CN104230053B - Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain - Google Patents
Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain Download PDFInfo
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- CN104230053B CN104230053B CN201410463036.3A CN201410463036A CN104230053B CN 104230053 B CN104230053 B CN 104230053B CN 201410463036 A CN201410463036 A CN 201410463036A CN 104230053 B CN104230053 B CN 104230053B
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- waste water
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Abstract
The invention discloses a kind of waste water neutralisation treatment method in sulphur phosphorus titanium industry chain, classify by Oil repellent including to different waste water, then neutralize filtration respectively by the precipitation method, the most common drain steps, makes the waste water after process be fully achieved national standard reference.The method is simple, without increasing extra cost burden, workman is physically easier to perform control, effectively prevent secondary neutralize, secondary press filtration and add the troublesome operation such as flocculant, have huge social effect, economic benefit and ecological benefits.
Description
Technical field
The present invention relates to titanizing work, phosphorous chemical industry, the process of sulfuric acid plant waste water, according to the classification process to waste water.
Background technology
Fluorine is one of element widely distributed in nature, mainly with fluorite (CaF2), ice crystal (Na3[AlF6]) and with
Fluor-apatite (Ca10(PO4)6F2) exist.Fluorine element containing about 2 grams～3 grams, is mainly distributed on bone, tooth in normal adult human body
In tooth, both has accumulated the fluorine of about 90%, and in blood, every milliliter contains 0.04 microgram～0.4 microgram.The fluorine master of needed by human body
Will be from drinking water.In drinking water, fluorinated volume is with 0.5～1.0mg/L conveniently, and less than this value, the incidence of disease of dental caries will rise
To 70～90%；If drinking the fluorine water quality concentration water higher than 1.0mg/L for a long time, then can cause fluorine pinta；Drink fluorine amount for a long time
More than 3-6mg/L, then it is easily caused fluorosis of bone so that marrow deformity.China's Fluorine Containing Groundwater is widely distributed, especially dry in northwest
Nonirrigated farmland district, there are about 70,000,000 people and drinks the fluorine-containing water exceeded standard, and causes fluorine poisoning in various degree, industrial fluorine-containing ore extraction,
The waste water of the discharges such as metal smelt, aluminium processing, plating, chemical fertilizer and agricultural chemicals often contains the fluoride of high concentration, causes environment dirty
Dye.
In dragon boa sulphur phosphorus titanium industry chain, the dish drainage of the dishwashing filter of phosphorous chemical industry and the de-magging mother liquor of phosphorus ore de-magging contain
The fluorine of high concentration.In titanium industry waste water, the waste water cleaning filter cloth also contains substantial amounts of fluorine, here the sand acid waste water of gas washing in SA production
The lowest because of fluorinated volume with titanium industry waste water, therefore it is collectively referred to as titanium industry waste water here, concrete each waste water component refers to table 1.
Table 1: the waste water component in sulphur phosphorus titanium industry chain
Currently, the process of domestic and international high-concentration fluorine-containing waste water generally has absorption method and the precipitation method two kinds.Wherein precipitation method master
Being applied to the process of industry fluoride waste, absorption method is mainly used in the process of drinking water.Additionally also has the exchange of freezing, ion
The methods such as method, ultrafiltration method for removing fluor, electrocoagulation, electrodialysis, reverse osmosis technology.
The precipitation method are that high-concentration fluorine-containing waste water processes one of widely used method, are by adding medicine or other medicine
Thing forms fluoride precipitation or flocculation sediment, is reached the purpose removed by the separation of solid, and medicament, reaction condition and solid-liquid divide
From effect determine the treatment effeciency of the precipitation method.The precipitation method are divided into again chemical precipitation method and coagulant sedimentation.Chemical precipitation method
Being mainly used in high-concentration fluorine-containing waste water to process, using more is calcium salt precipitation method, i.e. lime precipitation, by waste water
Add the chemicals such as calcium salt, make calcium ion and fluorine ion react generation CaF2Precipitation, realizes removing the F made in waste water-Mesh
's.This technique is simple and convenient, and expense is low, but comes with some shortcomings.After fluorine in wastewater content after process reaches 15mg/L, then add
Limewash, is hardly formed sediment, and therefore the method is generally suitable for coagulation or the pretreatment of high-concentration fluorine-containing waste water, very
Difficulty reaches GB primary standard.Accordingly, it would be desirable to add other salts or flocculant to improve the treatment effect of waste water.Coagulating sedimentation
Method is that micelle can adsorb by adding molysite and the big class coagulant of aluminium salt two in water, forming the micelle of positively charged in water
F in water-And mutually and gather and precipitate for floccule, to reach the purpose of fluorine removal.Coagulant sedimentation is typically only applicable to low fluorine
Waste water processes, typically by with neutralization precipitation method with the use of, it is achieved the process to high fluorine waste water.Owing to defluorination effect is stirred
The impact of the factor such as condition, sedimentation time, therefore water quality is not sufficiently stable, and other chemical reagent typically need to be coordinated to use and just can carry
High efficiency, therefore technique is complex.
Absorption method is to will be equipped with activated alumina, polyaluminium salts, brown coal adsorbent, functional fibre adsorbent, activated carbon etc.
The equipment of adsorbent is put in industrial wastewater, make fluorine ion by with solid dielectric carry out special or conventional ion exchange or
Chemical reaction, final absorption is removed on the sorbent, and adsorbent recovers exchange capacity also by regeneration.In order to ensure place
Reason effect, the pH value of waste water is unsuitable too high, and general control is about 5, and additionally the absorption temperature of adsorbent to be controlled by, it is impossible to too
High.The method is generally used for the process of low concentration fluoride waste, and effect is the most notable.Owing to cost is relatively low, and defluorination effect
Preferably, it is the important method of fluoride wastewater treatment.But its emphasis pH value is too low, after discharge, water ecological setting is had one fixing
Ring.
Producing for realizing the cleaning of titanium dioxide, dragon boa has made sulphur phosphorus titanium industry chain, it is achieved that recycling of spent acid.But
Meanwhile, also making kind of waste water become many, component becomes increasingly complex, i.e. has the waste water from titanium industry difference workshop, such as filter cloth
Wash water, Producing Titanium Dioxide workshop section one wash, two washes waste water etc., sand acid waste water that sulfuric acid plant produces and the waste water that phosphorous chemical industry produces, as
De-magging mother liquor, disc filter wash water etc..Process these waste water the most simultaneously and reach national environmental standard, bringing to this industrial chain
New challenge, particularly phosphorous chemical industry waste water contain substantial amounts of fluorine ion, by standard GB/T 8978-1996, in waste discharge
Oil repellent is not above 10ppm.At present high fluoride waste is first neutralized filtration once, carries out with low fluoride waste the most again
Neutralize and filter, although reached discharge standard, but process is loaded down with trivial details, relatively costly, reduces disposal ability, the most also because of production
Instability makes the waste water Oil repellent discharged the most up to standard.How in the case of not increasing production cost, it is achieved waste water up to standard
The simplicity of discharge and operation is that those skilled in the art thirst for solving the technical problem that always.
Summary of the invention
The waste water that it is an object of the invention to optimize in sulphur phosphorus titanium industry chain further processes, it is provided that a kind of processing cost pole
Low, the method relating to multiple chemical field waste water integrated treatment of works very well, technological process is simple, it is not necessary to carry out secondary neutralization
With secondary press filtration, being also not required to add other auxiliary agents such as flocculant, processing procedure is more not required to counter adjust pH value.
The present invention is achieved through the following technical solutions: waste water neutralisation treatment method in sulphur phosphorus titanium industry chain, comprises following step
Rapid: waste water is classified by (1) by Oil repellent；(2) the classification waste water that step (1) obtains is neutralized respectively, cures, press filtration
Obtain 2 kinds of filtrates；(3) by 2 kinds of filtrate dual disposals of step (2) gained.
Further, in described step (1), Oil repellent is higher than fluoride waste and Oil repellent the giving up less than 10ppm of 10ppm
Water separate collection.
Further, in described step (2), its neutralization pH value of the Oil repellent fluoride waste higher than 10ppm is controlled at 9-12,
Control at 8-10 with endpoint pH in the Oil repellent waste water less than 10ppm.
Further, in described step (3), the Oil repellent fluoride waste higher than 10ppm and the Oil repellent waste water less than 10ppm
Ratio 1:1-5.
Further, in described step (2), use by alkalescence calcified material regulation pH value.
Further, described alkalescence calcified material is carbide slag or milk of lime.
Sulphur phosphorus titanium industry chain incorporates titanizing work, phosphorous chemical industry and sulfuric acid Chemical Manufacture, effectively achieves the circulation of spent acid
Utilize, greatly reduce the three wastes.This method makes full use of the advantage of this industrial chain, and i.e. one class waste water is the most fluorine-containing or contains the lowest
Fluorine, as washed from titanium industry waste water, two waste water washed also have tail gas shower water etc., the waste water that gas washing in SA production produces, separately
One class waste water contains high fluorine, such as the cleaning filter cloth water of de-magging mother liquor, the waste water of dishwashing filter and the titanium industry of phosphorous chemical industry.Classification of waste
After, neutralize this two classes waste water, press filtration the most respectively, last filtrate dual disposal by a certain percentage respectively with alkalescence calcified material.
Reason has two: one high fluorine waste water to be neutralized after mixing can be more more than what fluorine removal after all waste water are mixed was removed, because of
For being difficult to further fluorine removal when Oil repellent reaches 15ppm.Second is, low fluorine waste water is 4-5 times of high fluorine waste water, low fluorine
After waste water separates so that low fluorine waste water has enough capacity to dilute the high fluorine waste water the most still exceeded standard.
The invention have the advantages that
1, it is not required to newly-increased any defluorinating agent, or buys flocculant etc.；
2, in workshop without any equipment such as newly-increased filter presses；
3, waste water dual disposal after coagulation can reach national grade one discharge standard；
4, processing cost is low；
5, it is easily controlled.
Detailed description of the invention
Embodiment 1
15m3Filter cloth wash water, 30m3De-magging mother liquor and 10m3Disc filter wash water mixes at neutralization pond, then uses calcium carbide
It is 9 that slag is neutralized to pH value, and cures 30 minutes, and it is 10 that titanium industry waste water is neutralized to pH value at another neutralization pond carbide slag, also
Same curing 30 minutes.The waste water of the two neutralization pond is carried out press filtration respectively, and filter cake stacking processes, and filtrate presses 1:1 volume ratio
Discharge.
Embodiment 2
15m3Filter cloth wash water, 60m3De-magging mother liquor and 10m3Disc filter wash water mixes at neutralization pond, then uses calcium carbide
It is 10 that slag is neutralized to pH value, and cures 60 minutes, and it is 9 that titanium industry waste water is neutralized to pH value at another neutralization pond carbide slag, also
Same curing 30 minutes.The waste water of the two neutralization pond is carried out press filtration respectively, and filter cake stacking processes, and filtrate presses 1:2 volume ratio
Discharge.
Embodiment 3
15m3Filter cloth wash water, 150m3De-magging mother liquor and 10m3Disc filter wash water mixes at neutralization pond, then electricity consumption
It is 11 that rock ballast is neutralized to pH value, and cures 30 minutes, and it is 8 that titanium industry waste water is neutralized to pH value at another neutralization pond carbide slag,
Curing 30 minutes too.The waste water of the two neutralization pond is carried out press filtration respectively, and filter cake stacking processes, and filtrate presses 1:5 volume
Ratio discharges.
Comparative example 1
The effect neutralized respectively after waste water being classified by Oil repellent for the ease of accurate evaluation, uses whole waste water to mix
Neutralize filtration after conjunction to contrast.1.5m3Filter cloth wash water, 25m3De-magging mother liquor, 1.5m3Disc filter wash water and 90m3Titanium industry is given up
Water mixes at neutralization pond, is then neutralized to pH value 8.9 with milk of lime, cures 60min, then press filtration, and filter cake is stacked
Processing, after waste water processes, water quality situation see table 2.
Table 2: water quality situation after waste water process
| Project | Oil repellent | PH value |
| Embodiment 1 | 8.0 | 8.7 |
| Embodiment 2 | 6.3 | 8.5 |
| Embodiment 3 | 5.6 | 7.8 |
| Comparative example 1 | 7.5 | 16 |
| National standard (GB8978-1996) | ＜ 10 | 6-9 |
Last it should be noted that above example is merely to illustrate technical scheme and unrestricted, although ginseng
Being described in detail technical scheme according to preferred embodiment, it will be appreciated by those skilled in the art that can be to the present invention
Technical scheme modify or equivalent, without deviating from the purpose and scope of the invention, it all should be contained the present invention's
In protection domain.
Claims (5)
1. waste water neutralisation treatment method in sulphur phosphorus titanium industry chain, it is characterised in that comprise the steps of
(1) waste water is classified by Oil repellent, Oil repellent higher than the fluoride waste of 10ppm and Oil repellent less than 10ppm's
Waste water separate collection；
(2) be neutralized respectively by the classification waste water that step (1) obtains, cure, press filtration obtains 2 kinds of filtrates；
(3) by 2 kinds of filtrate dual disposals of step (2) gained.
Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain the most according to claim 1, it is characterised in that described step
(2), in, its neutralization pH value of the Oil repellent fluoride waste higher than 10ppm is controlled at 9-12, to the Oil repellent waste water less than 10ppm
Neutralize endpoint pH to control at 8-10.
Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain the most according to claim 1, it is characterised in that described step
(3) in, the Oil repellent fluoride waste higher than 10ppm and Oil repellent waste water ratio 1:1-5 less than 10ppm.
Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain the most according to claim 1, it is characterised in that described step
(2), in, alkalescence calcified material regulation pH value is used.
Waste water neutralisation treatment method in sulphur phosphorus titanium industry chain the most according to claim 4, it is characterised in that described alkalescence calcium
Compound is carbide slag or milk of lime.
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| CN105036406A (en) * | 2015-07-02 | 2015-11-11 | 江西铜业股份有限公司 | Novel wastewater fluorine-removing technology |
| CN105417788A (en) * | 2015-12-23 | 2016-03-23 | 晏玲莉 | Waste water treatment device in sulfur-phosphorus-titanium industrial chain |
| CN111484159A (en) * | 2020-04-07 | 2020-08-04 | 广东湛化集团有限公司 | Fluoride treatment process for sewage of phosphorus chemical industry |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293717A (en) * | 2008-06-05 | 2008-10-29 | 佛山市三水凤铝铝业有限公司 | Method for processing and recycling wastewater containing fluorine, chromium ion |
| CN102276043A (en) * | 2011-08-11 | 2011-12-14 | 铜陵化学工业集团有限公司 | Method for treating fluorine-containing industrial wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293717A (en) * | 2008-06-05 | 2008-10-29 | 佛山市三水凤铝铝业有限公司 | Method for processing and recycling wastewater containing fluorine, chromium ion |
| CN102276043A (en) * | 2011-08-11 | 2011-12-14 | 铜陵化学工业集团有限公司 | Method for treating fluorine-containing industrial wastewater |
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Address after: 618200 Deyang city of Sichuan province Mianzhu new industrial zone longmang Chemical Industrial Zone Patentee after: Longbai Sichuan Titanium Co., Ltd Address before: 618200 Deyang city of Sichuan province Mianzhu new industrial zone longmang Chemical Industrial Zone Patentee before: SICHUAN LOMON TITANIUM Co.,Ltd. |
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