CN106277474A - The process recovery method of a kind of steel industry sulfuric acid pickling waste liquid and system thereof - Google Patents
The process recovery method of a kind of steel industry sulfuric acid pickling waste liquid and system thereof Download PDFInfo
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- CN106277474A CN106277474A CN201610869341.1A CN201610869341A CN106277474A CN 106277474 A CN106277474 A CN 106277474A CN 201610869341 A CN201610869341 A CN 201610869341A CN 106277474 A CN106277474 A CN 106277474A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000005554 pickling Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 27
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 26
- 239000010959 steel Substances 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000000909 electrodialysis Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000006228 supernatant Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000005273 aeration Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000001914 filtration Methods 0.000 claims description 22
- 235000021110 pickles Nutrition 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005276 aerator Methods 0.000 claims description 7
- 241000628997 Flos Species 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 5
- 229940069428 antacid Drugs 0.000 abstract description 3
- 239000003159 antacid agent Substances 0.000 abstract description 3
- 230000001458 anti-acid effect Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000605118 Thiobacillus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The process recovery method of a kind of steel industry sulfuric acid pickling waste liquid and system thereof, be used for steel and iron industry pickling lines by the acid solution that bipolar membrane electrodialysis equipment prepares and be used for pickling steel, save cost of material；And utilize the alkali liquor of bipolar membrane electrodialysis equipment to go to process sulfuric acid waste.And use the mode of reaction water tank bottom aeration to make reactant liquor be more fully mixed, and the oxygen of abundance is constantly provided in mixed solution, it is greatly shortened the response time.And with bag filter, mixed solution after reaction is filtered, supernatant and precipitate are carried out solid-liquid separation.After reaction, the sulfate radical in sulfuric acid waste is replaced out, the Fe in sulfuric acid waste2+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 can reclaim outer selling after drying.It is thus possible to realize the zero-emission of sulfuric acid waste.
Description
Technical field
The invention belongs to technical field of sewage, be specifically related to the process recovery method of a kind of steel industry sulfuric acid waste
And system.
Background technology
Before the plating of steel production process and spraying production unit, the iron scale of outer surface should be disposed.Remove at present
The mode of iron scale, basic use pickling technology, the acid solution that concentration is bigger carries out pickling processes to steel.So-called useless
Acid solution refers to that in pickle, the concentration of acid reduces after overpickling, and the content of iron salt increases, so that pickling ability can not meet
Speed of production and the pickle of prescription, still contain the acid about 5% mass ratio, also contain 20% ~ 24% in solution at this moment
Iron salt (FeSO4), due to serious corrosivity, it is put into " National Hazard refuse register ".If this acid pickle is not carried out
Processing, enter sewer or be discharged to neighbouring receiving water body the most outward, residual acid can corrode cement and concrete and periphery soil, and
Destroying the calcium carbonate balance in water body, and make animal dead in water, be harmful to crops, such waste liquid directly discharges the most serious
Pollute surrounding enviroment, violate country's " Law on Environmental Protection ", and cause significant wastage.
The processing method of steel and iron industry sulfuric acid waste mainly has neutralisation, sulphate of iron method, dialysis, life the most both at home and abroad
The methods such as thing method.
Neutralisation: typically use Calx, carbide slag or Caustic soda that it is neutralized process, makes pH value reach country's discharge mark
Discharge after standard.Its shortcoming is that to neutralize reagent cost high, expensive, and spent acid treating capacity receives restriction, and the sulfur in pickle liquor
Acid, FeSO4) etc. resource be not utilized effectively.
Sulphate of iron method use concentrate, cool down, the means such as crystallization, make ferrous sulfate crystallization separate out, and dry recovery.It lacks
Point is that equipment investment is big, and troublesome poeration processes frequently, and the production cycle is long, and energy consumption is high, can only reclaim ferrous sulfate, it is impossible to reclaim
Sulphuric acid.
Electroosmose process: utilize the effect of electric field, draws ion at electrode, through ion exchange membrane.Its shortcoming is consumption
Electricity is the highest.
Bioanalysis: generally oxidation pickle liquor French is carried out under conditions of PH is higher.Foreign study result shows, permissible
Aoxidize divalent iron salt with microorganism one Thiobacillus, then produce Huang hinge ferrovanadium in hydrolysis.Its shortcoming the method has certain limitation,
Need at NH4+Just can smoothly complete under conditions of existence.Operation and processing procedure are more complicated, are difficult to control reaction condition.
Summary of the invention
In order to overcome the problems of the prior art, the technical problem to be solved in the present invention is to provide a kind of energy-saving and environmental protection
And at steel and iron industry sulfuric acid waste treatment technology, no pollution during acid washing rolled steel can be realized, comply fully with the steel of environmental requirement
Material sulfuric acid waste process and reclaim method and system.
The process of the technical scheme is that a kind of steel industry sulfuric acid pickling waste liquid of the present invention
Recovery system, including single filter unit, reaction member and cascade filtration unit, acid pickle entrance passes through pipeline through water pump and valve
Door is connected to the filter inlet on single filter unit top, and the filter outlet of single filter unit bottom is connected by pipeline
To reaction member upper entrance, the reactant liquor outlet bottom reaction member is connected to cascade filtration by pipeline through water pump and valve
The filter inlet on unit top, the filter outlet of cascade filtration unit bottom is connected to circulating and recovering by pipeline through valve
Mouthful, described system also includes that bipolar membrane electrodialysis equipment, described bipolar membrane electrodialysis equipment include that alkali liquor circulating box, saline solution circulate
Case, acid cycle case and pole water circulating box, described circulating and recovering mouth is connected to the entrance of saline solution circulating box, described alkali by pipeline
The outlet of liquid circulating box is connected to reaction member upper entrance by pipeline, is additionally provided with uniformly bottom described reaction member intracavity
The aeration head of arrangement, described aeration head is connected to the air inlet bottom reaction member by pipeline, described air inlet also sets up
Having aerator, the outlet of described acid cycle case to be connected to pickling lines, the leakage fluid dram of described pickling lines connects spent acid
Liquid entrance.
Further, system also includes control module, the described PH value detector that is additionally provided with before valve pipeline, and pH value is examined
Surveying instrument to electrically connect with control module, described PH value detector is connected to floss hole, described valve and valve by pipeline via valve
Door is electric control valve and electrically connects with control module.
Further, described single filter unit and cascade filtration unit are bag filter.
Further, the application also provides for a kind of applying said system to return for the process of steel industry sulfuric acid pickling waste liquid
Receiving method, described method comprises the steps:
Step one, by the Na of prescribed concentration2SO4Solution is placed in the salt chamber circulating water groove of bipolar membrane electrodialysis equipment, starts double
Pole EDBM equipment, acid cycle groove carries out closed cycle 10-15 minute, the H of generation2SO4Solution concentration is also on continuous
Rise, work as H2SO4Solution concentration reach 5% mass than time, cause production line pickling lines by bypass, alkali liquor circulating box constantly enters
Row closed cycle, the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reach 4% mass than time, Bipolar Membrane electric osmose
Desorption device quits work；
Step 2, described acid pickle discharge from pickling lines, enter acid pickle entrance, are connected through water pump and valve by pipeline
Entering single filter unit, mixed solution is filtered by bag filter, removes large granular impurity and oil slick；
Step 3, filtrate step 2 obtained 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, inputted air from the bottom to top to reaction member by aeration head, make NaOH solution and sulphuric acid
Pickle liquor is the most sufficiently mixing in reaction member, and constantly aeration in mixed solution；
Step 5, mixed solution step 3 obtained are passed through in cascade filtration unit, and mixed solution is carried out by bag filter
Filtering, supernatant and precipitate are carried out solid-liquid separation, solid is Fe (OH)3Reclaim after drying；
In step 6, step 5 supernatant flow through PH value detector, when supernatant PH >=8, control module control under, open
Opening valve, supernatant enters saline solution circulating box by circulating and recovering mouth, when supernatant 6 < PH < when 8, under control module controls, is opened
Opening valve, supernatant enters municipal drainage by floss hole.
For prior art, the invention has the beneficial effects as follows: the sulphuric acid that bipolar membrane electrodialysis system prepares can return acid
Wash production line；The alkali liquor produced is for processing the Fe of sulfuric acid waste2+And replace out the sulfate radical in sulfuric acid waste and be back to use bipolar
EDBM system antacid alkaline again；This technology can process steel industry sulfuric acid waste, makes Fe2+All with Fe(OH)3Solid
Form precipitation is discharged；Replace out the sulfate radical of more than 95%；It is thus possible to realize the zero-emission of acid pickle.
This law has that current efficiency is high, can continuous and stable production, simple to operate, governance process be not required to add eo-acid or alkali, dress
Equipment in putting, pipeline, valve etc. all use anti-corrosion material and technology.Device anticorrosion is long for durable service life, No leakage, arranges
Compact, floor space is few, the operation low plurality of advantages of running expense, the most 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) sulphuric acid obtained, to be directly entered life
Product line uses；4) obtain side-product hydrated ferric oxide. simultaneously, rear barreled can be dried and sell；5) energy-conservation, resource regeneration, pollutes
Thing zero-emission, meets national requirements for environmental protection.
Accompanying drawing explanation
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 unit, 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 circulating box, 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.
Detailed description of the invention
The present invention is described in further detail by 1-4 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 it is not played any restriction effect.
As Figure 1-3, the application provides the process recovery system of a kind of steel industry sulfuric acid pickling waste liquid, including one-level
Filter element 1, reaction member 2 and cascade filtration unit 3, acid pickle entrance 4 is connected to one by pipeline through water pump 5 and valve 6
The filter inlet on level filter element 1 top, it is single that the filter outlet bottom single filter unit 1 is connected to reaction by pipeline
Unit's 2 upper entrances, the reactant liquor outlet bottom reaction member 2 is connected to cascade filtration unit by pipeline through water pump 5 and valve 6
The filter inlet on 3 tops, the filter outlet bottom cascade filtration unit 3 is connected to circulating and recovering by pipeline through valve 8
Mouthfuls 9, described system also include bipolar membrane electrodialysis equipment 10, described bipolar membrane electrodialysis equipment 10 include alkali liquor circulating box 11,
Saline solution circulating box 12, acid cycle case 13 and pole water circulating box 14, described circulating and recovering mouth 9 is connected to saline solution by pipeline and circulates
The entrance of case 12, the outlet of described alkali liquor circulating box 11 is connected to reaction member 2 upper entrance, described reaction member by pipeline
Being additionally provided with evenly distributed aeration head 15 bottom 2 intracavity, described aeration head 15 is connected to bottom reaction member 2 by pipeline
Air inlet 16, described air inlet 16 is additionally provided with aerator 17, and the outlet of described acid cycle case 13 is connected to pickling and produces
Line 18, the leakage fluid dram of described pickling lines 18 connects acid pickle entrance 4.
Further improve the efficiency of the process recovery system of steel industry sulfuric acid pickling waste liquid, also include control module
21, described before valve 8 pipeline, it is additionally provided with PH value detector 19, PH value detector 19 electrically connects with control module 21, described
PH value detector 19 is connected to floss hole 22 by pipeline via valve 20, and described valve 8 and valve 20 are electric control valve also
Electrically connect with control module 21.
Further improve the efficiency of the process recovery system of steel industry sulfuric acid pickling waste liquid, described single filter unit
1 and cascade filtration unit 3 be bag filter.
As shown in Figure 4, system described in the claims is used for the process recovery method of steel industry sulfuric acid pickling waste liquid,
Described method comprises the steps:
Step one, by the Na of prescribed concentration2SO4Solution is placed in the salt chamber circulating water groove 12 of bipolar membrane electrodialysis equipment 10, opens
Dynamic bipolar membrane electrodialysis equipment 10, acid cycle groove 13 carries out closed cycle 10-15 minute, the H of generation2SO4Solution concentration also exists
Constantly rise, work as H2SO4Solution concentration reach 5% mass than time, cause production line pickling lines 18 by bypass, alkali liquor circulates
Case 11 constantly carries out closed cycle, and the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reach 4% mass than time,
Bipolar membrane electrodialysis equipment 10 quits work, and for preventing bipolar membrane electrodialysis equipment 10 film from blocking, steel and iron industry sulfuric acid washing gives up
Liquid not directly enters bipolar membrane electrodialysis equipment 10, but the alkali liquor utilizing bipolar membrane electrodialysis equipment 10 to make goes and sulfuric acid waste
React；
Step 2, described acid pickle discharge from pickling lines 18, enter acid pickle entrance 4, by pipeline through water pump 5 and valve
6 connect entrance single filter unit 1, and mixed solution is filtered by bag filter, removes large granular impurity and oil slick；
Step 3, filtrate step 2 obtained outlet bottom single filter unit 1 enter reaction member 2 by pipeline,
The NaOH that will produce in the alkali liquor circulating box 11 of bipolar membrane electrodialysis equipment 10, adds reaction member 2 by pipeline；
Step 4, startup aerator 17, inputted air from the bottom to top to reaction member 2 by aeration head 15, make NaOH solution
Uniformly sufficiently mix in reaction member 2 with sulfuric acid pickling waste liquid, and constantly aeration in mixed solution；
Step 5, mixed solution step 3 obtained are passed through in cascade filtration unit 3, and mixed solution is carried out by bag filter
Filtering, supernatant and precipitate are carried out solid-liquid separation, solid is Fe (OH)3Reclaim after drying；
In step 6, step 5 supernatant flow through PH value detector 19, as PH=9, illustrate to react reaction in water tank and fill
Point, Fe in acid pickle2+Precipitate the most completely, supernatant after filtering be composition be Na2SO4With a small amount of NaOH, now control
Module 21 controls valve 8, and the liquid in pipeline is caused saline solution circulating box；As PH=8, in illustrating to react water tank, reaction is fully,
Fe in acid pickle2+Precipitate the most completely, supernatant after filtering be composition be Na2SO4With a small amount of NaOH, now control module
21 control valve 8, and the liquid in pipeline is caused saline solution circulating box；As supernatant PH=7, although in neutrality, but now solution
In still may contain the unprecipitated Fe of trace2+With a large amount of Na2SO4Solution, for preventing Fe2+Enter saline solution circulating box, at this moment control
Module 21 controls valve 20, liquid in pipeline is entered city planting ductwork, and meets environmental requirement；As supernatant PH=6, explanation
In reaction water tank, reaction is insufficient, is typically faintly acid, now containing a small amount of unprecipitated Fe in solution2+With a large amount of Na2SO4Molten
Liquid, for preventing Fe2+Entering saline solution circulating box, at this moment control module 21 controls valve 20, and liquid in pipeline is entered city planting ductwork,
And meet environmental requirement；Control module 21 uses PLC control system and man machine interface, and system reliability is high, and capacity of resisting disturbance is strong,
Perfect in shape and function, client is non-maintaining, forms human computer conversation.
In sum, bipolar membrane electrodialysis equipment is prepared acid solution is used for steel and iron industry pickling lines and is used for pickling steel
Material, saves cost of material；And utilize the alkali liquor of bipolar membrane electrodialysis equipment to go to process sulfuric acid waste.And use reaction water tank
The mode of bottom aeration makes reactant liquor be more fully mixed, and constantly provides the oxygen of abundance in mixed solution, is greatly shortened
Response time.And with bag filter, mixed solution after reaction is filtered, supernatant and precipitate are carried out solid-liquid separation.
After reaction, the sulfate radical in sulfuric acid waste is replaced out, the Fe in sulfuric acid waste2+Form Precipitation.Pass through bag type filtering
Supernatant after device filters can return to bipolar membrane electrodialysis equipment antacid alkaline again, greatly reduces raw material input cost.Heavy
Shallow lake thing is outer after can drying to be sold.It is thus possible to realize the zero-emission of sulfuric acid waste.This method treatment effect is obvious, can continuous-stable
Producing, equipment, pipe valve etc. all use anti-corrosion material, and anticorrosion is durable, and system operation running expense is low.
While embodiments of the present invention have been illustrated and described, for the ordinary skill in the art, can
These embodiments can be carried out multiple change without departing from the principles and spirit of the present invention to understand, revise, replace
Changing and modification, the scope of the present invention be defined by the appended.
Claims (4)
1. a process recovery system for steel industry sulfuric acid pickling waste liquid, including single filter unit (1), reaction member (2)
With cascade filtration unit (3), acid pickle entrance (4) is connected to single filter unit by pipeline through water pump (5) and valve (6)
(1) filter inlet on top, the filter outlet of single filter unit (1) bottom is connected to reaction member (2) by pipeline
Upper entrance, the reactant liquor outlet of reaction member (2) bottom is connected to cascade filtration by pipeline through water pump (5) and valve (6)
The filter inlet on unit (3) top, the filter outlet of cascade filtration unit (3) bottom is connected through valve (8) by pipeline
To circulating and recovering mouth (9), it is characterised in that: described system also includes bipolar membrane electrodialysis equipment (10), described Bipolar Membrane electric osmose
Desorption device (10) includes alkali liquor circulating box (11), saline solution circulating box (12), acid cycle case (13) and pole water circulating box (14), institute
Stating circulating and recovering mouth (9) and be connected to the entrance of saline solution circulating box (12) by pipeline, the outlet of described alkali liquor circulating box (11) is led to
Cross pipeline and be connected to reaction member (2) upper entrance, bottom described reaction member (2) intracavity, be additionally provided with evenly distributed aeration
Head (15), described aeration head (15) is connected to the air inlet (16) of reaction member (2) bottom, described air inlet (16) by pipeline
On be additionally provided with aerator (17), the outlet of described acid cycle case (13) is connected to pickling lines (18), and described pickling is raw
The leakage fluid dram producing line (18) connects acid pickle entrance (4).
The process recovery system of a kind of steel industry sulfuric acid pickling waste liquid the most as claimed in claim 1, it is characterised in that: system
Also include control module (21), on the pipeline between filter outlet and the valve (8) of described cascade filtration unit (3) bottom
Being additionally provided with PH value detector (19), PH value detector (19) electrically connects with control module (21), described PH value detector (19)
By pipeline via valve (20) be connected to floss hole (22), described valve (8) and valve (20) be electric control valve and with control
Molding block (21) electrically connects.
The process recovery system of a kind of steel industry sulfuric acid pickling waste liquid the most as claimed in claim 1, it is characterised in that: described
Single filter unit (1) and cascade filtration unit (3) are bag filter.
4. system described in the claims is for a process recovery method for steel industry sulfuric acid pickling waste liquid, and its feature exists
In: described method comprises the steps:
Step one, by the Na of prescribed concentration2SO4Solution is placed in salt chamber circulating water groove (12) of bipolar membrane electrodialysis equipment (10),
Starting bipolar membrane electrodialysis equipment (10), acid cycle groove (13) carries out closed cycle 10-15 minute, the H of generation2SO4Solution is dense
Degree is also constantly rising, and works as H2SO4Solution concentration reach 5% mass than time, cause production line pickling lines (18) by bypass,
Alkali liquor circulating box (11) carries out closed cycle simultaneously, and the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reaches
4% mass than time, bipolar membrane electrodialysis equipment (10) quits work；
Step 2, described acid pickle discharge from pickling lines (18), enter acid pickle entrance (4), by pipeline through water pump (5)
Connecting with valve (6) and enter single filter unit (1), mixed solution is filtered by bag filter, removes large granular impurity
And oil slick；
Step 3, filtrate step 2 the obtained outlet through single filter unit (1) bottom enter reaction member by pipeline
(2), the NaOH that will produce in the alkali liquor circulating box (11) of bipolar membrane electrodialysis equipment (10), add reaction member by pipeline
(2)；
Step 4, startup aerator (17), inputted air from the bottom to top to reaction member (2) by aeration head (15), make
NaOH solution uniformly sufficiently mixes in reaction member (2) with sulfuric acid pickling waste liquid, and constantly aeration in mixed solution；
Step 5, mixed solution step 3 obtained are passed through in cascade filtration unit (3), and mixed solution is entered by bag filter
Row filters, 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), and when supernatant PH >=8, control module (21) is controlled
Under system, Open valve (8), supernatant enters saline solution circulating box (12) by circulating and recovering mouth (9), when supernatant 6 < PH < when 8,
Under control module (21) controls, Open valve (20), supernatant enters municipal drainage by floss hole (22).
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| CN106702398A (en) * | 2017-03-17 | 2017-05-24 | 青岛大仓防腐有限公司 | Anti-corrosive acid washing method for steel pipe |
| 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 |
| CN109467121A (en) * | 2018-12-26 | 2019-03-15 | 江苏中研创星材料科技有限公司 | The method of the removal of impurities of metatitanic acid |
| CN115679125A (en) * | 2022-10-08 | 2023-02-03 | 武汉科技大学 | Method for adjusting pH of vanadium-containing pickle liquor |
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