CN1016849B - Scavenger for arsenic and heavy metal waste water - Google Patents
Scavenger for arsenic and heavy metal waste waterInfo
- Publication number
- CN1016849B CN1016849B CN 89109581 CN89109581A CN1016849B CN 1016849 B CN1016849 B CN 1016849B CN 89109581 CN89109581 CN 89109581 CN 89109581 A CN89109581 A CN 89109581A CN 1016849 B CN1016849 B CN 1016849B
- Authority
- CN
- China
- Prior art keywords
- charcoal
- yellow
- magnalium
- copperas
- carbonaceous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
The present invention provides a scavenger for arsenic and heavy metal waste water, which is formed by matching magnesium aluminum copiapite, the molecular formula of (Fe, Mg) (Fe, Al)-<4> (SO4)-<6> (OH)-<2>, 20H2O and formless charcoal by the weight proportion of 1: 1 to 4, wherein the magnesium aluminum copiapite is made by the method of soaking ferrohydrite by sulfuric acid. The product also comprises 2% to 8% of active silicon dioxide. The formless charcoal is natural active charcoal and is composed of the formless charcoal and a small amount of debris. The present invention is manufactured by hydrolyzing and isolating charcoal volcano depositing tuff not known by people at present.
Description
The present invention relates to the processing of trade effluent, is the scavenging agent of a kind of arsenic and heavy metal wastewater thereby.
The method of handling arsenic and heavy metal wastewater thereby at present mainly contains: handle lime one iron salt method of arsenic-containing waste water, make lime and arsenate or arsenous anion generate the calcium precipitation of indissoluble.Iron, aluminium salt such as ferrous sulfate, ferric sulfate, Indian red, Tai-Ace S 150 etc. form stable comple with arsenate or arsenous anion and are the characteristics arsenic removal of iron, aluminum metal oxyhydroxide sorption-coprecipitation.Handle mercury-containing waste water sulfuration method, metallic reducing method, chemical precipitation method, active carbon adsorption etc. are arranged, but water outlet is difficult to reach the following industrial wastewater discharge concentration of 0.05ppm, active carbon adsorption is only effective to low mercury waste water, but will add the gac of wastewater flow rate 5%.Handle heavy metal-containing waste water and adopt hydroxide precipitation method more at large, promptly in waste water, add lime, yellow soda ash and so on adjustment, be controlled at the treating water optimal ph and make metal ion and hydroxyl reaction generate the metal oxide precipitation of indissoluble.Therefore system of above-mentioned any medicament all is subjected to it self physics, the restriction of electrochemical conditions, contains multiple metal ion in waste water, just needs the use various medicaments carry out multiple section purification, and technology, equipment complexity are invested bigger; In addition, because of artificial gac costs an arm and a leg, about 6000 yuan/ton.The general user is difficult to bear.
Purpose of the present invention is exactly the shortcoming that overcomes above-mentioned prior art, simplifies the purification medicament and the processing unit of arsenic and heavy metal wastewater thereby, and it is abundant to obtain a kind of raw material sources, makes and easy to use, is easy to realize and improved the wastewater purificant of decontamination effect improving.
For achieving the above object, the present invention is achieved in that with " the dignified limestone in carbonaceous volcano " to be that activator obtains a kind of new iron content, magnalium ionic salt-magnalium yellow copperas with aqueous sulfuric acid oxidation acid leaching limonite; With this " the dignified limestone in carbonaceous volcano " segregation that is hydrolyzed rarely known by the people, obtain a kind of unformed carbon product simultaneously, the two is mixed with certain proportion, can obtain novel arsenic of the present invention and heavy metal wastewater purificant.
Arsenic provided by the invention and heavy metal wastewater purificant are the magnalium yellow copperas.Unformed charcoal Synergist S-421 95 product, this product by two kinds of compositions of magnalium yellow copperas and unformed charcoal by 1: the weight ratio of 1-4 cooperates to be formed, wherein:
1. the magnalium yellow copperas contains the active silica of 92～98% magnalium yellow copperas and 2～8%.
The magnalium yellow copperas is oyster white, yellow-white or yellowish green light green, is radiating fibers shape, warty crystallization, proportion 1.875, and hardness :～2, its chemical molecular formula is:
（Fe，Mg）（Fe，Al）
4（SO
4）
6（OH）
2·20H
2O
This material is soluble in water, and it is acid that its aqueous solution is, pH1.32～1.78; With the increase of molten concentration, be milk yellow, red-brown, blood red, black.
Active silica is a solubility silicon-dioxide, and it is dissolved in pH value of aqueous solution less than 4.8.
2. unformed charcoal is a kind of natural radioactivity charcoal, mainly is unformed charcoal and a small amount of sulfide, feldspar and quartzy landwaste.
Product magnalium yellow copperas provided by the invention.Unformed charcoal Synergist S-421 95 product divides two portions production, its method oxidation acid leaching and hydrolysis segregation on technical process and the equipment with hydrometallurgy on commonly used close, narrate respectively below.
1. the magnalium yellow copperas partly adopts oxidation acid leaching limonite manufactured, at first with the activator " the dignified limestone in carbonaceous volcano " of limonite and ore amount 1/10～1/5 (as magnesium in the ore, when aluminium is not enough with addition of alumina, magnesia) is crushed to below 1～3mm, carry out charge calculation and batching according to the chemical ingredients of ore and magnalium yellow copperas again, containing in the aqueous sulfuric acid of 100～200g/l in the batching input pneumatic blending leaching vat, in normal pressure and temperature slurrying, preimpregnation 2～24 hours, again this ore pulp is imported the protection against corrosion stirred leaching tank, heat to 90～95 ℃, under normal pressure, continue to leach 40～60 minutes, control terminal point pH＜2, solid-liquid separation then, supernatant liquor is heated, concentrate, crystallization promptly gets magnalium yellow copperas product.
Above-mentioned be the Fe in the limonite in the oxidation activator oxidation acid leaching limonite process with " the dignified limestone in carbonaceous volcano "
2O
3, MgO, Al
2O
3With effect of sulfuric acid, reaction formula is:
Second step: owing to no matter adopt carbonaceous volcano dignified limestone oxidized activating oxidation acid leaching process, perhaps use leach liquor to pass through the electric anode of electrolyzer, all can not make FeSO
4By the following formula complete oxidation is Fe
2(SO
4)
3, 2FeSO
4+ H
2SO
4+ 1/2O
2→ Fe
2(SO
4)
3+ H
2Therefore O, under controlling factors such as leach liquor residual sulfur acid content, leach liquor chemical constitution, temperature, promptly generates the magnalium yellow copperas, because the Fe in the molecular formula
2+And Mg
2+, Fe
3+And Al
3+Can exchange, so its chemical ingredients has certain rangeability.
Active silica in the magnalium yellow copperas is that the iron in the metal silicate in the acidleach process, copper, zinc one metalloid are replaced, and silicon-dioxide is by free and enter the magnalium yellow copperas.
2. unformed charcoal is to adopt " the dignified limestone in carbonaceous volcano " the method manufacturing of hydrolysis segregation.Raw material " the dignified limestone in carbonaceous volcano " is a kind of natural volcanic ash sedimentogeneous rock, identifies chemical analysis through the ore deposit rock: it is mainly by unformed charcoal and a small amount of sulfide, feldspar and the quartzy landwaste of being formed.This rock is known to be originated in the presinian system Kunyang group rock stratum of border, Yunnan, river Panxi Diqu, at present also industrial use, the economic worth of this rock of nobody's understanding both at home and abroad.Its manufacture method is: with " the dignified limestone in carbonaceous volcano " protolith input sieve aperture of extraction is on the sieve of 100mm, fetch water (comprise and return washing lotion) import hydrolysis segregation in the revolving drum machine, to sieve top gets rid of, the ore discharge of cylindrical machine, charcoal slurry separate with the rock slag, and charcoal slurry part is through precipitation or filter, dewater, be drying to obtain unformed charcoal product.
The unformed charcoal Synergist S-421 95 of product magnalium yellow copperas provided by the present invention product can be used for the arsenic and the heavy metal wastewater thereby of the various concentration of purifying treatment.For the carbon wastewater of high pH value, lower concentration, the pH value that adopts and once directly throw in product adjustment of the present invention, is controlled at treating water is the purification terminal point in 6.5～7.5.PH value alkaline waste water on the low side and acid waste water are adopted two sections purifying methods: one section purifies operation and adopts and once throw in pH value that milk of lime (comprising the backflow slag) adjusted, is controlled at treating water in 10.5～11.5, and two sections purify operation and adopt that once to throw in pH value that one section of product adjustment of the present invention, control purifies supernatant liquor be 6.5～7.5 to be the purification terminal point.
The scavenging agent consumption is: two sections lime consumptions that purify operation, 500～3450g/m
3Waste water; One, two sections magnalium yellow copperas that purify operations and unformed charcoal consumption respectively are 130 and 910g/m
3Waste water.
The unformed charcoal Synergist S-421 95 of the product magnalium yellow copperas product that the present invention obtains is by containing Mg
2+, Fe
2+, Al
3+, Fe
3+Metal sulfate-magnalium yellow copperas etc. multiple metal ion.Metal and nonmetal sulfide, active silica, unformed charcoal (natural radioactivity charcoal) and a small amount of landwaste are formed, and this composition has been established its many-sided function in to arsenic and heavy metal wastewater thereby purification:
1. the Fe in the magnalium yellow copperas
2+, Mg
2+, Fe
3+, Al
3+Deng Fe in the metal ion content
3+Account for 70%, other point 30%.In purification of waste water, have multiple effects such as chemical conversion, neutralization precipitation redox, can with As, Ba, Bi, Cd, the Cr in the waste water
3+, Cr
6+, Sn, Ag, Hg, Ti, V, Zn, Se, Mo etc. the metal ion reaction generate the indissoluble throw out and separate out, or be converted into the weak throw out of toxicity and separate out.
2. the sulfide precipitation that the sulfide in the unformed charcoal makes the metal ion of copper in the waste water, lead, mercury generate steel, plumbous mercury is separated out.
3. active silica exists in solution with the sol solution state, and when at the pH for the treatment of water＞4.8, its reunion of flocculating among various throw outs promotes and the sedimentation of accelerate precipitation thing becomes flocculation agent.Mg
2+, Al
3+Ion plays a part similar alum in muddy water, helps the precipitation of throw out, dirt to remove.
4. unformed charcoal be natural radioactivity charcoal and landwaste with the organism in its big specific surface area and the porosity planar water, produce look, flavor, smelly solubilised state and colloid pollution thing, heavy metal ion is played a part carrier and sorbent material.Through checking the unformed charcoal of this kind is 2～5 times of the artificial gac in Changsha to the decontamination effect improving of arsenic and heavy metal wastewater thereby.
Because product of the present invention is with chemical converting agent, sorbent material, flocculation agent, many-sides such as promotor and throw out carrier have been mixed together among a kind of scavenging agent of the unformed charcoal Synergist S-421 95 of magnalium yellow copperas product to the purification function of arsenic and heavy metal wastewater thereby, replace various wastewater and handled medicament, therefore, scavenging agent of the present invention can reach following effect under using method mentioned above: this wastewater purificant is in the acid of handling various concentration, when alkali contains arsenic and heavy metal wastewater thereby, can guarantee that all the arsenic of water outlet and heavy metal content stably are lower than the highest permission emission concentration of trade effluent and are near or below the concentration of Drinking Water water quality standard regulation: mercury wherein, plumbous, cadmium, chromium, zinc, copper, the clearance of iron reaches 99.99～99.90%, when arsenic content in the waste water is very low be 20 and during 100ppb water outlet to contain arsenic respectively be 14 and 30ppb, clearance 60～70%.Concrete effect sees Table 1, and wherein 1
#Be copper ore dressing tailings water, 2
#～4
#Be plumbous zinc ore smelting wastewater.
The resulting wastewater purificant of the present invention, its raw material are cheap abundant limonite, sulfuric acid etc., and limonite is to select its water-soluble, as to be easy to acidleach aspect, rather than grade; And " the dignified limestone in carbonaceous volcano " is a kind of natural volcanic ash sedimentogeneous rock of utilizing of not obtaining as yet, its exploitation is utilized as society and has opened up a kind of new industrial raw material, there is this rock stratum in the whole nation ten provinces, the natural radioactivity charcoal that this product obtains, and cheap have only hundreds of unit/ton.
Introduce the embodiment of a magnalium yellow copperas production method below.
1. prepare burden
The chemical analysis results of limonite in the present embodiment, magnesia, alumina and " the dignified limestone in carbonaceous volcano " sees Table 1.
Chemical molecular formula according to the magnalium yellow copperas
（Fe，Mg）（Fe，Al）
4（SO
4）
6（OH）
2·20H
2O
Atomic wts ratio in its chemical ingredients is:
Mg∶Al∶Fe＝1∶1∶8
Mg∶Al∶Fe
2+∶Fe
3+＝1∶1∶1∶7
Because the Al in the present embodiment in the limonite
2O
3Contain quantity not sufficient, except pressing 10: 1 weight ratios with addition of the dignified limestone in oxidation activity agent carbonaceous volcano with limonite, also need add the alumina that accounts for ingredients by weight 5%, promptly the weight ratio of limonite in the ore-burden, alumina and " the dignified limestone in carbonaceous volcano " is 85: 5: 10.
2. oxidation acid leaching processing method
Above-mentioned batching is crushed to below the 3mm, by solid-to-liquid ratio 1: drop into to contain in the 200g/l aqueous sulfuric acid and sizes mixing, at normal temperatures and pressures, pneumatic blending leached 2 hours, continued it, imported anticorrosion steel basin and was warming up to 90～95 ℃, under normal pressure, continue pneumatic blending 60 minutes, enter settling tank then.Its supernatant liquor is through concentrating, crystallization, promptly getting magnalium yellow copperas product.
Table 1
Material name chemical ingredients Wt%
T.Fe SiO
2Al
2O
3CaO MgO C S
Limonite 40 511 4--
Magnesia 1315 40--
Alumina 5 20 60 3 2--
Carbonaceous volcano 5 60 10 11 20 2.8
Dignified limestone
Table 2
Numbering 1
#2
#3
#4
#
Liquid water outlet before the liquid water outlet before the liquid water outlet before the liquid water outlet before the title
pH????10.55????7.39????2.30????7.30????3.48????7.76????3.48????6.60
As????0.02????0.014????0.08????0032????0.10????0030????0.024????0.016
Inspection Hg 0.004 0.0015 0.092 0.0013--0.049 N.D.
Test Cr----0.136 0.04 0.038 N.D.
Item Pb 0.12 0.02 2,320 00,081 6.65＜0.01 3.880 0.0926
Order Cd 0.016 0.0018 74.71 0.0059 35.0 0.021 8.852 0.0385
Or Cu 4.52 0.043 14.56 0.013 6.49 0.04 6.977 0.024
Zn 0.39 0.078 6130.44 1.08 2175.0 1.80 4696.7 0.660 is arranged
Evil Fe 402.43-178.86 is little 30.90 0.011--
Thing Mn----87.40 0.248--
Matter F 0.40 0.32 0.8 0.8 1.6 0.69 0.700 0.640
Contain SS------327.0 79.0
Amount CoD------35.50 3.89
(mg/L) sulfide------N.D. N.D.
Claims (2)
1, a kind of arsenic and heavy metal wastewater purificant of containing, it is characterized in that: form by magnalium yellow copperas and unformed charcoal, the magnalium yellow copperas is to be activator with the dignified limestone in carbonaceous volcano, make with the vitriol lixiviation limonite, unformed charcoal is the carbonaceous product that obtains with the dignified limestone in water treatment carbonaceous volcano, and magnalium yellow copperas and unformed charcoal weight ratio are 1: 1～4.
2, a kind of production method of wastewater purificant as claimed in claim 1 is characterized in that:
A. the method for preparing the magnalium yellow copperas is: be raw material with the limonite, the dignified limestone in carbonaceous volcano that adds ore amount 1/10～1/5 is an activator, through pulverizing, preparing burden, slurrying in the aqueous sulfuric acid of concentration 100～200g/l, preimpregnation then, leach and keep terminal point pH＜2, solid-liquid separation, supernatant liquor are heated, are concentrated, crystallization, obtain the magnalium yellow copperas.
B. the preparation method of unformed charcoal is: " the dignified limestone in carbonaceous volcano " protolith of extraction is sieved, fetches water, import the segregation that is hydrolyzed in the revolving drum machine, the ore discharge of cylindrical machine, charcoal slurry separate with the rock slag, and charcoal slurry part is through precipitating, dewater, be drying to obtain product
C. above-mentioned magnalium yellow copperas and unformed charcoal are mixed by 1: 1～4 ratio and promptly get the product scavenging agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109581 CN1016849B (en) | 1989-12-29 | 1989-12-29 | Scavenger for arsenic and heavy metal waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109581 CN1016849B (en) | 1989-12-29 | 1989-12-29 | Scavenger for arsenic and heavy metal waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043921A CN1043921A (en) | 1990-07-18 |
| CN1016849B true CN1016849B (en) | 1992-06-03 |
Family
ID=4858075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109581 Expired CN1016849B (en) | 1989-12-29 | 1989-12-29 | Scavenger for arsenic and heavy metal waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016849B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386141C (en) * | 2005-07-20 | 2008-05-07 | 上海自来水市北科技有限公司 | Composite absorption material for removing arsenic from water and its prepn. method |
| CN100460056C (en) * | 2006-05-12 | 2009-02-11 | 中国科学院生态环境研究中心 | Method for preparing sulfate akaganeite adsorbent for de-arsenation |
| 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 |
| CN102976434B (en) * | 2012-12-11 | 2014-01-15 | 常州大学 | Method for treating lead-containing wastewater |
| CN110302742B (en) * | 2019-08-13 | 2022-07-01 | 河南昶宜检测技术研究院有限公司 | Preparation and application method of nano material for selectively adsorbing heavy metals |
-
1989
- 1989-12-29 CN CN 89109581 patent/CN1016849B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043921A (en) | 1990-07-18 |
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