CN105537247B - A kind of method for solidifying arsenic-containing waste residue using industrial residue - Google Patents
A kind of method for solidifying arsenic-containing waste residue using industrial residue Download PDFInfo
- Publication number
- CN105537247B CN105537247B CN201610055287.7A CN201610055287A CN105537247B CN 105537247 B CN105537247 B CN 105537247B CN 201610055287 A CN201610055287 A CN 201610055287A CN 105537247 B CN105537247 B CN 105537247B
- Authority
- CN
- China
- Prior art keywords
- arsenic
- waste residue
- containing waste
- slag
- curing agent
- 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.)
- Active
Links
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 106
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 239000002893 slag Substances 0.000 claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000007885 magnetic separation Methods 0.000 claims abstract description 17
- 238000003723 Smelting Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 239000003818 cinder Substances 0.000 claims abstract description 12
- 239000012141 concentrate Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 5
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 4
- 229960002594 arsenic trioxide Drugs 0.000 claims description 4
- 229950008475 oxophenarsine Drugs 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- LAISNASYKAIAIK-UHFFFAOYSA-N [S].[As] Chemical compound [S].[As] LAISNASYKAIAIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- -1 ferrous metals Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 15
- 230000006641 stabilisation Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 11
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 238000010583 slow cooling Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- YHWIHIJJAZHSNF-UHFFFAOYSA-N O[As](O)(O)=O.[AsH3] Chemical compound O[As](O)(O)=O.[AsH3] YHWIHIJJAZHSNF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of method for solidifying arsenic-containing waste residue using industrial residue, comprise the following steps：(1) arsenic-containing waste residue is put into and adds water slurry in tank diameter, obtain pulp liquid；(2) arsenic curing agent is added in tank diameter and carries out curing reaction, wherein the arsenic curing agent is smelted furnace cinder or is the magnetic separation of iron ore concentrate that smelted furnace cinder obtains after ball milling, magnetic separation；(3) neutralization slag is added into tank diameter to be stirred, and finally carries out moulding by casting and natural curing obtains solid arsenic product.Waste residue caused by the technology utilization non-ferrous metals smelting works itself of the present invention, Material Cost is substantially zeroed, while and can realizes the excellent effect of the treatment of wastes with processes of wastes against one another, PROCESS FOR TREATMENT arsenic-containing waste residue of the invention so that arsenic curing degree reaches more than 94% in arsenic-containing waste residue.
Description
Technical field
The present invention relates to a kind of method that arsenic pollution is administered, more particularly to one kind to utilize industrial residue (smelted furnace cinder, neutralization
Slag) solidification arsenic-containing waste residue method.
Background technology
According to statistics, China produces about 500,000 tons of arsenic-containing waste residue per year, and the arsenic-containing waste residue hoarded is up to as many as more than 200 ten thousand tons.Consolidate containing arsenic
Banking up for body waste residue causes serious pollution hidden trouble to local soil and water environment, influences local or basin resident body and is good for
Health.Therefore, arsenic-containing waste residue efficiently, safety be manipulated so urgent problem to be solved.
Arsenic-containing waste innoxious process for treating mainly has conversion extractive technique, stabilization technology, solidification skill both at home and abroad at present
Art.Wherein stabilization technology due to treatment effect it is preferable, secondary pollution will not be produced, processing cost is relatively low and enjoys and looks steadily
Mesh.Main stabilization technique has calcium salt stabilization method, molysite stabilization method, vulcanization stabilization method.Calcium salt stabilization method processing cost is low, technique
Simply, it is presently the most a kind of conventional stabilization method, but there is also the shortcomings of reagent consumption is more, the quantity of slag is big, especially calcium salt
Solubility it is larger, property stable in the air is poor, and industrial applications prospect is limited.Molysite stablizing effect is preferable, but medicament be present
Consumption is big, the high deficiency of processing cost.Vulcanization stabilization method is simple to operate, and treatment effect is preferable, but the arsenones generated exist
There is the shortcomings that long-time stability are not high in environment.And it is difficult to the effective of arsenic for high arsenic waste residue, common antihunt means
It is stable.The application that Chinese Patent Application No. is 201110024560.7 discloses a kind of method for handling arsenic sulfide slag：First toward sulphur
Change in arsenic slag and add inorganic flocculating agent, after stirring；Solid powder adsorbent is added, is stirred；It is eventually adding asbestos
Suede stirs, and the Leaching of arsenic is up to standard after processing, but this method needs to use substantial amounts of inorganic flocculating agent and solid powder
Adsorbent, so that its cost is of a relatively high.Thus current, stabilization treatment method all can not be steady in low-cost solidification arsenic arsenic
The separation of arsenic is realized on the premise of fixed, especially for property is complicated, the high waste material containing arsenic of rate containing arsenic is also without appropriate steady
Determine method.Therefore, a kind of low cost, wide adaptability are found, the high process for stabilizing of waste material containing arsenic of stabilization efficiency seems very urgent.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of inexpensive, treatment of wastes with processes of wastes against one another
The method using industrial residue (smelted furnace cinder, neutralize slag) solidification arsenic-containing waste residue.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of method for being solidified arsenic-containing waste residue using industrial residue, is comprised the following steps：
(1) arsenic-containing waste residue is put into and adds water slurry in tank diameter, obtain pulp liquid；
(2) arsenic curing agent is added in tank diameter and carries out curing reaction, wherein the arsenic curing agent be smelted furnace cinder or
The magnetic separation of iron ore concentrate obtained for smelted furnace cinder after ball milling, magnetic separation；
(3) neutralization slag is added into tank diameter to be stirred, and finally carries out moulding by casting and natural curing obtains solid arsenic production
Thing.
Above-mentioned method, it is preferred that in the step (1), when the arsenic-containing waste residue is in alkaline or neutral, in addition to pair
Pulp liquid carries out adjusting pH steps so that the pH value of pulp liquid is 0.1~6；When the arsenic-containing waste residue is in acid, it is not necessary to slurry
Change liquid and carry out tune pH.
Above-mentioned method, it is preferred that in the step (1), in pulp liquid the mass percent concentration of slag be 10%~
50%.
Above-mentioned method, it is preferred that in the step (2), the addition of arsenic curing agent is with Fe3O4Molar amount, arsenic is solid
Fe in agent3O4Mole and arsenic-containing waste residue in the mole ratio of arsenic element be n (Fe3O4):N (As)=(0.10~3):1.
Above-mentioned method, it is preferred that the smelted furnace cinder includes copper weld pool clinker, copper converting clinker, antimony volatile smelting stove
One or more in slag, nickel fibers clinker, lead fuming furnace clinker；It is further preferred that the smelted furnace cinder is slow cooling clinker,
Under the conditions of slow cooling, be advantageous to the iron phase in clinker and migrate, assemble, grow up, crystallize, form magnetic iron ore crystal.Further preferably
, the smelting furnace is that copper converting slow cooling clinker selects copper tailings, because the needs of Floatation of Copper, clinker can slow cooling, ball milling.Ball milling makes
Magnetic iron ore crystal monomer dissociation is obtained, is advantageous to magneticly elect high-grade magnetic iron ore；The arsenic-containing waste residue include ore dressing, smelting, chemical industry,
The solid waste of Containing Sulfur arsenic, arsenic oxide arsenoxide, arsenate caused by Refuse Incineration Process.
Above-mentioned method, it is preferred that in the step (2), the purity of magnetic separation of iron ore concentrate is more than 40%；The grain of arsenic curing agent
Spend for the mesh of -200 mesh~-1000.
Above-mentioned method, it is preferred that in the step (3), neutralize slag and be selected from smeltery in waste acid processing or wastewater treatment
Process adds slag caused by milk of lime neutralization, and its main component is calcium sulfate；The neutralization slag is before tank diameter is added 150
1~4h is dried at~400 DEG C；The neutralization slag particle footpath is less than 0.5cm.
Above-mentioned method, it is preferred that in the step (3), the addition for neutralizing slag is total for arsenic-containing waste residue and arsenic curing agent
10wt%~100wt% of quality.
Above-mentioned method, it is preferred that in the step (2), the time of curing reaction is 0.5~5h；The step (3)
In, mixing time is 10~60min.
Above-mentioned method, it is preferred that in the step (3), the process of moulding by casting natural curing includes loading mould, shaken
10~30d of natural curing after dynamic 2~5min, 24h form removals.
Compared with prior art, the advantage of the invention is that：
The invention by industrial solid castoff smelted furnace cinder or smelted furnace cinder after slow cooling, ball milling, magnetic separation
Magnetic separation of iron ore concentrate is applied in the processing of arsenic-containing waste residue, in magnetic separation of iron ore concentrate the ferroso-ferric oxide crystal of lenticular to arsenic have compared with
Strong adsorptivity, the arsenic acid ion that a large amount of arsenic-containing waste residues discharge can be adsorbed；It is coprecipitated that calcium ion in neutralization slag can improve iron arsenic
Starch stability, strengthen arsenic fixation effect, while the plaster of paris for neutralizing the generation of slag drying and dewatering is gel rubber material, cementing can be given up containing arsenic
Slag and arsenic curing agent mixture, realize and stabilize solid arsenic.
Waste residue caused by the technology utilization non-ferrous metals smelting works itself of the present invention, Material Cost is substantially zeroed, simultaneously
And can realizes the excellent effect of the treatment of wastes with processes of wastes against one another, PROCESS FOR TREATMENT arsenic-containing waste residue of the invention so that arsenic curing degree reaches in arsenic-containing waste residue
To more than 94%.
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
A kind of method of the invention for solidifying arsenic-containing waste residue using industrial residue, the object of processing are the sulphur of certain copper smelting plant
Change arsenic slag, main chemical compositions and the Leaching analysis of the arsenic sulfide slag are shown in Table shown in 1, table 2 and table 3 respectively, specific bag
Include following steps:
(1) raw material prepares：Tailings after the copper smelting plant converting furnace slag flotation copper is obtained into magnetic separation of iron ore concentrate by magnetic separation,
It is standby；Fe in the magnetic separation of iron ore concentrate3O4Mass fraction be 80%, granularity is -400 mesh.By the smeltery in waste acid processing or useless
Neutralization slag caused by the addition milk of lime neutralization of water process process is crushed to particle diameter and is less than 0.5cm, is placed in 200 DEG C of drying 2h to nothing
Water state, it is standby.
(2) pretreatment of arsenic-containing waste residue：Arsenic-containing waste residue is put into tank diameter and adds water slurryization formation pulp liquid, in pulp liquid
Slag percent concentration is 30%, and the pH value of pulp liquid is 1.5.
(3) solid arsenic：The magnetic separation of iron ore concentrate of step (1) preparation is added in reactive tank (in the magnetic separation of iron ore concentrate of addition
Fe3O4Mole and tank diameter pulp liquid in the mole ratio of arsenic element be n (Fe3O4):N (As)=0.35:1) it is and pre- after
Arsenic sulfide slag after processing mixes 1h.
(4) solidify：It is accurate in the step of continuing to add arsenic-containing waste residue and magnetic separation of iron ore concentrate gross mass 80% into tank diameter (1)
Standby anhydrous neutralization slag, and stir 10min.
(5) post-process：The mixed material obtained after step (4) is loaded after mould, vibration 2min, 24h form removal in normal temperature
Lower natural curing 10d, obtain finally consolidating arsenic product.
The Leaching of final arsenic product arsenic admittedly is detected using Leaching authentication method (TCLP), the results are shown in Table
3。
The main chemical compositions of the arsenic sulfide slag of certain copper smelting plant of table 1
| Element | As | Pb | Cd |
| Content (%) | 30.10 | 0.15 | 0.0005 |
The arsenic sulfide slag thing phase of certain copper smelting plant of table 2
| Thing phase | Arsenones | Arsenate | Arsenic oxide arsenoxide | Elemental arsenic |
| Percentage (%) in slag | 21.36 | 1.16 | 7.15 | 0.43 |
Table 3 solidifies the leaching concentration value and arsenic curing degree of front and rear arsenic
The solid result of arsenic before and after the processing of TCLP methods measure arsenic-containing waste residue shows, at the Arsenic fixation method of the present embodiment
To manage, arsenic curing degree reaches 99.98% in arsenic-containing waste residue, Gu the concentration of arsenic is decreased obviously in the leachate of arsenic product, leaching concentration
By 1539mg.L-1It is reduced to 0.346mg.L-1, As Leaching is substantially lower than in the waste residue after solidification《Hazardous waste reflects
Other standard leaching characteristic identification》(GB5085.3-2007) threshold values (5mg.L is leached as defined in-1)。
Embodiment 2：
A kind of method of the invention for solidifying arsenic-containing waste residue using industrial slag, the object of processing are the vulcanization of certain copper smelting plant
Arsenic slag, main chemical compositions and the Leaching analysis of the arsenic sulfide slag are shown in Table shown in 4, table 5 and table 6, specifically included respectively
Following steps:
(1) raw material prepares：It is -800 mesh that tailings after the copper smelting plant converting furnace slag flotation copper is milled into granularity, standby
With.Neutralization slag is crushed to particle diameter and is less than 0.5cm, 200 DEG C of drying 2h are standby to anhydrous state.
(2) pretreatment of arsenic-containing waste residue：Arsenic-containing waste residue is put into tank diameter and adds water slurryization formation pulp liquid, in pulp liquid
Slag percent concentration is 20%, and the pH value of pulp liquid is 2.
(3) solid arsenic：Tailings (the Fe in tailings that step (1) prepares is added in reactive tank3O4Mole and tank diameter
The mole ratio of arsenic element is n (Fe in pulp liquid3O4):N (As)=0.50:1) after, mix and stir with pretreated arsenic sulfide slag
Mix 2h.
(4) solidify：In preparing in the step of continuing to add arsenic-containing waste residue and tailings gross mass 50% into tank diameter (1)
And slag, and stir 10min.
(5) post-process：The mixed material obtained after step (4) is loaded after mould, vibration 2min, 24h form removal in normal temperature
Lower natural curing 20d, obtain finally consolidating arsenic product.
The Leaching of final arsenic product arsenic admittedly is detected using Leaching authentication method (TCLP), the results are shown in Table
6。
The main chemical compositions of the arsenic sulfide slag of certain copper smelting plant of table 4
| Element | As | Pb | Cd |
| Content (%) | 30.10 | 0.15 | 0.0005 |
The arsenic sulfide slag thing phase of certain copper smelting plant of table 5
| Thing phase | Arsenones | Arsenate | Arsenic oxide arsenoxide | Elemental arsenic |
| Percentage in slag | 21.36 | 1.16 | 7.15 | 0.43 |
Table 6 solidifies the leaching concentration value and arsenic curing degree of front and rear arsenic
The solid result of arsenic before and after the processing of TCLP methods measure arsenic-containing waste residue shows, at the Arsenic fixation method of the present embodiment
To manage, arsenic curing degree reaches 99.92% in arsenic-containing waste residue, Gu the concentration of arsenic is decreased obviously in the leachate of arsenic product, leaching concentration
By 1539mg.L-1It is reduced to 1.296mg.L-1, the Leaching of arsenic is substantially lower than in the waste residue after solidification《Hazardous waste reflects
Other standard leaching characteristic identification》(GB5085.3-2007) threshold values As (5mg.L are leached as defined in-1)。
Claims (8)
- A kind of 1. method for solidifying arsenic-containing waste residue using industrial residue, it is characterised in that comprise the following steps：(1) arsenic-containing waste residue is put into and adds water slurry in tank diameter, obtain pulp liquid；(2) arsenic curing agent is added in tank diameter and carries out curing reaction, wherein the arsenic curing agent is smelted furnace cinder or is smelting The magnetic separation of iron ore concentrate that furnace slag obtains after ball milling, magnetic separation；The addition of arsenic curing agent is with Fe3O4Molar amount, arsenic curing agent Middle Fe3O4Mole and arsenic-containing waste residue in the mole ratio of arsenic element be n (Fe3O4):N (As)=(0.10~3):1；(3) neutralization slag is added into tank diameter to be stirred, and finally carries out moulding by casting and natural curing obtains solid arsenic product；Institute State to neutralize slag and add in milk of lime in waste acid processing or wastewater treatment process selected from smeltery and be with caused slag, its main component Calcium sulfate；The neutralization slag dries 1~4h before tank diameter is added at 150~400 DEG C；The neutralization slag particle footpath is less than 0.5cm。
- 2. the method as described in claim 1, it is characterised in that in the step (1), when the arsenic-containing waste residue in alkalescence or in Property when, in addition to pulp liquid carry out adjust pH steps so that the pH value of pulp liquid be 0.1~6.
- 3. the method as described in claim 1, it is characterised in that in the step (1), the mass percent of slag is dense in pulp liquid Spend for 10%~50%.
- 4. the method as described in claim 1, it is characterised in that the smelted furnace cinder include copper weld pool clinker, copper converting clinker, One or more in antimony volatile smelting clinker, nickel fibers clinker, lead fuming furnace clinker；The arsenic-containing waste residue includes ore dressing, smelting Refining, chemical industry, Containing Sulfur arsenic, arsenic oxide arsenoxide, the solid waste of arsenate caused by Refuse Incineration Process.
- 5. the method as described in claim 1, it is characterised in that in the step (2), the purity of magnetic separation of iron ore concentrate is more than 40%；The granularity of arsenic curing agent is the mesh of -200 mesh~-1000.
- 6. the method as described in claim 1, it is characterised in that in the step (3), the addition for neutralizing slag is arsenic-containing waste residue With 10wt%~100wt% of arsenic curing agent gross mass.
- 7. the method as described in any one of claim 1~6, it is characterised in that in the step (2), the time of curing reaction For 0.5~5h；In the step (3), mixing time is 10~60min.
- 8. the method as described in any one of claim 1~6, it is characterised in that in the step (3), moulding by casting is supported naturally The process of shield includes loading mould, vibrates 10~30d of natural curing after 2~5min, 24h form removals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610055287.7A CN105537247B (en) | 2016-01-27 | 2016-01-27 | A kind of method for solidifying arsenic-containing waste residue using industrial residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610055287.7A CN105537247B (en) | 2016-01-27 | 2016-01-27 | A kind of method for solidifying arsenic-containing waste residue using industrial residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105537247A CN105537247A (en) | 2016-05-04 |
| CN105537247B true CN105537247B (en) | 2018-02-09 |
Family
ID=55817075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610055287.7A Active CN105537247B (en) | 2016-01-27 | 2016-01-27 | A kind of method for solidifying arsenic-containing waste residue using industrial residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105537247B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007430B (en) * | 2016-05-12 | 2018-06-19 | 昆明理工大学 | A kind of copper ashes base iron system oxalate chemical bonding material and application thereof |
| CN106082722B (en) * | 2016-06-24 | 2018-08-31 | 昆明理工大学 | A kind of cementitious material and its application |
| CN107913893A (en) * | 2017-11-13 | 2018-04-17 | 中南大学 | A kind of method using biomass solid waste residue containing arsenate |
| CN108620409A (en) * | 2018-03-14 | 2018-10-09 | 中南大学 | A method of fixing arsenic-containing waste using high-temperature liquid furnace slag |
| CN108580513B (en) * | 2018-04-18 | 2022-02-11 | 中南大学 | Hot-pressing sintering and curing method for arsenic sulfide slag |
| CN109622563B (en) * | 2018-12-17 | 2020-12-29 | 北京高能时代环境技术股份有限公司 | Method for vitrification solidification of arsenic-containing waste residues by utilizing flotation tailings |
| CN110482672A (en) * | 2019-07-25 | 2019-11-22 | 昆明理工大学 | A method of arsenic in waste acid is efficiently removed for source of iron in situ with magnetic iron ore |
| CN110745984A (en) * | 2019-10-15 | 2020-02-04 | 昆明理工大学 | Harmless treatment method for arsenic-containing polluted acid in nonferrous smelting |
| CN112657998B (en) * | 2019-10-16 | 2022-09-30 | 北京矿冶科技集团有限公司 | Chemical pretreatment agent and chemical pretreatment method for calcium sulfate slag of gold smelting acid station |
| CN111204940A (en) * | 2020-01-09 | 2020-05-29 | 中国铝业股份有限公司 | Treatment method of copper smelting sludge |
| CN111530895A (en) * | 2020-05-19 | 2020-08-14 | 宁夏大学 | Method for high-stability solidification of arsenic slag and tailing slag |
| CN112317513B (en) * | 2020-10-26 | 2021-09-07 | 湖南有色金属研究院有限责任公司 | Method for stabilizing arsenic-containing waste residue |
| CN113233824A (en) * | 2021-06-02 | 2021-08-10 | 昆明理工大学 | Preparation method of tin tailing based low-permeability heavy metal solidified body for underground filling |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11267606A (en) * | 1998-03-26 | 1999-10-05 | Ube Ind Ltd | Treatment of waste and its apparatus |
| JP5188298B2 (en) * | 2007-08-09 | 2013-04-24 | Ｄｏｗａメタルマイン株式会社 | Method for processing non-ferrous smelting intermediates containing arsenic |
| CN102218428A (en) * | 2011-01-20 | 2011-10-19 | 杭州大地环保有限公司 | Treatment method of arsenic slag |
| CN102249609B (en) * | 2011-04-29 | 2013-06-12 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
| CN103331289B (en) * | 2013-06-09 | 2015-04-08 | 中南大学 | Arsenic fixation method |
| CN103406333B (en) * | 2013-08-14 | 2015-08-26 | 路域生态工程有限公司 | A kind of Safe disposal method for high-concentration arsenic residue |
| CN103553197B (en) * | 2013-11-05 | 2014-12-31 | 红河学院 | Method for removing arsenic and antimony in industrial wastewater by using smelting furnace slag |
| CN105215047B (en) * | 2014-08-15 | 2017-11-21 | 江苏理工学院 | Stable Solidification Method of Arsenic Sulfide Waste Residue |
| CN104438288B (en) * | 2014-11-19 | 2016-03-23 | 中南大学 | A kind of containing the stable of arsenic in arsenic waste material and separation method |
| CN104475431B (en) * | 2015-01-01 | 2017-09-29 | 扬州杰嘉工业固废处置有限公司 | A kind of stabilisation curing of high poison waste residue |
-
2016
- 2016-01-27 CN CN201610055287.7A patent/CN105537247B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105537247A (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105537247B (en) | A kind of method for solidifying arsenic-containing waste residue using industrial residue | |
| He et al. | A critical review on approaches for electrolytic manganese residue treatment and disposal technology: Reduction, pretreatment, and reuse | |
| CN107789787B (en) | Stabilizing agent for repairing arsenic-containing waste residue and using method | |
| Lan et al. | A novel method for solidification/stabilization of Cd (II), Hg (II), Cu (II), and Zn (II) by activated electrolytic manganese slag | |
| CN103011726B (en) | Solidification treatment process of smelting waste of lead and zinc | |
| CN101457269B (en) | Process for directly producing sponge iron by microwave carbothermal reduction steel metallurgical iron-bearing dust | |
| CN109574319A (en) | The solid arsenic technique of the high arsenic waste acid of non-ferrous metal metallurgy | |
| CN104418560A (en) | Curing agent for treating heavy metal pollution and heavy metal curing method | |
| CN105294023A (en) | Method for repairing heavy metal-polluted soil by using red mud granular material | |
| CN102974601A (en) | Arsenic pollution soil stabilizer and method for repairing contaminated soil | |
| CN110482672A (en) | A method of arsenic in waste acid is efficiently removed for source of iron in situ with magnetic iron ore | |
| CN113332654B (en) | Preparation method of bulk solid waste-based environment-friendly powder material | |
| CN104927871A (en) | Heavy metal stabilizer and method for stabilizing soil heavy metal through same | |
| CN107759176A (en) | The solid waste comprehensive utilization of slag powders makes building material | |
| CN109453493A (en) | Stabilization agent and its preparation method and application for handling the waste residue containing beryllium | |
| CN108773882A (en) | A kind of Inorganic complex coagulant and its preparation method and application | |
| CN105622022B (en) | A kind of sludge curing agent using alkaline residue | |
| CN104030545B (en) | For the solidification and stabilization method of port engineering car carwash mud | |
| CN114436622B (en) | Subgrade filling material based on manganese tailing slag and preparation method and application thereof | |
| CN108298854B (en) | Sludge solidification/stabilization curing agent and preparation method and application thereof | |
| CN110743125A (en) | Stabilizing agent for repairing arsenic slag and application method thereof | |
| CN113603377B (en) | Cement produced by utilizing electrolytic manganese slag and production method thereof | |
| CN113754400B (en) | Cemented filling material for mine and preparation method and application thereof | |
| CN106282534A (en) | The stable curing method of arsenic acid scum | |
| CN111661993A (en) | Sludge curing agent and preparation method and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |