CN116693272A - Tungsten slag recycling method and tungsten slag curing material - Google Patents
Tungsten slag recycling method and tungsten slag curing material Download PDFInfo
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- CN116693272A CN116693272A CN202311000470.3A CN202311000470A CN116693272A CN 116693272 A CN116693272 A CN 116693272A CN 202311000470 A CN202311000470 A CN 202311000470A CN 116693272 A CN116693272 A CN 116693272A
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- tungsten slag
- curing
- tungsten
- iron
- roasting
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 75
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010937 tungsten Substances 0.000 title claims abstract description 74
- 239000002893 slag Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 16
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000007873 sieving Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 12
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000004484 Briquette Substances 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 abstract description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000011449 brick Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000003238 silicate melt Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/023—Fired or melted materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/144—Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application belongs to the field of comprehensive utilization of hazardous wastes, and relates to a tungsten slag recycling method and a tungsten slag curing material; the method comprises the following steps: s1, mixing: adding tungsten slag and iron oxide scale, performing ball milling treatment or crushing treatment, and sieving to obtain mixed fine materials; s2, roasting: briquetting and roasting the mixed fine materials obtained in the step S1, and grinding and sieving the obtained materials to obtain roasted fine materials; s3, curing: and (2) adding ammonium dihydrogen phosphate/potassium dihydrogen phosphate into the roasting fine material obtained in the step (S2), adding water, fully and uniformly mixing to obtain a slurry, pouring the slurry into a mould, and curing to obtain the cured material. The application cooperatively utilizes the iron oxide in the iron scale and the tungsten slag, and realizes the recycling of the tungsten slag by supplementing iron elements through the iron scale; the characteristic of high iron content in tungsten slag is fully utilized, and the high-strength curing material is prepared by exciting the activity of iron, so that the high-efficiency curing of arsenic and lead is realized, and the curing material is saved.
Description
Technical Field
The application belongs to the field of comprehensive utilization of hazardous wastes, and particularly relates to a tungsten slag recycling method and a tungsten slag curing material.
Background
The tungsten smelting method is different from the common metal smelting method, generally does not adopt a high-temperature smelting method to extract tungsten, and the existing tungsten smelting process in China mainly comprises alkaline leaching. The solid waste residue produced by the wet process of various tungsten mineral raw materials is called tungsten slag, so that the tungsten slag is tungsten alkaline leaching slag. Generally, about 0.8t tungsten slag is generated per 1t of tungsten primary product, and the lower the grade of tungsten concentrate is, the higher the tungsten slag generation amount of unit product is, and the tungsten slag generation amount of low-grade tungsten concentrate can be as high as 1-1.3t. According to the measurement and calculation, the annual production amount of the tungsten slag in China at present exceeds 10 ten thousand t, and the number of the accumulated tungsten slag in the history reaches more than 100 ten thousand t.
The chemical composition of tungsten slag varies with the raw material composition of tungsten mineral and additives in the smelting process, but has some common characteristics: 1) A small amount of tungsten (1.0-4.0%) in the tungsten slag and valuable rare metals such as tantalum, niobium and the like are commonly associated, and the rare metals are enriched in the tungsten slag (Ta) in the process of treating tungsten concentrate by an alkaline method 2 O 5 0.1～0.5%，Nb 2 O 5 0.5 to 1.0 percent) and has high comprehensive utilization value. 2) The tungsten slag contains various toxic and harmful substances such as arsenic, lead, copper, zinc and the like, has strong leaching toxicity and great environmental hazard, and is recorded in the name of national hazardous waste (2021 edition)They are classified as hazardous waste and require strict environmental risk management.
Tungsten slag is an important nonferrous metal secondary resource and has higher comprehensive recycling value. With the continuous consumption of mineral resources and the continuous increase of the demands for the metals, the comprehensive recovery of valuable metals in tungsten slag is increasingly emphasized. In recent years, many researchers have intensively studied recovery of valuable metals in tungsten slag, and the main recovery targets include tungsten, niobium, tantalum, and the like. In addition, the tungsten slag can be used for producing wear-resistant materials, W, nb, ti, cr, mn and other elements in the tungsten slag can react with carbon to form carbide with higher melting point, and the carbide can be used as an additive of the wear-resistant materials for producing grinding balls, so that the performance and the service life of the grinding balls can be improved. Although the method can realize partial recycling of tungsten slag, no good method exists for full recycling of tungsten slag and heavy metal control, and further development of an efficient tungsten slag treatment and recycling method is needed.
Disclosure of Invention
The application aims to provide a tungsten slag recycling method and a tungsten slag curing material, which at least solve one of the problems of high secondary pollution, difficult heavy metal curing and the like in the existing tungsten slag recycling method.
In order to achieve the above purpose, the application adopts the following technical scheme:
a tungsten slag recycling method comprises the following steps:
s1, mixing: adding tungsten slag and iron oxide scale, performing ball milling treatment or crushing treatment, and sieving to obtain mixed fine materials;
s2, roasting: briquetting and roasting the mixed fine materials obtained in the step S1, and grinding and sieving the obtained materials to obtain roasted fine materials;
s3, curing: and (2) adding ammonium dihydrogen phosphate/potassium dihydrogen phosphate into the roasting fine material obtained in the step (S2), adding water, fully and uniformly mixing to obtain a slurry, pouring the slurry into a mould, and curing to obtain the cured material.
The technical principle of the application comprises:
(1) Firstly, uniformly mixing tungsten slag and iron oxide scale, ball-milling and roasting, so that the close contact of the tungsten slag and the iron oxide scale can be ensured, ferric oxide in the iron oxide scale and silicon dioxide in the tungsten slag can be ensured to react to generate ferric silicate melt, part of ferric oxide is converted into ferrous oxide and ferric oxide which are easy to react with dihydrogen phosphate (ammonium dihydrogen phosphate/potassium dihydrogen phosphate), and a foundation is provided for subsequent gelation reaction.
(2) Ferrous oxide, ferric silicate and elementary iron form ferric phosphate cementing materials under the action of ammonium dihydrogen phosphate/potassium dihydrogen phosphate, and ammonium dihydrogen phosphate/potassium dihydrogen phosphate also react with zinc to form phosphate cementing materials.
Preferably, in step S1, the mass ratio of the tungsten slag to the iron scale is 3:1-5:1 (such as 3.5:1, 4.0:1, 4.5:1, etc.).
Preferably, in step S1, the rotation speed of the ball milling process is 300-600rmp (such as 350 rmp, 400 rmp, 450 rmp, 500 rmp, 550 rmp, etc.), the time is 1-2h (such as 70min, 80min, 90min, 100min, 110min, etc.), and the ball-to-material ratio is 20:1-40:1 (such as 25:1, 30:1, 35:1, etc.). The ball milling treatment can lead the mixture in the step S1 to be more uniform, and the reaction in the step S3 is easier in the roasting process.
Preferably, in step S1, the ball-milled material is sieved through a 100-mesh sieve, in other words, the particle size of the mixed fine material is substantially less than 150 μm.
Preferably, in step S2, the briquette volume is less than 30 cm 3 。
Preferably, in step S2, the baking temperature is 900-1100 ℃ (such as 920 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1080 ℃ and the like), and the baking time is 2-4 hours (such as 2.5 hours, 3 hours, 3.5 hours and the like).
Preferably, in step S2, the number of sieves is greater than 200 mesh, in other words the particle size of the calcined fines is substantially less than 75 μm.
Preferably, in step S3, the mass ratio of the calcined fine material to the monoammonium phosphate/potassium dihydrogen phosphate is 3:1-7:1 (e.g., 3.2:1, 3.5:1, 4:1, 5:1, 6:1, 7:1, etc.).
Preferably, in step S3, the water-cement ratio (liquid-solid ratio, mass ratio) is 0.18-0.24 (e.g., 0.20, 0.22, etc.). In the step S3, ammonium dihydrogen phosphate/potassium dihydrogen phosphate and water can be added separately, or can be added after preparing into a dihydrogen phosphate solution.
The tungsten slag solidified material is prepared by adopting the method. The tungsten slag solidified material can be used as a building material, a pavement material or a wall material.
Compared with the prior art, the scheme of the application has the following beneficial effects:
1) Iron oxide in the iron scale and tungsten slag are cooperatively utilized, and iron elements are supplemented through the iron scale, so that the tungsten slag is harmless and recycled, secondary pollution is not generated in the process, and the method has the characteristics of environmental friendliness, low energy consumption and simplicity in operation;
2) The characteristic of high iron content in tungsten slag is fully utilized, the curing material with better strength is prepared by exciting the activity of iron, the efficient curing of arsenic and lead is realized, the curing material is saved, and meanwhile, the product can be used as a building material;
3) The obtained tungsten slag solidified material has good strength performance, and the leaching concentration of lead, arsenic, copper and zinc is lower than the water requirements of three water quality standards (GB 3838-2002) of surface water environment.
Drawings
Fig. 1 is a process flow diagram of a method for recycling tungsten slag according to a preferred embodiment of the present application.
Detailed Description
The following examples are given to illustrate the present application in further detail, but the scope of the present application is not limited to the following examples.
The examples do not identify specific experimental procedures or conditions, which may be followed by procedures or conditions that are routine procedures described in the literature in this field.
The reagents and starting materials used in the examples were the same as those commercially available except as otherwise indicated.
The tungsten slag used in the examples was obtained from a company in the state of Ganz, jiangxi, and analyzed by XRD, the amorphous material was more, and the main crystalline mineral composition was iron oxide, manganese oxideThe iron spinel additionally contains a small amount of anorthite. The XRF results are shown in Table 1, fe in elemental form 2 O 3 The content is 36.84%, the MnO content is 21.28%, siO 2 Content of 7.08%, SO 3 The content is 4.36%.
TABLE 1 tungsten slag Components
The concentration of harmful heavy metals in the tungsten slag sample leaching solution is measured according to the sulfuric acid nitric acid method (HJ/T299-2007) of the solid waste leaching toxicity leaching method, as follows: lead 5.7mg/L, arsenic 12.3mg/L, copper 3.2mg/L, zinc 15.4mg/L.
The iron scale used in the examples is obtained from 4 st of Tangshan, hebei, and its composition is 20.6% Fe 2 O 3 、14.3%Fe 3 O 4 61.6% FeO and 3.5% Fe element.
Example 1
The method for recycling tungsten slag, the basic process flow of which is shown in fig. 1, comprises the following steps:
(1) Mixing 500g of tungsten slag and 100g of iron scale, ball-milling for 1h at a ball-material ratio of 20:1 and a rotating speed of 500rpm, and sieving with a 100-mesh sieve to obtain mixed fine materials;
(2) Dry-pressing the mixed fine materials into small blocks with the size of 2 x 2cm, roasting at 1000 ℃ for 2 hours, and crushing the obtained materials again and sieving the crushed materials with a 200-mesh sieve to obtain roasted fine materials;
(3) Adding 150g of ammonium dihydrogen phosphate into 550g of roasting fine material, adding water according to the ratio of water to ash of 0.20, fully and uniformly mixing to obtain slurry, pouring the slurry into a mould, and curing to obtain the cured material.
Compressive strength testing method for cured material samples referring to GB/T4111-2013 concrete block and brick test method, the concentration of harmful heavy metals in the leaching solution of the sample material is measured according to the sulfuric acid method (HJ/T299-2007) of solid waste leaching toxicity leaching method. Through testing, the compressive strength of the obtained cured material is 26.8MPa, and the cured material has better strength; the leaching concentration is 0.027mg/L of lead, 0.023mg/L of arsenic, 0.012mg/L of copper and 0.340mg/L of zinc, which are lower than the requirements of three water types of surface water environment quality standards (GB 3838-2002).
Example 2
The method for recycling tungsten slag, the basic process flow of which is shown in fig. 1, comprises the following steps:
(1) Mixing 500g of tungsten slag and 150g of iron scale, ball-milling for 2 hours at a ball-material ratio of 40:1 and a rotating speed of 350rpm, and sieving with a 100-mesh sieve to obtain mixed fine materials;
(2) Dry-pressing the mixed fine materials into small blocks with the size of 2 x 2cm, roasting at 1050 ℃ for 2 hours, and crushing the obtained materials again and sieving the crushed materials with a 200-mesh sieve to obtain roasted fine materials;
(3) 130g of ammonium dihydrogen phosphate is added into 500g of roasting fine material, water is added according to the proportion of water to ash ratio of 0.20, the mixture is fully and uniformly mixed to obtain slurry, the slurry is poured into a mould, and the curing is carried out to obtain the curing material.
According to the same method as that of the example 1, the compressive strength of the obtained cured material is 34.5MPa, and the cured material has better strength; the leaching concentration of lead is 0.035mg/L, arsenic is 0.029mg/L, copper is 0.018mg/L, zinc is 0.611mg/L, which is lower than the water requirements of three water classes of surface water environment quality standard (GB 3838-2002).
Example 3
The method for recycling tungsten slag provided in this example is different from example 1 only in step (3). The method specifically comprises the following steps:
(1) Mixing 500g of tungsten slag and 100g of iron scale, ball-milling for 1h at a ball-material ratio of 20:1 and a rotating speed of 500rpm, and sieving with a 100-mesh sieve to obtain mixed fine materials;
(2) Dry-pressing the mixed fine materials into small blocks with the size of 2 x 2cm, roasting at 1000 ℃ for 2 hours, and crushing the obtained materials again and sieving the crushed materials with a 200-mesh sieve to obtain roasted fine materials;
(3) Adding 80g of ammonium dihydrogen phosphate into 550g of roasting fine material, adding water according to the ratio of water to ash of 0.20, fully and uniformly mixing to obtain slurry, pouring the slurry into a mould, and curing to obtain the cured material.
Compressive strength testing method for cured material samples referring to GB/T4111-2013 concrete block and brick test method, the concentration of harmful heavy metals in the leaching solution of the sample material is measured according to the sulfuric acid method (HJ/T299-2007) of solid waste leaching toxicity leaching method. Through testing, the compressive strength of the obtained cured material is 10.3MPa, and the cured material has better strength; the leaching concentration is 0.046mg/L of lead, 0.041mg/L of arsenic, 0.26mg/L of copper and 0.82mg/L of zinc, which are all lower than the requirements of three water types of surface water environment quality standards (GB 3838-2002).
Example 4
The method for recycling tungsten slag provided in this example is different from example 1 only in step (1). The method specifically comprises the following steps:
(1) Mixing 500g of tungsten slag and 100g of iron scale, then crushing the mixture by a crusher, and sieving the mixture with a 100-mesh sieve to obtain mixed fine materials;
(2) Dry-pressing the mixed fine materials into small blocks with the size of 2 x 2cm, roasting at 1000 ℃ for 2 hours, and crushing the obtained materials again and sieving the crushed materials with a 200-mesh sieve to obtain roasted fine materials;
(3) Adding 150g of ammonium dihydrogen phosphate into 550g of roasting fine material, adding water according to the ratio of water to ash of 0.20, fully and uniformly mixing to obtain slurry, pouring the slurry into a mould, and curing to obtain the cured material.
Compressive strength testing method for cured material samples referring to GB/T4111-2013 concrete block and brick test method, the concentration of harmful heavy metals in the leaching solution of the sample material is measured according to the sulfuric acid method (HJ/T299-2007) of solid waste leaching toxicity leaching method. Through testing, the compressive strength of the obtained cured material is 23.4MPa, and the cured material has better strength; the leaching concentration is 0.032mg/L of lead, 0.029mg/L of arsenic, 0.032mg/L of copper and 0.460mg/L of zinc, which are lower than the requirements of three water types of surface water environment quality standards (GB 3838-2002).
In the present application, unless otherwise understood in conjunction with the text, the expression "a/B" should be interpreted as any of the following three parallel cases: a, A is as follows; b, a step of preparing a composite material; a and B. For example, ammonium dihydrogen phosphate/potassium dihydrogen phosphate should be construed as being possible in any of three parallel cases: ammonium dihydrogen phosphate; potassium dihydrogen phosphate; ammonium dihydrogen phosphate and potassium dihydrogen phosphate.
It is also to be noted that, in the present application, the relative terms are to be construed as follows unless otherwise understood in conjunction with the entirety. Relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the application has been disclosed by the foregoing description of specific embodiments thereof, it will be appreciated that those skilled in the art may devise various modifications, adaptations, or equivalents of the application within the spirit and scope of the appended claims. Such modifications, improvements, or equivalents are intended to be included within the scope of this application as claimed.
Claims (10)
1. The tungsten slag recycling method is characterized by comprising the following steps of:
s1, mixing: adding tungsten slag and iron oxide scale, performing ball milling treatment or crushing treatment, and sieving to obtain mixed fine materials;
s2, roasting: briquetting and roasting the mixed fine materials obtained in the step S1, and grinding and sieving the obtained materials to obtain roasted fine materials;
s3, curing: and (2) adding ammonium dihydrogen phosphate/potassium dihydrogen phosphate into the roasting fine material obtained in the step (S2), adding water, fully and uniformly mixing to obtain a slurry, pouring the slurry into a mould, and curing to obtain the cured material.
2. The method according to claim 1, wherein in step S1, the mass ratio of the tungsten slag to the iron scale is 3:1-5:1.
3. The method according to claim 1, wherein in the step S1, the ball milling process is performed at a rotational speed of 300-600rmp for 1-2 hours and a ball-to-material ratio of 20:1-40:1.
4. The method according to claim 1, wherein in step S1, the particle size of the mixed fines is less than 150 μm.
5. The method according to claim 1, wherein in step S2 the briquette volume is less than 30 cm 3 。
6. The method according to claim 1, wherein in step S2, the firing temperature is 900 to 1100 ℃ and the firing time is 2 to 4 hours.
7. The method according to claim 1, wherein in step S2, the particle size of the calcined fines is less than 75 μm.
8. The method according to claim 1, wherein in step S3, the mass ratio of the calcined fines to the monoammonium phosphate/monopotassium phosphate is 3:1-7:1.
9. The method according to claim 8, wherein in step S3, the liquid-solid ratio is 0.18 to 0.24.
10. A tungsten slag solidified material prepared by the method of any one of claims 1-9.
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