CN106277486A - The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof - Google Patents
The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof Download PDFInfo
- Publication number
- CN106277486A CN106277486A CN201610869340.7A CN201610869340A CN106277486A CN 106277486 A CN106277486 A CN 106277486A CN 201610869340 A CN201610869340 A CN 201610869340A CN 106277486 A CN106277486 A CN 106277486A
- Authority
- CN
- China
- Prior art keywords
- pipeline
- valve
- reaction member
- acid
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005554 pickling Methods 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 230000008569 process Effects 0.000 title claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 29
- 239000010959 steel Substances 0.000 title claims abstract description 29
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 238000000909 electrodialysis Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 26
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 25
- 235000021110 pickles Nutrition 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 238000005276 aerator Methods 0.000 claims description 7
- 241000628997 Flos Species 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 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
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002689 soil Substances 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
- 208000033999 Device damage Diseases 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 iron ion Chemical class 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
- 238000005555 metalworking Methods 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
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor 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 hydrochloride 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 chloride ion in hydrochloride waste is replaced out, the Fe in hydrochloride 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 hydrochloride 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 hydrochloride waste
And system.
Background technology
Steel rolling in steel and iron industry, metallic article etc. are required for pickling and remove the iron scale of steel surface and other are miscellaneous
Thing, typically uses chlorohydric acid pickling.Wash the residual acid of steel surface with water to potcher after pickling.In descaling bath the ferrum of acid solution from
After sub-concentration reaches controlling value, discharging acid pickle, acid solution is newly changed in displacement.Therefore acid cleaning process has the discharge of hydrogen chloride emission, acid
Property waste water discharge, and substantial amounts of spent acid discharge.In acid pickle, iron ion mass concentration is in about 120g/L, hydrogen chloride quality
Mark < 10%.Owing to acid waste liquid has serious corrosivity, the most it is put into " National Hazard refuse register ".If to this
Acid waste liquid does not processes, and enters sewer or is discharged to neighbouring receiving water body the most outward, and residual acid can corrode cement and coagulation
Soil and periphery soil, and destroy the calcium carbonate balance in water body, and make animal dead in water, it is harmful to crops, such waste liquid
Directly discharge not only severe contamination surrounding enviroment, violate country's " Law on Environmental Protection ", and cause significant wastage.
Metal-working industry mainly has acid-base neutralization method, regeneration of hydrochloric acid for the processing method of hydrochloride waste the most both at home and abroad
Method, evaporative crystallization method.
Acid-base neutralization method: typically use Calx, carbide slag or Caustic soda that it is neutralized process, makes pH value reach country row
Discharge after putting standard.Its shortcoming is to neutralize reagent cost height, and expensive, spent acid treating capacity is restricted, and in pickle liquor
HCL, FeCl2It is not utilized effectively etc. resource.The gas diffusion generated in processing procedure, causes secondary pollution；Mud
Amount is big, remaining salt residue treatment difficulty.
Regeneration of hydrochloric acid method: regeneration of hydrochloric acid method all uses the mode of heating evaporation, spray burning, the most domestic regeneration of hydrochloric acid
Device is all to introduce, and its technique is that acid pickle directly heats recovery hydrochloric acid and ferrum oxide, and the large-scale iron and steel of minority is combined
Enterprise uses Lurgi process=method.Process technique one-time investment is big, operation and maintenance cost is high, device damage is serious, the most medium and small for this
Enterprise is difficult to bear.
Evaporative crystallization method: be prone to volatilization and characteristic soluble in water according to hydrogen chloride, and ferrous chloride is at hydrochloric acid solution
The rule of middle dissolubility, employing steam heats indirectly, negative pressure evaporation concentration technology, and the condensed device of gas that evaporation produces is condensed into
For dilute hydrochloric acid, return Pickling-shop and reuse；Acid pickle, after evaporation and concentration makes ferrous chloride reach finite concentration, cools down dense
Contracting liquid makes ferrous chloride separate out with the form of crystallization, then is performing centrifugal separation on obtaining the crystal of ferrous chloride.This process technology investment
Greatly, operation and maintenance cost is high, equipment energy consumption is high, and intermittent operation.
In this context, with membrane technology for relying on, having developed successfully spent acid equipment for reclaiming, it has and is easily achieved
Technological transformation, rate of return on investment are high, easily operated, be easily maintained, operating cost is low, automaticity high.Spent acid returns
Spent acid reuse can be processed with equipment, change harmful to treasure, also bring high economic benefit while solving environmental issue for enterprise, make
The most considerable with prospect with field, there is huge investment repayment and be worth.
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 hydrochloride waste treatment technology, no pollution during acid washing rolled steel can be realized, comply fully with the steel of environmental requirement
Material hydrochloride waste process and reclaim method and system.
The process of the technical scheme is that a kind of steel industry hydrochloric acid pickling waste liquor 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, owing to hydrochloric acid has volatility, so described reaction member top is sealed construction, and with put
Being provided with seal gasket on the gap of reaction member top pipeline, the reactant liquor bottom reaction member exports by pipeline through water
Pump and valve are connected to the filter inlet on cascade filtration unit top, and the filter outlet of cascade filtration unit bottom is by pipe
Road is connected to circulating and recovering mouth through valve, and described system also includes bipolar membrane electrodialysis equipment, described bipolar membrane electrodialysis equipment
Including alkali liquor circulating box, saline solution circulating box, acid cycle case and pole water circulating box, described circulating and recovering mouth is connected to by pipeline
The entrance of saline solution circulating box, described acid cycle case is provided with sealing lid, and the outlet of described alkali liquor circulating box is by pipeline even
It is connected to reaction member upper entrance, bottom described reaction member intracavity, is additionally provided with evenly distributed aeration head, described aeration head
It is connected to the air inlet bottom reaction member by pipeline, described air inlet is additionally provided with aerator, described acid cycle case
Outlet be connected to pickling lines, the leakage fluid dram of described pickling lines connects acid pickle 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 hydrochloric acid pickling waste liquor
Receiving method, described method comprises the steps:
Step one, the NaCl solution of prescribed concentration is placed in the salt chamber circulating water groove of bipolar membrane electrodialysis equipment, starts bipolar
EDBM equipment, acid cycle groove carries out closed cycle 10-15 minute, and the HCl solution concentration of generation is also constantly rising, when
HCl solution concentration reach 5% mass than time, cause production line pickling lines 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 reach 4% mass than time, bipolar membrane electrodialysis equipment
Quit 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 hydrochloric 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 hydrochloric acid that bipolar membrane electrodialysis system prepares can return acid
Wash production line；The alkali liquor produced is for processing the Fe of hydrochloride waste2+And replace out the chloride ion in hydrochloride waste and be back to use bipolar
EDBM system antacid alkaline again；This technology can process steel industry hydrochloride waste, makes Fe2+All with Fe(OH)3Solid
Form precipitation is discharged；Replace out the salt acid group 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) hydrochloric 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 one iron and steel of a kind of steel industry hydrochloric acid pickling waste liquor
The process recovery system of industry hydrochloric acid pickling waste liquor, including single filter unit 1, reaction member 2 and cascade filtration unit 3, useless
Acid solution entrance 4 is connected to the filter inlet on single filter unit 1 top by pipeline through water pump 5 and valve 6, owing to hydrochloric acid has
Having volatility, for preventing hydrochloric acid from volatilizing in course of reaction, described reaction member 2 top is sealed construction, and anti-with being placed in
Answering and be provided with seal gasket on the gap of unit 2 top pipeline, the filter outlet bottom single filter unit 1 is by pipeline even
Being connected to reaction member 2 upper entrance, the reactant liquor outlet bottom reaction member 2 is connected to two by pipeline through water pump 5 and valve 6
The filter inlet on level filter element 3 top, the filter outlet bottom cascade filtration unit 3 is connected through valve 8 by pipeline
To circulating and recovering mouth 9, described system also includes that 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 by pipeline
To the entrance of saline solution circulating box 12, owing to hydrochloric acid has volatility, so being provided with sealing lid on described acid cycle case 13,
The outlet of described alkali liquor circulating box 11 is connected to reaction member 2 upper entrance by pipeline, bottom described reaction member 2 intracavity also
Being provided with evenly distributed aeration head 15, described aeration head 15 is connected to the air inlet 16 bottom reaction member 2, institute by pipeline
Stating and be additionally provided with aerator 17 on air inlet 16, the outlet of described acid cycle case 13 is connected to pickling lines 18, described acid
The leakage fluid dram washing production line 18 connects acid pickle entrance 4.
Further improve the efficiency of the process recovery system of steel industry hydrochloric acid pickling waste liquor, 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 hydrochloric acid pickling waste liquor, 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 hydrochloric acid pickling waste liquor,
Described method 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, starts
Bipolar membrane electrodialysis equipment 10, acid cycle groove 13 carries out closed cycle 10-15 minute, and the HCl solution concentration of generation is not yet
Disconnected rise, when HCl solution concentration reach 5% mass than time, cause production line pickling lines 18 by bypass, alkali liquor circulating box
11 constantly carry out closed cycle, and the NaOH solution concentration of generation is also constantly rising, when NaOH concentration reach 4% mass than time, double
Pole EDBM equipment 10 quits work, for preventing bipolar membrane electrodialysis equipment 10 film from blocking, and steel and iron industry hydrochloric acid pickling waste liquor
Not directly enter bipolar membrane electrodialysis equipment 10, but the alkali liquor utilizing bipolar membrane electrodialysis equipment 10 to make goes to enter with hydrochloride waste
Row reaction；
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 hydrochloric acid pickling waste liquor, 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 NaCl and a small amount of NaOH, now control mould
Block 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, useless
Fe in acid solution2+Precipitate the most completely, supernatant after filtering be composition be NaCl and a small amount of NaOH, now control module 21 is controlled
Valve 8 processed, causes saline solution circulating box by the liquid in pipeline；As supernatant PH=7, although in neutrality, but in solution still now
The unprecipitated Fe of trace may be contained2+With a large amount of Na2Cl solution, for preventing Fe2+Enter saline solution circulating box, at this moment control module 21
Control valve 20, liquid in pipeline is entered city planting ductwork, and meets environmental requirement；As supernatant PH=6, reaction water is described
In case, reaction is insufficient, is typically faintly acid, now containing a small amount of unprecipitated Fe in solution2+With a large amount of NaCl solution, it is anti-
Only Fe2+Entering saline solution circulating box, at this moment control module 21 controls valve 20, liquid in pipeline enters city planting ductwork, and meets
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, and function is complete
Kind, 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 hydrochloride 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 chloride ion in hydrochloride waste is replaced out, the Fe in hydrochloride 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 hydrochloride 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 hydrochloric acid pickling waste liquor, 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, described reaction member (2) top is sealed construction, and with on the gap being placed in reaction member (2) top pipeline
Being provided with seal gasket, the reactant liquor outlet of reaction member (2) bottom is connected to two by pipeline through water pump (5) and valve (6)
The filter inlet on level filter element (3) top, the filter outlet of cascade filtration unit (3) bottom passes through pipeline through valve
(8) circulating and recovering mouth (9) it is connected to, it is characterised in that: described system also includes bipolar membrane electrodialysis equipment (10), described bipolar
EDBM equipment (10) includes 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 the entrance of saline solution circulating box (12) by pipeline, on described acid cycle case (13)
Being provided with sealing lid, the outlet of described alkali liquor circulating box (11) is connected to reaction member (2) upper entrance by pipeline, described instead
Answering and be additionally provided with evenly distributed aeration head (15) bottom unit (2) intracavity, described aeration head (15) is connected to instead by pipeline
Answer the air inlet (16) of unit (2) bottom, described air inlet (16) is additionally provided with aerator (17), described acid cycle case
(13) outlet is connected to pickling lines (18), and the leakage fluid dram of described pickling lines (18) connects acid pickle entrance (4).
The process recovery system of a kind of steel industry hydrochloric acid pickling waste liquor 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 hydrochloric acid pickling waste liquor 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 hydrochloric acid pickling waste liquor, and its feature exists
In: described method comprises the steps:
Step one, the NaCl solution of prescribed concentration 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, and the HCl solution of generation is dense
Degree is also constantly rising, when HCl solution 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 hydrochloric acid pickling waste liquor, 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；
In step 6, step 5 supernatant flow through PH value detector (19), when supernatant PH >=8, control module (21)
Under control, Open valve (8), supernatant enters saline solution circulating box (12) by circulating and recovering mouth (9), when supernatant 6 < PH < 8
Time, under control module (21) controls, Open valve (20), supernatant enters municipal drainage by floss hole (22).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610869340.7A CN106277486A (en) | 2016-10-01 | 2016-10-01 | The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610869340.7A CN106277486A (en) | 2016-10-01 | 2016-10-01 | The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106277486A true CN106277486A (en) | 2017-01-04 |
Family
ID=57716734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610869340.7A Pending CN106277486A (en) | 2016-10-01 | 2016-10-01 | The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106277486A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107900914A (en) * | 2017-12-14 | 2018-04-13 | 天通银厦新材料有限公司 | Sapphire high pressure waterjet device |
| CN108751533A (en) * | 2018-06-05 | 2018-11-06 | 苏州聚微环保科技有限公司 | A kind of processing method of the acidic rinse waste water suitable for process of metal working |
| CN111233044A (en) * | 2020-03-09 | 2020-06-05 | 福建坚石电力线路器材有限公司 | Process method for recycling hot galvanizing pickling waste liquid through reduced pressure aeration |
| CN114593368A (en) * | 2020-12-07 | 2022-06-07 | 阳江宏旺实业有限公司 | Waste acid system with internal circulation structure |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01130782A (en) * | 1987-11-18 | 1989-05-23 | Shinko Pfaudler Co Ltd | Regeneration and recovery of nitric acid-hydrofluoric acid mixture |
| JP2005052794A (en) * | 2003-08-07 | 2005-03-03 | Shigeru Kitani | Method and apparatus for treating aqueous solution |
| JP2008188479A (en) * | 2007-01-31 | 2008-08-21 | Nisshin Steel Co Ltd | Method and apparatus for treating waste acid liquid |
| JP4428582B1 (en) * | 2009-06-17 | 2010-03-10 | 株式会社富士クリーン | Method and apparatus for producing acid and alkali from leachate |
| CN101705495A (en) * | 2009-11-27 | 2010-05-12 | 同济大学 | Recycling method of waste acid from stainless steel acid washing process |
| CN104261590A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Treatment method and system for high concentration salt-containing wastewater for production of nigrosine |
| CN204356171U (en) * | 2014-12-18 | 2015-05-27 | 上海艾希尔化工产品有限公司 | Portable spent pickle liquor treatment system |
| CN204981294U (en) * | 2015-08-26 | 2016-01-20 | 合肥众诚热电有限公司 | Chemistry neutralization pond waste water circulation neutralization and emission PH on -line monitoring system |
| CN105254084A (en) * | 2015-11-13 | 2016-01-20 | 北京国电富通科技发展有限责任公司 | Bipolar membrane electrodialysis treatment method and device for desulfurization wastewater |
| CN206089294U (en) * | 2016-10-01 | 2017-04-12 | 辽宁中成永续水工科技有限公司 | Steel industry hydrochloric acid pickling liquid waste's processing recovery system |
-
2016
- 2016-10-01 CN CN201610869340.7A patent/CN106277486A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01130782A (en) * | 1987-11-18 | 1989-05-23 | Shinko Pfaudler Co Ltd | Regeneration and recovery of nitric acid-hydrofluoric acid mixture |
| JP2005052794A (en) * | 2003-08-07 | 2005-03-03 | Shigeru Kitani | Method and apparatus for treating aqueous solution |
| JP2008188479A (en) * | 2007-01-31 | 2008-08-21 | Nisshin Steel Co Ltd | Method and apparatus for treating waste acid liquid |
| JP4428582B1 (en) * | 2009-06-17 | 2010-03-10 | 株式会社富士クリーン | Method and apparatus for producing acid and alkali from leachate |
| CN101705495A (en) * | 2009-11-27 | 2010-05-12 | 同济大学 | Recycling method of waste acid from stainless steel acid washing process |
| CN104261590A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Treatment method and system for high concentration salt-containing wastewater for production of nigrosine |
| CN204356171U (en) * | 2014-12-18 | 2015-05-27 | 上海艾希尔化工产品有限公司 | Portable spent pickle liquor treatment system |
| CN204981294U (en) * | 2015-08-26 | 2016-01-20 | 合肥众诚热电有限公司 | Chemistry neutralization pond waste water circulation neutralization and emission PH on -line monitoring system |
| CN105254084A (en) * | 2015-11-13 | 2016-01-20 | 北京国电富通科技发展有限责任公司 | Bipolar membrane electrodialysis treatment method and device for desulfurization wastewater |
| CN206089294U (en) * | 2016-10-01 | 2017-04-12 | 辽宁中成永续水工科技有限公司 | Steel industry hydrochloric acid pickling liquid waste's processing recovery system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107900914A (en) * | 2017-12-14 | 2018-04-13 | 天通银厦新材料有限公司 | Sapphire high pressure waterjet device |
| CN108751533A (en) * | 2018-06-05 | 2018-11-06 | 苏州聚微环保科技有限公司 | A kind of processing method of the acidic rinse waste water suitable for process of metal working |
| CN111233044A (en) * | 2020-03-09 | 2020-06-05 | 福建坚石电力线路器材有限公司 | Process method for recycling hot galvanizing pickling waste liquid through reduced pressure aeration |
| CN111233044B (en) * | 2020-03-09 | 2022-07-08 | 福建坚石电力线路器材有限公司 | Process method for recycling hot galvanizing pickling waste liquid through reduced pressure aeration |
| CN114593368A (en) * | 2020-12-07 | 2022-06-07 | 阳江宏旺实业有限公司 | Waste acid system with internal circulation structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102603097B (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN103466829B (en) | High-concentration ammonia nitrogen waste water treatment method and system thereof | |
| CN206089281U (en) | Steel industry sulphuric acid pickling liquid waste's processing recovery system | |
| CN106277486A (en) | The process recovery method of a kind of steel industry hydrochloric acid pickling waste liquor and system thereof | |
| CN107585968B (en) | A kind of chlor-alkali brine waste processing system and method | |
| CN106380016A (en) | Steel pickling wastewater treatment and reuse method and device | |
| CN206089294U (en) | Steel industry hydrochloric acid pickling liquid waste's processing recovery system | |
| CN108793652B (en) | Pickling sludge recycling treatment device and technology | |
| CN106495356A (en) | The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor | |
| CN106277474A (en) | The process recovery method of a kind of steel industry sulfuric acid pickling waste liquid and system thereof | |
| CN102976535B (en) | Method for processing and recycling strong brine by membrane desalination process | |
| CN103663777B (en) | A method for treating wastewater containing hydrofluoric acid in a factory | |
| CN108149017A (en) | A kind of mould liquid that stews replaces Alkaline etchant and recycles the system and technique of aluminium hydroxide | |
| CN111039474A (en) | Power plant circulating water treatment system and method | |
| CN107399863B (en) | Combined treatment system and method for boiler chemical cleaning wastewater and air preheater flushing water | |
| CN206778176U (en) | A kind of processing system of ammonia-contaminated gas | |
| CN205803179U (en) | A kind of acid washing phosphorization waste water treatment device | |
| CN206219405U (en) | A kind of complexes of the zero-emission that becomes for coal chemical industry enterprises reverse osmosis concentrated water | |
| CN210656480U (en) | Adopt washing cigarette waste water retrieval and utilization processing apparatus of DTRO device | |
| CN107585944A (en) | Circulating water multifunctional purifying processing device and its circulating water treatment process | |
| CN107986308A (en) | A kind of workshop system and technique for stewing mould liquid production aluminium hydroxide | |
| CN208632266U (en) | A kind of industrial circulating cooling water Zero discharging system | |
| CN112176346A (en) | Regenerant of phosphorus/sulfur mixed acid for chemical polishing, online regeneration method and system adopted by same | |
| CN206927718U (en) | The Water Treatment in Circulating Cooling System of ozone cooperative film process | |
| CN212269728U (en) | High-efficient chemical industry reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |