
EDBM equipment, acid cycle groove are carried out closed cycle 10-15 minutes, the HCl solution concentration of generation also constantly rising, when
When HCl solution concentration reaches 5% mass ratio, production line pickling lines are caused by bypass, alkali liquor circulating box constantly carries out closed circuit
Circulation, the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reaches 4% mass ratio, bipolar membrane electrodialysis equipment
Quit work；
Step 2, the acid pickle are discharged from pickling lines, enter acid pickle entrance, are connected through water pump and valve by pipeline
Single filter unit is entered, mixed solution is filtered by bag filter, remove large granular impurity and oil slick；
Step 3, the filtrate for obtaining step 2 enter reaction member through the outlet of single filter unit bottom by pipeline, will
The NaOH produced in the alkali liquor circulating box of bipolar membrane electrodialysis equipment, adds reaction member by pipeline；
Step 4, startup aerator, air is input into reaction member from the bottom to top by aeration head, NaOH solution and nitric acid is made
Fluohydric acid. mixed acid pickle liquor is uniform in reaction member sufficiently to be mixed, and constantly to aeration in mixed solution；
Step 5, the mixed solution that step 3 is obtained is passed through in cascade filtration unit, mixed solution is carried out by bag filter
Filter, supernatant and precipitate are carried out solid-liquid separation, solid is Fe (OH)3Reclaim after drying；
Supernatant in step 6, step 5 flows through PH value detector, when supernatant PH >=8, under control module control, opens
Valve is opened, supernatant enters saline solution circulating box by circulating and recovering mouth, when supernatant 6<PH<When 8, under control module control, open
Valve is opened, supernatant enters municipal drainage by floss hole.
For prior art, the invention has the beneficial effects as follows：Nitric hydrofluoric acid mixing obtained in bipolar membrane electrodialysis system
Acid can return pickling lines；The alkali liquor of generation is used for the Fe for processing nitric hydrofluoric acid mixing acid waste liquid2+And replace out nitric acid
Nitrate anion and fluorion in Fluohydric acid. mixing acid waste liquid is back to use bipolar membrane electrodialysis system antacid alkaline again；The technology energy
Steel industry nitric hydrofluoric acid mixing acid waste liquid is processed, Fe is made2+All with Fe（OH)3Solid form precipitation is discharged；Replace out
More than 95% nitric hydrofluoric acid mixing acid group；So as to realize the zero-emission of acid pickle.
There is this law high current efficiency, energy continuous and stable production, simple to operate, governance process to be not required to plus eo-acid or alkali, dress
Equipment, pipeline, valve in putting etc. are using anti-corrosion material and technology.The durable long service life of device anti-corrosion, No leakage, arrangement
Compact, floor space is few, the plurality of advantages for operating running expense low, specifically also includes following features： 1）Flow process is succinct, energy-conservation,
Easy to operate, floor space is little； 2）System consumption is few, and operating cost is relatively low；3）The nitric hydrofluoric acid mixed acid for obtaining,
To be directly entered production line use；4）Obtain side-product hydrated ferric oxide. simultaneously, rear barreled can be dried and sold；5）Energy-conservation, resource
Regeneration, zero release of pollutant meet national requirements for environmental protection.
Description of the drawings
Fig. 1 is the structural representation that pickle liquor of the present invention processes recovery system；
Fig. 2 is the control module principle schematic of the present invention；
Fig. 3 is bipolar membrane electrodialysis equipment operation principle schematic diagram of the present invention；
Fig. 4 is the process chart that pickle liquor of the present invention processes recovery method.
In figure：1 single filter unit, 2 reaction members, 3 cascade filtration units, 4 acid pickle entrances, 5 water pumps, 6 valves, 8
Valve, 9 circulating and recovering mouths, 10 bipolar membrane electrodialysis equipment, 11 alkali liquor circulating boxes, 12 saline solution circulating boxes, 13 acid cycle casees, 14
Pole water circulation case, 15 aeration heads, 16 air inlets, 17 aerators, 18 state pickling lines, 19 PH value detector mouths, 20 valves,
21 control modules, 22 floss holes.
Specific embodiment
1-4 is described in further detail to the present invention below in conjunction with the accompanying drawings, it is noted that embodiment described below is intended to
It is easy to the understanding of the present invention, and any restriction effect is not risen to which.
As Figure 1-3, the application provides a kind of process of steel industry nitric hydrofluoric acid mixed acid pickle liquor and reclaims
A kind of process recovery system of steel industry nitric hydrofluoric acid mixed acid pickle liquor of system, including single filter unit 1, reaction
Unit 2 and cascade filtration unit 3, acid pickle entrance 4 are connected to 1 top of single filter unit by pipeline through water pump 5 and valve 6
Filter inlet, as nitric hydrofluoric acid mixed acid has volatility, for preventing nitric hydrofluoric acid mixed acid in course of reaction
Middle volatilization, 2 top of the reaction member are sealed construction, and are provided with being placed on the gap of 2 top pipeline of reaction member
Seal gasket, the filter outlet of 1 bottom of single filter unit are connected to 2 upper entrance of reaction member by pipeline, and reaction is single
The reactant liquor outlet of first 2 bottoms is connected to the filter inlet on 3 top of cascade filtration unit by pipeline through water pump 5 and valve 6,
The filter outlet of 3 bottom of cascade filtration unit is connected to circulating and recovering mouth 9 by pipeline through valve 8, and the system also includes
Bipolar membrane electrodialysis equipment 10, the bipolar membrane electrodialysis equipment 10 include that alkali liquor circulating box 11, saline solution circulating box 12, acid solution are followed
Ring case 13 and pole water circulation case 14, the circulating and recovering mouth 9 is connected to the entrance of saline solution circulating box 12 by pipeline, due to nitric acid
Do not only have volatility with the mixed liquor of Fluohydric acid., and see that light easily decomposes, so the casing of the acid cycle case 13 is by impermeable
Light material is made and is additionally provided with closure in its water tank upper, and the outlet of the alkali liquor circulating box 11 is connected to instead by pipeline
2 upper entrance of unit, 2 intracavity bottom of the reaction member is answered to be additionally provided with evenly distributed aeration head 15, the aeration head 15
The air inlet 16 that 2 bottom of reaction member is connected to by pipeline, is additionally provided with aerator 17, the acid solution on the air inlet 16
The outlet of circulating box 13 is connected to pickling lines 18, the leakage fluid dram connection acid pickle entrance 4 of the pickling lines 18.
The efficiency of the further process recovery system for improving steel industry nitric hydrofluoric acid mixed acid pickle liquor, also wraps
Include control module 21, described PH value detector 19, PH value detector 19 and 21 electricity of control module is additionally provided with before 8 pipeline of valve
Connection, the PH value detector 19 are connected to floss hole 22 by pipeline via valve 20, and the valve 8 and valve 20 are electricity
Control valve is simultaneously electrically connected with control module 21.
The efficiency of the further process recovery system for improving steel industry nitric hydrofluoric acid mixed acid pickle liquor, described
Single filter unit 1 and cascade filtration unit 3 are bag filter.
As shown in figure 4, system described in the claims is used for steel industry nitric hydrofluoric acid mixed acid pickle liquor
Recovery method is processed, methods described comprises the steps：
Step one, the NaCl solution of prescribed concentration is placed in the salt chamber circulating water groove 12 of bipolar membrane electrodialysis equipment 10, is started
Bipolar membrane electrodialysis equipment 10, acid cycle groove 13 are carried out closed cycle 10-15 minutes, and the HCl solution concentration of generation is not yet
Disconnected rising, when HCl solution concentration reaches 5% mass ratio, causes production line pickling lines 18, alkali liquor circulating box by bypass
11 constantly carry out closed cycle, and the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reaches 4% mass ratio, double
Pole EDBM equipment 10 quits work, and for preventing 10 film of bipolar membrane electrodialysis equipment from blocking, steel and iron industry nitric hydrofluoric acid is mixed
Close sour pickle liquor and not directly enter bipolar membrane electrodialysis equipment 10, but the alkali liquor that is made using bipolar membrane electrodialysis equipment 10 is gone
Reacted with nitric hydrofluoric acid mixing acid waste liquid；
Step 2, the acid pickle are discharged from pickling lines 18, enter acid pickle entrance 4, by pipeline through water pump 5 and valve
6 connections enter single filter unit 1, and mixed solution is filtered by bag filter, remove large granular impurity and oil slick；
Step 3, the filtrate for obtaining step 2 enter reaction member 2 through the outlet of 1 bottom of single filter unit by pipeline,
The NaOH that will be produced in the alkali liquor circulating box 11 of bipolar membrane electrodialysis equipment 10, adds reaction member 2 by pipeline；
Step 4, startup aerator 17, air is input into reaction member 2 from the bottom to top by aeration head 15, NaOH solution is made
Uniformly sufficiently mix in reaction member 2 with nitric hydrofluoric acid mixed acid pickle liquor, and constantly to aeration in mixed solution；
Step 5, the mixed solution that step 3 is obtained is passed through in cascade filtration unit 3, mixed solution is carried out by bag filter
Filter, supernatant and precipitate are carried out solid-liquid separation, solid is Fe (OH)3Reclaim after drying；
Supernatant in step 6, step 5 flows through PH value detector 19, as PH=9, illustrates that reacting reaction in water tank fills
Point, Fe in acid pickle2+Precipitate completely, supernatant after filtering is that composition is NaNO3, NaF and a small amount of NaOH, this time control
Liquid in pipeline is caused saline solution circulating box by 21 control valve 8 of molding block；As PH=8, illustrate that reacting reaction in water tank fills
Point, Fe in acid pickle2+Precipitate completely, supernatant after filtering is that composition is NaNO3, NaF and a small amount of NaOH, this time control
Liquid in pipeline is caused saline solution circulating box by 21 control valve 8 of molding block；As supernatant PH=7, although in neutrality, but this
When solution in may still contain micro unprecipitated Fe2+With a large amount of NaNO3, NaF mixed solutions, for preventing Fe2+Enter saline solution to follow
Ring case, at this moment liquid in pipeline is entered city planting ductwork, and meets environmental requirement by 21 control valve 20 of control module；Work as supernatant
During liquid PH=6, illustrate to react and react in water tank insufficient, typically in faintly acid, now containing unprecipitated Fe on a small quantity in solution2+
With a large amount of NaNO3, NaF mixed solutions, for preventing Fe2+Saline solution circulating box is entered, at this moment 21 control valve 20 of control module, will pipe
In road, liquid enters city planting ductwork, and meets environmental requirement；Control module 21 is using PLC control system and man machine interface, system
Reliability is high, and strong antijamming capability, perfect in shape and function, client are non-maintaining, forms human computer conversation.
In sum, will be prepared for bipolar membrane electrodialysis equipment that acid solution is used for steel and iron industry pickling lines for pickling steel
Material, saves cost of material；And go to process nitric hydrofluoric acid mixing acid waste liquid using the alkali liquor of bipolar membrane electrodialysis equipment.And
By the way of reaction water tank bottom aeration it is more fully mixed reactant liquor, and the oxygen of abundance is constantly provided into mixed solution
Gas, greatly shortens the response time.And mixed solution after reaction is filtered with bag filter, supernatant and precipitate are entered
Row solid-liquid separation.After reaction, nitrate anion and fluorion in nitric hydrofluoric acid mixing acid waste liquid are replaced out, nitric hydrofluoric acid
Fe in mixing acid waste liquid2+Form Precipitation.Supernatant after being filtered by bag filter can return to bipolar membrane electrodialysis
Equipment antacid alkaline again, greatly reduces raw material input cost.Precipitate is outer after can drying to be sold.So as to realize nitric acid
The zero-emission of Fluohydric acid. mixing acid waste liquid.This method treatment effect is obvious, energy continuous and stable production, and equipment, pipe valve etc. are
Using anti-corrosion material, anti-corrosion is durable, and system operatio running expense is low.
While embodiments of the present invention have been illustrated and described, for the ordinary skill in the art, may be used
These embodiments can be carried out with multiple changes without departing from the principles and spirit of the present invention, changed, replaced to understand
Change and modification, the scope of the present invention be defined by the appended.
Claims (4)
1. the processing system of steel industry nitric hydrofluoric acid mixed acid pickle liquor, including single filter unit（1）, reaction member
（2）With cascade filtration unit（3）, acid pickle entrance（4）By pipeline through water pump（5）And valve（6）It is connected to single filter list
Unit（1）The filter inlet on top, single filter unit（1）The filter outlet of bottom is connected to reaction member by pipeline
（2）Upper entrance, the reaction member（2）Top is sealed construction, and be placed in reaction member（2）The gap of top pipeline
On be provided with seal gasket, reaction member（2）The reactant liquor outlet of bottom is by pipeline through water pump（5）And valve（6）It is connected to
Cascade filtration unit（3）The filter inlet on top, cascade filtration unit（3）The filter outlet of bottom is by pipeline through valve
（8）It is connected to circulating and recovering mouth（9）, it is characterised in that：The system also includes bipolar membrane electrodialysis equipment（10）, described bipolar
EDBM equipment（10）Including alkali liquor circulating box（11）, saline solution circulating box（12）, acid cycle case（13）With pole water circulation case
（14）, the circulating and recovering mouth（9）Saline solution circulating box is connected to by pipeline（12）Entrance, the acid cycle case（13）'s
Casing is made up of light tight material and top is additionally provided with closure, the alkali liquor circulating box（11）Outlet connected by pipeline
To reaction member（2）Upper entrance, the reaction member（2）Intracavity bottom is additionally provided with evenly distributed aeration head（15）, institute
State aeration head（15）Reaction member is connected to by pipeline（2）The air inlet of bottom（16）, the air inlet（16）On also set up
There is aerator（17）, the acid cycle case（13）Outlet be connected to pickling lines（18）, pickling lines (18)
Leakage fluid dram connection acid pickle entrance（4）.
2. a kind of process recovery system of steel industry nitric hydrofluoric acid mixed acid pickle liquor as claimed in claim 1, its
It is characterised by：System also includes control module（21）, in the cascade filtration unit（3）The filter outlet and valve of bottom
（8）Between pipeline on be additionally provided with PH value detector（19）, PH value detector（19）With control module（21）Electrical connection, described
PH value detector（19）By pipeline via valve（20）It is connected to floss hole（22）, the valve（8）And valve（20）It is
Electric control valve and control module（21）Electrical connection.
3. a kind of process recovery system of steel industry nitric hydrofluoric acid mixed acid pickle liquor as claimed in claim 1, its
It is characterised by：The single filter unit（1）With cascade filtration unit（3）It is bag filter.
4. system described in a kind of the claims is used for the process recovery of steel industry nitric hydrofluoric acid mixed acid pickle liquor
Method, it is characterised in that：Methods described comprises the steps：
Step one, the NaCl solution of prescribed concentration is placed in bipolar membrane electrodialysis equipment（10）Salt chamber circulating water groove（12）In,
Start bipolar membrane electrodialysis equipment（10）, acid cycle groove（13）Closed cycle 10-15 minutes are carried out, the HCl solution of generation is dense
Degree is also constantly rising, and when HCl solution concentration reaches 5% mass ratio, causes production line pickling lines by bypass（18）,
Alkali liquor circulating box（11）Closed cycle is carried out simultaneously, the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reaches
During 4% mass ratio, bipolar membrane electrodialysis equipment（10）Quit work；
Step 2, the acid pickle are from pickling lines（18）Discharge, enters acid pickle entrance（4）, by pipeline through water pump（5）
And valve（6）Connection enters single filter unit（1）, mixed solution filtered by bag filter, removes large granular impurity
And oil slick；
Step 3, the filtrate for obtaining step 2 are through single filter unit（1）The outlet of bottom enters reaction member by pipeline
（2）, by bipolar membrane electrodialysis equipment（10）Alkali liquor circulating box（11）The NaOH of interior generation, adds reaction member by pipeline
（2）；
Step 4, startup aerator（17）, air is passed through aeration head（15）It is input into reaction member from the bottom to top（2）, make
NaOH solution is with nitric hydrofluoric acid mixed acid pickle liquor in reaction member（2）Interior uniform sufficiently mixing, and constantly to mixing
Aeration in solution；
Step 5, the mixed solution that step 3 is obtained is passed through cascade filtration unit（3）Interior, mixed solution is entered by bag filter
Row is filtered, and supernatant and precipitate are carried out solid-liquid separation, and solid is Fe (OH)3Reclaim after drying；
Supernatant in step 6, step 5 flows through PH value detector（19）, when supernatant PH >=8, control module（21）Control
Under system, Open valve（8）, supernatant is by circulating and recovering mouth（9）Enter saline solution circulating box（12）, when supernatant 6<PH<When 8,
Control module（21）Under control, Open valve（20）, supernatant is by floss hole（22）Enter municipal drainage.
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| CN201610869339.4A CN106495356A (en) | 2016-10-01 | 2016-10-01 | The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892281A (en) * | 2017-10-31 | 2018-04-10 | 浙江海洋大学 | A kind of system and method for reclaiming sulphur relieving haperacidity |
| CN108341514A (en) * | 2018-01-25 | 2018-07-31 | 傅云峰 | The processing method of the waste water generated in graphite acid system purification process |
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| CN107892281A (en) * | 2017-10-31 | 2018-04-10 | 浙江海洋大学 | A kind of system and method for reclaiming sulphur relieving haperacidity |
| CN107892281B (en) * | 2017-10-31 | 2020-11-13 | 浙江海洋大学 | System and method for recovering sulfuric acid |
| CN108341514A (en) * | 2018-01-25 | 2018-07-31 | 傅云峰 | The processing method of the waste water generated in graphite acid system purification process |
| CN108341514B (en) * | 2018-01-25 | 2021-03-30 | 傅云峰 | Method for treating wastewater generated in purification process by using graphite acid method |
| CN110078261A (en) * | 2019-05-20 | 2019-08-02 | 中国恩菲工程技术有限公司 | Handle the method and system of waste water |
| CN110078261B (en) * | 2019-05-20 | 2024-02-09 | 中国恩菲工程技术有限公司 | Method and system for treating wastewater |
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