CN106381399A - Method for recovering tellurium from high-tellurium residues - Google Patents
Method for recovering tellurium from high-tellurium residues Download PDFInfo
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- CN106381399A CN106381399A CN201610854575.9A CN201610854575A CN106381399A CN 106381399 A CN106381399 A CN 106381399A CN 201610854575 A CN201610854575 A CN 201610854575A CN 106381399 A CN106381399 A CN 106381399A
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- Prior art keywords
- tellurium
- slag charge
- residues
- hydrochloric acid
- hydrogen peroxide
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- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 135
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 12
- 229910052745 lead Inorganic materials 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000002893 slag Substances 0.000 claims description 57
- 238000001354 calcination Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 16
- 239000004332 silver Substances 0.000 abstract description 14
- 229910003069 TeO2 Inorganic materials 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 12
- 230000004044 response Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011669 selenium Substances 0.000 description 9
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910018162 SeO2 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 229910004273 TeO3 Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ULLRFUHXXXZSCT-UHFFFAOYSA-N [O].[O].Cl Chemical compound [O].[O].Cl ULLRFUHXXXZSCT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical group [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering tellurium from high-tellurium residues in an efficient and environment-friendly mode. The method includes the steps of breaking the high-tellurium residues, slowly adding hydrochloric acid and hydrogen peroxide into the high-tellurium residues, controlling the temperature and continuously stirring to carry out oxidizing leaching; carrying out liquid-solid separation after the residues are completely dissolved, wherein tellurium oxide as the major element enters leaching solutions, valuable metal such as Pb and Ag enters leaching residues in the mode of chloride salt, and lead and silver residues return to a lead smelting system to recover the valuable metal; and adjusting the pH value of the tellurium-containing leaching solutions to be 5.0-6.0 through sodium hydroxide solutions, obtaining TeO2 sediments, carrying out liquid preparation after TeO2 is roasted and nitrate is removed and returning to the electrodeposition process to directly recover the tellurium. According to the method, the high-tellurium residues is directly leached to recover the tellurium through the hydrochloric acid and the hydrogen peroxide, the direct recovery rate of the tellurium can reach above 95%, so that efficient recovery of the tellurium is realized, the recovery rate of silver can reach above 99.0%, and the recovery rate of lead can reach above 97.6%. The method has the advantages that the technological processes are simple, needed equipment is reduced, the production cost is low, the environment friendliness is high and the comprehensive recovery degree is high, thereby having wide application prospects.
Description
Technical field
The present invention relates to non-ferrous metal technical field of wet metallurgy, particularly to a kind of side reclaiming tellurium from high tellurium slag charge
Method.
Background technology
A kind of slag charge higher containing tellurium can be produced in tellurium smelting process, the tellurium overwhelming majority therein is in the form of metallic tellurium
Exist, separately contain the valuable element such as part lead, silver, antimony, such as tellurium casting mold slag is exactly such a slag charge.Most of enterprise is typically
This slag charge is directly returned silver and smelts refinement oxide pyrogenic process operation, the later stage makes the tellurium slag stage and carries out enriching and recovering, due to tellurium metal
It is easy to volatilization, scattered characteristic in high temperature, if direct return silver is smelted its metallic tellurium response rate of pyrogenic process operation and do not reached
40%, not only cause waste of raw materials, the response rate low, the method also has operation length, production cost height, operating condition simultaneously
Badly, the shortcomings of deficiency in economic performance.In addition, World Nonferrous Metals the 1st phase《The direct high efficiente callback new technology of melting waste slag containing tellurium》
Mention, using nitric acid, directly tellurium casting mold slag is carried out with Oxidation Leaching, leachate adds sodium sulfide remove impurity, after remove impurity, add the neutralization of piece alkali
Obtain tellurium dioxide, tellurium dioxide returns conventional electrodeposition operation through liquid making.Feasible on this technological principle, but tellurium metal more difficult by oxygen
Change, it is unqualified that this technique haves such problems as that response speed is slow, cycle length and remove impurity are not thoroughly easily caused tellurium product.Therefore develop
A kind of casting mold slag from tellurium, the technique of direct high efficiente callback tellurium has important practical significance.
Content of the invention
In view of this, it is an object of the invention to proposing a kind of method reclaiming tellurium from high tellurium slag charge, the method has
Flow process is simple, growth cycle is short, low cost, synthetical recovery degree are high, process intensification the features such as.
Based on above-mentioned purpose, a kind of method reclaiming tellurium from high tellurium slag charge that the present invention provides, comprise the following steps：
A, will high tellurium slag charge crush after pour in retort, into retort, be then slowly added to hydrochloric acid and hydrogen peroxide, no
Disconnected stirring carries out Oxidation Leaching, carries out solid-liquid separation, obtain leachate containing tellurium and leached mud after the dissolving completely of high tellurium slag charge；
B, leached mud return lead smelting system and reclaim Pb, Ag valuable metal, and leachate containing tellurium adds neutralization reagent, in reaching
Carry out solid-liquor separation with after terminal, obtain tellurium dioxide precipitation；
C, tellurium dioxide precipitation are removed after nitre deselenization through calcining, carry out sodium hydroxide liquid making, enter back into conventional electrodeposition operation, obtain
To tellurium ingot.
In the present invention, it is preferred to, the component content of described high tellurium slag charge is：Te 70～75%, Pb 0.5～1.0%,
Ag 0.05～0.10%.
In the present invention, it is preferred to, high tellurium slag charge described in step a crush after granularity≤10mm.
In the present invention, it is preferred to, the temperature of Oxidation Leaching described in step a is 50～90 DEG C.
In the present invention, it is preferred to, hydrochloric acid described in step a is industrial concentrated hydrochloric acid, described hydrochloric acid and described high tellurium slag
The mass ratio of material is 1.1～2.5:1.
In the present invention, it is preferred to, the industrial hydrogen peroxide that hydrogen peroxide described in step a is 20～40% for content, described
Hydrogen peroxide is 1.5～3 with the mass ratio of described high tellurium slag charge:1.
In the present invention, it is preferred to, neutralization reagent described in step b is sodium hydroxide solution, the pH of described neutralization terminal
It is worth for 5.0～6.0.
In the present invention, it is preferred to, the precipitation of tellurium dioxide described in step c is through calcining except the condition of nitre deselenization is：Control
350～450 DEG C of temperature, temperature retention time 5～8h, tellurium dioxide is white.
Se and Te belongs to VIA main group, and they have many aspects similar in nature, therefore selenium be metallic tellurium produce in
Difficult detached impurity.Deselenization adopts and first neutralizes the method calcined afterwards.Neutralisation is to utilize TeO2And SeO2The difference of dissolubility in water
Different (SeO2In water, dissolubility is very big, and TeO2Dissolubility very little in water).During neutralization, alkaline solution will be slowly added to, pH
Harmonize.The selenium of total amount 70% can be removed with neutralisation.During the heavy tellurium of neutralization, in solution, part Se also can be with SeO2Form precipitates,
Needs carry out calcining deselenization.Calcining deselenization principle be：The fusing point of selenium dioxide is 340 DEG C, and 315 DEG C start to distil, and TeO2
Just start to volatilize more than 450 DEG C, therefore control 350～450 DEG C of temperature, temperature retention time 5～8h, make SeO2Volatilization removes.Forge
Burning deselenization temperature control is extremely important, and too low selenium is difficult to volatilize, too high TeO2Bonding can be softened or melt, selenium and its oxide expand
Dissipate and be obstructed, selenium is difficult to volatilize.Calcining deselenization process is simple, substantially, after calcining, 99% about selenium is removed effect, tellurium dioxide
Se content, below 0.006%, has reached the purpose of purification tellurium oxide.
Tellurium electrodeposition operation makees cathode and anode with corrosion resistant plate, under direct current electro ultrafiltration, TeO3 2-Obtain electronics in negative electrode to separate out
Metallic tellurium, OH-In anode ejected electron precipitated oxygen, electrolyte is Sodium tellurite. solution, and reaction equation is as follows：
Negative electrode：TeO3 2-+3H2O+4e=Te+6OH-
Anode：4OH-4e=2H2O+O2↑
The present invention using the Technology thinking of the high tellurium slag charge of hydrochloric acid dioxygen water process is：High tellurium slag charge is after crushing anti-
Answer in tank and directly to use hydrochloric acid hydrogen peroxide to leach, using hydrogen peroxide strong oxidizing property in acid condition by the metal in high tellurium slag charge
Tellurium is oxidized to Te4+Selectivity enters in leachate, and the valuable element such as lead, silver is entered in slag with muriatic form, and leached mud returns
Return lead smelting system and reclaim the valuable element such as Ag, Pb, leachate obtains tellurium dioxide by neutralization regulation pH to 5.0～6.0 and sinks
Form sediment, tellurium dioxide precipitation removes nitre deselenization through calcining, and the optimal conditions of its calcination stage are：Control 350～450 DEG C of temperature, insulation
Time 5～8h, tellurium dioxide is white can to carry out alkaline liquid making, enter back into conventional electrodeposition operation.During the reaction that is related to
Principle is as follows：
The hydrochloric acid hydrogen peroxide oxidation stage：Te+4H++4H2O2=Te4++6H2O+O2↑
The process remove impurity stage：Pb2++2Cl-=PbCl2↓
Ag++Cl-=AgCl ↓
Piece alkali neutralization stage：Te4++4OH-=TeO2↓+2H2O
The alkaline liquid making stage：TeO2+ NaOH=Na2TeO3+H2O
Compared with prior art, the method for the present invention has the advantages that：
(1) present invention directly leaches high tellurium slag charge using hydrochloric acid hydrogen peroxide and reclaims tellurium, technological process is short, consumption of raw materials is low,
Non-environmental-pollution, environmental protection, the direct yield of tellurium can reach more than 95% it is achieved that the high efficiente callback of tellurium.The present invention simultaneously
The leached mud that method produces can return lead smelting system and reclaim the valuable metal such as Pb, Ag, and silver raising recovery rate reaches more than 99.0%,
Lead recovery reaches more than 97.6%.
(2) present invention has that technological process is simple, equipment needed thereby is few, low production cost strong to adaptability to raw material, comprehensive returns
Receipts degree height, process intensification, the features such as do not produce waste gas, therefore there is significant economic benefit and certain application prospect.
Brief description
Accompanying drawing is with reference to specific process embodiment, specifically understands technique trend.
Fig. 1 is the method flow diagram that the present invention reclaims tellurium from high tellurium slag charge.
Specific embodiment
For making the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in more detail.
Embodiment 1
The present embodiment reclaims the method flow diagram of tellurium as shown in figure 1, comprising the following steps that from high tellurium slag charge：
By high for 5000g tellurium slag charge (Te 73.18%, 3659g；Pb 0.64%, 32g；Ag 0.055%, 2.75g) crush
To granularity≤10mm, the 16L preparing in advance hydrochloric acid hydrogen peroxide mixed solution is slowly added in retort and is stirred continuously, carries out
Oxidation Leaching；Wherein, in the Oxidation Leaching stage, hydrochloric acid is industrial concentrated hydrochloric acid, the industry that hydrogen peroxide is 20～40% for content
Hydrogen peroxide, hydrochloric acid is 1.1 with the mass ratio of high tellurium slag charge:1, hydrogen peroxide is 1.5 with the mass ratio of high tellurium slag charge:1；Control temperature
70～80 DEG C, carry out solid-liquor separation after the dissolving completely of high tellurium slag charge and must contain tellurium leachate and leached mud, leached mud returns pyrogenic process refining
Lead system reclaims the valuable element such as Ag, Pb.It is 6 that leachate sodium hydroxide solution is neutralized pH to terminal, after solid-liquor separation
Obtain tellurium dioxide precipitation, remove through calcining and after nitre deselenization, obtain tellurium dioxide weight 4665.85g, sample analysis tellurium content 77.3%
(tellurium metal amount 3606.7g), its tellurium response rate is up to 98.57%, silver raising recovery rate ＞ 99.4%, lead recovery ＞ 97.6%.Institute
Obtain tellurium dioxide and enter conventional liquid making, electrodeposition operation.
Embodiment 2
The present embodiment reclaims the method flow diagram of tellurium as shown in figure 1, comprising the following steps that from high tellurium slag charge：
By high for 5000g tellurium slag charge (Te 71.08%, 3554g；Pb 0.79%, 39.5g；Ag 0.062%, 3.1g) crush
To granularity≤10mm, the 12L preparing in advance hydrochloric acid hydrogen peroxide mixed solution is slowly added in retort and is stirred continuously, carries out
Oxidation Leaching；Wherein, in the Oxidation Leaching stage, hydrochloric acid is industrial concentrated hydrochloric acid, the industry that hydrogen peroxide is 20～40% for content
Hydrogen peroxide, hydrochloric acid is 2.5 with the mass ratio of high tellurium slag charge:1, hydrogen peroxide is 3 with the mass ratio of high tellurium slag charge:1；Control temperature 70
～80 DEG C, carry out solid-liquor separation after the dissolving completely of high tellurium slag charge and must contain tellurium leachate and leached mud, leached mud returns pyrometallurgical smelting of lead
System reclaims the valuable element such as Ag, Pb.It is 6 that leachate sodium hydroxide solution is neutralized pH to terminal, after solid-liquor separation
To tellurium dioxide precipitation, remove through calcining and after nitre deselenization, obtain tellurium dioxide weight 4598.7g, sample analysis tellurium content 74.12% (tellurium
Amount of metal 3408.56g), its tellurium response rate reaches 95.91%, silver raising recovery rate ＞ 99.0%, lead recovery ＞ 98.1%.Gained two
Tellurium oxide enters conventional liquid making, electrodeposition operation.
Embodiment 3
The present embodiment reclaims the method flow diagram of tellurium as shown in figure 1, comprising the following steps that from high tellurium slag charge：
By high for 5000g tellurium slag charge (Te 70.01%, 3501g；Pb 0.85%, 42.5g；Ag 0.071%, 3.55g) break
It is broken to granularity≤10mm, the 14L preparing in advance hydrochloric acid hydrogen peroxide mixed solution is slowly added in retort and is stirred continuously, enters
Row Oxidation Leaching；Wherein, in the Oxidation Leaching stage, hydrochloric acid is industrial concentrated hydrochloric acid, the work that hydrogen peroxide is 20～40% for content
Industry hydrogen peroxide, hydrochloric acid is 2.0 with the mass ratio of high tellurium slag charge:1, hydrogen peroxide is 2.5 with the mass ratio of high tellurium slag charge:1；Control temperature
50～70 DEG C of degree, carries out solid-liquor separation after the dissolving completely of high tellurium slag charge and must contain tellurium leachate and leached mud, leached mud returns pyrogenic process
Refining lead system reclaims the valuable element such as Ag, Pb.It is 5 that leachate sodium hydroxide solution is neutralized pH to terminal, solid-liquor separation
After obtain tellurium dioxide precipitation, through calcining except obtaining tellurium dioxide weight 4552.5g, sample analysis tellurium content after nitre deselenization
74.60% (tellurium metal amount 3396.6g), its tellurium response rate reaches 97.01%, silver raising recovery rate ＞ 99.2%, lead recovery ＞
97.9%.Gained tellurium dioxide enters conventional liquid making, electrodeposition operation.
Comparative example 1
This comparative example adopts concentrated nitric acid (commercially available) replacement hydrochloric acid hydrogen peroxide mixed solution, remaining step in the Oxidation Leaching stage
All with embodiment 1.Remove through calcining and after nitre deselenization, obtain tellurium dioxide weight 4522.2g, sample analysis tellurium content 72.9% (tellurium metal
Amount 3296.7g), its tellurium response rate is up to 90.1%, silver raising recovery rate ＞ 97.4%, lead recovery ＞ 95.1%.Gained titanium dioxide
Tellurium enters conventional liquid making, electrodeposition operation.
Comparative example 2
This comparative example adopts concentrated nitric acid (commercially available) replacement hydrochloric acid hydrogen peroxide mixed solution, remaining step in the Oxidation Leaching stage
All with embodiment 2.Remove through calcining and after nitre deselenization, obtain tellurium dioxide weight 4148.8g, sample analysis tellurium content 71.7% (tellurium metal
Amount 2974.7g), its tellurium response rate is up to 83.7%, silver raising recovery rate ＞ 92.3%, lead recovery ＞ 90.3%.Gained titanium dioxide
Tellurium enters conventional liquid making, electrodeposition operation.
Comparative example 3
This comparative example adopts concentrated nitric acid (commercially available) replacement hydrochloric acid hydrogen peroxide mixed solution, remaining step in the Oxidation Leaching stage
All with embodiment 3.Remove through calcining and after nitre deselenization, obtain tellurium dioxide weight 4113.5g, sample analysis tellurium content 72.6% (tellurium metal
Amount 2986.4g), its tellurium response rate is up to 85.3%, silver raising recovery rate ＞ 91.8%, lead recovery ＞ 92.5%.Gained titanium dioxide
Tellurium enters conventional liquid making, electrodeposition operation.
Can be seen that the present invention by the comparing result of embodiment 1-3 and comparative example 1-3 directly to leach using hydrochloric acid hydrogen peroxide
High tellurium slag charge reclaims tellurium, and the direct yield of tellurium be can reach more than 95%, significantly larger than directly leached using concentrated nitric acid in comparative example 1-3
The direct yield of tellurium during high tellurium slag charge, silver and the response rate of lead are also significantly larger than silver-colored in comparative example 1-3 and lead the response rate simultaneously.And
And the present invention directly leaches high tellurium slag charge using hydrochloric acid hydrogen peroxide and reclaims tellurium, environmentally safe, environmental protection, synthetical recovery journey
Degree is high.
In sum, the present invention directly leaches high tellurium slag charge using hydrochloric acid hydrogen peroxide and reclaims tellurium, and technological process is short, raw material disappears
The low, non-environmental-pollution of consumption, environmental protection, the direct yield of tellurium can reach more than 95% it is achieved that the high efficiente callback of tellurium.Simultaneously this
The leached mud that bright method produces can return lead smelting system and reclaim the valuable metal such as Pb, Ag, and silver raising recovery rate reaches 99.0%
More than, lead recovery reaches more than 97.6%.The present invention has that technological process is simple, equipment needed thereby is few, strong to adaptability to raw material,
Low production cost, synthetical recovery degree height, process intensification, the features such as do not produce waste gas, therefore have significant economic benefit and
Certain application prospect.
Those of ordinary skill in the art should be understood：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (inclusion claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also be combined between the technical characteristic in different embodiments, and there is the different aspect of the present invention as above
Many other changes, in order to simple and clear they do not provide in details.Therefore, all within the spirit and principles in the present invention,
Any omission of being made, modification, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of method of tellurium that reclaims from high tellurium slag charge is it is characterised in that comprise the following steps：
A, will high tellurium slag charge crush after pour in retort, then into retort, be slowly added to hydrochloric acid and hydrogen peroxide, constantly stir
Mix and carry out Oxidation Leaching, carry out solid-liquid separation after the dissolving completely of high tellurium slag charge, obtain leachate containing tellurium and leached mud；
B, leached mud return lead smelting system and reclaim Pb, Ag valuable metal, and leachate containing tellurium adds neutralization reagent, reach neutralization eventually
Carry out solid-liquor separation after point, obtain tellurium dioxide precipitation；
C, tellurium dioxide precipitation are removed after nitre deselenization through calcining, carry out sodium hydroxide liquid making, enter back into conventional electrodeposition operation, obtain tellurium
Ingot.
2. the method for tellurium that reclaims from high tellurium slag charge according to claim 1 is it is characterised in that the one-tenth of described high tellurium slag charge
Point content is：Te 70～75%, Pb 0.5～1.0%, Ag 0.05～0.10%.
3. the method for tellurium that reclaims from high tellurium slag charge according to claim 1 is it is characterised in that high tellurium described in step a
Granularity≤10mm after slag charge is broken.
4. the method reclaiming tellurium from high tellurium slag charge according to claim 1 is it is characterised in that aoxidize described in step a
The temperature leaching is 50～90 DEG C.
5. the method for tellurium that reclaims from high tellurium slag charge according to claim 1 is it is characterised in that hydrochloric acid described in step a
For industrial concentrated hydrochloric acid, described hydrochloric acid is 1.1～2.5 with the mass ratio of described high tellurium slag charge:1.
6. the method for tellurium that reclaims from high tellurium slag charge according to claim 1 is it is characterised in that dioxygen described in step a
The industrial hydrogen peroxide that water is 20～40% for content, described hydrogen peroxide is 1.5～3 with the mass ratio of described high tellurium slag charge:1.
7. the method reclaiming tellurium from high tellurium slag charge according to claim 1 is it is characterised in that neutralize described in step b
Reagent is sodium hydroxide solution, and the pH value of described neutralization terminal is 5.0～6.0.
8. the method for tellurium that reclaims from high tellurium slag charge according to claim 1 is it is characterised in that dioxy described in step c
Change tellurium precipitation through calcining except the condition of nitre deselenization is：Control 350～450 DEG C of temperature, temperature retention time 5～8h, tellurium dioxide is in white
Color.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868298A (en) * | 2017-02-24 | 2017-06-20 | 中南大学 | A kind of method for processing tellurium slag |
| CN107827089A (en) * | 2017-12-15 | 2018-03-23 | 清远先导材料有限公司 | Method for separating and recovering tellurium dioxide in cuprous telluride compound waste |
| CN110127632A (en) * | 2019-05-13 | 2019-08-16 | 四川大学 | A method of recycling tellurium from bismuth telluride base semiconductor refrigeration sheet waste material |
| CN110306064A (en) * | 2019-08-09 | 2019-10-08 | 郴州市金贵银业股份有限公司 | A method of tellurium, bismuth, lead are recycled from tellurium lead slag |
| CN110482496A (en) * | 2019-09-19 | 2019-11-22 | 李旭意 | A method of recycling tellurium from Pt Pd concentrate |
| CN112479163A (en) * | 2020-12-08 | 2021-03-12 | 昆明理工大学 | Method for preparing high-purity tellurium dioxide powder by quickly removing impurity selenium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060275191A1 (en) * | 2005-06-03 | 2006-12-07 | Brookhaven Science Associates, Llc | System and method for separating tellurium from cadmium waste |
| CN102491287A (en) * | 2011-12-11 | 2012-06-13 | 郴州市金贵银业股份有限公司 | Process for separating and recovering selenium from selenium-containing material |
| CN102517451A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering tellurium copper from tellurium slag |
| CN102992280A (en) * | 2011-09-13 | 2013-03-27 | 郴州市金贵银业股份有限公司 | Technology for extracting tellurium dioxide from tellurium-containing smelting slag |
| CN104445101A (en) * | 2014-11-26 | 2015-03-25 | 阳谷祥光铜业有限公司 | Method for extracting copper and tellurium from copper telluride residues |
| CN104928483A (en) * | 2015-05-15 | 2015-09-23 | 西北矿冶研究院 | Method for comprehensively recovering silver, selenium, tellurium and copper from copper telluride residues |
-
2016
- 2016-09-27 CN CN201610854575.9A patent/CN106381399B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060275191A1 (en) * | 2005-06-03 | 2006-12-07 | Brookhaven Science Associates, Llc | System and method for separating tellurium from cadmium waste |
| CN102992280A (en) * | 2011-09-13 | 2013-03-27 | 郴州市金贵银业股份有限公司 | Technology for extracting tellurium dioxide from tellurium-containing smelting slag |
| CN102491287A (en) * | 2011-12-11 | 2012-06-13 | 郴州市金贵银业股份有限公司 | Process for separating and recovering selenium from selenium-containing material |
| CN102517451A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering tellurium copper from tellurium slag |
| CN104445101A (en) * | 2014-11-26 | 2015-03-25 | 阳谷祥光铜业有限公司 | Method for extracting copper and tellurium from copper telluride residues |
| CN104928483A (en) * | 2015-05-15 | 2015-09-23 | 西北矿冶研究院 | Method for comprehensively recovering silver, selenium, tellurium and copper from copper telluride residues |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868298A (en) * | 2017-02-24 | 2017-06-20 | 中南大学 | A kind of method for processing tellurium slag |
| CN107827089A (en) * | 2017-12-15 | 2018-03-23 | 清远先导材料有限公司 | Method for separating and recovering tellurium dioxide in cuprous telluride compound waste |
| CN107827089B (en) * | 2017-12-15 | 2020-10-30 | 清远先导材料有限公司 | Method for separating and recovering tellurium dioxide in cuprous telluride compound waste |
| CN110127632A (en) * | 2019-05-13 | 2019-08-16 | 四川大学 | A method of recycling tellurium from bismuth telluride base semiconductor refrigeration sheet waste material |
| CN110127632B (en) * | 2019-05-13 | 2022-09-02 | 四川大学 | Method for recovering tellurium from bismuth telluride-based semiconductor refrigeration sheet waste |
| CN110306064A (en) * | 2019-08-09 | 2019-10-08 | 郴州市金贵银业股份有限公司 | A method of tellurium, bismuth, lead are recycled from tellurium lead slag |
| CN110482496A (en) * | 2019-09-19 | 2019-11-22 | 李旭意 | A method of recycling tellurium from Pt Pd concentrate |
| CN112479163A (en) * | 2020-12-08 | 2021-03-12 | 昆明理工大学 | Method for preparing high-purity tellurium dioxide powder by quickly removing impurity selenium |
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