CN105621582B - A kind of method of the water-soluble heavy metal ion of mechanical force curing - Google Patents
A kind of method of the water-soluble heavy metal ion of mechanical force curing Download PDFInfo
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- CN105621582B CN105621582B CN201510794231.9A CN201510794231A CN105621582B CN 105621582 B CN105621582 B CN 105621582B CN 201510794231 A CN201510794231 A CN 201510794231A CN 105621582 B CN105621582 B CN 105621582B
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- heavy metal
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000227 grinding Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 ion compound Chemical class 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000003801 milling Methods 0.000 claims abstract description 9
- 239000010814 metallic waste Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000001661 cadmium Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 229910001576 calcium mineral Inorganic materials 0.000 claims 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000001681 protective effect Effects 0.000 abstract description 3
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 239000010808 liquid waste Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 16
- 238000007711 solidification Methods 0.000 description 15
- 230000008023 solidification Effects 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000004277 Ferrous carbonate Substances 0.000 description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 235000019268 ferrous carbonate Nutrition 0.000 description 3
- 229960004652 ferrous carbonate Drugs 0.000 description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000011667 zinc carbonate Substances 0.000 description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- YZANXQPEQJOLRZ-UHFFFAOYSA-N [Zn].[Cd].[Mn] Chemical compound [Zn].[Cd].[Mn] YZANXQPEQJOLRZ-UHFFFAOYSA-N 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical class [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical class [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical group [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- RBUOVFCQLHVYOQ-UHFFFAOYSA-J dizinc disulfate Chemical compound [Zn+2].[Zn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RBUOVFCQLHVYOQ-UHFFFAOYSA-J 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a kind of methods for curing water-soluble heavy metal ion, using mechanical force grinding means, solution containing water-soluble heavy metal ion compound is mixed with curing agent, it is then placed in grinding machine, it is 7~45 to control ratio of grinding media to material, and grinding rate is 100~1200rpm, and milling time is 20~240min, wet type cured article is obtained, that is, realizes the curing of water-soluble heavy metal ion.This method cationic cure significant effect, it is efficient, it is simple for process, it is environmentally protective, it is at low cost, the fields such as high-concentration heavy metal waste water liquid waste processing are can be applied to, are suitble to promote and apply.
Description
Technical field
The invention belongs to Essential Chemistry fields, and in particular to a kind of method of the water-soluble heavy metal ion of mechanical force curing.
Background technology
Heavy metal refers generally to density more than 4.5 grams of metals per cubic centimeter, about 45 kinds, such as copper (Cu), lead (Pb), zinc
(Zn), iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd) etc..It is derived from a wealth of sources heavy metal ion, is related to chemical industry, mine,
Machine-building, metallurgical, the industries such as electronics and instrument.Water-soluble heavy metal ion is soluble among water body, it is impossible to be dropped by microorganism
Solution, can only occur various forms mutually convert and disperse, enrichment process.Ion runs up to certain limit in water body, will
Serious harm is generated, and may be by the direct or indirect human body of food chain forever to water body, water plant and aquatic animal system
Long property poisoning, it is even carcinogenic to cause a variety of diseases.Therefore, the curing (non-aqueous to dissolve) of heavy metal ion is removed water for administering and going
Heavy metal ion plays an important role and meaning in body.Water-soluble heavy metal ion is after curing process, meeting and solid
Particle coprecipitation gets off and no longer dissolves out, by filtering or settling, it is possible to reach purifying water body, administer the mesh of water pollution
's.
Chemical precipitation is that curing heavy metal ion main method, principle are to make waste water by chemical reaction both at home and abroad at present
The middle heavy metal that dissolved state is presented is changed into heavy metal compound not soluble in water, including neutralization precipitation object, sulfide precipitation
Method, ferrite coprecipitation.The most commonly used is neutralization precipitation method, common neutralizer has sodium hydroxide (NaOH), carbonic acid
Sodium (Na2CO3), ammonium hydroxide (NH3·H2O), lime (CaO) and calcium hydroxide (Ca (OH)2), metal ion is made to be reacted with hydroxyl (- OH),
Generate metal ion compound not soluble in water.But pure chemistry method curing heavy metal ion is used, control condition is more stringent,
Needed during processing stringent control formed the optimal pH of hydroxide and its in precipitation process flocculate granular size.This
Outside, in flocculation process, the dosage of flocculant is susceptible to deviation, and formation heavy metal hydroxide flco is less than normal, sedimentation speed
Degree is slower.And cured product can also have pollution in alkalinity to environment.Therefore, a kind of curing of new high-efficiency environment friendly
Urgently propose.
Invention content
The object of the present invention is to provide a kind of method that mechanical force cures water-soluble heavy metal ion, this method cationic cures
Significant effect, it is efficient, it is simple for process, it is environmentally protective, it is at low cost, the fields such as the processing of heavy metal wastewater thereby waste liquid are can be applied to,
It is suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：Using mechanical force grinding means,
Solution containing water-soluble heavy metal ion compound with curing agent is mixed, is then placed in grinding machine, control ratio of grinding media to material for 7~
45, grinding rate is 100~1200rpm, and milling time is 20~240min, obtains wet type cured article, that is, realizes water-soluble weight
The curing of metal ion.
In said program, the solution containing water-soluble heavy metal ion compound is water-soluble heavy metal ion solid
The mixture of compound and water.
In said program, the solution containing water-soluble heavy metal ion compound is contains water-soluble heavy metal ion
The high concentration heavy metal waste liquid of compound.
In said program, the curing agent is CaCO3Chemical reagent or calcium carbonate mineral.
In said program, the calcium carbonate mineral is lime stone or calcite etc..
In said program, the water solubility heavy metal ion includes but not limited in ferrous iron, copper, zinc, nickel, manganese, cadmium ion
One or more.
In said program, the water solubility heavy metal ion compound includes but not limited to ferrous salt, mantoquita, zinc salt, nickel
One or more of salt, manganese salt, cadmium salt.
In said program, the ferrous salt, mantoquita, zinc salt, nickel salt, manganese salt, cadmium salt are their sulfate.
In said program, the grinding machine includes but not limited to planetary ball mill and Ball-stirring mill.
In said program, the molar ratio of the water solubility heavy metal ion compound and curing agent is 1/3<N (water solubility weights
Metal ion compound):N (curing agent)<1.
In said program, the water solubility heavy metal ion compound is 0.1 with curing agent gross mass and the solid-to-liquid ratio of water
~10.0g/mL.
In said program, water-soluble heavy metal ion compound and the total matter of curing agent in the high concentration heavy metal waste liquid
Amount and the solid-to-liquid ratio of water are 0.1~10.0g/mL.
The present invention is using mechanical force grinding means, by water-soluble heavy metallic salt (water-soluble heavy metal ion compound)
It is transformed into carbonate not soluble in water or noncrystal, realizes the curing of heavy metal ion.During grinding, in anhydrous condition
Under, it is pure solid phase reaction between heavy metallic salt and calcium carbonate, reaction is difficult to be smoothed out, and the realization of heavy metal ion difficulty cured
Journey.In the environment of a small amount of water, heavy metallic salt and calcium carbonate can realize calcium ion and metal ion under conditions of mechanical lapping
Dissociation, sulfate radical recombines with calcium ion, forms stable calcium sulfate precipitation, metal ion is then combined with carbonate, shape
Into carbonate not soluble in water, basic principle can be expressed as：
Wherein, Me represents the heavy metal ion such as Fe, Cu, Zn, Cd, Mn and Ni.
The beneficial effects of the invention are as follows：
1) curing agent that the present invention uses is cheap and easy to get, and the mechanical force method being related to is simple for process, environmentally protective.
2) present invention has very well ferrous (Fe), copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn) and cadmium (Cd) plasma
Solidification effect, process object it is wide in range.
3) solidification process to one or more single water-soluble heavy metal ion can be achieved, and curing degree is high, curing degree can
It realizes close to 100%, solidification effect is notable.
4) curing application surface of the present invention is extensive, can be applied to the necks such as the processing of high-concentration heavy metal waste water waste liquid
Domain.
Description of the drawings
Fig. 1 is the XRD spectrum of gained wet type cured article after grinding 60min in the embodiment of the present invention 1
Fig. 2 is the XRD spectrum of gained wet type cured article after grinding 30min in the embodiment of the present invention 2
Fig. 3 is the XRD spectrum of 3 gained wet type cured article of the embodiment of the present invention
Fig. 4 is the XRD spectrum of 4 gained wet type cured article of the embodiment of the present invention.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Following embodiment unless specific instructions, the commercially available chemical reagent of reagent or industrial products of use.
Equipment is as follows used in following embodiment：
Grinding machine：Germany goes at express speed 7 types of planetary ball mill Pulverisette；Constant temperature blender with magnetic force：Shanghai Mei Ying Pus instrument
Instruments and meters Manufacturing Co., Ltd speeds literary 524G types；It is measured using full spectrum direct-reading Inductively coupled plasma optical emission spectrometer (ICP) solid
The concentration of effects of ion after change, PerkinElmer companies of the U.S., Optima 4300DV models；Using turning target X-ray diffraction
Instrument (XRD) characterizes the object phase of milled processed products therefrom, Japanese RIGAKU companies, D/MAX-RB types.Centrifuge is Hunan He Xi
The table model high speed centrifuge that instrument and equipment Co., Ltd provides, H/T16MM types.
Embodiment 1
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
By 2.78g ferrous sulfate (FeSO4·7H2) and 1.3g calcium carbonate (CaCO O3) mixture be put into the grinding of 50mL
In tank, the zirconium ball and 2.5mL distilled water of 150g diameters 15mm, ratio of grinding media to material 37 are added in, solid-to-liquid ratio 1.63g/mL is placed in grinding machine
Middle setting rotating speed is 400rpm, and milling time is respectively 30min, 60min, obtains wet type cured article after the completion of grinding, you can real
The solidification process of existing water solubility heavy metal ion.
Fig. 1 is the XRD spectrum of gained wet type cured article when 60min is ground in the present embodiment, as seen from Figure 1 sulfuric acid
Ferrous and calcium carbonate is transformed to ferrous carbonate (FeCO after mechanical lapping3), goethite (FeOOH) and calcium sulfate.This table
Bright, the ferrous ion in ferrous sulfate after treatment, is precipitated in the form of ferrous carbonate and goethite and is fixed up, calcium then with
The form precipitation of calcium sulfate.
Wet type cured article obtained by the present embodiment is washed respectively in the distilled water of 2 parts of 200mL, carries out magnetic agitation,
3h is stirred with the mixing speed of 550rpm at 25 DEG C.After slightly standing, centrifuging and taking supernatant takes 2mL to be diluted to from centrifugate
50mL, send ICP test solution in iron ion concentration, calculate iron ion curing degree ([1-n (and curing rear solution in metal from
Son)/n (metal ion before curing)] × 100), it the results are shown in Table 1.
The solidification effect of water-soluble heavy metal iron ion in 1 embodiment 1 of table
As can be seen from Table 1, the method for the invention can realize the curing separation process of iron ion under the conditions of mechanical force,
And its curing degree, close to 100%, solidification effect is notable.
Embodiment 2
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
By 2.41g zinc sulfate (ZnSO4) and the mixture of 1.5g calcium carbonate be put into the grinding pot of 50mL, add in 30g it is straight
The zirconium ball of diameter 15mm and 0.4mL distilled water, ratio of grinding media to material 7.66, solid-to-liquid ratio 9.8g/mL are placed in setting grinding rotating speed in grinding machine
For 1200rpm, milling time is respectively 30min, 60min, obtains wet type cured article after the completion of grinding, realizes heavy metal ion
Solidification process.
The X-ray diffraction analysis result that the present embodiment grinds gained wet type cured article by 30min is shown in Fig. 2, can by Fig. 2
To find out that zinc sulfate and calcium carbonate after grinding, are transformed to zinc carbonate (ZnCO3) and calcium sulfate, this shows in zinc sulfate
Zinc ion is precipitated in the form of zinc carbonate and is fixed up, and calcium is then precipitated in the form of calcium sulfate.
Wet type cured article obtained by the present embodiment is washed respectively in the distilled water of 2 parts of 200mL, carries out magnetic agitation,
3h is stirred with the mixing speed of 550rpm at 25 DEG C.After slightly standing, centrifuging and taking supernatant takes 2mL to be diluted to from centrifugate
50mL send the concentration of iron ion in ICP test solution, calculates the curing degree of iron ion, the results are shown in Table 2.
The solidification effect of heavy metal zinc ion in 2 embodiment 2 of table
As can be seen from Table 2, the method for the invention can realize the curing separation process of zinc ion under the conditions of mechanical force,
And its solidification effect is notable.
Embodiment 3
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
By 2.49g copper sulphate (CuSO4·5H2O it) is put into the grinding pot of 50mL, adds in the mixture of 1.0g calcium carbonate
The zirconium ball of 150g 15mm and 30mL distilled water, ratio of grinding media to material is 43.47 at this time, and solid-to-liquid ratio is 0.11g/mL, is placed in grinding machine and sets
Rotating speed is 100rpm, milling time 60min, obtains wet type cured article after the completion of grinding, realizes the curing of heavy metal ion
Journey.
The X-ray diffraction analysis result of wet type cured article is shown in Fig. 3, as seen from Figure 3, copper sulphate obtained by the present embodiment
With calcium carbonate after grinding, basic copper carbonate and calcium sulfate are transformed to, this shows the copper ion in copper sulphate with alkali formula carbon
The form of sour copper is fixed up, and calcium is then fixed up in the form of calcium sulfate.
Wet type cured article obtained by the present embodiment is washed in the distilled water of 250mL, carries out magnetic agitation, at 25 DEG C with
The mixing speed stirring 3h of 550rpm.After slightly standing, centrifuging and taking supernatant takes 2mL to be diluted to 50mL, send ICP from centrifugate
The concentration of iron ion in solution is tested, the curing degree of iron ion is calculated, the results are shown in Table 3.
The solidification effect of heavy metal copper ion in 3 embodiment 3 of table
As can be seen from Table 3, the method for the invention can realize the curing separation process of copper ion under the conditions of mechanical force,
And its solidification effect is notable.
Embodiment 4
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
By 1.00g ferrous sulfate, 0.61g copper sulphate, 0.15g nickel sulfates, 0.15g manganese sulfates, 0.15g cadmium sulfates, 0.15g
The mixture of zinc sulfate and 1.6g calcium carbonate is put into the grinding pot of 50mL, adds in the zirconium ball and 2.5mL distilled water of 150g 15mm
(1.00g ferrous sulfate, 0.61g copper sulphate, 0.15g nickel sulfates, 0.15g manganese sulfates, 0.15g cadmium sulfates, 0.15g zinc sulfate and
3.0g calcium carbonate is equivalent to high concentration heavy metal waste liquid in 2.5mL), solid-to-liquid ratio is 2.08g/mL at this time, is placed in grinding machine and sets
Rotating speed is 550rpm, milling time 120min, obtains wet type cured article after the completion of grinding, realizes the curing of heavy metal ion
Journey.
The X-ray diffraction analysis result of wet type cured article is shown in Fig. 4 obtained by the present embodiment, as seen from Figure 4 six kinds of gold
After grinding 120min together with the sulfate mixture of category and calcium carbonate, XRD objects phase only shows the characteristic peak of calcium sulfate, this shows
Six heavy metal species ions are fixed up with amorphous form, and calcium ion is then precipitated with sulfuric acid calcium form.
Wet type cured article obtained by the present embodiment is washed in the distilled water of 200mL, carries out magnetic agitation, at 25 DEG C with
The mixing speed stirring 3h of 550rpm.After slightly standing, centrifuging and taking supernatant takes 2mL to be diluted to 50mL, send ICP from centrifugate
The concentration of iron ion in solution is tested, calculates curing degree ([1-n (metal ion in curing rear solution)/n (curings of iron ion
Preceding metal ion)] × 100), it the results are shown in Table 4.
The solidification effect of contents of many kinds of heavy metal ion in 4 embodiment 4 of table
| Heavy metal ion | Solution ion concentration (mg/L) before curing process | Supernatant ion concentration (mg/L) after curing process | Curing degree (%) |
| Fe | 54.36 | 0 (not detecting) | 100 |
| Cu | 42.31 | 0.016 | 99.96 |
| Ni | 9.11 | 0.336 | 96.31 |
| Mn | 13.17 | 1.166 | 91.15 |
| Cd | 17.71 | 0.033 | 99.81 |
| Zn | 9.17 | 0.61 | 93.35 |
As can be seen from Table 4, the method for the invention can realize consolidating for iron cupro-nickel manganese cadmium zinc ion under the conditions of mechanical force
Change, and its solidification effect is notable, can detach iron cupro-nickel manganese cadmium zinc ion from high concentration heavy metal waste liquid.
Embodiment 5
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
The mixture of 2.49g copper sulphate and 1.3g lime stones is put into the grinding pot of 50mL, adds in the zirconium of 150g 15mm
Ball and 1mL distilled water, it is 400rpm, milling time 60min to be placed in grinding machine and set rotating speed, and wet type curing is obtained after the completion of grinding
Product, you can realize the curing of heavy metal ion, solidification effect is good.
Embodiment 6
A kind of method of the water-soluble heavy metal ion of mechanical force curing, includes the following steps：
The mixture of 2.78g ferrous sulfate and 1.5g calcites is put into the grinding pot of 50mL, adds in 150g 15mm's
Zirconium ball and 2.5mL distilled water, it is 400rpm, milling time 60min to be placed in grinding machine and set rotating speed, and wet type is obtained after the completion of grinding
Cured article, you can realize the curing of heavy metal ion, solidification effect is good.
The foregoing is merely the preferred embodiment of the present invention, it is noted that those of ordinary skill in the art are come
It says, without departing from the concept of the premise of the invention, makes several modifications and variations, these belong to the protection model of the present invention
It encloses.
Claims (7)
- A kind of 1. method of the water-soluble heavy metal ion of mechanical force curing, which is characterized in that include the following steps：Using mechanical force Solution containing water-soluble heavy metal ion compound with curing agent is mixed, is then placed in grinding machine, control ball by grinding means For material than being 7~45, grinding rate is 100~1200rpm, and milling time is 20~240min, obtains wet type cured article, that is, realizes The curing of water-soluble heavy metal ion；The curing agent is CaCO3Chemical reagent or calcium carbonate mineral；The water solubility heavy metal ion compound is ferrous salt, mantoquita, zinc salt, nickel salt, manganese salt, one kind in cadmium salt or several Kind；The ferrous salt, mantoquita, zinc salt, nickel salt, manganese salt, cadmium salt are their sulfate.
- 2. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 1, which is characterized in that described to contain The solution of water-soluble heavy metal ion compound is the mixture of water-soluble heavy metal ion solid chemical compound and water.
- 3. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 1, which is characterized in that described to contain The solution of water-soluble heavy metal ion compound is the high concentration heavy metal waste liquid containing water-soluble heavy metal ion compound.
- 4. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 1, which is characterized in that the carbonic acid Calcium mineral are lime stone or calcite.
- 5. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 1, which is characterized in that described water-soluble Property heavy metal ion compound and curing agent molar ratio be 1/3<N (water-soluble heavy metal ion compound):N (curing agent)< 1。
- 6. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 2, which is characterized in that described water-soluble Property heavy metal ion compound and curing agent gross mass and the solid-to-liquid ratio of water be 0.1~10.0g/mL.
- 7. the method for the water-soluble heavy metal ion of mechanical force curing according to claim 3, which is characterized in that described highly concentrated The water-soluble heavy metal ion compound spent in heavy metal waste liquid is 0.1~10.0g/ with curing agent gross mass and the solid-to-liquid ratio of water mL。
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