CN107324534A - A kind of method that utilization ferriferous oxide handles the waste acid containing arsenic - Google Patents

A kind of method that utilization ferriferous oxide handles the waste acid containing arsenic Download PDF

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Publication number
CN107324534A
CN107324534A CN201710581619.XA CN201710581619A CN107324534A CN 107324534 A CN107324534 A CN 107324534A CN 201710581619 A CN201710581619 A CN 201710581619A CN 107324534 A CN107324534 A CN 107324534A
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China
Prior art keywords
waste acid
arsenic
ferriferous oxide
containing arsenic
acid containing
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CN201710581619.XA
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Chinese (zh)
Inventor
王�华
李勋
祝星
祁先进
韦龙华
徐媛
李勇
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CN201710581619.XA priority Critical patent/CN107324534A/en
Publication of CN107324534A publication Critical patent/CN107324534A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5272Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/103Arsenic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The present invention relates to a kind of method that utilization ferriferous oxide handles the waste acid containing arsenic, belong to hydrometallurgical technology and Waste Disposal Technology field.Ferriferous oxide is added in waste acid containing arsenic by the inventive method, ferriferous oxide and waste acid react generation solidliquid mixture, are filtrated to get stable arsenic-containing solid material, realize the removing of arsenic in waste acid containing arsenic, and the harm of arsenic is prevented, reach the purpose that waste acid is handled using cheap source of iron;This technological operation is simple, production cost is low, to environmental beneficial, with broader market prospects.

Description

A kind of method that utilization ferriferous oxide handles the waste acid containing arsenic
Technical field
The present invention relates to a kind of method that utilization ferriferous oxide handles the waste acid containing arsenic, belong to hydrometallurgical technology and discarded object Processing technology field.
Background technology
At present, China's blister copper yield is every year 520000 tons or so, and these copper largely use the sulphur in pyrometallurgical smelting, copper mine Element is separated during the pyrometallurgical smelting of copper for relieving haperacidity, and a large amount of acid waste waters can be produced in acid manufacturing processes, referred to as " dirty Acid ".Arsenic of the association in copper mine in the smelting process of copper(As), cadmium(Cd), lead(Pb), copper(Cu), zinc(Zn), mercury(Hg)、 Selenium(Se)Enter acid-making process Deng with flue gas during smelting, the purification by acid-making process to flue gas during smelting so that flue gas qualified discharge. And impurity element of the association in copper mine then largely enters in " waste acid " periodically extracted out.It is estimated that producing 100000 tons of copper smeltings per year The supporting lime-iron salt method technique in refinery produces about 10,000 tons of gypsum tailings per year, and thus, China Copper smelting industry will produce million every year The slag sludge of gypsum containing arsenic of ton or so.And whole Chinese smelting industry, the waste material containing arsenic stored up over the years is up to tens million of tons. The gypsum tailings containing arsenic that smeltery and its neighboring area are stored up for a long time may by poor management in terms of the reason for, be taken as General industry solid waste and scattered away from regulatory area, so as to cause soil or Farmland contamination, arable land heavy metal pollution is tight Agricultural product quality, indirect hazard human health are threatened again.
Cut-off will be to the end of the year 2015, and China possesses at the iron ore place of production 1995 altogether, and iron ore finds out the t of resource reserve 578.72 hundred million (storages 118.36 hundred million t, the t of basic unit price 213.57 hundred million are measured, stock number 365.15 hundred million is t).At whole nation exploitation mining area and capital construction mining area 696, account for With the t of reserves 20,200,000,000, the 44% of the whole reserves of iron ore is accounted for.Substantial amounts of iron ore is mainly used in industrial iron and steel smelting, and steel is being used During be converted into ferriferous oxide due to the reason such as getting rusty, aoxidizing, at present, substantial amounts of ferriferous oxide can not obtain effective profit With, the present invention obtains the characteristic of molysite using ferriferous oxide and acid reaction, and ferriferous oxide and waste acid hybrid reaction are handled into waste acid, Cheap ferriferous oxide can be comprehensively utilized and administer waste acid, low-cost resource is effectively utilized.
The content of the invention
It is an object of the invention to provide a kind of method that utilization ferriferous oxide handles the waste acid containing arsenic, this method is to utilize iron oxygen Compound is reacted with waste acid, the matter containing arsenic stablized, and prevents the harm of arsenic, realizes the mesh that waste acid is handled with cheap ferriferous oxide , this method is simple to operate, and cost is low, has to environmental protection and certain actively promotes effect.
Technical scheme is as follows:Ferriferous oxide is added in waste acid containing arsenic first, certain time is reacted under normal temperature, Mixed solution is obtained, mixed solution pH is adjusted, is heated to certain temperature and reacts after a period of time, obtain solidliquid mixture, is filtered, Solid-state matter containing arsenic and filtrate are obtained, flocculant is added into filtrate and carries out purified treatment, that is, completes the place to the waste acid containing arsenic Reason.
The method for being handled the waste acid containing arsenic in the present invention using ferriferous oxide, is comprised the following steps that:
(1)Ferriferous oxide is added into waste acid containing arsenic, wherein iron arsenic mol ratio is 1:1-3:1,1 ~ 4h of stirring reaction under normal temperature, are obtained To mixed solution;
(2)Regulating step(1)The pH value of middle mixed solution is 1 ~ 3, and mixed solution then is heated into 70 ~ 90 DEG C, reaction 6 ~ 12h, obtains solidliquid mixture;
(3)Filtration step(2)In solidliquid mixture, filter residue is matter containing arsenic;
(4)To step(3)Flocculant is added in obtained filtrate and carries out purified treatment, wherein flocculant is DMDS for ammonia Base sodium formate.
Ferriferous oxide source is wide in the present invention, and price is low, while serve the effect of conditioning agent and reactant, reached with Cheap ferriferous oxide handles the purpose of the waste acid containing arsenic, reduces production cost, economically feasible.
Beneficial effects of the present invention:
(1)The inventive method is utilized in ferriferous oxide and waste acid, is greatly reduced the solid produced in waste acid processing procedure and is given up Gurry, it is economic and environment-friendly;
(2)The inventive method reacts ferriferous oxide and waste acid, generates stable matter containing arsenic, realizes effective place of waste acid Reason, reduces the murder by poisoning degree of metallic arsenic;
(3)The inventive method handles waste acid using ferriferous oxide, and with the solution after flocculant purified treatment, makes arsenic and other Heavy metal ion is from Transfer in Aqueous Solution moves to the sediments such as the inactive ferric arsenate of chemical property, and supernatant is work up to standard Industry water, it is simple with operating procedure, it is with low cost, the features such as high treating effect.
Simple possible of the present invention, cost is relatively low, and treatment effect is preferably, beneficial to environmental protection, while being the waste acid containing arsenic Processing is there is provided a kind of new technical method, with wide application prospect.
Embodiment
The present invention is described in further detail below by embodiment, but the scope of the present invention is not limited in described Hold.
Embodiment 1:Waste acid containing arsenic is handled using ferriferous oxide, concrete operations are as follows:
(1)Waste acid respectively constitutes constituent concentration, as shown in table 1,
The waste acid each component concentration of table 1.(mg/L)
As Cu H Zn Cd F
13000 512.03 1.68 840.94 145.95 3214.12
(2)Weigh a certain amount of Fe3O4, it is added in above-mentioned waste acid solution, iron arsenic mol ratio is 1:1, stirring reaction 1 is small under normal temperature When, obtain mixed solution;
(3)Use NaOH regulating steps(2)Mixed solution pH be 3, by the mixed solution regulated be heated to 70 DEG C reaction 6h, Obtain solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 2.(mg/L)
As Cu H Zn Cd F
353.6 212 0..001 256 46 1423
From above-mentioned data, the removal efficiency of arsenic has reached 97.28% in the waste acid of the present embodiment 1, and the content of other components is also obtained Certain reduction is arrived, it is possible to achieve effective processing of waste acid.
Embodiment 2:The method that the waste acid containing arsenic is handled using ferriferous oxide, is comprised the following steps that:
(1)Waste acid is respectively constituted shown in constituent concentration be the same as Example 1;
(2)Weigh a certain amount of Fe3O4, it is added in above-mentioned waste acid solution, wherein iron arsenic mol ratio is 1:1, stir under normal temperature anti- Answer 3 hours, obtain mixed solution;
(3)Use NaOH regulating steps(2)Mixed solution pH be 2, by the mixed solution regulated be heated to 80 DEG C reaction 8h, Obtain solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 3.(mg/L)
As Cu H Zn Cd F
55.56 201 0.013 241 39 1236
From above-mentioned data, the removal efficiency of arsenic has reached 99.57% in the waste acid of the present embodiment 2, and the content of other components is also obtained Certain reduction is arrived, it is possible to achieve effective processing of waste acid.
Embodiment 3:The method that the waste acid containing arsenic is handled using ferriferous oxide, is comprised the following steps that:
(1)Waste acid is respectively constituted shown in constituent concentration be the same as Example 1;
(2)Weigh a certain amount of Fe3O4, it is added in above-mentioned waste acid solution, wherein iron arsenic mol ratio is 2:1, stir under normal temperature anti- Answer 4 hours, obtain mixed solution,;
(3)Use NaOH regulating steps(2)Mixed solution pH be 1, by the mixed solution regulated be heated to 90 DEG C reaction 12h, obtains solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 4.(mg/L)
As Cu H Zn Cd F
391.6 123 0..125 165 27 847
From above-mentioned data, the removal efficiency of arsenic has reached 96.99% in the waste acid of the present embodiment 3, and the content of other components is also obtained Certain reduction is arrived, it is possible to achieve effective processing of waste acid.
Embodiment 4:The method that the waste acid containing arsenic is handled using ferriferous oxide, is comprised the following steps that:
(1)Waste acid is respectively constituted shown in constituent concentration be the same as Example 1;
(2)Weigh a certain amount of Fe3O4, it is added in above-mentioned waste acid solution, wherein iron arsenic mol ratio is 3:1, stir under normal temperature anti- Answer 2 hours, obtain mixed solution;
(3)Use NaOH regulating steps(2)Mixed solution pH be 2, by the mixed solution regulated be heated to 90 DEG C reaction 12h, obtains solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 5.(mg/L)
As Cu H Zn Cd F
9.018 96 0.134 114 23 543
From above-mentioned data, the removal efficiency of the waste acid of the present embodiment has reached 99.93%, and the content of other components is also obtained Certain reduction, it is possible to achieve effective processing of waste acid.
Embodiment 5:The method that the waste acid containing arsenic is handled using ferriferous oxide, is comprised the following steps that:
(1)Waste acid is respectively constituted shown in constituent concentration be the same as Example 1;
(2)Weigh a certain amount of Fe2O3, it is added in above-mentioned waste acid solution, wherein iron arsenic mol ratio is 3:1, stir under normal temperature anti- Answer 2 hours, obtain mixed solution;
(3)Use NaOH regulating steps(2)Mixed solution pH be 2, by the mixed solution regulated be heated to 90 DEG C reaction 12h, obtains solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 6.(mg/L)
As Cu H Zn Cd F
18.021 95 0.133 113 24 560
From above-mentioned data, the removal efficiency of the waste acid of the present embodiment has reached 99.86%, and the content of other components is also obtained Certain reduction, it is possible to achieve effective processing of waste acid.
Embodiment 6:The method that the waste acid containing arsenic is handled using ferriferous oxide, is comprised the following steps that:
(1)Waste acid is respectively constituted shown in constituent concentration be the same as Example 1;
(2)A certain amount of FeO is weighed, is added in above-mentioned waste acid solution, wherein iron arsenic mol ratio is 3:1, stirring reaction 2 under normal temperature Hour, obtain mixed solution;
(3)Use NaOH regulating steps(2)Mixed solution pH be 2, by the mixed solution regulated be heated to 90 DEG C reaction 12h, obtains solidliquid mixture;
(4)Use filter plant filtration step(3)Obtained solidliquid mixture, obtains arsenic-containing solid material and filtrate, will contain arsenic and consolidate State material carries out stacking processing, and addition flocculant SDD carries out purified treatment into filtrate.
(5)The filtrate each component concentration of table 7.(mg/L)
As Cu H Zn Cd F
23.52 87 0.124 107 21 558
From above-mentioned data, the removal efficiency of the waste acid of the present embodiment has reached 99.81%, and the content of other components is also obtained Certain reduction, it is possible to achieve effective processing of waste acid.

Claims (3)

1. a kind of method that utilization ferriferous oxide handles the waste acid containing arsenic, it is characterised in that carry out as follows:
(1)1 ~ 4h of stirring reaction under ferriferous oxide, normal temperature is added into waste acid containing arsenic, mixed solution is obtained;
(2)Regulating step(1)The pH value of middle mixed solution is 1 ~ 3, and mixed solution then is heated into 70 ~ 90 DEG C, reaction 6 ~ 12h, obtains solidliquid mixture;
(3)Filtration step(2)In solidliquid mixture, filter residue is matter containing arsenic;
(4)To step(3)Flocculant is added in obtained filtrate and carries out purified treatment.
2. the method that utilization ferriferous oxide according to claim 1 handles the waste acid containing arsenic, it is characterised in that:Step(1)Iron Arsenic mol ratio is 1:1-3:1.
3. the method that utilization ferriferous oxide according to claim 1 handles the waste acid containing arsenic, it is characterised in that:Step(4)In Flocculant is SDD.
CN201710581619.XA 2017-07-17 2017-07-17 A kind of method that utilization ferriferous oxide handles the waste acid containing arsenic Pending CN107324534A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547777A (en) * 2020-05-22 2020-08-18 昆明理工大学 Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite
CN111569823A (en) * 2020-05-22 2020-08-25 昆明理工大学 Method for removing arsenic by adsorbing iron-manganese oxide/mesoporous silicon oxide adsorbent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553197A (en) * 2013-11-05 2014-02-05 红河学院 Method for removing arsenic and antimony in industrial wastewater by using smelting furnace slag
KR20140070727A (en) * 2012-11-26 2014-06-11 한국지질자원연구원 Adsorbent, Method for producing the adsorbent and Method for remediation of contaminated water using the same
CN104860445A (en) * 2015-06-03 2015-08-26 安徽新中远化工科技有限公司 Method for treating arsenic-containing wastewater by using pyrite cinder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140070727A (en) * 2012-11-26 2014-06-11 한국지질자원연구원 Adsorbent, Method for producing the adsorbent and Method for remediation of contaminated water using the same
CN103553197A (en) * 2013-11-05 2014-02-05 红河学院 Method for removing arsenic and antimony in industrial wastewater by using smelting furnace slag
CN104860445A (en) * 2015-06-03 2015-08-26 安徽新中远化工科技有限公司 Method for treating arsenic-containing wastewater by using pyrite cinder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547777A (en) * 2020-05-22 2020-08-18 昆明理工大学 Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite
CN111569823A (en) * 2020-05-22 2020-08-25 昆明理工大学 Method for removing arsenic by adsorbing iron-manganese oxide/mesoporous silicon oxide adsorbent
CN111547777B (en) * 2020-05-22 2022-01-28 昆明理工大学 Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite

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