CN109402379A - The method of tungstenic solid arsenic removal - Google Patents
The method of tungstenic solid arsenic removal Download PDFInfo
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- CN109402379A CN109402379A CN201811207963.3A CN201811207963A CN109402379A CN 109402379 A CN109402379 A CN 109402379A CN 201811207963 A CN201811207963 A CN 201811207963A CN 109402379 A CN109402379 A CN 109402379A
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- tungstenic
- solid
- arsenic
- tungsten
- removal
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 184
- 239000007787 solid Substances 0.000 title claims abstract description 171
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 91
- 239000010937 tungsten Substances 0.000 claims abstract description 91
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000012545 processing Methods 0.000 claims abstract description 36
- 239000012141 concentrate Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 241001062472 Stokellia anisodon Species 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 abstract description 30
- 239000002910 solid waste Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 14
- 239000002699 waste material Substances 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- XUHJGXBPMAPKDW-UHFFFAOYSA-N [As].[Fe]=S Chemical compound [As].[Fe]=S XUHJGXBPMAPKDW-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 229910052964 arsenopyrite Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002795 fluorescence method Methods 0.000 description 4
- 238000004927 wastewater treatment sludge Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- -1 Sulphur compound Chemical class 0.000 description 3
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 3
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LAISNASYKAIAIK-UHFFFAOYSA-N [S].[As] Chemical compound [S].[As] LAISNASYKAIAIK-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/06—Rotary-drum furnaces, i.e. horizontal or slightly inclined adapted for treating the charge in vacuum or special atmosphere
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/03—Calcining
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods of tungstenic solid arsenic removal, this method comprises: (1) dries tungstenic solid, to obtain dry tungstenic solid；(2) the dry tungstenic solid is subjected to fine grinding processing, to obtain tungstenic solid particle；(3) the tungstenic solid particle is sent to rotary furnace, is 1-100m in flow velocity3It is calcined under the nitrogen or argon atmosphere of/h, to obtain arsenic removal tungstenic solid and containing arsenic gas；Wherein, in step (1), the tungstenic solid is to smelt at least one of resulting dreg containing arsenic selected from tungsten concentrate, tungsten slag and tungsten concentrate.On the one hand this method can remove arsenic from tungsten concentrate, tungsten concentrate is avoided to generate dangerous solid waste again in smelting process；On the one hand the arsenic in the dangerous waste generated-tungsten slag, the mud of tungsten containing arsenic can be removed, to meet discharge standard.
Description
Technical field
The invention belongs to Tungsten smelting environment protection fields, specifically, the present invention relates to the methods of tungstenic solid arsenic removal.
Background technique
Tungsten smelting is the important component in tungsten industrial chain, and caustic digestion-ion-exchange process is that China is black, white Tungsten smelting
Prevailing technology.Caustic digestion process can generate the tungsten slag that slag rate is 40% or so, in the middle arsenic (the arsenic content containing 0.1-0.6wt%
It is dangerous solid waste higher than 0.1wt%)；And ion-exchange process can generate a large amount of industrial wastewater, to reach the waste water
Mark discharge, enterprise generally use the harmful elements such as the arsenic in chemical precipitation method purification, cause to produce a large amount of wastewater treatment
Sludge, arsenic content in the middle is also more than 0.1% (as dangerous waste).According to statistics, 1 ton of APT of every production will generate 800-900kg's
Tungsten slag, 400 kilograms of wastewater treatment sludge will generate nearly 100,000 tons of tungsten slags, 50,000 tons based on national annual 120000 tons of yield of APT
Wastewater treatment sludge.But Tungsten smelting enterprise has no time to attend to the processing for smelting solid waste under the pressure of the production pressure of main product APT substantially
And recycling, its cheap even loses money instead of making money is given into the local processing enterprise for specializing in Tungsten smelting solid waste, such as the tungsten smelting of Ganzhou Prefecture
Refining solid waste concentrates on Dayu Donghong Tin Products Co., Ltd. and is handled.But the existing processing to Tungsten smelting solid waste is also only extracted
Tungsten in solid waste.
As Tungsten smelting waste residue is classified as hazardous waste by State Ministry of Environmental Protection in 2016, (arsenic content is higher than in solid waste
0.1wt%), meanwhile, State Ministry of Environmental Protection in 2018 is in People's Republic of China's state environment protecting standard " Tungsten smelting waste residue utilization
Dispose pollution control technology specification " clear stipulaties Tungsten smelting waste residue is " ammonium paratungstate production process generation again in (its is recommended that original text)
Solid waste, including tungsten slag, molybdenum removal slag, wastewater treatment sludge ", so that the situation of Tungsten smelting industry fixed-end forces have occurred it is huge
Become.On the one hand, country will impose environmentally friendly tax to dangerous waste, and the collecting standard for Tungsten smelting industry is 1000 yuan/ton, this is undoubtedly
By the profit of skiving Tungsten smelting enterprise significantly；On the other hand, previous Tungsten smelting fixed-end forces enterprise handles qualification without dangerous waste,
The solid waste that can not continue to the generation of Tungsten smelting enterprise, causes the solid waste of Tungsten smelting enterprise " no one ventured is wanted, and pile up like a mountain " occur
Difficult situation.Meanwhile National Environmental Protection Agency requires the suspending operations for consolidation of Tungsten smelting enterprise, need to deal carefully with Tungsten smelting waste residue can be extensive
Demutation produces.The whole industry is helpless to this status.Therefore, it is even entire to have become restriction China's Tungsten smelting for the disposition of Tungsten smelting waste residue
The new bottleneck and problem of Chemical analysis survival and development.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is a kind of method for proposing tungstenic solid arsenic removal.On the one hand this method can remove arsenic from tungsten concentrate, avoid
Tungsten concentrate generates dangerous solid waste again in smelting process；It on the one hand can will be in the dangerous waste that generated-tungsten slag, the mud of tungsten containing arsenic
Arsenic remove, to meet discharge standard.
In one aspect of the invention, the invention proposes a kind of method of tungstenic solid arsenic removal, realities according to the present invention
Example is applied, this method comprises:
(1) tungstenic solid is dried, to obtain dry tungstenic solid；
(2) the dry tungstenic solid is subjected to fine grinding processing, to obtain tungstenic solid particle；
(3) the tungstenic solid particle is sent to rotary furnace, is 1-100m in flow velocity3Under the nitrogen or argon atmosphere of/h into
Row calcining, to obtain arsenic removal tungstenic solid and containing arsenic gas；
Wherein, in step (1), the tungstenic solid is resulting containing arsenic selected from the smelting of tungsten concentrate, tungsten slag and tungsten concentrate
At least one of sludge.
The method of tungstenic solid arsenic removal according to an embodiment of the present invention, by the way that (tungsten concentrate, tungsten slag and tungsten are smart by tungstenic solid
Mining and metallurgy refines at least one of resulting dreg containing arsenic) drying and processing is carried out, the moisture removal in tungstenic solid can be reduced water
Divide the influence to subsequent tungstenic solid particle in calcination process, is conducive to the arsenic removal efficiency for improving tungstenic solid；By that will dry
Tungstenic solid carries out fine grinding processing, advantageously reduces the partial size of tungstenic solid particle, and then is conducive to improve tungstenic solid particle
Calcination efficiency in rotary furnace further increases the arsenic removal efficiency of tungstenic solid；In rotary furnace, tungstenic solid particle is in flow velocity
For 1-100m3It is calcined under the nitrogen or argon atmosphere of/h, and the arsenic in tungstenic solid particle is mainly with sulphur arsenic iron
(FeAsS) form exists, and sulphur arsenic iron can decompose under the atmosphere of nitrogen or argon gas, obtains FeS, As2And As4, meanwhile, contain
Sulphur compound in tungsten solid particle can also decompose, and generate sulfurous gas, and part sulfurous gas and arsenic form arsenones, i.e. tungstenic
Solid particle is calcined by rotary furnace, and arsenic content can be obtained in the 0.1wt% arsenic removal tungstenic below for meeting national emission standard
Solid and contain As2、As4With arsenones containing arsenic gas.On the one hand arsenic can be removed from tungsten concentrate by this method as a result,
Tungsten concentrate is avoided to generate dangerous solid waste again in smelting process；It on the one hand can be by the dangerous waste generated-tungsten slag, tungsten containing arsenic
Arsenic in mud removes, to meet discharge standard.
In addition, the method for tungstenic solid arsenic removal according to the above embodiment of the present invention can also have following additional technology
Feature:
In some embodiments of the invention, the method for above-mentioned tungstenic solid arsenic removal further comprises: (4) described will contain arsenic
Gas is successively cooled down and is gathered dust processing, to obtain solid containing arsenic.Be conducive to recycle solid containing arsenic as a result,.
In some embodiments of the invention, in step (1), the moisture content of the dry tungstenic solid is not more than
5wt%.Be conducive to improve the arsenic removal efficiency of tungstenic solid as a result,.
In some embodiments of the invention, in step (1), arsenic content is 0.1-2.2wt% in the tungsten concentrate.
In some embodiments of the invention, in step (1), arsenic content is 0.1-0.45wt% in the tungsten slag.
In some embodiments of the invention, in step (1), arsenic content is 2-4.5wt% in the dreg containing arsenic.
In some embodiments of the invention, in step (2), the partial size of the tungstenic solid particle is not more than
0.15mm.Be conducive to improve the calcination efficiency of tungstenic solid particle as a result,.
In some embodiments of the invention, in step (3), the flow velocity of the nitrogen or argon gas is 5-50m3/h.By
This, can further improve the arsenic removal efficiency of tungstenic solid.
In some embodiments of the invention, in step (3), the temperature of the calcination processing is 650-950 degrees Celsius,
Soaking time is 0.1-4h.It can further improve the arsenic removal efficiency of tungstenic solid as a result,.
In some embodiments of the invention, in step (3), the temperature of the calcination processing is 700-800 degrees Celsius,
Soaking time is 0.5-1.5h.It can further improve the arsenic removal efficiency of tungstenic solid as a result,.
In some embodiments of the invention, in step (3), the arsenic removal efficiency of the arsenic removal tungstenic solid is not less than
87.1%.Arsenic content can be obtained as a result, in the 0.1wt% arsenic removal tungstenic solid below for meeting national emission standard.
In some embodiments of the invention, it in step (4), gathers dust described in the progress when handling, the solid containing arsenic
Temperature be lower than 400 degrees Celsius.The recycling of the solid containing arsenic can be further facilitated as a result,.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram of tungstenic solid arsenic removal according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram of the tungstenic solid arsenic removal of further embodiment according to the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the invention proposes a kind of method of tungstenic solid arsenic removal, realities according to the present invention
Example is applied, with reference to Fig. 1, this method comprises:
S100: tungstenic solid is dried
In the step, tungstenic solid is dried, to obtain dry tungstenic solid.Wherein, tungstenic solid be selected from
Tungsten concentrate, tungsten slag and tungsten concentrate smelt at least one of resulting dreg containing arsenic.Inventors have found that by by tungstenic solid
(tungsten concentrate, tungsten slag and tungsten concentrate smelt at least one of resulting dreg containing arsenic) carries out drying and processing, can be by tungstenic solid
In moisture removal, reduce influence of the moisture to subsequent tungstenic solid particle in calcination process, be conducive to improve tungstenic solid
Arsenic removal efficiency.Specifically, water can make subsequent tungstenic solid particle easily agglomerate in calcination process, reduce the hole of material,
Nitrogen or argon gas enter it is insufficient, to influence the removal efficiency of tungstenic solid particle arsenic.
According to one embodiment of present invention, the moisture content of dry tungstenic solid is not particularly restricted, art technology
Personnel can select according to actual needs, a specific embodiment according to the present invention, the moisture content of dry tungstenic solid
5wt% can be not more than.Inventors have found that the lower the moisture content of dry tungstenic solid the better, if dry tungstenic solid is aqueous
Rate is excessively high, and a part of heat can be not only taken away in calcination process, more will lead to material agglomeration, reduces the hole ratio of material,
To influence the removing of arsenic inside material.
Still another embodiment in accordance with the present invention, arsenic content is 0.1-2.2wt% in tungsten concentrate, and arsenic content is in tungsten slag
0.1-0.45wt%, arsenic content is 2-4.5wt% in dreg containing arsenic.Wherein, tungsten slag and dreg containing arsenic are Tungsten smelting enterprises
Common solid waste, and its arsenic content is higher, belongs to the hazardous waste that State Ministry of Environmental Protection is classified as.By using this method, one side energy
Arsenic is removed from tungsten concentrate, tungsten concentrate is avoided to generate dangerous solid waste again in smelting process；On the one hand it can will produce
Arsenic in raw dangerous waste-tungsten slag, the mud of tungsten containing arsenic removes, to meet discharge standard.
S200: dry tungstenic solid is subjected to fine grinding processing
In the step, dry tungstenic solid is subjected to fine grinding processing, to obtain tungstenic solid particle.Inventors have found that
Fine grinding processing is carried out by the way that tungstenic solid will be dried, advantageously reduces the partial size of tungstenic solid particle, and then is conducive to improve and contain
Calcination efficiency of the tungsten solid particle in rotary furnace, further increases the arsenic removal efficiency of tungstenic solid.
According to one embodiment of present invention, the partial size of tungstenic solid particle is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, such as the partial size of tungstenic solid particle can be not more than 0.15mm.Inventors have found that
If the partial size of tungstenic solid is excessive, the porosity of material is small, and the surface area of tungstenic solid particle reduces, then itself and nitrogen or argon gas
Contact area reduce, the two insufficient contact, so influence separating by extraction.
S300: tungstenic solid particle is sent to rotary furnace, is 1-100m in flow velocity3It is carried out under the nitrogen or argon atmosphere of/h
Calcining
In the step, tungstenic solid particle is sent to rotary furnace, is 1-100m in flow velocity3Under the nitrogen or argon atmosphere of/h
It is calcined, to obtain arsenic removal tungstenic solid and containing arsenic gas.Inventors have found that tungstenic solid particle exists in rotary furnace
Flow velocity is 1-100m3It is calcined under the nitrogen or argon atmosphere of/h, and the arsenic in tungstenic solid particle is mainly with sulphur arsenic iron
(FeAsS) form exists, and sulphur arsenic iron can decompose under the atmosphere of nitrogen or argon gas, obtains FeS, As2And As4, meanwhile, contain
Sulphur compound in tungsten solid particle can also decompose, and generate sulfurous gas, and part sulfurous gas and arsenic form arsenones, i.e. tungstenic
Solid particle is calcined by rotary furnace, and arsenic content can be obtained in the 0.1wt% arsenic removal tungstenic below for meeting national emission standard
Solid and contain As2、As4With arsenones containing arsenic gas.Meanwhile if the gas flow rate of nitrogen or argon gas is too low, in rotary furnace
Air be difficult in a short time all exclusion, sulphur arsenic iron (FeAsS) in air atmosphere be easy generate ferric arsenate
(FeAsSO4)；And if the gas flow rate of nitrogen or argon gas is excessively high, is not dramatically increasing the de- of the arsenic of tungstenic solid particle
It also will increase process costs while except rate, be unfavorable for the economy of enterprise.
According to one embodiment of present invention, more preferably, the flow velocity of nitrogen or argon gas can be 5-50m3/h.Invention human hair
It is existing, when the temperature of calcination processing is not less than 650 DEG C, flow velocity 5-50m3/ h has been able to meet and take away in tungstenic solid particle
The condition of arsenic, and obtain preferably dearsenification effect.If the gas flow rate of nitrogen or argon gas is too low, arsenic steam cannot be arranged in time
Rotary furnace out；And if the gas flow rate of nitrogen or argon gas is excessively high, though can still increase the removal efficiency of arsenic to a certain extent,
Increased costs are unfavorable for improving the economy of enterprise.
The condition of still another embodiment in accordance with the present invention, calcination processing is not particularly restricted, those skilled in the art
It can be selected according to actual needs, for example, the temperature of calcination processing can be 650-950 degrees Celsius, soaking time can be with
For 0.1-4h.Inventors have found that if the temperature of calcination processing is too low (being lower than 650 DEG C), the sulphur arsenic in tungstenic solid particle
Iron decomposition rate under the atmosphere of nitrogen or argon gas is very slow, it is difficult to form steam containing arsenic；And if the temperature of calcination processing is excessively high (high
In 950 DEG C), then process energy consumption is larger.If soaking time is too short, tungstenic solid particle is decomposed not exclusively, cannot be taken off well
Arsenic removal；If soaking time is too long, the effect of removing arsenic of tungstenic solid particle has increase accordingly cost without more excellent, reduces place
Manage efficiency.
According to still another embodiment of the invention, more preferably, the temperature of calcination processing can be 700-800 degrees Celsius, protect
The warm time can be 0.5-1.5h.Inventors have found that the decomposition temperature of the sulphur arsenic iron in tungstenic solid particle is about 650 DEG C,
Temperature is improved, its decomposition is conducive to, within the scope of 700-800 DEG C, decomposition rate increases, can (1.5h within a short period of time
It is interior), effectively remove arsenic.And more than 800 DEG C, although the removal efficiency of arsenic increased, corresponding energy consumption increases.
According to still another embodiment of the invention, by using the above method, the arsenic removal efficiency of resulting arsenic removal tungstenic solid
Not less than 87.1%, it is of great significance to existing Tungsten smelting enterprise.It as a result, on the one hand can be by arsenic from tungsten by using this method
It is removed in concentrate, tungsten concentrate is avoided to generate dangerous solid waste again in smelting process；On the one hand the dangerous waste-that can will have been generated
Arsenic in tungsten slag, the mud of tungsten containing arsenic removes, to meet discharge standard.
The method of tungstenic solid arsenic removal according to an embodiment of the present invention, by the way that (tungsten concentrate, tungsten slag and tungsten are smart by tungstenic solid
Mining and metallurgy refines at least one of resulting dreg containing arsenic) drying and processing is carried out, the moisture removal in tungstenic solid can be reduced water
Divide the influence to subsequent tungstenic solid particle in calcination process, is conducive to the arsenic removal efficiency for improving tungstenic solid；By that will dry
Tungstenic solid carries out fine grinding processing, advantageously reduces the partial size of tungstenic solid particle, and then is conducive to improve tungstenic solid particle
Calcination efficiency in rotary furnace further increases the arsenic removal efficiency of tungstenic solid；In rotary furnace, tungstenic solid particle is in flow velocity
For 1-100m3It is calcined under the nitrogen or argon atmosphere of/h, and the arsenic in tungstenic solid particle is mainly with sulphur arsenic iron
(FeAsS) form exists, and sulphur arsenic iron can decompose under the atmosphere of nitrogen or argon gas, obtains FeS, As2And As4, meanwhile, contain
Sulphur compound in tungsten solid particle can also decompose, and generate sulfurous gas, and part sulfurous gas and arsenic form arsenones, i.e. tungstenic
Solid particle is calcined by rotary furnace, and arsenic content can be obtained in the 0.1wt% arsenic removal tungstenic below for meeting national emission standard
Solid and contain As2、As4With arsenones containing arsenic gas.On the one hand arsenic can be removed from tungsten concentrate by this method as a result,
Tungsten concentrate is avoided to generate dangerous solid waste again in smelting process；It on the one hand can be by the dangerous waste generated-tungsten slag, tungsten containing arsenic
Arsenic in mud removes, to meet discharge standard.
According to an embodiment of the invention, the method for above-mentioned tungstenic solid arsenic removal further comprises with reference to Fig. 2:
S400: arsenic gas will be contained and successively cooled down and gathered dust processing
In the step, arsenic gas will be contained and successively cooled down and gathered dust processing, to obtain solid containing arsenic.Specifically, returning
The temperature containing arsenic gas being discharged in converter is at 600 DEG C or more, and before recycling solid containing arsenic, it is cold will to contain arsenic gas progress in advance
But it handles, makes its temperature convenient for gathering dust, meanwhile, because changing containing atmosphere locating for arsenic gas, containing the part arsenic simple substance in arsenic gas
It can be reacted with the oxygen in air, obtain arsenic oxide, be present in solid containing arsenic.It should be noted that the tool of cooling treatment
Body mode is not particularly restricted, and those skilled in the art can select according to actual needs.
According to one embodiment of present invention, gather dust handle when, the temperature of the solid containing arsenic can be Celsius lower than 400
Degree.Inventors have found that arsenic is existed with gas form if temperature is excessively high, it is not easy to precipitation of sublimating, when temperature is lower than 400 DEG C
When, arsenic can be enriched in dust chamber.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Arsenic content is all made of Atomic Fluorescence Spectrometry in tungstenic solid matter in embodiment.
Embodiment 1
It takes white tungsten fine ore (it is 0.76wt% that atomic fluorescence method, which measures arsenic content) to be dried, is to obtain moisture content
The drying tungstenic solid of 5wt%；Above-mentioned dry tungstenic solid is subjected to fine grinding processing, obtains the tungstenic solid that partial size is 0.15mm
Particle；Gained tungstenic solid particle is divided into 7 groups, every group of 100kg, number A, B, C, D, E, F, G；By each group tungstenic solid particle
It send respectively and takes different sintering temperatures (650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C) to rotary furnace,
Flow velocity is 15m3It is respectively sintered 1h under the nitrogen atmosphere of/h, obtains each corresponding arsenic removal tungstenic solid and containing arsenic gas；By gained
Cooled down containing arsenic gas, processing of gathering dust is carried out to it when being cooled to 400 degrees Celsius or less, to obtain solid containing arsenic, and
Resulting arsenic removal tungstenic solid uses Atomic Fluorescence Spectrometry, obtains being sintered under each sintering temperature in resulting arsenic removal tungstenic solid
Arsenic content, as shown in table 1:
Arsenic content and arsenic removal efficiency in resulting arsenic removal tungstenic solid are sintered under the different sintering temperatures of table 1
| Number | Sintering temperature/DEG C | Arsenic content % in arsenic removal tungstenic solid | Arsenic removal efficiency % |
| A | 650 | 0.1 | 87.1 |
| B | 700 | 0.087 | 88.75 |
| C | 750 | 0.039 | 94.96 |
| D | 800 | 0.019 | 97.54 |
| E | 850 | 0.013 | 98.32 |
| F | 900 | 0.011 | 98.58 |
| G | 950 | 0.01 | 98.71 |
Embodiment 2
It takes white tungsten fine ore (it is 0.76wt% that atomic fluorescence method, which measures arsenic content) to be dried, is to obtain moisture content
The drying tungstenic solid of 5wt%；Above-mentioned dry tungstenic solid is subjected to fine grinding processing, obtains the tungstenic solid that partial size is 0.15mm
Particle；Gained tungstenic solid particle is divided into 2 groups, every group of 100kg, number H and I；By each group tungstenic solid particle send respectively to
Rotary furnace each leads into nitrogen and argon gas, is 15m in flow velocity3The condition that/h, sintering temperature are 750 DEG C, soaking time is 1h
Under be sintered, obtain each corresponding arsenic removal tungstenic solid and containing arsenic gas；It cools down, is cooled to containing arsenic gas by resulting
Processing of gathering dust is carried out to it at 400 degrees Celsius or less, to obtain solid containing arsenic, and resulting arsenic removal tungstenic solid uses atom
Fluorescence spectrometry obtains the arsenic content being sintered in resulting arsenic removal tungstenic solid under each sintering atmosphere, as shown in table 2:
Arsenic content and arsenic removal efficiency in resulting arsenic removal tungstenic solid are sintered under the different sintering atmospheres of table 2
| Number | Sintering atmosphere | Arsenic content % in arsenic removal tungstenic solid | Arsenic removal efficiency % |
| H | Nitrogen | 0.039 | 94.96 |
| I | Argon gas | 0.068 | 91.21 |
Embodiment 3
It takes white tungsten fine ore (it is 0.76wt% that atomic fluorescence method, which measures arsenic content) to be dried, is to obtain moisture content
The drying tungstenic solid of 5wt%；Above-mentioned dry tungstenic solid is subjected to fine grinding processing, obtains the tungstenic solid that partial size is 0.15mm
Particle；Gained tungstenic solid particle is divided into 6 groups, every group of 100kg, number J, K, L, M, N and O；By each group tungstenic solid particle
It is sent respectively to rotary furnace, controls each sample under the atmosphere of different nitrogen flow rates, be respectively sintered under 750 DEG C of sintering temperature
1h obtains each corresponding arsenic removal tungstenic solid and containing arsenic gas；It is cooled down resulting containing arsenic gas, it is Celsius to be cooled to 400
Processing of gathering dust is carried out to it when below degree, to obtain solid containing arsenic, and resulting arsenic removal tungstenic solid uses atomic fluorescence method
Measurement, obtains the arsenic content being sintered in resulting arsenic removal tungstenic solid under each nitrogen flow rate, as shown in table 3:
Arsenic content and arsenic removal efficiency in resulting arsenic removal tungstenic solid are sintered under the different nitrogen flow rates of table 3
| Number | Nitrogen flow rate (m3/h) | Arsenic content % in arsenic removal tungstenic solid | Arsenic removal efficiency % |
| J | 5 | 0.089 | 88.49 |
| K | 15 | 0.039 | 94.96 |
| L | 25 | 0.032 | 95.86 |
| M | 45 | 0.026 | 96.64 |
| N | 65 | 0.026 | 96.78 |
| O | 85 | 0.025 | 96.77 |
Embodiment 4
Taking tungsten concentrate (arsenic content 0.76wt%), tungsten slag (arsenic content 0.26wt%) and dreg containing arsenic respectively, (arsenic contains
Amount is 3.62wt%) it is dried, respectively obtain the drying tungstenic solid that moisture content is 5wt%, 4.5wt% and 2wt%；It will be upper
It states dry tungstenic solid and carries out fine grinding processing respectively, obtain the tungstenic solid particle that partial size is 0.15mm；100kg is respectively taken, is compiled
Number P, Q and R；Each group tungstenic solid particle is sent respectively to rotary furnace, is 15m in flow velocity3It is calcined under the nitrogen atmosphere of/h,
Calcination temperature is 750 DEG C, sintering time 1h, obtains each corresponding arsenic removal tungstenic solid and containing arsenic gas；Contain arsenic for resulting
Gas is cooled down, and carries out processing of gathering dust to it when being cooled to 400 degrees Celsius or less, to obtain solid containing arsenic, and it is resulting
Arsenic removal tungstenic solid uses Atomic Fluorescence Spectrometry, and the arsenic for obtaining being sintered under each tungstenic solid in resulting arsenic removal tungstenic solid contains
Amount, as shown in table 4:
The different tungstenic solids of table 4 are sintered arsenic content and arsenic removal efficiency in resulting arsenic removal tungstenic solid
| Number | Tungstenic solids versions | Arsenic content % in arsenic removal tungstenic solid | Arsenic removal efficiency % |
| P | Tungsten concentrate | 0.039 | 94.96 |
| Q | Tungsten slag | 0.034 | 87.18 |
| R | Dreg containing arsenic | 0.089 | 97.58 |
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method of tungstenic solid arsenic removal characterized by comprising
(1) tungstenic solid is dried, to obtain dry tungstenic solid；
(2) the dry tungstenic solid is subjected to fine grinding processing, to obtain tungstenic solid particle；
(3) the tungstenic solid particle is sent to rotary furnace, is 1-100m in flow velocity3It is forged under the nitrogen or argon atmosphere of/h
It burns, to obtain arsenic removal tungstenic solid and containing arsenic gas；
Wherein, in step (1), the tungstenic solid is to smelt resulting dreg containing arsenic selected from tungsten concentrate, tungsten slag and tungsten concentrate
At least one of.
2. the method according to claim 1, wherein further comprising:
(4) it is successively cooled down described and gathered dust processing containing arsenic gas, to obtain solid containing arsenic.
3. the method according to claim 1, wherein in step (1), the moisture content of the dry tungstenic solid
No more than 5wt%.
4. the method according to claim 1, wherein arsenic content is 0.1- in the tungsten concentrate in step (1)
2.2wt%；
Optional, arsenic content is 0.1-0.45wt% in the tungsten slag；
Optional, arsenic content is 2-4.5wt% in the dreg containing arsenic.
5. the method according to claim 1, wherein the partial size of the tungstenic solid particle is not in step (2)
Greater than 0.15mm.
6. the method according to claim 1, wherein the flow velocity of the nitrogen or argon gas is 5- in step (3)
50m3/h。
7. the method according to claim 1, wherein the temperature of the calcination processing is 650- in step (3)
950 degrees Celsius, soaking time 0.1-4h.
8. the method according to the description of claim 7 is characterized in that the temperature of the calcination processing is 700- in step (3)
800 degrees Celsius, soaking time 0.5-1.5h.
9. the method according to claim 1, wherein in step (3), the arsenic removal efficiency of the arsenic removal tungstenic solid
Not less than 87.1%.
10. according to the method described in claim 2, it is characterized in that, in step (4), gather dust described in the progress when handling, institute
The temperature of the solid containing arsenic is stated lower than 400 degrees Celsius.
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| CN111286619A (en) * | 2020-02-03 | 2020-06-16 | 袁桐 | Recycling device of tungsten smelting waste residues |
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