CN104874402A - Preparation of vanadium-titanium steel slag-based zinc ferrite catalyst and method for treating printing and dyeing wastewater - Google Patents
Preparation of vanadium-titanium steel slag-based zinc ferrite catalyst and method for treating printing and dyeing wastewater Download PDFInfo
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- CN104874402A CN104874402A CN201510185120.8A CN201510185120A CN104874402A CN 104874402 A CN104874402 A CN 104874402A CN 201510185120 A CN201510185120 A CN 201510185120A CN 104874402 A CN104874402 A CN 104874402A
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- vanadium
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- titanium
- zinc ferrite
- converter slag
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Abstract
The invention discloses preparation of a vanadium-titanium steel slag-based zinc ferrite catalyst and a method for treating printing and dyeing wastewater. Magnetic vanadium-titanium steel slag is obtained by taking industrial solid waste, namely vanadium-titanium steel slag, as a raw material, and carrying out crushing, screening, acid pickling, magnetic separation and other processes; the magnetic vanadium-titanium steel slag, sodium silicate and zinc oxide are mixed and subjected to ball milling according to a certain mass ratio, so that vanadium-titanium zinc ferrite powder is obtained; the vanadium-titanium zinc ferrite powder and hydrogen peroxide are added according to a certain mass ratio so as to treat the printing and dyeing wastewater; finally, the vanadium-titanium zinc ferrite powder and the treated printing and dyeing wastewater are separated by adopting a magnetic separation method, and the vanadium-titanium zinc ferrite powder can be repeatedly utilized. According to the invention, the industrial solid waste, namely vanadium-titanium steel slag, is taken as the raw material, the treatment effect on the printing and dyeing wastewater is good, the cost is low, the production process is simple, and the operation cost is greatly reduced.
Description
Technical field
The present invention relates to the preparation method that a kind of reclamation of solid wastes makes sorbing material, particularly relate to a kind of preparation of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst and the method for the treatment of of dyeing and printing.
Background technology
Slag is a kind of trade waste produced in steelmaking process, accounts for 15% ~ 20% of crude steel output.The composition of slag is comparatively complicated, the oxide formed after being mainly oxidized containing steel scrap and Al, Si, Mn etc. contained by molten iron in slag, the slag formers such as the lime added, fluorite, as the iron scale, sintering deposit, iron ore etc. of cooling agent or oxidant, the stove material be etched and furnace lining material, the deoxidation products of alloy, the component such as silt in the desulfurization product of slag and metal charge.The density of slag is about: 1700-2000kg/cm
3, Heat stability is good, to the strong adaptability of pH value.The main chemical compositions of slag is CaO, SiO
2, Fe
2o
3, Al
2o
3, MnO, MgO, P
2o
5, free radical CaO and f-CaO.Due to the difference of process for making, steel grade etc., slag appearance difference is comparatively large, and color also can change with the change of basicity, and from low to high, slag is gray, taupe gray and canescence respectively for basicity.Current China produces steel per year and has reached 500,000,000 tons, and produce about 8,000 ten thousand tons, slag per year, 300,000,000 tons, the slag stored up in addition, China's steel slag amount of banking up about 400,000,000 tons, takes up an area about 20,000 mu.If stacked for a long time, not only take valuable land resource, but also pollute the environment.
Dyeing waste water is mainly derived from dyeing and printing process process.Dyeing and printing process be broadly divided into pretreatment (singe, destarch, kiering, bleaching and mercerising), dyeing, the operation such as stamp and arrangement.Wherein, pretreatment stage will discharge desized wastewater, kiering waste water, bleaching effluent and mercerizing waste water, and dyeing process can discharge dyeing waste-water, and revenue stamp process can discharge printing waste water and soap lye waste water, arranging process can discharge arrangement waste water, and the waste water quality feature of each operation is not identical.Totally see, dyeing waste water have that displacement is large, colourity is high, stink is large, COD content is high, complicated component and changeable feature; In addition, also comparatively large containing multiple bio-toxicity in dyeing waste water and be difficult to the material of degrading; Moreover, in dyeing waste water, COD is much higher compared with BOD, so its biodegradability is also poor.According to related documents, color degree of dyeing waste water can reach more than 4000 times sometimes, and COD can reach 2000-3000mg/L, and Alkali reduction popular in recent years and sea island filament technique, make again COD in waste water be elevated to several ten thousand mg/L therefore, dyeing waste water is one of putative unmanageable organic industrial sewage.
Methods of Color Removal of Dyestuff Effluent conventional at present has absorption method, flocculence, oxidizing process, electrolysis and biochemical process etc., wherein absorption method is the common process of decoloring dye waste water, the high disposal cost of charcoal absorption makes it apply to be very limited, and the sorbing material finding high efficiency low cost at present becomes the focus of scholars's extensive concern.
At present to the research of steel slag utilization new way more popular be make sorbing material process waste water.But slag makes adsorbent is at present substantially all directly utilize slag porous, and specific area is large, slag is directly used as sorbing material process effluent containing heavy metal ions by the characteristic of surface band negative electrical charge.Owing to containing the heavy metal ion such as iron, lead, mercury, chromium in slag, as directly made sorbing material, how to prevent the heavy metal ion stripping in slag, secondary pollution is brought to handled waste water, simultaneously when adsorbent reaches capacity, slag just loses the effect of adsorption bleaching, needs by method process such as high temperature, make the dye molecule degraded being adsorbed in slag surface, bring secondary pollution like this.Therefore, how scale, non-secondary pollution, the difficult problem that high added value recycling steel slag utilization faces.
Summary of the invention
Basic ideas of the present invention are: containing abundant TiO in converter slag containing vanadium and titanium oxides
2, V
2o
5, Fe
2o
3, Fe
3o
4these materials have photocatalysis performance a bit, some has magnetic, some can form Fenton reagent with hydrogen peroxide and have Strong oxdiative performance, adopt the zinc oxide of solid phase method and interpolation to carry out ball milling and prepare magnetic vanadium titanium zinc ferrite catalyst powder, this catalyst fines has photocatalysis performance, magnetic and Fenton oxidation ability, then adopt multiphase photocatalysis technology that this catalyst fines is worked in coordination with hydrogen peroxide treatment of dyeing and printing, finally utilize this ferritic magnetic behavior, adopt magnetic selection method to realize vanadium titanium zinc ferrite catalyst powder to be separated with the dyeing waste water after process, vanadium titanium zinc ferrite catalyst powder reuses.
The object of the present invention is to provide a kind of preparation of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst and the method for the treatment of of dyeing and printing.
In order to realize above-mentioned task, the present invention takes following technical solution:
The preparation of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst and the method for the treatment of of dyeing and printing, it is characterized in that, with industrial solid castoff converter slag containing vanadium and titanium oxides for raw material, through broken, screening, pickling, magnetic converter slag containing vanadium and titanium oxides is obtained after the techniques such as magnetic separation, by magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials compare mixing and ball milling by certain quality, obtain magnetic vanadium titanium zinc ferrite catalyst powder, magnetic vanadium titanium zinc ferrite catalyst powder and hydrogen peroxide treatment of dyeing and printing is added by certain mass ratio, dyeing waste water after finally adopting magnetism separate method to be separated vanadium titanium zinc ferrite catalyst powder and to process, vanadium titanium zinc ferrite catalyst powder reuses.
Described with industrial solid castoff converter slag containing vanadium and titanium oxides for raw material, through broken, screening, magnetic converter slag containing vanadium and titanium oxides is obtained after the technique such as pickling, magnetic separation, magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials are compared mixing and ball milling by certain quality, obtain magnetic vanadium titanium zinc ferrite catalyst powder, it is characterized in that, preparation magnetic vanadium titanium zinc ferrite catalyst powder comprises the following steps:
(1) utilize disintegrating machine that converter slag containing vanadium and titanium oxides is broken, and sieve classification obtain the converter slag containing vanadium and titanium oxides of 20-40 order granularity;
(2) converter slag containing vanadium and titanium oxides obtained being added respectively concentration is in the sulfuric acid of 0.5-3.0mol/L, vibration 1-1.5 hour, and filtering drying, obtains the converter slag containing vanadium and titanium oxides after acidifying;
(3) by the magnetic separator sorting of the converter slag containing vanadium and titanium oxides after acidifying by magnetic induction intensity 10000-15000 GS, magnetic converter slag containing vanadium and titanium oxides is obtained;
(4) by magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials in mass ratio (20-30): (1-2): (0.5-1) mixing and ball milling, screening obtains 120-200 object magnetic vanadium titanium zinc ferrite catalyst powder.
Described adds magnetic vanadium titanium zinc ferrite catalyst powder and hydrogen peroxide treatment of dyeing and printing by certain mass ratio, it is characterized in that, in dyeing waste water, magnetic vanadium titanium zinc ferrite powder addition is 0.1-3g/L, pH value of waste water is 2-6, UV-irradiation 0.25-1h, hydrogen peroxide addition is 0.5-3mL/L.
accompanying drawing illustrates:
Fig. 1 is the preparation flow figure of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst
Fig. 2 is the effect of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst photocatalysis treatment actual dye wastewater.
detailed description of the invention:
embodiment 1
Take Sichuan converter slag containing vanadium and titanium oxides 10kg, pass through crusher in crushing, be sieved into 20 object slags, be that 1:0.03 adds sulfuric acid according to slag and sulfuric acid weight ratio, vibrate 1.5 hours, filter, dry 1 hour at 60-80 DEG C, be the magnetic separator magnetic separation of 10000GS at employing magnetic intensity, obtain magnetic converter slag containing vanadium and titanium oxides, by magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials 25:1:0.5 mixing and ball milling in mass ratio, screening acquisition 150 object magnetic vanadium titanium zinc ferrite catalyst powder.
embodiment 2
Magnetic vanadium titanium zinc ferrite catalyst powder embodiment 1 obtained takes 100g, adds 0.5L hydrogen peroxide to 1m simultaneously
3in certain dyeing waste water of double fluid of Sichuan, former water pH value is 4.5, COD is 3830.1mg/L, and colourity is black, and through 15min illumination, COD clearance is 95.6%, and percent of decolourization is 99.5%.Before and after treatment of dyeing wastewater, comparative test result is shown in accompanying drawing " effect of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst photocatalysis treatment actual dye wastewater ".
Claims (3)
1. the preparation of converter slag containing vanadium and titanium oxides base zinc ferrite catalyst and the method for the treatment of of dyeing and printing, it is characterized in that, with industrial solid castoff v-ti magnetite slag for raw material, through broken, screening, pickling, magnetic converter slag containing vanadium and titanium oxides is obtained after the techniques such as magnetic separation, by magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials compare mixing and ball milling by certain quality, obtain magnetic vanadium titanium zinc ferrite catalyst powder, magnetic vanadium titanium zinc ferrite catalyst powder and hydrogen peroxide treatment of dyeing and printing is added by certain mass ratio, dyeing waste water after finally adopting magnetism separate method to be separated vanadium titanium zinc ferrite catalyst powder and to process, vanadium titanium zinc ferrite catalyst powder reuses.
2. according to claim 1 with industrial solid castoff converter slag containing vanadium and titanium oxides for raw material, through broken, screening, magnetic converter slag containing vanadium and titanium oxides is obtained after the technique such as pickling, magnetic separation, magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials are compared mixing and ball milling by certain quality, obtain magnetic vanadium titanium zinc ferrite catalyst powder, it is characterized in that, preparation magnetic vanadium titanium zinc ferrite catalyst powder comprises the following steps:
(1) utilize disintegrating machine that converter slag containing vanadium and titanium oxides is broken, and sieve classification obtain the converter slag containing vanadium and titanium oxides of 20-40 order granularity;
(2) converter slag containing vanadium and titanium oxides obtained being added respectively concentration is in the sulfuric acid of 0.5-3.0mol/L, vibration 1-1.5 hour, and filtering drying, obtains the converter slag containing vanadium and titanium oxides after acidifying;
(3) by the magnetic separator sorting of the converter slag containing vanadium and titanium oxides after acidifying by magnetic induction intensity 10000-15000 GS, magnetic converter slag containing vanadium and titanium oxides is obtained;
(4) by magnetic converter slag containing vanadium and titanium oxides, sodium metasilicate, zinc oxide three kinds of materials in mass ratio (20-30): (1-2): (0.5-1) mixing and ball milling, screening obtains 120-200 object magnetic vanadium titanium zinc ferrite catalyst powder.
3. according to claim 1 by certain mass ratio interpolation magnetic vanadium titanium zinc ferrite catalyst powder and hydrogen peroxide treatment of dyeing and printing, it is characterized in that, in dyeing waste water, magnetic vanadium titanium zinc ferrite catalyst powder addition is 0.1-3g/L, pH value of waste water is 2-6, UV-irradiation 0.25-1h, hydrogen peroxide addition is 0.5-3mL/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105817234A (en) * | 2016-04-08 | 2016-08-03 | 李政 | Method for extracting nanometer multi-metal oxide loaded activated carbon fibers |
| CN109107525A (en) * | 2018-09-25 | 2019-01-01 | 中国环境科学研究院 | More metal zeroth order mercury absorbents of a kind of converter slag containing vanadium and titanium oxides load and preparation method thereof |
| CN113755899A (en) * | 2021-08-06 | 2021-12-07 | 莫永明 | Sectional type electrolytic cell for recycling steel slag |
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| CN101551173A (en) * | 2006-09-29 | 2009-10-07 | 山东天虹弧板有限公司 | Method for compounding solid netted black porcelain sunlight absorbing layer on ceramic hollow slab |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105817234A (en) * | 2016-04-08 | 2016-08-03 | 李政 | Method for extracting nanometer multi-metal oxide loaded activated carbon fibers |
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| CN109107525A (en) * | 2018-09-25 | 2019-01-01 | 中国环境科学研究院 | More metal zeroth order mercury absorbents of a kind of converter slag containing vanadium and titanium oxides load and preparation method thereof |
| CN113755899A (en) * | 2021-08-06 | 2021-12-07 | 莫永明 | Sectional type electrolytic cell for recycling steel slag |
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