CN102826681A - Method for comprehensively processing waste water and exhaust gas from lead-zinc smeltery - Google Patents

Method for comprehensively processing waste water and exhaust gas from lead-zinc smeltery Download PDF

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Publication number
CN102826681A
CN102826681A CN2012103158677A CN201210315867A CN102826681A CN 102826681 A CN102826681 A CN 102826681A CN 2012103158677 A CN2012103158677 A CN 2012103158677A CN 201210315867 A CN201210315867 A CN 201210315867A CN 102826681 A CN102826681 A CN 102826681A
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China
Prior art keywords
water
nanofiltration
level
stage
lead
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CN2012103158677A
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Chinese (zh)
Inventor
卢伯福
虞美辉
孙洪贵
李振峰
陈洪景
雷细良
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XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
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XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
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Priority to CN2012103158677A priority Critical patent/CN102826681A/en
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Abstract

The invention discloses a method for comprehensively processing waste water and exhaust gas from a lead-zinc smeltery, which is characterized in that the waste water in a workshop is subjected to press filtration and then enters into first-stage micro-filtration, the water generated by the first-stage micro-filtration enters into first-stage nanofiltration, concentrated water from the first-stage nanofiltration enters into a first-stage stirring pool, and is stirred in the first-stage stirring pool then the pH value is regulated to 6-7, the concentrated water enters into a first-stage concentrated sludge pool and is subjected to first-stage sludge concentration, the generated water enables second-stage nanofiltration, concentrated water from the second-stage nanofiltration enters into a second-stage stirring pool, then the pH value of the concentrated water from nanofiltration is regulated to 10-13, fuel gas is introduced in the second-stage stirring pool while stirring for removing calcium, the fuel gas is introduced in the second-stage stirring pool for removing calcium, and enters into a second-stage concentrated sludge pool and enables second-stage sludge condensation, a supernatant enters into the first-stage stirring pool, and the water generated from first-stage nanofiltration and second-stage nanofiltration for further processing. The technical scheme has the advantages that the discharge of the greenhouse gas carbon dioxide is reduced, the usage of medicine sodium carbonate is reduced, and the processing cost is saved.

Description

A kind of wastewater in lead-zinc metallurgical refinery and waste gas integrated conduct method
Technical field
The present invention relates to the waste water and gas process field, particularly relate to a kind of wastewater in lead-zinc metallurgical refinery and waste gas integrated conduct method.
Background technology
Wastewater in lead-zinc metallurgical refinery is handled, and adopts one section milk of lime neutralisation both at home and abroad usually, be heavy metal ion production precipitation of hydroxide in the waste water in slag, make supernatant water contain heavy metal ion and can arrive discharging standards, can enter in the rivers.Owing to still contain higher Cl in this supernatant water -(400-500mg/L), Ca 2+(700-800mg/L), SO 4 2-(2500-3500mg/L), decapacitation will be lacked part and be back to outside pyrometallurgical smelting shrend slag and the silver-colored flotation make up water, for the big zinc hydrometallurgy of water consumption, because of it contains Cl -High and can not use, simultaneously because of containing Ca 2+Height, pipeline are prone to fouling and stop up, and cause difficulty to reuse.So this supernatant water, major part can only enter rivers.In in the aforesaid method and slag, contain a certain amount of Zn, Cd, this slag is returned zinc leach and reclaim also difficulty very of Zn, Cd, especially for the smeltery of a large amount of use zinc oxide ores, owing to contain Mg in the ore deposit 2+, Cl -Higher, cause to contain Mg in the waste water 2+, Cl -High.Adopt one section neutralisation of milk of lime, Mg 2+All be deposited in the slag, the quantity of slag is big, causes slag to contain impurity such as Zn, Cd and gets back to Zn system again, causes vicious cycle, makes the Zn, the Cd that reclaim in the waste water become a difficult problem.
Yunnan Xiangyun Feilong Nonferrous Metals Co., Ltd. built up industrial osmosis filtration facility in 2005; With reaching the BW specification of quality with the high calcium supernatant water of output with reverse osmosis membrane filtration in one section milk of lime; Boiler of feeding uses, thereby avoids the volumetric expansion of zinc smelting water.Will add the yellow soda ash deliming before the single-filtering earlier reaches below the 3mg/L; Could get into osmosis filtration through sand filtration, gac filter, cationic exchange, ultrafiltration again, therefore increase the consumption of yellow soda ash, production cost is risen; Brought sodium ion simultaneously into, its disadvantage is obvious.
Smeltery, Shaoguan adopts the smelting wastewater of " one section neutralization+chemical deliming+pre-treatment (sand filtration+gac filter+ultrafiltration)+nanofiltration " this factory of art breading, utilizes nanofiltration to handle divalent ion (heavy metal ion and Ca in the waste water 2+, Mg 2+, SO 4 2-Deng), output " receive fresh water " is back to production, be suitable for for pyrometallurgical smelting factory, but this method can not be removed the Cl in the waste water -For the monovalent ion of representative, for the big zinc hydrometallurgy of the water yield, Cl -To the electrolytic harm of zinc, this method can't solve.Chemical in addition calcium remover band people foreign ion accumulates in waste water, can't accomplish wastewater zero discharge, can only reach the purpose that reduces quantity discharged.
Yunnan Xiangyun Feilong Nonferrous Metals Co., Ltd. and Xiamen Starmem Film Technology Co., Ltd.; A kind of zero emission method of wastewater in lead-zinc metallurgical refinery is disclosed in the patent No. is the Chinese invention patent " zero emission method of wastewater in lead-zinc metallurgical refinery " of ZL 200910094062.2; Adopt two sections neutralization reactions: (1) is in first section neutralization reaction pond, with supernatant water behind the heavy Mg of second section neutralization reaction output and smelting wastewater reaction, terminal point pH=7.5-8; The deposition underflow; Return zinc after the press filtration and leach recovery Zn, Cd, supernatant water partly gets into second section neutralization reaction, and part gets into and filters operation in addition; (2) in second section neutralization reaction, with in one section with the part supernatant water and milk of lime reaction of output, terminal point pH=12-13 precipitates underflow, press filtration, the filter residue that contains Ca, Mg send the slag storehouse to store up; Modulate pH=5.5-6.5 with the part supernatant water in addition of output with dilute sulphuric acid in (3) first sections, use combination of membrane filtration, the various drainages of generation are delivered to each corresponding operation of lead-zinc smelting factory.Zn of the present invention, the Cd recovery are high, contain Ca, filter residue that Mg is high does not return the zinc smelting system, and the water of this technology output can fully recovering, has realized wastewater zero discharge, and water-deficient area and no current water are received the area of dirt, and be significant.But in this technology in the secondary with mainly be the calcium sulfate that contains saturation concentration in the supernatant, be prone to cause the obstruction of nf membrane in the nanofiltration system and reduce the time limit of service of nf membrane; The treating method of common process forms ZG 301 through adding yellow soda ash or sodium hydroxide at present, yet processing can cause sodium ion aggravation accumulation like this, forms ion and expands, and when having increased production cost, has also increased the difficulty of follow-up reverse-osmosis treated.
In the metallurgical industry, staple is CO in the boiler smoke 2Deng gas, at present main flue gas processing method is back directly being discharged in the atmosphere such as process dedusting, desulfurization, CO 2Be greenhouse gases, excessively discharging will cause harm such as Greenhouse effect, global warming, glacier thawing, sea-level rise.
Summary of the invention
To the problems referred to above, the objective of the invention is to design that a kind of processing efficiency is high, running cost is low, handle the wastewater in lead-zinc metallurgical refinery and the waste gas integrated conduct method of waste water and waste gas simultaneously.
For achieving the above object, technical scheme proposed by the invention is: a kind of wastewater in lead-zinc metallurgical refinery and waste gas integrated conduct method is characterized in that: workshop waste water is after press filtration; Get into the one-level micro-filtration, the one-level micro-filtration produces water and carries out the one-level nanofiltration, and the dense water of one-level nanofiltration gets into the one-level agitated pool; In the one-level agitated pool, behind stirring and the accent pH to 6-7, get into the dense mud sump of one-level product water after one-level mud concentrates and carry out the secondary micro-filtration, secondary micro-filtration product water carries out the secondary nanofiltration; The dense water of secondary nanofiltration gets into the secondary agitated pool; Regulate the dense water pH=10-13 of nanofiltration, the secondary agitated pool feeds the boiler smoke deliming in stirring, in the secondary agitated pool after the deliming of feeding boiler smoke; Get into the dense mud sump of secondary after secondary mud concentrates, supernatant gets into the one-level agitated pool; Water is produced in the one-level nanofiltration, water reuse or further processing are produced in the secondary nanofiltration.
Further, the preferred CO of described boiler smoke 2Content is more than or equal to 15% boiler smoke.
Further, the preferred boiler smoke after dedusting, desulfurization of described boiler smoke.
Further, stirring in the one-level agitated pool and transferring pH to 6-7 is that employing adds the milk of lime adjust pH, and described pH value preferred 6.5.
Further, regulate the pH value preferred 11 of the dense water of nanofiltration.
Further, described workshop waste water ph is 3-4.
Further, the dense water and the backwash water of described one-level micro-filtration generation are returned the pressure filter press filtration.
Further, the described secondary micro-filtration dense water that produces water and backwash water are back to the dense mud sump of one-level to carry out one-level mud concentrated.
Further, water is produced in described one-level nanofiltration, the secondary nanofiltration is produced water and further is treated to the industrial osmosis filtration of employing; The reuse of industry reverse osmosis produced water, industrial reverse osmosis concentrated water is used for domestic water such as plant area afforests water, sanitary water etc.
Further, water is produced in described one-level nanofiltration, the secondary nanofiltration is produced the further processing of water and comprised that also industrial osmosis filtration product water gets into low pressure reverse osmosis, and low pressure reverse osmosis produces water and is used for BW, and the dense water of low pressure reverse osmosis returns industrial r-o-circulating filtration.
Adopt technique scheme, wastewater in lead-zinc metallurgical refinery of the present invention and waste gas integrated conduct method, the advantage that has is:
1) utilize boiler smoke under the situation of pH=10-13, form ZG 301 with the calcium ion reaction, such advantage is both can reduce the greenhouse gases emission of carbon-dioxide, has reduced the use of medicament yellow soda ash again, practices thrift processing cost;
2) reverse osmosis membrane produces water and further produces boiler feedwater, can reduce conventional zwitterion resin bed production boiler feedwater regeneration with acid, alkali, reduces the acidic and alkaline waste water discharging, and what sodium, cl ions got in the water body is less;
3) owing to there has not been the interpolation of additional agent; Sodium, cl ions can be through moisture taking away in the solid slag; Can make the easier balance of water body ion in the factory like this, water body is constantly recycled through equipment, need not remove sodium-chlor through evaporation concentration; Can accomplish lower running cost, good energy saving performance.
Description of drawings
Fig. 1 is wastewater in lead-zinc metallurgical refinery of the present invention and waste gas integrated conduct method basic flow sheet.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is further specified.
As shown in Figure 1; Wastewater in lead-zinc metallurgical refinery of the present invention and waste gas integrated conduct method, concrete steps be workshop waste water (the pH value is 3-4) after press filtration, get into the one-level micro-filtration; The one-level micro-filtration produces water and carries out the one-level nanofiltration, and dense water and backwash water that the one-level micro-filtration produces are returned the pressure filter press filtration; The dense water of one-level nanofiltration gets into the one-level agitated pool, in the one-level agitated pool, stirs and accent pH to 6-7, preferably adds milk of lime and transfers; After pH is preferably 6.5, gets into the dense mud sump of one-level product water after one-level mud concentrates and carry out the secondary micro-filtration, the secondary micro-filtration produces water and carries out the secondary nanofiltration; Dense water and backwash water that the secondary micro-filtration produces water are back to the dense mud sump of one-level, and the dense water of secondary nanofiltration gets into the secondary agitated pool, regulates the dense water pH=10-13 of nanofiltration; Preferred pH is 11, and the secondary agitated pool feeds the boiler smoke deliming in stirring, in the secondary agitated pool after the deliming of feeding boiler smoke; Get into the dense mud sump of secondary after secondary mud concentrates, supernatant gets into the one-level agitated pool; The one-level nanofiltration is produced water, secondary nanofiltration product water reuse or is further handled, and further handles to comprise the industrial osmosis filtration of employing; The industry osmosis filtration is produced water and is got into low pressure reverse osmosis, and low pressure reverse osmosis produces water and is used for BW, and the dense water of low pressure reverse osmosis returns industrial r-o-circulating filtration, and industrial reverse osmosis concentrated water is used for domestic water such as plant area afforests water, sanitary water etc.
Further, the preferred CO of described boiler smoke 2Content is more than or equal to 15% boiler smoke.
Further, the preferred boiler smoke after dedusting, desulfurization of described boiler smoke.
During practical implementation; The result that aforesaid method is used for the wastewater in lead-zinc metallurgical refinery off gas treatment is a following table; The thing that needs explanation, maximum innovation of the present invention is in the dense water of secondary nanofiltration, to feed boiler smoke, feeds boiler smoke (CO in the flue gas in the secondary nanofiltration so following table only provides 2Content is greater than 15%) data results.
From we can find out as a result, behind the feeding flue gas, the clearance of Ca2+ is greater than more than 50% in the dense water in the dense water of secondary nanofiltration; Form ZG 301 with the calcium ion reaction; Both can reduce the greenhouse gases emission of carbon-dioxide, reduce the use of medicament yellow soda ash, practice thrift processing cost; Simultaneously owing to there has not been the interpolation of additional agent; Sodium, cl ions can be through moisture taking away in the solid slag; Can make the easier balance of water body ion in the factory like this, water body is constantly recycled through equipment, need not remove sodium-chlor through evaporation concentration; Can accomplish lower running cost, good energy saving performance.
Although specifically show and introduced the present invention in conjunction with preferred embodiment; But the those skilled in the art should be understood that; In the spirit and scope of the present invention that do not break away from appended claims and limited; In form with on the details the present invention is made various variations, be protection scope of the present invention.

Claims (10)

1. wastewater in lead-zinc metallurgical refinery and waste gas integrated conduct method, it is characterized in that: workshop waste water gets into the one-level micro-filtration after press filtration; The one-level micro-filtration produces water and carries out the one-level nanofiltration, and the dense water of one-level nanofiltration gets into the one-level agitated pool, after in the one-level agitated pool, stirring and transferring pH to 6-7; Get into the dense mud sump of one-level product water after one-level mud concentrates and carry out the secondary micro-filtration; The secondary micro-filtration produces water and carries out the secondary nanofiltration, and the dense water of secondary nanofiltration gets into the secondary agitated pool, regulates the dense water pH=10-13 of nanofiltration; The secondary agitated pool feeds the boiler smoke deliming in stirring; After feeding the boiler smoke deliming in the secondary agitated pool, get into the dense mud sump of secondary after secondary mud concentrates, supernatant gets into the one-level agitated pool; Water is produced in the one-level nanofiltration, water reuse or further processing are produced in the secondary nanofiltration.
2. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: described boiler smoke CO 2Content is more than or equal to 15% boiler smoke.
3. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: described boiler smoke is the boiler smoke after dedusting, desulfurization.
4. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: stirring in the one-level agitated pool and transferring pH to 6-7 is that employing adds the milk of lime adjust pH.
5. a kind of wastewater in lead-zinc metallurgical refinery according to claim 4 and waste gas integrated conduct method is characterized in that: described pH value is 6.5.
6. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: the pH value of regulating the dense water of nanofiltration is 11.
7. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: described workshop waste water ph is 3-4.
8. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: dense water and backwash water that described one-level micro-filtration produces are returned the pressure filter press filtration; Dense water and backwash water that described secondary micro-filtration produces water are back to the dense mud sump of one-level.
9. a kind of wastewater in lead-zinc metallurgical refinery according to claim 1 and waste gas integrated conduct method is characterized in that: water is produced in described one-level nanofiltration, the secondary nanofiltration is produced water and further is treated to the industrial osmosis filtration of employing.
10. a kind of wastewater in lead-zinc metallurgical refinery according to claim 9 and waste gas integrated conduct method is characterized in that: water is produced in described one-level nanofiltration, the secondary nanofiltration is produced the further processing of water and comprised that also industrial osmosis filtration product water gets into low pressure reverse osmosis and filters.
CN2012103158677A 2012-08-27 2012-08-27 Method for comprehensively processing waste water and exhaust gas from lead-zinc smeltery Pending CN102826681A (en)

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CN105621769A (en) * 2014-11-04 2016-06-01 中国石油化工股份有限公司 High concentration wastewater zero-emission method
CN112645520A (en) * 2020-11-10 2021-04-13 常熟市电热合金材料厂有限公司 Recycling method of sludge press-filtration wastewater

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN105621769A (en) * 2014-11-04 2016-06-01 中国石油化工股份有限公司 High concentration wastewater zero-emission method
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