CN108285233A - A kind of method of Recovery Purifying titanium white waste liquid - Google Patents
A kind of method of Recovery Purifying titanium white waste liquid Download PDFInfo
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- CN108285233A CN108285233A CN201710012546.2A CN201710012546A CN108285233A CN 108285233 A CN108285233 A CN 108285233A CN 201710012546 A CN201710012546 A CN 201710012546A CN 108285233 A CN108285233 A CN 108285233A
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- waste liquid
- lignite
- titanium white
- particle
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- 239000007788 liquid Substances 0.000 title claims abstract description 81
- 239000002699 waste material Substances 0.000 title claims abstract description 77
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 50
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 50
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 239000003077 lignite Substances 0.000 claims abstract description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 238000001728 nano-filtration Methods 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 52
- 239000012466 permeate Substances 0.000 claims description 27
- 239000012141 concentrate Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- -1 iron ion Chemical class 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009300 dissolved air flotation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
- C01B17/902—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by dialysis
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Water Treatments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of method of Recovery Purifying titanium white waste liquid, titanium white waste liquid passes sequentially through regulating reservoir, coarse rack, ultraviolet activation lignite absorption gas floatation separation device, level-one nanofiltration membrane system, two level nanofiltration membrane system and obtains the dilute sulfuric acid that can be recycled.This method has broken away from the treatment technology thinking of existing titanium white waste liquid, the metal ion in the creative nanofiltration membrane titanium white waste liquid using two-stage, the method for generating clean dilute sulfuric acid.This can substantially reduce treatment cost of waste liquor, reduce environmental protection pressure.
Description
Technical field
The present invention relates to a kind of methods of Recovery Purifying titanium white waste liquid, belong to the field of waste water treatment in environmental protection.
Background technology
Titanium dioxide is a kind of most widely used, the maximum inorganic white pigment of dosage as important one of industrial chemicals,
Yield accounts for the 80% of world's white pigment total output, is widely used in the fields such as pigment, coating, ceramics, aviation.China possesses rich
Rich titanium ore resource, such as super-huge mineral reserve that PZH vanadic-titanomagnetite is world-famous.The production method of titanium dioxide has at present
Sulfuric acid process, chloridising and hydrochloric acid method, China mainly use sulfuric acid process.In sulfate process titanium dioxide production, sulfuric acid is as intermediate
Medium, it is only involved in reaction without entering final products.Therefore it will be generated in sulfuric acid method titanium pigment production process a large amount of acid
Waste liquid, discharge are mainly derived from the processes such as acidolysis purification, concentration, hydrolysis, washing.Often production 1t titanium dioxides will generate sulfuric acid concentration
For 20% waste liquid 8t or so, sulfuric acid concentration is 2% waste liquid 80t or so, wherein mainly contain free sulfuric acid, ferrous sulfate,
The sulfate and titanium dioxide particle and other insoluble suspended matters of metatitanic acid and other metal ions.It produces in process of production
Raw a large amount of acid waste liquids, if without processing direct emission, it will corrosion sewer causes water pollution, soil acidification to deteriorate
Ecological environment seriously endangers the life of resident nearby and the production of industrial or agricultural and development, and causes the serious waste of resource.
In currently available technology there are two types of the processing methods of processing recycling titanium white waste liquid：Absorption method and neutralisation.
(1) absorption method
The purpose of absorption method is recycling free acid therein, including evaporation concentration method, membrane separation process and extraction.
It is sufficiently expensive that waste acid concentration equipment used in the spent acid that is discharged in titanium white production is administered using concentration method, energy consumption and
Operating cost is also very high, and the cost of concentrated vitriol is expensive more than purchase sulfuric acid, it is difficult to be received by medium and small titanium white production enterprise.
Waste acid concentration will be hydrolyzed using traditional thin film evaporation unit, then produce general calcium fertilizer, but there are product marketings
It is wideless, and sulfate is precipitated in concentration process, the problems such as technique is unsmooth, processing capacity is low, limit the popularization of this method.
Extraction is a kind of very effective hydrochlorate separation method, it has balancing speed fast, good separating effect, handles energy
Power is big, and acid recovering rate is high, and product design, purity are high and are easily achieved the advantages that automatically controlling, and are a kind of great development prospects
Spent acid processing method.But the cost of the method recovery acid is too high.
(2) neutralisation：
Neutralisation includes mainly milk of lime neutralization, alkaline waste water neutralization, blending method etc..
In lime and general processing method is lime or carbide slag neutralization precipitation to be added, therefore will produce a large amount of barren rock
Cream.The method of this neutralization precipitation does not simply fail to recycling sulfuric acid resource, and causes prodigious environmental protection pressure.
Using the alkaline waste water neutralisation treatment generated in other Chemical Manufactures so that two kinds of wastes can qualified discharge, can
Reduce simple treatment cost.Such as using in titanium white waste acid and black liquid and flocculating setting processing is carried out, each can be made discarded
Pollutant is all comprehensively utilized, and two kinds of waste liquids is made to become comprehensive improvement from input improvement.In the treatment of wastes with processes of wastes against one another and to reach
The comprehensive treatment of waste liquid is a kind of ideal secondary useless administration way, but by objective condition such as factory condition, plant area's ambient enviroments
It restricts.
Blending is neutralized with olivine, product SiO2Solid and MgSO4Solution.Solid SiO2Can store up safely or
It is further processed, the MgSO after precipitation removes heavy metal ion4Solution can discharge, and will not be polluted to environment.This method
Generally invest bigger, FeSO in spent acid4、TiO2Equal impurity need to be separated off according to production technology.
How efficient process these titanium white waste liquids, economically recycle valuable constituent therein, it has also become sulfuric acid process is given birth to
Produce an important technology problem of titanium white, and the significant problem of puzzlement environmental protection and titanium dioxide industry development.
Invention content
To solve the deficiencies in the prior art, the present invention provides one kind, especially a kind of to use two-stage NF membrane mistake
Filter the metal ion in titanium white waste liquid, the method for generating clean dilute sulfuric acid.
The concrete scheme of the present invention is as follows：Titanium white waste liquid enters regulating reservoir by pipeline, is collected and stablizes tune herein
After section, coarse rack is entered by the outlet of regulating reservoir, the major diameter solid matter in waste liquid is removed at this, then passes through coarse rack
Outlet enter ultraviolet activation-lignite absorption gas floatation separation device, waste liquid removes remaining titanium dioxide particle and other herein
After insoluble suspended matter, the outlet that gas floatation separation device is adsorbed by ultraviolet activation-lignite enters level-one nanofiltration membrane system, and one
Waste liquid is separated into 1 grade of concentrate and 1 grade of permeate by grade nanofiltration membrane system, and 1 grade of permeate is pumped into two level nanofiltration membrane system again, after
Continuous to be separated into 2 grades of concentrates and 2 grades of permeate, 2 grades of permeate are that clean dilute sulfuric acid is discharged into sulfuric acid collecting pit, recycling profit
With.
Wherein, blocky lignite raw material adsorbs the purified treatment material of gas floatation separation device as ultraviolet activation-lignite, leads to
The lignite feed hopper crossed at the top of device enters the present apparatus, and is broken for thin lignite by spherical grinder grinding below
Grain, the thin lignite particle after grinding break process are delivered to bottom of device, while titanium white through thin lignite particle conveyance conduit
By entering bottom of device positioned at the inlet valve of present apparatus left lower, thin lignite particle is sufficiently mixed waste liquid with waste liquid, and
It being uniformly distributed in inside whole device, the underwater ultraviolet generater of 8 be now placed on device left side wall and right side wall starts,
To the thin lignite particle emission ultraviolet radiation being evenly distributed in waste liquid, it is irradiated with the lignite particle of activation
Remaining titanium dioxide particle and the other insoluble suspended matters in waste liquid can be fully adsorbed, be now placed in bottom of device 6 are super
Thin bubble aeration head starts to be aerated into waste liquid, makes to generate a large amount of ultra-fine bubbles in waste liquid, thin lignite particle is in ultra-fine bubble
Air supporting acts on float downward, is gradually converged at waste liquid liquid level, ultimately forms thin lignite particles float residue, be now placed on device
1 electronic pusher of the side on the left of water surface site is started to work, and the thin lignite particles float residue near the water surface is pushed
Lignite particle to right side arranges mouth and is discharged the present apparatus, while treated that waste liquid passes through device lower right side by adsorption cleaning
Water discharging valve be discharged the present apparatus, and enter level-one nanofiltration membrane system.
Wherein, in order to improve the rate of recovery of sulfuric acid, the entrance that 2 grades of concentrates are returned to level-one nanofiltration membrane system carries out again
It is separated by filtration.
Wherein, in the dilute sulfuric acid obtained, iron concentration is less than 150mg/L, and calcium ion is less than 10mg/L, and magnesium ion is less than
10mg/L。
Wherein, level-one nanofiltration membrane system, two level nanofiltration membrane system include high pressure putamina, nanofiltration membrane component, and membrane module will be molten
Liquid is divided into concentrate and permeate, and nanofiltration membrane component is pressure-driven rolled membrane module, operating pressure be 300PSI~
1200PSI。
Wherein, the dischargeable capacity of ultraviolet activation-lignite absorption gas floatation separation device is 355m3, lignite feed hopper
Dischargeable capacity is 75m3, the operating voltage of spherical grinder is 380V, rated power 3.6kW.
Wherein, the operating voltage of the ultra-fine bubble aeration head of ultraviolet activation-lignite absorption gas floatation separation device is 40V,
Gas flow is 2.5m3/ h, aeration resistance 165mmHg can generate the bubble of a diameter of 0.6mm.
Wherein, the operating voltage of the underwater ultraviolet generater of ultraviolet activation-lignite absorption gas floatation separation device is
220V, can generation wavelength be 310nm ultraviolet radiation, service life is up to 5000h.
By this system treated waste liquid, the removal efficiency of remaining titanium dioxide particle is up to 99.4%.
The advantage of the invention is that：
(1) this method has broken away from the treatment technology thinking of existing titanium white waste liquid, creative utilization two-stage NF membrane mistake
Filter the metal ion in titanium white waste liquid, the method for generating clean dilute sulfuric acid.This can substantially reduce treatment cost of waste liquor, reduce ring
Packing pressure.In obtained dilute sulfuric acid, iron concentration is less than 150mg/L, and calcium ion is less than 10mg/L, and magnesium ion is less than 10mg/
L。
(2) adsorption capacity of the lower lignite of calorific value to small size particle substance is utilized, lignite particle is given up with titanium white
Liquid is sufficiently mixed, and under ultraviolet irradiation activation, the remaining titanium dioxide that lignite particle can be adsorbed fully in waste liquid is micro-
Grain and other insoluble suspended matters, then pneumatically supported means are aerated by the bottom, make to be adsorbed with the thin brown of remaining titanium dioxide particle
Coal particle can be such that it is separated from the water, to reach remaining titanium in removal waste liquid floating to the water surface by means such as machinery push
The purpose of white powder particle ensure that the normally and efficiently progress of subsequent nano-filtration separation.
(3) the generated lignite particle for being adsorbed with remaining titanium dioxide particle in this method decontamination process,
Only it need to pass through easy-to-use drying and processing, you can be applied to the industries such as heat supply, thermal power generation.
(4) this method uses pure physical means, by ultraviolet activation and lignite suction-operated come in waste liquid
Remaining titanium dioxide particle and other insoluble suspended matters carry out purified treatment, without using any chemical substance, to eliminate
The risk for introducing the chemical substance for endangering bigger, fundamentally avoids secondary pollution.
(5) this method design principle is advanced, and occupation area of equipment is small, and construction cost is relatively low, and treatment effect is preferable, fortune
Row maintenance cost is very low, is conducive to promote and apply on a large scale.
Description of the drawings
Fig. 1 is the equipment schematic diagram of the present invention.
In figure：1- regulating reservoirs, 2- coarse racks, 5- ultraviolet activations-lignite absorption gas floatation separation device, 6- level-one NF membranes
System, 7- two levels nanofiltration membrane system, 8- sulfuric acid collecting pits
Fig. 2 is the schematic diagram of ultraviolet activation-lignite absorption gas floatation separation device.
The ultra-fine bubble aeration head of 51- inlet valves, 52-, the underwater ultraviolet generaters of 53-, the thin lignite particle delivery pipes of 54-
The thin lignite particle of road, 55-, 56- lignite feed hopper, 57- spherical grinders, 58- bulk lignite raw material, the electronic pushers of 59-,
510- lignite particles arrange mouth, 511- water discharging valves
Specific implementation mode
As shown in Figure 1, titanium white waste liquid enters regulating reservoir 1 by pipeline, it is collected herein and after stable regulation, passes through tune
The outlet in section pond enters coarse rack 2, and the major diameter solid matter in waste liquid is removed at this, is then entered by the outlet of coarse rack
Ultraviolet activation-lignite adsorbs gas floatation separation device 5, and waste liquid removes remaining titanium dioxide particle and other insoluble suspensions herein
After object, the outlet that gas floatation separation device 5 is adsorbed by ultraviolet activation-lignite enters level-one nanofiltration membrane system 6, level-one NF membrane
Waste liquid is separated into 1 grade of concentrate and 1 grade of permeate by system 6, and 1 grade of permeate is pumped into two level nanofiltration membrane system 7, continues to detach again
At 2 grades of concentrates and 2 grades of permeate, 2 grades of permeate are that clean dilute sulfuric acid is discharged into sulfuric acid collecting pit 8, are recycled.In order to
2 grades of concentrates are returned to the entrance separation for re-filtering of level-one nanofiltration membrane system 6 by the rate of recovery for improving sulfuric acid；Wherein, purple
Outside line activation-lignite absorption 5 shell of gas floatation separation device uses glass steel material, and left lower is equipped with inlet valve 51, right
Side lower part is equipped with water discharging valve 511, and bottom of device has been mounted side by side 6 ultra-fine bubble aeration heads 52, and device two side is respectively side by side
4 underwater ultraviolet generaters 53 are installed, are equipped with lignite feed hopper 56 at the top of device, internal storage has blocky lignite raw material
58,56 lower section of lignite feed hopper is 1 spherical grinder 57, and 57 lower section of spherical grinder is connected with thin lignite particle conveyance conduit
54, thin lignite particle conveyance conduit 54 extends to bottom of device, and 1 electricity is equipped on the left of water surface site above device
Dynamic pusher 59, right side are equipped with lignite particle and arrange mouth 510；Wherein, blocky lignite raw material 58 is as ultraviolet activation-lignite absorption
The purified treatment material of gas floatation separation device 5 enters the present apparatus by the lignite feed hopper 56 at the top of device, and by under it
The grinding of spherical grinder 57 of side is broken for thin lignite particle 55, and the thin lignite particle 55 after grinding break process is through thin brown
Coal particle conveyance conduit 54 is delivered to bottom of device, while titanium white waste liquid passes through the inlet valve 51 positioned at present apparatus left lower
Into bottom of device, thin lignite particle 55 is sufficiently mixed with waste liquid, and is uniformly distributed in inside whole device, and device is now placed in
8 underwater ultraviolet generaters 53 on left side wall and right side wall start, to the thin lignite particle 55 being evenly distributed in waste liquid
Emit ultraviolet radiation, the remaining titanium white being irradiated in the meeting of the lignite particle 55 fully absorption waste liquid of activation
Powder particle and other insoluble suspended particulates, at this point, 6 ultra-fine bubble aeration heads 52 positioned at bottom of device start into waste liquid
Aeration makes to generate a large amount of ultra-fine bubbles in waste liquid, and thin lignite particle 55 acts on float downward in the air supporting of ultra-fine bubble, in waste liquid water
It is gradually converged at face, ultimately forms thin lignite particle 55 and float residue, be now placed in 1 above device on the left of water surface site
The electronic pusher 59 in portion is started to work, and the lignite particle that the thin lignite particle 55 floating residue near the water surface is pushed to right side is arranged
Simultaneously the present apparatus is discharged in mouth 510, after drying and processing, can be used for the industries such as heat supply, thermal power generation, while passing through adsorption cleaning
Treated, and the present apparatus is discharged by the water discharging valve 511 of device lower right side in waste liquid, and enters nanofiltration process；Wherein, ultraviolet
The dischargeable capacity of line activation-lignite absorption gas floatation separation device is 355m3, the dischargeable capacity of lignite feed hopper is 75m3, ball
The operating voltage of shape grinder is 380V, rated power 3.6kW；Wherein, ultraviolet activation-lignite absorption dissolved air flotation dress
It sets, the operating voltage of ultra-fine bubble aeration head is 40V, gas flow 2.5m3/ h, aeration resistance 165mmHg can be produced
The bubble of raw a diameter of 0.6mm；Wherein, ultraviolet activation-lignite adsorbs gas floatation separation device, underwater ultraviolet generater
Operating voltage is 220V, can generation wavelength be 310nm ultraviolet radiation, service life is up to 5000h.
Embodiment one：Titanium white waste liquid 20L is taken, wherein containing sulfuric acid 16%, iron ion 33.5g/L, calcium ion 400mg/L,
Magnesium ion 2500mg/L.By nanofiltration membrane system, under 500-1000PSI pressure conditions, the filtrate be separated into 10 liters 1 grade it is dense
Contracting liquid and 10 liters of 1 grade of permeate.Metal ion in 1 grade of concentrate is concentrated, and wherein iron ion is 65g/L.1 grade of permeate
Middle sulfuric acid content is increased to 17%, and iron ion is reduced to 2g/L, calcium ion 50mg/L, magnesium ion 100mg/L.By this 10 liters 1 grade
Permeate is again by nanofiltration membrane system, under 400-600PSI pressure, generates 2 liters of 2 grades of concentrates and 8 liters of 2 grades of permeate.2
In grade permeate, sulfuric acid concentration 17%, iron concentration 110mg/L, calcium ion concentration 5mg/L, magnesium ion concentration is
5mg/L.2 grades of permeate are clean dilute sulfuric acid.
In this embodiment, metal ion content is lower than titanium white waste liquid in 2 grades of concentrates of second of film process, wherein sulphur
Acid content 17%, iron ion content only have 9.6g/L, calcium ion concentration 230mg/L, magnesium ion concentration 480mg/L.Even
In continuous production process, 2 grades of concentrates can be returned to be handled together with 1 grade of NF membrane feeding liquid, can increase final 2 grades so thoroughly
Cross the rate of recovery of liquid.
Embodiment two：Titanium white mother liquor waste liquid 18L is taken, wherein containing sulfuric acid 18%, iron ion 35g/L, calcium ion 450mg/
L, magnesium ion 2500mg/L.2 liters of 2 grades of concentrates in the filtrate and embodiment one are mixed into 20L feeding liquids, wherein containing sulphur
Acid 17.9%, iron ion 32.5g/L, calcium ion 428mg/L, magnesium ion 2298mg/L.The feeding liquid is entered into nanofiltration membrane system
Processing, under 500-1100PSI pressure conditions, which is separated into 9.5 liters of 1 grade of concentrates and 10.5 liters of 1 grade of permeate.
Sulfuric acid content is increased to 18.9% in 1 grade of permeate, and iron ion is reduced to 2.1g/L, calcium ion 46mg/L, magnesium ion 125mg/
L.By 10.5 liters of 1 grade of permeate again by nanofiltration membrane system, under 400-600PSI pressure, generate 2 liters of 2 grades of concentrates and
8.5 liters of 2 grades of permeate.In 1 grade of permeate, sulfuric acid concentration 18.9%, iron concentration 117mg/L, calcium ion concentration
For 5.3mg/L, magnesium ion concentration 5.9mg/L.1 grade of permeate is clean dilute sulfuric acid.
In this embodiment, metal ion content is lower than feeding liquid in 2 grades of concentrates of second of film process, wherein sulfuric acid
Content 18.9%, iron ion content only have 10.6g/L, calcium ion concentration 220mg/L, magnesium ion concentration 630mg/L.Even
In continuous production process, 2 grades of concentrates can be returned to be handled together with feeding liquid, can increase returning for final 2 grades of permeate in this way
Yield.
Claims (8)
1. a kind of method of Recovery Purifying titanium white waste liquid, which is characterized in that titanium white waste liquid enters regulating reservoir by pipeline, herein into
Row is collected with after stable regulation, enters coarse rack by the outlet of regulating reservoir, and the major diameter solid matter in waste liquid is removed at this,
Then ultraviolet activation-lignite is entered by the outlet of coarse rack and adsorbs gas floatation separation device, waste liquid removes remaining titanium herein
After white powder particle and other insoluble suspended matters, the outlet that gas floatation separation device is adsorbed by ultraviolet activation-lignite enters one
Waste liquid is separated into 1 grade of concentrate and 1 grade of permeate by grade nanofiltration membrane system, level-one nanofiltration membrane system, and 1 grade of permeate is pumped into two again
Grade nanofiltration membrane system, continues to be separated into 2 grades of concentrates and 2 grades of permeate, 2 grades of permeate are that clean dilute sulfuric acid is discharged into sulfuric acid
Collecting pit recycles.
2. the method for Recovery Purifying titanium white waste liquid according to claim 1, which is characterized in that blocky lignite raw material is as purple
The purified treatment material of outside line activation-lignite absorption gas floatation separation device, is entered by the lignite feed hopper at the top of device
The present apparatus, and thin lignite particle is broken for by spherical grinder grinding below, the thin lignite after grinding break process
Particle is delivered to bottom of device through thin lignite particle conveyance conduit, at the same titanium white waste liquid by positioned at present apparatus left lower into
Penstock enters bottom of device, and thin lignite particle is sufficiently mixed with waste liquid, and is uniformly distributed in inside whole device, is now placed in
8 underwater ultraviolet generaters on device left side wall and right side wall start, to the thin lignite particle being evenly distributed in waste liquid
Emit ultraviolet radiation, remaining titanium dioxide in waste liquid can fully be adsorbed by being irradiated with the lignite particle of activation
Particle and other insoluble suspended matters, 6 ultra-fine bubble aeration heads for being now placed in bottom of device start to be aerated into waste liquid, make
A large amount of ultra-fine bubbles are generated in waste liquid, thin lignite particle acts on float downward in the air supporting of ultra-fine bubble, at waste liquid liquid level gradually
Convergence, ultimately forms thin lignite particles float residue, is now placed in 1 electronic push on the left of water surface site above device
Device is started to work, and the thin lignite particles float residue near the water surface is pushed to lignite particle row's mouth on right side and this dress is discharged
It sets, while the present apparatus is discharged by the water discharging valve of device lower right side by adsorption cleaning treated waste liquid, and enter one
Grade nanofiltration membrane system.
3. the method for Recovery Purifying titanium white waste liquid according to claim 1 or 2, which is characterized in that in order to improve sulfuric acid
2 grades of concentrates are returned to the entrance separation for re-filtering of level-one nanofiltration membrane system by the rate of recovery.
4. the method for Recovery Purifying titanium white waste liquid according to claim 1 or 2 or 3, which is characterized in that obtained dilute sulfuric acid
In, iron concentration is less than 150mg/L, and calcium ion is less than 10mg/L, and magnesium ion is less than 10mg/L.
5. the method for Recovery Purifying titanium white waste liquid according to claim 1 or 2, which is characterized in that wherein level-one NF membrane
System, two level nanofiltration membrane system include high pressure putamina, nanofiltration membrane component, and solution is divided into concentrate and permeate by membrane module, is received
Filter membrane component is pressure-driven rolled membrane module, and operating pressure is 300PSI~1200PSI.
6. the method for Recovery Purifying titanium white waste liquid according to claim 2, which is characterized in that ultraviolet activation-lignite is inhaled
The dischargeable capacity of attached gas floatation separation device is 355m3, the dischargeable capacity of lignite feed hopper is 75m3, the work of spherical grinder
It is 380V, rated power 3.6kW to make voltage.
7. the method for Recovery Purifying titanium white waste liquid according to claim 2, which is characterized in that ultraviolet activation-lignite is inhaled
The operating voltage of the ultra-fine bubble aeration head of attached gas floatation separation device is 40V, gas flow 2.5m3/ h, aeration resistance are
165mmHg can generate the bubble of a diameter of 0.6mm.
8. the method for Recovery Purifying titanium white waste liquid according to claim 2, which is characterized in that ultraviolet activation-lignite is inhaled
The operating voltage of the underwater ultraviolet generater of attached gas floatation separation device be 220V, can generation wavelength be 310nm ultraviolet light
Radiation.
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Cited By (2)
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