CN109550771A - The minimizing technology and removal device of organic pollutant in industrial waste salt - Google Patents
The minimizing technology and removal device of organic pollutant in industrial waste salt Download PDFInfo
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- CN109550771A CN109550771A CN201811512864.6A CN201811512864A CN109550771A CN 109550771 A CN109550771 A CN 109550771A CN 201811512864 A CN201811512864 A CN 201811512864A CN 109550771 A CN109550771 A CN 109550771A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 112
- 238000005516 engineering process Methods 0.000 title claims abstract description 28
- 239000002440 industrial waste Substances 0.000 title claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 64
- 230000003647 oxidation Effects 0.000 claims abstract description 60
- 238000005406 washing Methods 0.000 claims abstract description 58
- 238000001914 filtration Methods 0.000 claims abstract description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 44
- 239000011780 sodium chloride Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010865 sewage Substances 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 238000005188 flotation Methods 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims description 75
- 238000002425 crystallisation Methods 0.000 claims description 56
- 230000008025 crystallization Effects 0.000 claims description 55
- 238000001471 micro-filtration Methods 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 229910020935 Sn-Sb Inorganic materials 0.000 claims description 15
- 229910008757 Sn—Sb Inorganic materials 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- 238000005374 membrane filtration Methods 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 13
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000007781 pre-processing Methods 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 210000001367 artery Anatomy 0.000 claims 1
- 235000021050 feed intake Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 238000003672 processing method Methods 0.000 abstract description 4
- -1 after handling 1~3h Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 238000011282 treatment Methods 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 12
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000002101 nanobubble Substances 0.000 description 4
- 210000000952 spleen Anatomy 0.000 description 4
- 210000002784 stomach Anatomy 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention relates to a kind of minimizing technology and removal device for organic pollutant in industrial waste salt, specific steps include: abraum salt is soluble in water, saline sewage is made by pretreatment, adjusts the pH value of saline sewage to neutrality；Carry out by-pass filtration；Then with electrocatalytic oxidation method decomposing organic pollutant, after handling 1~3h, alkali is added to adjust pH value to alkalinity；Micro-nano air-flotation process is carried out again, carries out secondary filtration；To treated, saline sewage is successively evaporated, crystallizes, washing process, until crystal salt reaches preassigned.The present invention handles the processing method that combines with micro-nano air bearing using electro-catalysis, high-efficient, applied widely, process flow is simple, controllability is strong.
Description
Technical field
The invention belongs to industrial waste salt processing technology fields, in particular to the minimizing technology of organic pollutant in industrial waste salt
And removal device.
Background technique
It is usually constructed with the abraum salt containing various poisonous and harmful substances in industrial processes to generate, the annual by-product salt slag in the whole nation is just
Up to 5,000,000 tons or more, and many factories produce " swell-warehouse " phenomenon, and processing difficulty is very big.The processing of chemical industry abraum salt is at present simultaneously
Without corresponding standard, a large amount of poisonous and harmful substances are contained in abraum salt, most enterprises are as dangerous solidification disposal of waste, thus
Enterprise will undertake huge dangerous solidification disposal of waste expense.As serious hope of the people to green environment is more strong, as environmental protection is wanted
That asks steps up, it is necessary to reasonable processing disposition is carried out to solid abraum salt, to realize that it, to the innoxious of environment, is realized discarded
Effective comprehensive reutilization of resource.
For the processing of such abraum salt, the measure being usually taken at present has: (1) landfill disposal.But this method needs to occupy
The serious waste of land resource is caused in a large amount of place, while the percolate that waste residue generates can be to the ecology of underground water and periphery
System causes to seriously threaten.(2) chemical oxidization method is handled.After being cleaned with saturation byproduct salt, a certain amount of chemical oxygen is added
Organic pollutant is carried out oxidation processes by agent, such as sodium hypochlorite, hydrogen peroxide, ozone etc., to obtain clean salinity.
But this method higher cost, condition control difficulty is big, and treatment effeciency cannot be guaranteed, is easy to cause secondary pollution.(3) carrying out washing treatment.
By abraum salt water or organic solvent washing, the impurity in abraum salt is washed away as far as possible, and washing mother liquid evaporation generates high-concentration waste water and uses
Biochemical treatment and advanced oxidation processes processing reduce the COD of waste water, and cleaning solution is prepared in reuse.Treated, and abraum salt passes through
It can be used for chlorine industry after centrifugal drying.But the method application range is small, is appropriate only for that impurity content is few and impurity component is simple
Abraum salt, and its organic pollutant removal efficiency is lower.(4) high temperature oxidation process.Make abraum salt high-temperature process in abraum salt
Organic impurities is oxidized to CO at high temperature2, CO, vapor, with achieve the purpose that remove organic impurities.But the method is processed
The problems such as Cheng Zhong, the equipment such as fluidized bed furnace, rotary kiln easily cause ring formation, agglomeration at high temperature, it is more difficult to realize industrialization.(5) it precipitates
Crystallisation dissolves abraum salt with water, lye is then added and is reacted, and part metals ion will form hydroxide precipitating, solution
In remaining main component be sodium chloride, then carry out slag, water separation, by sunning can recycle salinity.But the method is organic
Pollutant removal is poor, and recycling salinity purity is low, and application range is small.
How a kind of new abraum salt processing disposal technology is designed and developed out, to reach organic pollutant removal efficiency in abraum salt
Height, salinity can be recycled sufficiently, and operating condition method is easy, and the small effect waited of occupied ground area is finally reached and drops as far as possible
The effect of reduction process cost, this has become numerous chemical companies and environmental protection administration urgent problem to be solved at this stage.
Summary of the invention
The purpose of the present invention is in order to solve the above problem, the present invention provides a kind of removal of organic pollutant in industrial waste salt
Method and removal device solve the prior art energy consumption is high, low efficiency, Yi Yinfa secondary pollution, the technologies such as take up a large area and ask
Topic.
According to an aspect of the present invention, a kind of minimizing technology of organic pollutant in industrial waste salt is provided, including following
Step:
Abraum salt is soluble in water, the saline sewage of extra fine quality score is made through magnetic agitation and heating ultrasound pretreatment,
Remove saline sewage surface scum；The pH value of pretreated saline sewage is adjusted to 7.0~10.0, uses fixed partial size
Microfiltration membranes carry out by-pass filtration to the saline sewage after micro-nano air bearing；Filtered saliferous is handled using electrocatalytic oxidation method
Sewage is powered using pulse direct current, and square wave output, duty ratio is set as 3:1~8:1, and pulse frequency is set as 0.01~1Hz,
The processing time is 1~3h；Electrocatalytic oxidation treated saline sewage pH value is adjusted to 11.0~13.0, then carries out micro-nano gas
Floating processing, when processing, remove surface scum in time；Then saline sewage after micro-nano air-flotation process is subjected to secondary filtration；It will
The saline sewage obtained after secondary filtration is evaporated crystallization, whenever saline sewage volume is reduced to the fixed proportion of original volume,
Then stop evaporative crystallization, the crystal salt for reaching preassigned of precipitation is recycled, the crystal salt washing of standard not up to standard carries out three-level
Filtration step, uncrystallized residue saline sewage and washing filtrate converge progress electrocatalytic oxidation processing again, are further continued for evaporating
Crystallization, until the crystal salt being precipitated entirely reaches preassigned.
Wherein, in pre-treatment step, the revolving speed of magnetic agitation is 10~500rpm, and heating temperature is 40~60 DEG C, ultrasound
The power of processing is 50~150W, and the processing time is 10~30min, mass fraction >=25.0% of saline sewage obtained.
Wherein, in electrocatalytic oxidation processing step, use titanium mesh or stainless steel plate as cathode, use Ti-base Sn-Sb
One of electrode, Ti-base Sn-Sb middle layer lead dioxide electrode, titanium-based ruthenium iridium electrode or platinum electrode are used as anode, wherein titanium-based
Tin antimony electrode is a kind of nonactive electrode that antimony pentoxide doping stannic oxide coating is coated in titanium plate；Among Ti-base Sn-Sb
Layer lead dioxide electrode is one kind using titanium plate as substrate, and antimony pentoxide doping stannic oxide coating is middle layer, brown lead oxide
For the nonactive electrode of surface-active layer；Titanium-based ruthenium iridium electrode passed through by the Titanium base after sanding and polishing acid etch containing ruthenic oxide and
It is prepared by the sol impregnation brushing of iridium dioxide；Platinum electrode is metal platinum coating electrode.
Wherein, in micro-nano air-flotation process step, it is aerated the air bubble of generation, partial size is between 50nm~10 μm, gas
Body flow velocity is 3~10m3/ h, bubble residence time in saline sewage is 2~10min.
Wherein, the micro-filtration membrane aperture of by-pass filtration is 0.45 μm, and the micro-filtration membrane aperture of secondary filtration is 0.22 μm, three-level mistake
The micro-filtration membrane aperture of filter is 0.11 μm, and every grade of processing time is 10~30min, and every grade of transmembrane pressure is 0.05~0.20MPa.
Wherein, in evaporative crystallization water-washing step, evaporating temperature is 60~100 DEG C, and saline sewage is evaporated to original volume
20~40%；When washing process, below standard crystal salt and pure water or the mass ratio of deionized water are 2:1~5:1.
According to another aspect of the present invention, the removal device that the minimizing technology uses is provided, including the pre- place being sequentially communicated
Manage subsystem, microfiltration membranes by-pass filtration subsystem, electrocatalytic oxidation processing subsystem, micro-nano air bearing subsystem, microfiltration membranes two
Grade filter subsystem and evaporative crystallization subsystem, and the washing with the crystal salt not up to standard outlet connection of evaporative crystallization subsystem
Subsystem and the microfiltration membranes three-stage filtration subsystem connected with the outlet for washing subsystem, microfiltration membranes three-stage filtration subsystem go out
The concentrated solution outlet of mouth and evaporative crystallization subsystem is connected with the entrance of electrocatalytic oxidation processing subsystem again, forms circulation；It goes
Except device further includes providing the power subsystem of electric energy for subsystems.
Wherein, removal device further includes crystal salt storage box and slag charge storage box, at slag charge storage box and electrocatalytic oxidation
The bottom slag notch for managing subsystem is connected to by control valve, and the crystal salt outlet of crystal salt storage box and washing subsystem bottom is logical
Cross control valve connection.
Wherein, preprocessing subsystem includes filling pocket, equipped with magnetic stirring apparatus and ultrasonic probe and is affixed on the pool wall that feeds intake
Heating plate, micro-filtrate membrane filtration subsystem include the filter being sequentially communicated and the filtering ponds equipped with microfiltration membranes, at electrocatalytic oxidation
Reason subsystem includes being catalyzed pond, anode plate, cathode plate and the slag charge below the anode plate and cathode plate in catalysis pond to collect
Case, micro-nano air bearing subsystem include reactive tank and reaction tank bottom setting micro-nano aeration head and be suspended from above reactive tank
Scraper plate device, evaporative crystallization subsystem includes evaporative crystallization pond, another heating plate and blender；Washing subsystem includes washing pool
With another blender.
Magnetic stirring apparatus, ultrasonic probe, heating plate, filter, anode plate, cathode plate, micro-nano aeration head, scraper plate device,
Another heating plate, blender and another blender are connect with power subsystem.
In the present invention, use titanium mesh or stainless steel plate as cathode, among Ti-base Sn-Sb electrode, Ti-base Sn-Sb
One of layer lead dioxide electrode, titanium-based ruthenium iridium electrode or platinum electrode are used as anode, and above-mentioned electrode is analysed in electrocatalytic oxidation
On the one hand oxygen liberation of hydrogen can play the role of watercourse aeration, on the other hand can increase water disturbance；It is straight using pulse in electrocatalytic oxidation
Stream power supply, square wave output, under conditions of duty ratio is 5:1, pulse frequency is 0.1Hz, more small gas can be precipitated in electrode
Bubble, further enhances air flotation effect, in combination with the strong oxidation for all kinds of active oxygen radicals that electrode generates, it is easier to beat
The transmission structure of oil emulsion, strengthens electrochemical treatments effect in broken saline sewage.
Further, gas flow rate is set as 3~10m when micro-nano air bearing3/ h, residence time of the bubble in saline sewage
It is set as 2~10min, micro-nano bubble diameter is set as being distributed between 50nm~10 μm, the micro-nano bubble ratio table generated in this way
Area is big, and capturing ability is strong, can not only give full play of micro-nano pneumatically supported effect, moreover it is possible to which greatly prolong equipment uses the longevity
Life saves energy consumption.For solution after electrocatalytic oxidation is handled, most of higher hardly degraded organic substance of molecular weight is oxidized decomposition
, can be with the mineralising that is decomposed of high degree at this time using micro-nano air-flotation process at the lesser organic matter of molecular weight, and can float
Colloidal solid in solution out.Under the operating condition that the invention provides, at electrocatalytic oxidation processing technique and micro-nano air bearing
The combination of reason technology can produce synergistic effect, double treatment effect.
Using magnetic agitation heat ultrasound pretreatment accelerate abraum salt solution rate, due to activation energy reduction and ultrasound
Cavitation can further increase substantially the solubility of abraum salt, reduce the treating capacity of salting liquid, to be conducive to raising processing
Efficiency.
The invention has the following advantages:
1. the abraum salt processing method combined using electro-catalysis processing with air-float filtration processing method, high treating effect, place
It is more to manage pollutant kind；Electrocatalysis oxidation apparatus processing capacity is strong, applied widely, electrode plate durable, with individual electricity
Catalytic oxidation technologies or the processing of micro-nano air-float filtration are compared, this purification efficiency is up to 90% or more, and individual electro-catalysis
Oxidation technology or the purification efficiency of micro-nano air-float filtration processing are only 20~30%.
2. this method raw material is cheap and easy to get, treated crystal salt recoverable, convenient for extensive in actual production
Using practical value with higher.
3. this method is low for equipment requirements, equipment is simple, easy maintenance, and operating cost is low.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 shows the minimizing technology processing flow schematic diagram of embodiment according to the present invention；
Fig. 2 shows the removal device schematic diagrames of embodiment according to the present invention.
Specific embodiment
The illustrative embodiments of the disclosure are more fully described below with reference to accompanying drawings.Although showing this public affairs in attached drawing
The illustrative embodiments opened, it being understood, however, that may be realized in various forms the disclosure without the reality that should be illustrated here
The mode of applying is limited.It is to be able to thoroughly understand the disclosure on the contrary, providing these embodiments, and can be by this public affairs
The range opened is fully disclosed to those skilled in the art.
The present invention, which provides, a kind of can effectively remove in industrial waste salt the method for organic pollutant and suitable for this method
Specific device.The basic idea of the invention is that successively using pre-treatment step, micro-filtrate membrane filtration step, electrocatalytic oxidation processing
Step, micro-nano air bearing step and evaporative crystallization water-washing step handle abraum salt, by using specific electrode and upper
It states and sets parameter appropriate in step, the effect of above-mentioned steps is effectively superimposed, the treatment process of organic matter is made to become letter
It is single, effective.
As shown in Figure 1, in a kind of industrial waste salt organic pollutant minimizing technology, comprising the following steps:
1, pretreatment: abraum salt is soluble in water, it is carried out sufficiently in the case where speed of agitator is 10~500rpm with magnetic stirring apparatus
It being mixed, carries out heating 10~30min of ultrasonic treatment at being 40~60 DEG C in heating temperature, ultrasonic power is set as 50~
150W is prepared into the salt water of mass fraction >=25.0%；Solution upper layer dross is removed with scraper plate；It is adjusted with hydrochloric acid and sodium hydroxide
Solution ph is to 7.0~10.0.
2, micro-filtrate membrane filtration: the processing of microfiltration membranes by-pass filtration is carried out to solution, pretreated solution is placed in 0.45 μm
In micro-filtrate membrane filtration device, micro-filtrate membrane filtration processing is carried out to it, to remove the particulate matter in solution.
3, electrocatalytic oxidation processing: carrying out electrocatalytic oxidation processing to the solution after by-pass filtration, big in solution to remove
The organic pollutant of amount.By micro-filtrate membrane filtration, treated that solution is placed in electrocatalysis oxidation reaction slot, is inserted into anode plate and yin
Pole plate, external D.C. regulated power supply, pulse direct current power supply, square wave output, duty ratio are set as 5:1, and pulse frequency is set as
0.1Hz is powered and carries out electrocatalytic oxidation 1~3h of processing, after electrocatalytic oxidation processing, extremely with sodium hydrate regulator solution pH value
11.0~13.0.
4, micro-nano air-flotation process micro-nano air bearing: is carried out to abraum salt liquid.Solution after electrocatalytic oxidation is placed in reaction
In slot, reaction tank bottom is laid with micro-nano air flotation device, and external D.C. regulated power supply carries out solution in reactive tank micro-nano
10~30min of air-flotation process promotes the dissolved oxygen in water body, fast implements reoxygenation.During air bearing, solution table is removed per minute
Generate dross 1~3 time of face, carries out secondary filtration processing with 0.22 μm of microfiltration membranes after micro-nano air-flotation process.
5, crystallization, crystallization salinity washing process evaporative crystallization: are evaporated to solution.After the processing of microfiltration membranes secondary filtration
Supernatant liquor be placed in crystallizing evaporator, evaporating temperature be 60~100 DEG C at be evaporated crystallization, crystallization treatment to solution
Volume is decreased to the 20~40% of original volume, and uncrystallized surplus solution, which is placed in electrocatalysis oxidation reaction slot, carries out electrocatalytic oxidation
Change reprocessing, processing step and method are same as above.Crystal salt is tested according to the physical and chemical index of Nacl, if test meets
Dry salt-the secondary standard of refining industrial salt-industry in " Nacl " (GB/T5462-2015) then recycles crystal salt.If
It tests below standard, then processing is rinsed to crystal salt with pure water or deionized water, crystal salt and pure water or go when washing process
The mass ratio of ionized water is 2:1~5:1.Three-stage filtration processing is carried out with 0.11 μm of microfiltration membranes to the crystal salt after washing process,
Washing filtrate is placed in progress electrocatalytic oxidation reprocessing in electrocatalysis oxidation reaction slot, and processing step and method are same as above；To filtering
Treated, and crystal salt is tested again, until reuse after the crystal salt test of reprocessing is up to standard.
The method for generation of micro-nano bubble specifically: compressed air or oxygen are injected into pump, mixed in the nozzle of pump
The stable bubble of indoor formation carries out two-phase flow；At jet expansion in the form of comprising a large amount of micro-bubble brins or liquidus
It sprays.Since bubble sprays liquid in the form of comprising a large amount of micro-bubble brins or liquidus the extrusion shearing effect of liquid
Out；In the minimum distance for leaving spout, due to the acute variation of bubble external and internal pressure, promote bubble sharply swelling fracture, together
When by surrounding liquid sheet breakup, subtle particle swarm is formed, to be further formed micro-nano bubble.It is aerated the air generated
Bubble, for partial size between 50nm~10 μm, gas flow rate is 3~10m3/ h, bubble in saline sewage residence time be 2~
10min。
The processing time of three kinds of grade filterings is set as 10~30min, and transmembrane pressure is set as 0.05~
0.20MPa.Use titanium mesh or stainless steel plate as cathode, uses Ti-base Sn-Sb electrode, Ti-base Sn-Sb middle layer titanium dioxide
One of lead electrode, titanium-based ruthenium iridium electrode or platinum electrode are used as anode, and wherein Ti-base Sn-Sb electrode is that one kind applies in titanium plate
Cover the nonactive electrode of antimony pentoxide doping stannic oxide coating；Ti-base Sn-Sb middle layer lead dioxide electrode is one kind with titanium
Plate is substrate, and antimony pentoxide doping stannic oxide coating is middle layer, and brown lead oxide is the nonactive electrode of surface-active layer；
Titanium-based ruthenium iridium electrode passes through the sol impregnation brushing system containing ruthenic oxide and iridium dioxide by the Titanium base after sanding and polishing acid etch
It is standby；Platinum electrode is metal platinum coating electrode.
To cooperate the minimizing technology, the present invention also provides a kind of removal devices suitable for the minimizing technology.Such as Fig. 2 institute
Show, which includes the preprocessing subsystem 1 being sequentially communicated, microfiltration membranes by-pass filtration subsystem 2, electrocatalytic oxidation processing
Subsystem 3, micro-nano air bearing subsystem 4, microfiltration membranes secondary filtration subsystem 6, evaporative crystallization subsystem 5, and tied with evaporation
The washing subsystem 7 and the microfiltration membranes connected with the outlet for washing subsystem 7 that the crystal salt not up to standard outlet of matted crystal system 5 is connected
The concentrated solution outlet of three-stage filtration subsystem 8, the outlet of microfiltration membranes three-stage filtration subsystem 8 and evaporative crystallization subsystem 5 again with
The entrance of electrocatalytic oxidation processing subsystem 3 is connected, and circulation is formed；Removal device further includes providing electric energy for subsystems
Power subsystem.
Preprocessing subsystem 1 includes filling pocket 11, equipped with magnetic stirring apparatus 12 and ultrasonic probe 13 and is affixed on the pool wall that feeds intake
Heating plate 14, micro-filtrate membrane filtration subsystem includes the filter 100 being sequentially communicated and the filtering ponds 200 equipped with microfiltration membranes, electricity
Catalytic oxidation treatment subsystem 3 include catalysis pond and positioned at catalysis pond inside anode plate, cathode plate and be located at catalysis pond in
Anode plate and cathode plate below slag charge collecting box, micro-nano air bearing subsystem 4 includes reactive tank and setting in reaction tank bottom
The micro-nano aeration head 41 set and the scraper plate device 42 being suspended from above reactive tank, evaporative crystallization subsystem 5 include evaporative crystallization pond 51,
Another heating plate 52 and blender；Washing subsystem 7 includes washing pool 71 and another blender.
Magnetic stirring apparatus 12, ultrasonic probe 13, heating plate 14, filter 100, anode plate, cathode plate, micro-nano aeration head
41, scraper plate device 42, another heating plate 52, blender and another blender are connect with power subsystem.
Removal device further includes crystal salt storage box 10 and slag charge storage box 11, at slag charge storage box 11 and electrocatalytic oxidation
The bottom slag notch for managing subsystem 3 is connected to by control valve, and crystal salt storage box 10 and the crystal salt of washing 7 bottom of subsystem go out
Mouth passes through control valve and is connected to.The number of anode plate and cathode plate is three groups, and anode plate and cathode plate are along electrocatalytic oxidation processing
The height of subsystem 4 is arranged, and the distance between every group of anode plate and cathode plate are 10~30mm.When the knot for entering washing subsystem
It when brilliant salt passes through test, opens crystal salt and exports corresponding control valve, realize that crystal salt up to standard is returned using crystal salt storage box
It receives.11 not timing of slag charge storage box is opened, for collecting the organic pollutant left when electrocatalytic oxidation processing.
Pipeline between interconnected two subsystems is equipped with control valve and pressure pump, needs to connect internal system
When logical, opening controlling valve door and pressure pump realize conversion of the processed material in system using pressure difference.
The minimizing technology of organic pollutant in industrial waste salt of the invention will be done by way of specific embodiment below
It further illustrates.
A kind of minimizing technology X1 of the industrial waste salt of embodiment 1
Industrial waste salt to be processed is 1 ton.Abraum salt is soluble in water, speed of agitator 300rpm；Heating temperature is maintained at
50℃；Ultrasonic time is 15min, ultrasonic power 100W, the salt water that mass fraction is 25.0% is prepared into, with hydrochloric acid and hydrogen-oxygen
Change sodium and adjusts solution ph to 8.0.Micro-filtrate membrane filtration processing is carried out to solution later, is used in the case where transmembrane pressure is 0.10MPa
0.45 μm of micro-filtrate membrane filtration 10min.
Then electrocatalytic oxidation processing is carried out to solution, electrocatalytic oxidation treatment process middle-jiao yang, function of the spleen and stomach pole plate selects Ti/SnO2-
Sb2O5(Ti-base Sn-Sb) electrode, cathode plate are selected sanding and polishing treated titanium mesh, are powered using pulse direct current, square wave is defeated
Out, duty ratio 5:1, pulse frequency 0.1Hz, electrolysis time 0.5h, current density 15mA/cm2, pole plate spacing is
30mm, solution ph is adjusted to 11.0 after electrocatalytic oxidation processing.Then micro-nano air-flotation process is carried out to solution.Micro-nano air bearing
10min, gas flow rate 5m3/ h removes solution upper layer dross with scraper plate.Then solution is carried out at microfiltration membranes secondary filtration
Reason, in the case where transmembrane pressure is 0.15MPa with 0.22 μm of microfiltration membranes secondary filtration 10min.
Then crystallization, crystallization salinity washing process are evaporated to solution.Supernatant liquor heats steaming in crystallizing evaporator
Hair crystallization, evaporating temperature are 80 DEG C, and crystallization treatment degree is selected as liquor capacity and is decreased to 15%, are tested crystal salt,
Washing process and secondary washing process carried out to below standard crystal salt with pure water, crystal salt and pure water when washing process
Mass ratio is 3:1, carries out the processing of microfiltration membranes three-stage filtration to the crystal salt after washing process, in the case where transmembrane pressure is 0.15MPa
With 0.22 μm of microfiltration membranes three-stage filtration 10min.The secondary place of electrocatalytic oxidation is carried out to uncrystallized surplus solution and washing filtrate
It manages and handles three times.
Analysis test:
Process flow is numbered, the organic pollutant content under the corresponding process of each number is monitored.Dirty salt is molten
As shown in table 1, the important indicator variation of abraum salt is as shown in table 2 for the important water quality indicator variation of liquid.
Table 1: processing data of the dirty salting liquid under corresponding process
| 2. pre-processing | 3. electro-catalysis is handled | 4. air-float filtration | 6. secondary electro-catalysis processing | 8. electro-catalysis is handled three times | |
| TOC(mg/L) | 1190 | 900 | 722 | 213 | 8 |
| Total nitrogen (mg/L) | 710 | 210 | 190 | 70 | 5 |
| Ammonia nitrogen (mg/L) | 590 | 95 | 80 | 10 | 2 |
Table 2: industrial waste salt data before and after the processing
| 1. as former state | 5. a batch crystallization | 7. two batches of crystallizations | 9. three batches of crystallizations | |
| TOC(mg/kg) | 3600 | 60.12 | 11.50 | 1.02 |
| NaCl (%) | 90.52 | 98.21 | 98.89 | 99.31 |
| Total nitrogen (mg/kg) | 2200 | 15.2 | 2.1 | 0.6 |
| Ammonia nitrogen (mg/kg) | 1800 | 3.6 | 0.7 | 0.3 |
A kind of minimizing technology X2 of the industrial waste salt of embodiment 2
Embodiment 2 is the variation of embodiment 1, and difference is, in the case where transmembrane pressure is 0.15MPa with 0.22 μm of microfiltration membranes
15min is filtered, electrocatalytic oxidation treatment process middle-jiao yang, function of the spleen and stomach pole plate selects Ti/SnO2-Sb2O5/PbO2(Ti-base Sn-Sb middle layer dioxy
Change lead) electrode, electrolysis time 3h, current density 20mA/cm2, pole plate spacing is 20mm, solution after electrocatalytic oxidation processing
PH value is adjusted to 10.5, micro-nano air bearing 30min, gas flow rate 10m3/ h, it is micro- with 0.11 μm in the case where transmembrane pressure is 0.20MPa
Filter membrane secondary filtration 15min carries out a washing process to below standard crystal salt with pure water, is 0.20MPa in transmembrane pressure
It is secondary to carry out electrocatalytic oxidation to uncrystallized surplus solution and washing filtrate by lower 0.11 μm of microfiltration membranes three-stage filtration 15min
Processing, the mass ratio of crystal salt and pure water is 2:1 when washing process.
Analysis test:
Through detecting, after the TOC value in abraum salt preprocessing solution is reduced to electrocatalytic oxidation secondary treatment by 1190mg/L
6mg/L；Total nitrogen content is reduced to 4mg/L by 710mg/L；Ammonia-nitrogen content is reduced to 2mg/L by 590mg/L.
TOC value in abraum salt original sample is reduced to the 1.01mg/kg after a washing process by 3600mg/kg；Sodium chloride contains
Amount is improved by 90.52% to 99.41%；Total nitrogen content is reduced to 0.5mg/kg by 2200mg/kg；Ammonia-nitrogen content is by 1800mg/
Kg is reduced to 0.2mg/kg.
A kind of minimizing technology X3 of the industrial waste salt of embodiment 3
Abraum salt is soluble in water, and speed of agitator 10rpm, heating temperature is maintained at 40 DEG C, ultrasonic time 30min, surpasses
Acoustical power is 50W, is prepared into the salt water that mass fraction is 25.0%, solution upper layer dross is removed with scraper plate, with hydrochloric acid and hydrogen-oxygen
Change sodium and adjusts solution ph to 7.0；Micro-filtrate membrane filtration processing is carried out to solution, in the case where transmembrane pressure is 0.05MPa with 0.45 μm
Micro-filtrate membrane filtration 10min.Electrocatalytic oxidation processing is carried out to solution, electrocatalytic oxidation treatment process middle-jiao yang, function of the spleen and stomach pole plate selects Ti/
RuO2-IrO2(titanium-based ruthenium iridium) electrode, cathode plate are selected sanding and polishing treated titanium mesh, are powered using pulse direct current, side
Wave output, duty ratio 8:1, pulse frequency 1Hz, electrolysis time 3h, current density 30mA/cm2, pole plate spacing is
20mm, solution ph is adjusted to 13.0 after electrocatalytic oxidation processing；It will treated the micro-nano air bearing 20min of salt water, gas flow rate
For 10m3/ h, bubble residence time in saline sewage are 2min, and bubble diameter is 50nm or so；Microfiltration membranes two are carried out to solution
Grade filtration treatment, in the case where transmembrane pressure is 0.05MPa with 0.22 μm of microfiltration membranes secondary filtration 10min.
Crystallization, crystallization salinity washing process are evaporated to solution.Supernatant liquor after electro-catalysis is in crystallizing evaporator
Heating evaporation crystallization, evaporating temperature are 100 DEG C, and crystallization treatment degree is selected as liquor capacity and is decreased to 20%.To crystal salt into
Row test, carries out a washing process and secondary washing process to below standard crystal salt with pure water, to the knot after washing process
Brilliant salt carries out the processing of microfiltration membranes three-stage filtration, in the case where transmembrane pressure is 0.05MPa with 0.11 μm of microfiltration membranes three-stage filtration 10min.
Electrocatalytic oxidation secondary treatment is carried out to uncrystallized surplus solution and washing filtrate and is three times handled, crystal salt when washing process
Mass ratio with pure water is 5:1.
Analysis test:
Through detecting, TOC value in abraum salt preprocessing solution by 1190mg/L is reduced to electrocatalytic oxidation, and treated three times
5mg/L；Total nitrogen content is reduced to 7mg/L by 710mg/L；Ammonia-nitrogen content is reduced to 3mg/L by 590mg/L.
TOC value in abraum salt original sample is reduced to secondary washing treated 1.12mg/kg by 3600mg/kg；NaCl content
It is improved by 90.52% to 99.42%；Total nitrogen content is reduced to 0.6mg/kg by 2200mg/kg；Ammonia-nitrogen content is by 1800mg/kg
It is reduced to 0.3mg/kg.
A kind of minimizing technology X4 of the industrial waste salt of embodiment 4
Abraum salt is soluble in water, and speed of agitator 500rpm, heating temperature is maintained at 60 DEG C, ultrasonic time 10min, surpasses
Acoustical power is 150W, is prepared into the salt water that mass fraction is 60.0%, solution upper layer dross is removed with scraper plate, with hydrochloric acid and hydrogen-oxygen
Change sodium and adjusts solution ph to 10.0；Micro-filtrate membrane filtration processing is carried out to solution, in the case where transmembrane pressure is 0.20MPa with 0.45 μm
Micro-filtrate membrane filtration 30min；Electrocatalytic oxidation processing is carried out to solution, electrocatalytic oxidation treatment process middle-jiao yang, function of the spleen and stomach pole plate selects platinum electricity
Pole, cathode plate are selected sanding and polishing treated titanium mesh, are powered using pulse direct current, square wave output, duty ratio 3:1,
Pulse frequency is 0.1Hz, electrolysis time 1h, current density 10mA/cm2, pole plate spacing is 10mm, electrocatalytic oxidation processing
Solution ph is adjusted to 11.0 afterwards；By the micro-nano air bearing 30min of residual brine, gas flow rate 3m3/ h, bubble is in saline sewage
Residence time is 10min, and bubble diameter is 10 μm or so；The processing of microfiltration membranes secondary filter is carried out to solution, is in transmembrane pressure
With 0.22 μm of microfiltration membranes secondary filter 10min under 0.20MPa.
Crystallization, crystallization salinity washing process are evaporated to solution.Supernatant liquor after electro-catalysis is in crystallizing evaporator
Heating evaporation crystallization, evaporating temperature are 60 DEG C, and crystallization treatment degree is selected as liquor capacity and is decreased to 15%.Crystal salt is carried out
Test, carries out a washing process and secondary washing process to below standard crystal salt with pure water, to the crystallization after washing process
Salt carries out the processing of microfiltration membranes three-stage filtration, in the case where transmembrane pressure is 0.20MPa with 0.11 μm of microfiltration membranes three-stage filtration 10min.It is right
Uncrystallized surplus solution and washing filtrate electrocatalytic oxidation secondary treatment and handle three times, when washing process crystal salt with
The mass ratio of pure water is 2:1.
Analysis test:
Through detecting, TOC value in abraum salt preprocessing solution by 1190mg/L is reduced to electrocatalytic oxidation, and treated three times
7mg/L；Total nitrogen content is reduced to 7mg/L by 710mg/L；Ammonia-nitrogen content is reduced to 2mg/L by 590mg/L.
TOC value in abraum salt original sample is reduced to secondary washing treated 1.03mg/kg by 3600mg/kg；NaCl content
It is improved by 90.52% to 99.40%；Total nitrogen content is reduced to 0.7mg/kg by 2200mg/kg；Ammonia-nitrogen content is by 1800mg/kg
It is reduced to 0.3mg/kg.
Comparative example
It takes and is handled with embodiment 1 with 1 ton of industrial waste salt of batch.Without pretreatment and electrocatalytic oxidation processing step
Suddenly, abraum salt is directly configured to the saline sewage that mass fraction is 25.0%, then carries out micro-nano air bearing step and evaporation knot
Crystalline substance processing.Other treatment conditions are consistent with embodiment 1.
Analysis detection:
Through detecting, after the TOC value in abraum salt preprocessing solution is reduced to micro-nano air bearing single treatment by 1190mg/L
1095mg/L；825mg/L after micro-nano air bearing secondary treatment, micro-nano air bearing treated three times 621mg/L；Total nitrogen content
The 557mg/L of micro-nano air bearing single treatment is reduced to by 710mg/L；389mg/L after micro-nano air bearing secondary treatment, micro-nano
The 196mg/L that rice air bearing is handled three times；The 460mg/L that ammonia-nitrogen content is reduced to micro-nano air bearing primary by 590mg/L, it is micro-nano
Air bearing secondary treatment 343mg/L, the 211mg/L that micro-nano air bearing is handled three times.
TOC value in abraum salt original sample is reduced to the 2102mg/kg after a collection of crystallization treatment, two batches of crystallizations by 3600mg/kg
The 1041mg/kg of processing, the 469mg/k of three batch processings；Sodium chloride content is improved extremely after a collection of crystallization treatment by 90.52%
92.12%, it improves after improving after two batches of crystallization treatments to 92.97%, three batch of crystallization treatment to 93.25%；Total nitrogen content by
2200mg/kg is reduced to 1522mg/kg after a collection of crystallization treatment, 967mg/kg after two batches of crystallization treatments, after three batches of crystallization treatments
501mg/kg；Ammonia-nitrogen content is reduced to 1321mg/kg after a collection of crystallization treatment by 1800mg/kg, after two batches of crystallization treatments
814mg/kg, 376mg/kg after three batches of crystallization treatments.
It is compared by the processing result of comparative example and embodiment 1 it is found that individually micro-nano air bearing and electrocatalytic oxidation are anti-
The treatment effect for coping with waste water and TOC in abraum salt, total nitrogen and ammonia nitrogen is relatively weak, and the recovery efficiency of pairing target abraum salt
It is lower, but work as above-mentioned two step and be overlapped mutually along with pre-treatment step (i.e. the processing method of embodiment 1), can but it make
Treatment effect and treatment effeciency double, this two step of explanation produces synergistic effect in the treatment process to organic matter.
To sum up, the method for removing organic pollutant in industrial waste salt of the invention, is used in combination preconditioning technique, microfiltration membranes
Filtering, electrocatalytic oxidation, micro-nano air bearing, evaporative crystallization technique greatly improve the removal effect of organic pollutant in abraum salt
Rate effectively removes the impurity in industrial waste salt, and can sufficiently recycle salinity, and processing cost is greatly lowered.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of the claim
Subject to enclosing.
Claims (9)
1. the minimizing technology of organic pollutant in industrial waste salt, which comprises the following steps:
Abraum salt is soluble in water, the saline sewage of extra fine quality score is made through magnetic agitation and heating ultrasound pretreatment, removes
Saline sewage surface scum；
The pH value of pretreated saline sewage is adjusted to 7.0~10.0, using microfiltration membranes to saliferous with hydrochloric acid and sodium hydroxide
Sewage carries out by-pass filtration；
Filtered saline sewage, pulse direct current power supply, square wave output, duty ratio 3:1~8:1, arteries and veins are handled using electrocatalytic method
Rushing frequency is 0.01~1Hz, 2~30mA/cm of current density2；
Electro-catalysis treated saline sewage pH value is adjusted to 11.0~13.0 with sodium hydroxide, then is carried out at micro-nano air bearing
Reason, when processing, remove surface scum in time；
Then saline sewage after micro-nano air-flotation process is subjected to secondary filtration；
The saline sewage obtained after secondary filtration is successively evaporated crystallization washing process, three are carried out to the crystal salt after washing
Grade filtering, remaining saline sewage and washing filtrate converge progress electrocatalytic oxidation processing again, are further continued for evaporative crystallization, until analysis
Crystal salt out entirely reaches preassigned.
2. minimizing technology as described in claim 1, which is characterized in that wherein the revolving speed of the magnetic agitation be 10~
500rpm, heating temperature are 40~60 DEG C, and the power of ultrasonic treatment is 50~150W, and the processing time is 10~30min, obtained
Mass fraction >=25.0% of saline sewage.
3. minimizing technology as described in claim 1, which is characterized in that wherein in the electro-catalysis processing step, use titanium
Metal plate or stainless steel plate use Ti-base Sn-Sb electrode, Ti-base Sn-Sb middle layer lead dioxide electrode, titanium-based ruthenium iridium as cathode
One of electrode or platinum electrode are used as anode, and wherein Ti-base Sn-Sb electrode is that one kind coats antimony pentoxide doping in titanium plate
The nonactive electrode of tin dioxide coatings；Ti-base Sn-Sb middle layer lead dioxide electrode is one kind using titanium plate as substrate, five oxidations
Two stibium doping stannic oxide coatings are middle layer, and brown lead oxide is the nonactive electrode of surface-active layer；Titanium-based ruthenium iridium electrode by
Titanium base after sanding and polishing acid etch is through the sol impregnation brushing preparation containing ruthenic oxide and iridium dioxide；Platinum electrode is metal
Platinum coating electrode.
4. minimizing technology as described in claim 1, which is characterized in that
In air-flotation process step, it is aerated the air bubble of generation, for partial size between 50nm~10 μm, gas flow rate is 3~10m3/
H, bubble residence time in saline sewage is 2~10min.
5. minimizing technology as described in claim 1, which is characterized in that
The micro-filtration membrane aperture of by-pass filtration is 0.45 μm, and the micro-filtration membrane aperture of secondary filtration is 0.22 μm, the micro-filtration of three-stage filtration
Membrane aperture is 0.11 μm, and every grade of processing time is 10~30min, and every grade of transmembrane pressure is 0.05~0.20MPa.
6. minimizing technology as described in claim 1, which is characterized in that
In evaporative crystallization water-washing step, evaporating temperature is 60~100 DEG C, and saline sewage is evaporated to the 20~40% of original volume；
When washing process, below standard crystal salt and pure water or the mass ratio of deionized water are 2:1~5:1.
7. the removal device that the minimizing technology as described in claim 1~6 is any uses, which is characterized in that including being sequentially communicated
Preprocessing subsystem (1), microfiltration membranes by-pass filtration subsystem (2), electrocatalytic oxidation processing subsystem (3), micro-nano air bearing
Subsystem (4), microfiltration membranes secondary filtration subsystem (6) and evaporative crystallization subsystem (5), and with the evaporative crystallization subsystem
(5) the washing subsystem (7) that crystal salt not up to standard outlet is connected and the micro-filtration with the outlet connection of washing subsystem (7)
Film three-stage filtration subsystem (8), the filtrate (liquid and the evaporative crystallization subsystem of the microfiltration membranes three-stage filtration subsystem (8)
(5) concentrated solution outlet is connected with the entrance of the electrocatalytic oxidation processing subsystem (3) again, forms circulation；The removal dress
Set further includes that the power subsystem of electric energy is provided for subsystems.
8. removal device as claimed in claim 7, which is characterized in that
The removal device further includes crystal salt storage box (10) and slag charge storage box (11), the slag charge storage box (11) and institute
The bottom slag notch for stating electrocatalytic oxidation processing subsystem (3) is connected to by control valve, the crystal salt storage box (10) and institute
The crystal salt outlet for stating washing subsystem (7) bottom is connected to by control valve.
9. removal device as claimed in claim 7, which is characterized in that
The preprocessing subsystem (1) includes filling pocket (11), is equipped with magnetic stirring apparatus (12) and ultrasonic probe (13) and is affixed on
Feed intake the heating plate (14) of pool wall, and the micro-filtrate membrane filtration subsystem includes the filter (100) being sequentially communicated and is equipped with micro-filtration
The filtering ponds (200) of film, the electrocatalytic oxidation processing subsystem (3) include catalysis pond, anode plate, cathode plate and are located at catalysis
The slag charge collecting box below the anode plate and cathode plate in pond, the micro-nano air bearing subsystem (4) include reactive tank and
Micro-nano aeration head (41) in reaction tank bottom setting and the scraper plate device (42) that is suspended from above reactive tank, the evaporative crystallization are sub
System (5) includes evaporative crystallization pond (51), another heating plate (52) and blender；The washing subsystem (7) includes washing pool
(71) and another blender；
The magnetic stirring apparatus (12), the ultrasonic probe (13), the heating plate (14), the filter (100), the sun
Pole plate, the micro-nano aeration head (41), the scraper plate device (42), another heating plate (52), described stirs the cathode plate
It mixes device and another blender is connect with the power subsystem.
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| CN109956483A (en) * | 2019-04-12 | 2019-07-02 | 河海大学 | A kind of innoxious and method of resource of chemical industry abraum salt |
| CN110054203A (en) * | 2019-04-12 | 2019-07-26 | 河海大学 | A kind of method of resource of industrial waste salt |
| CN110328218A (en) * | 2019-07-30 | 2019-10-15 | 湖南中森环境科技有限公司 | A kind of resource utilization method of organic pollution salt slag |
| CN110548750A (en) * | 2019-09-05 | 2019-12-10 | 上海晶宇环境工程股份有限公司 | Waste salt recycling treatment process and special equipment thereof |
| CN112830614A (en) * | 2021-04-07 | 2021-05-25 | 上海电气集团股份有限公司 | Method and device for treating industrial waste salt |
| CN114522443A (en) * | 2022-04-22 | 2022-05-24 | 徐州宏武纳米科技有限公司 | Ultrasonic oscillation type nanocrystal extraction and separation device |
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