CN102976434B - Method for treating lead-containing wastewater - Google Patents
Method for treating lead-containing wastewater Download PDFInfo
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- CN102976434B CN102976434B CN201210538638.1A CN201210538638A CN102976434B CN 102976434 B CN102976434 B CN 102976434B CN 201210538638 A CN201210538638 A CN 201210538638A CN 102976434 B CN102976434 B CN 102976434B
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- amorphous silica
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Abstract
The invention discloses a method for treating lead-containing wastewater. The method is characterized in that an adsorbing material is prepared from the following raw materials in percent by mass: 20-50 percent of modified attapulgite, 20-40 percent of hydrotalcite and 30-40 percent of amorphous silicon dioxide, wherein the amorphous silicon dioxide is a silicon product obtained by treating silica lapilli tuff with water. The method has the advantages of simple process procedure, lower operation cost, no sludge generation, and remarkable lead removal effect, and is high in removal rate of above 99 percent because the concentration of the remained lead ions in water after being subjected to primary treatment is less than 0.6mg/L and is lower than a first-class emission standard specified by the state.
Description
Technical field
The present invention relates to a kind for the treatment of process of lead waste water, particularly process the waste water of lead concentration within the scope of 10～200mg/L, belong to field of waste water treatment in environment protection.
Background technology
Lead is the element that distributed in nature is very wide, is also one of normal element using in industry, at occurring in nature, mainly with sulphided form, exist, be only metallic state on a small quantity, and often and the element such as zinc, copper coexist.Lead and compound thereof are a kind of nondegradable environmental pollutant, can flow in a large number environment by waste water,waste gas and industrial residue, by food chain, soil, water and air, enter directly or indirectly human body, infringement hemopoietic system, cause anaemia, neural system peripheral nerve inflammation, also can flow into cerebral tissue with blood, infringement cerebellum and brain cortex cell, disturb metabolic activity, cause brain injury, and Toxicity of Lead is lasting, the transformation period reaches 10 years, be difficult for being discharged by human body, the Lead contamination of any degree all can have a negative impact to HUMAN HEALTH.Total lead in waste water is first kind pollutent, and lead waste water must reach first kind pollutent maximum permissible concentration emission standard as need discharge ，Zong Qian workshop discharge outlet.
At present, process heavy metal in waste water lead ion, industrial general employing chemical precipitation method, ion exchange method, electrolytic process.In addition, liquid-film method and biosorption process are the treatment processs of emerging lead waste water, at present in conceptual phase, are developing direction from now on.Chemical precipitation method equipment is simple, easy to operate, treatment effect is good, at present, more general to the processing application of the lead waste water of high density, large flow, but expense is high, treatment capacity is little, poor selectivity, sludge quantity are large, mud is difficult for processing, easily causing secondary pollution.Ion exchange method has that floor space is little, convenient management, lead ion decreasing ratio are high, and process the proper regenerated liquid that makes and reclaim as resource, can not cause secondary pollution to environment, but one-time investment is large, working cost is high, resin vulnerable to pollution or oxidation deactivation, regeneration is frequent, and also there is certain difficulty in regeneration problem.Electrolytic process technical maturity, has clearance high, non-secondary pollution, and the heavy metal recoverable precipitating, changes adaptability to waste water quality stronger, and the reaction times is short, but energy consumption is large while processing a large amount of waste water, and electrode metal consumption is large, is not suitable for high-concentration waste water.Liquid-film method has purified water quality, again enriching and recovering heavy metal, play double effects, but because liquid film technology difficulty is large,, poor performance few for the preparation of the tensio-active agent kind of emulsifying agent liquid film, demulsification technology do not pass a test etc., have hindered the industrialization of this method.Biosorption process is not used chemical agent, sludge quantity is few, non-secondary pollution, discharge water can reuses, in bacterium mud, the recyclable and bacterium mud of metal can be used as fertilizer, microorganism is good to lead ion treatment effect under lower concentration, but is subject to pH value, temperature, concentration of metal ions, biomembranous culture condition, the heavy metal ion that coexists etc. compared with multifactor impact.
Summary of the invention
The object of the invention is: for overcoming the deficiencies in the prior art, a kind for the treatment of process of lead waste water is provided, this invented technology flow process is simple, running cost is low, obvious processing effect, and after primary treatment, in water, residual plumbum ion concentration is less than 0.6mg/L, first discharge standard lower than national regulation, clearance, up to more than 99%, produces without precipitation, can not cause secondary pollution.
The technical solution used in the present invention is: a kind for the treatment of process mountain of lead waste water is attapulgite modified, hydrotalcite and amorphous silica are the sorbing material that raw material is prepared into, by quality ratio, attapulgite modified 20～50%, hydrotalcite 20～40%, amorphous silica 20～40%.
Described attapulgite modified be to take attapulgite as raw material, the dignified limestone in volcano is activator, uses hydrochloric acid acidleach, then mixes metallic iron ion and magnesium ion is prepared from; Described hydrotalcite is through being ground into 80 object particles, then passes through alkali cleaning acidleach, high-temperature activation; Described amorphous silica is to obtain siliceous product with the dignified limestone in water treatment volcano.
The method of modifying of described attapulgite is: take attapulgite as raw material, adding the ore amount 1/10 dignified limestone in～1/5 volcano is activator, through pulverizing, preparing burden, then slurrying in the aqueous hydrochloric acid that is 100～200mg/L in mass concentration, preimpregnation, add wherein the iron ion of 2M and the magnesium ion of 1M, solid-liquid separation, solid matter form through 800 ℃～900 ℃ high-temperature activations for 6～8 hours again.
The preparation method of described amorphous silica is: " the dignified limestone in volcano " protolith of extraction is sieved, fetched water, segregation is hydrolyzed in importing revolving drum machine, silicon slurry is separated with rock slag, and discharges from cylindrical machine, and silicon slurry part is through precipitating, dewater, be drying to obtain product.
Application method of the present invention is: the attapulgite preparing, hydrotalcite and amorphous silica are re-dubbed to deleading agent in mass ratio, regulating pH value is 9.7～12.3, at normal temperature and pressure slurrying, preimpregnation 3～16h, more this ore pulp is imported to protection against corrosion stirred leaching tank; Heat to 70～90 ℃, continue to leach 35～60min under normal pressure, joining lead tolerance is in 10～200mg/L waste water, and after stirring 20～45min, water outlet can reach national grade one discharge standard, and clearance is more than 99%.
The invention has the beneficial effects as follows:
(1) technical process is simple, and running cost is low;
(2) obvious processing effect, after primary treatment, in water, residual plumbum ion concentration is less than 0.6mg/L, and lower than the first discharge standard of national regulation, clearance is up to more than 99%;
(3) the present invention is when the heavy metal wastewater therebies such as acid, the alkali of processing various concentration is leaded, and the heavy metal content such as lead that all can guarantee water outlet are stably lower than the highest permission emission concentration of trade effluent and be near or below the concentration of Drinking Water matter standard code.
Embodiment
Treatment process by attapulgite modified, hydrotalcite and amorphous silica, be the sorbing material that raw material is prepared into, by quality ratio, attapulgite modified 20～50%, hydrotalcite 20～40%, amorphous silica 20～40%.
Described attapulgite modified be to take attapulgite as raw material, the dignified limestone in volcano is activator, uses hydrochloric acid acidleach, then mixes metallic iron ion and magnesium ion is prepared from; Described hydrotalcite is through being ground into 80 object particles, then passes through alkali cleaning acidleach, high-temperature activation; Described amorphous silica is to obtain siliceous product with the dignified limestone in water treatment volcano.
The method of modifying of described attapulgite is: take attapulgite as raw material, adding the ore amount 1/10 dignified limestone in～1/5 volcano is activator, through pulverizing, preparing burden, then slurrying in the aqueous hydrochloric acid that is 100～200mg/L in mass concentration, preimpregnation, add wherein the iron ion of 2M and the magnesium ion of 1M, solid-liquid separation, solid matter form through 800 ℃～900 ℃ high-temperature activations for 6～8 hours again.
The preparation method of described amorphous silica is: " the dignified limestone in volcano " protolith of extraction is sieved, fetched water, segregation is hydrolyzed in importing revolving drum machine, silicon slurry is separated with rock slag, and discharges from cylindrical machine, and silicon slurry part is through precipitating, dewater, be drying to obtain product.
Application method of the present invention is: the attapulgite preparing, hydrotalcite and amorphous silica are re-dubbed to deleading agent in mass ratio, regulating pH value is 9.7～12.3, at normal temperature and pressure slurrying, preimpregnation 3～16h, more this ore pulp is imported to protection against corrosion stirred leaching tank; Heat to 70～90 ℃, continue to leach 35～60min under normal pressure, joining lead tolerance is in 10～200mg/L waste water, and after stirring 20～45min, water outlet can reach national grade one discharge standard, and clearance is more than 99%.
Example 1: choose attapulgite 20%, 40% hydrotalcite and 40% amorphous silica that prepare and be re-dubbed in mass ratio deleading agent, regulating pH value is 9.7, at normal temperature and pressure slurrying, preimpregnation 3h, then imports protection against corrosion stirred leaching tank by this ore pulp; Heat to 70 ℃, continue to leach 35min under normal pressure, joining zinc content is in 200mg/L waste water, and after stirring 20min, in water outlet, zinc content is 0.6mg/L, and clearance is 99.7%.
Example 2: choose attapulgite 30%, 30% hydrotalcite and 40% amorphous silica that prepare and be re-dubbed in mass ratio deleading agent, regulating pH value is 11.2, at normal temperature and pressure slurrying, preimpregnation 10h, then imports protection against corrosion stirred leaching tank by this ore pulp; Heat to 80 ℃, continue to leach 50min under normal pressure, joining zinc content is in 150mg/L waste water, and after stirring 30min, in water outlet, zinc content is 0.3mg/L, and clearance is 99.8%.
Example 3: choose 40% attapulgite, 40% hydrotalcite and 20% amorphous silica that prepare and be re-dubbed in mass ratio deleading agent, regulating pH value is 12.3, at normal temperature and pressure slurrying, preimpregnation 16h, then imports protection against corrosion stirred leaching tank by this ore pulp; Heat to 90 ℃, continue to leach 60min under normal pressure, joining zinc content is in 50mg/L waste water, and after stirring 45min, in water outlet, zinc content is 0.1mg/L, and clearance is 99.8%.
Claims (4)
1. the treatment process of a lead waste water, it is characterized in that: attapulgite modified, the hydrotalcite preparing and amorphous silica are re-dubbed to deleading agent in mass ratio, regulating pH value is 9.7-12.3, slurrying at normal temperatures and pressures, preimpregnation 3-16h, more this ore pulp is imported to protection against corrosion stirred leaching tank; Heat to 70～90 ℃, under normal pressure, continue to leach 35～60min, joining lead tolerance is in 10～200mg/L waste water, after stirring 20～45min, water outlet can reach national grade one discharge standard, and clearance is more than 99%, described deleading agent by quality ratio, attapulgite modified 20～50%, hydrotalcite 20～40%, amorphous silica 20～40%.
2. a kind for the treatment of process of lead waste water according to claim 1, is characterized in that: described attapulgite modified be to take attapulgite as raw material, the dignified limestone in volcano is activator, uses hydrochloric acid acidleach, then mixes metallic iron ion and magnesium ion is prepared from; Described hydrotalcite is through being ground into 80 object particles, then passes through alkali cleaning acidleach, high-temperature activation; Described amorphous silica is to obtain siliceous product with the dignified limestone in water treatment volcano.
3. the treatment process of a kind of lead waste water according to claim 1, it is characterized in that: the method for modifying of attapulgite is: take attapulgite as raw material, adding the ore amount 1/10 dignified limestone in～1/5 volcano is activator, through pulverizing, preparing burden, then slurrying in the aqueous hydrochloric acid that is 100～200mg/L in mass concentration, preimpregnation, then add wherein the iron ion of 2M and the magnesium ion of 1M, solid-liquid separation, solid matter form through 800 ℃～900 ℃ high-temperature activations for 6～8 hours.
4. the treatment process of a kind of lead waste water according to claim 1, it is characterized in that: the preparation method of amorphous silica is: " the dignified limestone in volcano " protolith of extraction is sieved, fetched water, segregation is hydrolyzed in importing revolving drum machine, silicon slurry is separated with rock slag, and discharge from cylindrical machine, silicon slurry part is through precipitating, dewater, be drying to obtain product.
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| CN201210538638.1A CN102976434B (en) | 2012-12-11 | 2012-12-11 | Method for treating lead-containing wastewater |
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| DE102012012367B4 (en) * | 2012-06-21 | 2014-03-27 | Ftu Gmbh Forschung Und Technische Entwicklung Im Umweltschutz | ACTIVATED TRACING, ITS MANUFACTURE AND USE |
| DE102014113620A1 (en) | 2014-09-22 | 2016-03-24 | Ftu Gmbh | Pozzolans for exhaust gas purification |
| CN115155508B (en) * | 2022-07-06 | 2024-01-05 | 上海交通大学 | FeS/LDH nano adsorbent and synthetic method and application thereof |
| CN116116881B (en) * | 2023-01-29 | 2024-02-23 | 西部矿业股份有限公司 | Method for cooperatively treating lead-containing wastewater by utilizing modified stone coal vanadium extraction smelting waste residues |
| CN116444054B (en) * | 2023-06-14 | 2023-08-29 | 济南山源环保科技有限公司 | Boiler water treatment agent and preparation method thereof |
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| CN102284279A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Attapulgite/silicon dioxide composite powder and preparation method thereof |
| CN102336461A (en) * | 2010-07-27 | 2012-02-01 | 中国科学院过程工程研究所 | Method for removing metal ions from aqueous solution by use of hydrotalcite |
| CN102464398A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Method for treating zincky waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7309437B2 (en) * | 2004-01-07 | 2007-12-18 | The Texas A&M University System | Compositions and methods for removal of toxic metals and radionuclides |
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| CN1043921A (en) * | 1989-12-29 | 1990-07-18 | 张明 | A kind of arsenic and heavy metal wastewater purificant |
| US5397500A (en) * | 1993-03-08 | 1995-03-14 | Lee; Jong-Chan | Compositions for treating waste water which contains heavy metals |
| CN102284279A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Attapulgite/silicon dioxide composite powder and preparation method thereof |
| CN102336461A (en) * | 2010-07-27 | 2012-02-01 | 中国科学院过程工程研究所 | Method for removing metal ions from aqueous solution by use of hydrotalcite |
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Effective date of registration: 20160129 Address after: 516323 Guangdong County of Huidong Province town of Liang stone Liao Nan Keng Patentee after: Huizhou Dongjiang Veolia Environmental Service Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |