CN105088262B

CN105088262B - A kind of method of optical electro-chemistry metallurgical extraction semiconductor element

Info

Publication number: CN105088262B
Application number: CN201410211364.4A
Authority: CN
Inventors: 刘芳洋; 顾鄂宁; 杨佳; 蒋良兴; 唐定; 李劼
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2014-05-19
Filing date: 2014-05-19
Publication date: 2019-02-01
Anticipated expiration: 2034-05-19
Also published as: CN105088262A

Abstract

The present invention relates to a kind of method of optical electro-chemistry metallurgical extraction semiconductor element, the optical electro-chemistry for particularly relating to the semiconductor elements such as tellurium, germanium, selenium, silicon, tin, antimony and bismuth is extracted, and belongs to technical field of wet metallurgy.The present invention introduces irradiation light in electrolytic deposition pond, toward cathode, is deposited by optical electro-chemistry, semiconductor is obtained on cathode；Being electrolysed electrolyte used is the conducting liquid containing semiconductor element；The semiconductor element includes at least one of tellurium, germanium, selenium, silicon, tin, antimony and bismuth；It is more than or equal to the photon of institute's deposited semiconductor band gap width in the irradiation light containing energy.The present invention has the advantages such as process is short, low energy consumption, high production efficiency, the rate of recovery are high, at low cost, environmental-friendly, is convenient for large-scale industrial production and application.

Description

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element

Technical field

The present invention relates to a kind of method of optical electro-chemistry metallurgical extraction semiconductor element, particularly relate to tellurium, germanium, selenium, silicon, The optical electro-chemistry of tin, antimony and bismuth etc. is extracted, and optical electro-chemistry metallurgical technology field is belonged to.

Background technique

Semiconductor element refers to the simple substance element with characteristic of semiconductor, as silicon, germanium, boron, selenium, tellurium, tin, carbon, iodine, phosphorus, The elements such as arsenic, antimony, bismuth and sulphur, conductive capability are situated between conductor and insulator, and general resistivity is 10^-7~10^-3Ω·m Between.Due to its special semiconducting behavior, this dvielement, especially tellurium, germanium, silicon, selenium, antimony and bismuth these types semiconductor element Element is often utilized in electronics and electrical industry by people, such as manufactures solar battery, diode, thermo-electric device, detector, crystalline substance Body pipe, rectifier, integrated circuit, thin film field-effect device and gunn effect device, temperature difference electric engine etc..

But the extraction process of these semiconductor elements is there are energy consumption height at present, process flow is complicated, disposal of pollutants is more, raw Produce various problems such as low efficiency.

Such as semiconductor element tellurium, germanium and selenium are rare and scatter element, this general dvielement is seldom excavated to certainly in nature Right concentrate, substantially all with other non-ferrous metal associations, it is original with the intermediate products of metallurgy, chemical industry operation that the modern industry, which is extracted substantially, Material, such as the earth of positive pole, flue dust, sour mud, residue.Industrial production selenium production method main technique is by the earth of positive pole, cigarette ash and acid It is dissolved after mud oxidizing roasting, then in Na₂SO₃Or SO₂The selenium of oxidation state is restored under effect, but this kind of conventional method In technical process, often increase along with the quantity of slag, valuable element loses with slag and toxic gas SO₂Use etc. be unfavorable for production control The problem of processed, while this traditional handicraft is easy to generate the exhaust gas containing arsenic, sulphur, seriously polluted and product purity is low.Due to tellurium and The normal association of selenium also often coexists in the earth of positive pole, at present for the extraction process of industrial tellurium in mineral both in metallurgical technology Mainly there is alkali leaching to divide tellurium technique and oxidation acid leaching tellurium technique.Alkali leaching divides tellurium technique to be that the earth of positive pole is carried out to sulphation copper removal, gasification Except leaching tellurium concentrate with sodium hydroxide solution after selenium, sodium tellurite solution is obtained.Leachate neutralizes with sulfuric acid, and generates thick oxidation Tellurium precipitating.Precipitated oxides are repeated twice, then carry out aqueous solution electrolysis, can must contain the tellurium that tellurium is 98%~99%.Oxidizing acid Leaching tellurium technique is to be replaced to obtain copper tellurium compound precipitating with copper powder after the earth of positive pole to be carried out to oxidation acid leaching, and gained copper tellurium compound is also (first segment oxidation acid leaching copper, second segment alkali leach tellurium) is leached using two sections, then be electrolysed tellurium from alkali immersion liquid, this two Kind technique is directed to the process of first segment acidleach copper, second segment alkali leaching tellurium, and such soda acid is used alternatingly, and leads to impurity (arsenic, silicon Deng) content increases, reagent consumption increases, waste water is not easy to handle, is unfavorable for the problems such as plant operation management.And last electrolysis Refinement step also due to tellurium characteristic of semiconductor, lead to that deposition rate is slow, production efficiency is low, power consumption is big.The refinement of germanium is then It is using the germanite after purification or the mining dissolving with hydrochloric acid of the germanium sulfide after oxidation and to distill, using the volatility of germanium tetrachloride come real Now extract, will extract after obtained germanium tetrachloride hydrolysis is changed into germanium dioxide, lower than 540 DEG C of temperature with hydrogen reducing just Obtain germanium simple substance.The technique of this high temperature reduction not only increases production cost, and the use of inflammable and explosive hydrogen also has Very high risk.

Purification for silicon generallys use base Siemens Method or improved Siemens, i.e., with anhydrous HCl dchlorine metallurgy grade Silicon, then the trichlorosilane of acquisition or silicon tetrachloride are subjected to hydrogen reducing, HIGH-PURITY SILICON can be obtained.Whole process energy consumption height, by-product Object is more, discharge is more, long flow path and equipment investment are big.The smelting of tin, antimony and bismuth mainly has a pyrogenic process and two kinds of wet process: thermal process by It is controversial in waste residue, exhaust gas and the high energy consumption that it is generated；Wet extraction process is increasingly becoming the main side developed at present To, such as tin and antimony mainly extracts by using the technique of leachate electrochemical deposition, but still exist there are current density and Efficiency is lower, deposition process needs the problems such as further strengthening.For bismuth, then ferric iron-Hot-acid Leaching Residues in Hydrochloric Acid System is mainly used Bismuth mineral, then carry out displacement to leachate with iron powder or iron plate and obtain sponge bismuth, this needs to consume a large amount of high-purity iron powder, and iron from Sub- concentration is easy to cause equipment corrosion rate to accelerate when high, impurity separation is difficult, once more and waste discharge increases for reagent consumption The problems such as big.

Electrochemical deposition metallurgy method has many advantages, such as equipment and simple process, low in cost, pollution-free, in hydrometallurgy It is widely used.But since (resistivity is generally 10 for the feature of semiconductor conductive capability difference^-7~10^-3Between Ω m), institute With electrochemical deposition metallurgical technology semiconductor element extraction in using be not especially extensively (the relatively high tellurium of electric conductivity, Except tin and antimony), especially for the semiconductor element of relatively high, the conductive sexual deviation of the band gap widths such as germanium, selenium, silicon, industry On do not use the method for electrochemical deposition to extract because as semiconductor element constantly deposits on electrode, the conduction of electrode With that will decrease, the transmission of electronics will be suppressed property, cause extraction process that can not carry out.

With advances in technology with the development of society, human society constantly rises the demand of this kind of semiconductor element. If energy is efficient, low energy consumption, extracts to low pollution this dvielement, the performance of enterprises will be greatly improved, and can make resource that must use sufficiently Benefit.

Summary of the invention

It is an object of the invention to overcome the problems such as energy consumption during conventional semiconductors element extraction is high, and loss late is big, mention For a kind of process is short, the rate of recovery is high, metallurgical extraction technique at low cost, comprehensive utilization clean energy resource.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention is irradiated in electrodeposition groove with light Cathode is deposited by optical electro-chemistry, and semiconductor is obtained on cathode；Being electrolysed electrolyte used is the conduction liquid containing semiconductor element Body；The semiconductor element includes at least one of tellurium, germanium, selenium, silicon, tin, antimony, bismuth；It irradiates in the light of cathode and contains energy Amount is more than or equal to the photon of institute's deposited semiconductor band gap width；When optical electro-chemistry deposited semiconductor element, tank voltage is controlled More than or equal to 0.1V, preferably 0.1~12V, cathodic reduction curent density is more than or equal to 1A/m².Preferably 1~800A/m²。

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the optical electro-chemistry metallurgy are extracted Element is the element with characteristic of semiconductor, includes that people are known well at present and the institute with characteristic of semiconductor that is not knowing well There is element, this dvielement is typically in the IV-VIA race of the periodic table of elements；The optical electro-chemistry metallurgy institute extracting method is related to From the process of extraction semiconductor element simple substance in the solution containing semiconductor element and under illumination condition under illumination condition The process of electrochemistry purification is carried out to impure semiconductor piece ability or plate.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, can between yin-yang the two poles of the earth of electrodeposition groove To be equipped with diaphragm, having on the diaphragm can be by the pore of semiconductor element to be deposited.The aperture of the diaphragm is 0.1~60 μm, preferably 5~40 μm, further preferably 5~25 μm.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the diaphragm select cellular plastic plate, pottery One of porcelain, sintered glass, asbestos gauge.Preferably one of cellular plastic plate, sintered glass.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the intensity for irradiating the light of cathode is 1~ 9000mW/cm².Preferably 10~300mW/cm², further preferably 50~150mW/cm²。

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, semiconductor element oxidation state and/or simple substance Form stable dispersion in the electrolytic solution；The concentration of semiconductor element is 1~9000mmol/L in the electrolyte, preferably 50~5000mmol/L, further preferably 100~3000mmol/L.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the cathode are selected from stainless steel, titanium sheet, thoroughly One of bright conductive layer, semiconductor simple substance to be deposited.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, anode are selected from inert electrode, containing to be deposited One of conductive material of semiconductor element.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, when anode is containing semiconductor element to be deposited Conductive material when, with light irradiate anode, irradiate in the light of anode containing energy be more than or equal to anode in it is to be deposited The photon of semiconductor element simple substance or its compound band gap width；The intensity for irradiating the light of anode is 1~9000mW/cm²；It is excellent It is selected as 10~300mW/cm², further preferably 50~150mW/cm²。

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the pH value of the electrolyte are -1~14.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention when electrolytic deposition, controls the temperature of electrolyte Degree is 10~95 DEG C；Preferably 10~80 DEG C, further preferably 20~60 DEG C.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, using constant voltage or constant current or pulse electricity Stream carries out electrolytic deposition.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, irradiate the light of cathode and/or anode by One of stable light source, light-pulse generator, fluctuation light source provide.The intensity for irradiating the light of cathode and/or anode is 1~ 9000mW/cm²。

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, provides the light of irradiation cathode and/or anode The light source of line in the sun, xenon lamp, tungsten halogen lamp, Metal halogen lamp, incandescent lamp, fluorescent lamp, LED light, mercury lamp, laser at least one Kind.When cathode introduces irradiation light, the photon that light source issues must some or all of arrival cathode surface；When yin-yang the two poles of the earth When introducing irradiation light, two pole surface of yin-yang has photon arrival, the route of transmission of photon can be direct projection, transmission, reflection or The modes such as refraction.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, control electrolytic deposition time are 1~500 small When.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, the spacing between cathode and anode is 5~ 500mm.Preferably 10~300mm, further preferably 20~100mm.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, when electrolytic deposition, cathode deposition potential Reference system is hydrogen electrode (NHE)；

When electrolytic deposition tellurium, control cathodic reduction curent density is 10~800A/m², preferably 10~500A/m², into One step is preferably 50~200A/m², control bath voltage be 0.1~10.0V, preferably 0.3~6V, further preferably 0.3~4V, control cathode deposition potential are 0~-5V, preferably -0.1~-2V, further preferably -0.1~-1V, control electricity Solving sedimentation time is 1~320 hour, preferably 10~200 hours, further preferably 50~100 hours；Or

When electrolytic deposition germanium, control cathodic reduction curent density is 1~310A/m², preferably 1~200A/m², further Preferably 5~80A/m², control bath voltage be 0.1~8.0V, preferably 0.5~6.0V, further preferably 1.0~ 5.0V, control cathode deposition potential be -0.8~-4.5V, preferably -1.0~-4.0V, further preferably -1.0~-3.0V, Controlling the electrolytic deposition time is 1~480 hour, preferably 10~200 hours, further preferably 50~100 hours；Or

When electrolytic deposition selenium, control cathodic reduction curent density is 1~320A/m², preferably 1~200A/m², further Preferably 5~100A/m², control bath voltage is 0.1~5V, preferably 0.1~3V, further preferably 0.2~3V, control Cathode deposition potential processed is 0~-3V, preferably 0~-2V, further preferably -0.1~-1V, and the control electrolytic deposition time is 1 ~500 hours, preferably 5~300 hours, further preferably 50~100 hours；Or

When electrolytic deposition silicon, control cathodic reduction curent density is 1~300A/m², preferably 1~150A/m², further Preferably 1~70A/m², control bath voltage is 1~12V, preferably 1~7V, further preferably 2~6V, controls cathode Deposition potential is 0~-5V, preferably -1~-5V, further preferably -1~-4V, and the control electrolytic deposition time is 1~450 small When, preferably 5~200 hours, further preferably 40~100；Or

When electrolytic deposition tin, control cathodic reduction curent density is 20~600A/m², preferably 50~400A/m², into one Step is preferably 100~300A/m², control bath voltage be 0.1~7V, preferably 0.1~5V, further preferably 0.2~ 3V, control cathode deposition potential are 0~-4V, preferably -0.5~-2.5V, further preferably -0.5~-1.9V, control electricity Solving sedimentation time is 1~240 hour, preferably 5~200 hours, further preferably 50~100 hours；Or

When electrolytic deposition antimony, control cathodic reduction curent density is 10~780A/m², preferably 50~700A/m², into one Step is preferably 100~600A/m², control bath voltage be 0.1~8V, preferably 0.1~4V, further preferably 0.1~ 2.5V, control cathode deposition potential are 0~-4V, preferably -0.1~-2V, further preferably -0.1~1.2V, control electrolysis Sedimentation time is 1~240 hour, preferably 1~100 hour, further preferably 1~50 hour；Or

When electrolytic deposition bismuth, control cathodic reduction curent density is 10~700A/m², preferably 50~600A/m², into one Step is preferably 100~400A/m², control bath voltage be 0.1~8V, preferably 0.5~6V, further preferably 0.5~ 4V, control cathode deposition potential are 0~-5V, preferably -0.1~-2V, further preferably -0.1~-1V, and control electrolysis is heavy The product time is 1~240 hour, preferably 5~100, further preferably 10~50 hours.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, while two kinds of electrolytic deposition or being led with upper half When body, control cathodic reduction curent density is 1~800A/m², preferably 5~400A/m², further preferably 50~200A/ m², control bath voltage is 0.1~12V, preferably 0.1~6V, further preferably 0.1~2.5V, control cathode deposition Potential is 0~-5V, preferably -0.1~-3V, further preferably -0.1~-2V, and control electrolytic deposition is 1~500 hour, Preferably 5~300 hours, further preferably 50~200 hours.

A kind of method of optical electro-chemistry metallurgical extraction semiconductor element of the present invention, while when electrolytic deposition tellurium selenium, control yin Pole reduction current density is 1~500A/m², preferably 5~400A/m², further preferably 50~200A/m², control electrolytic cell Voltage is 0.1~8V, preferably 0.1~6V, further preferably 0.1~2.5V, and control cathode deposition potential is 0~-5V, excellent It is selected as -0.1~-3V, further preferably -0.1~-2V, control electrolytic deposition is 1~360 hour, and preferably 5~300 is small When, further preferably 50~200 hours.When electrolytic deposition, the reference system of the cathode deposition potential is hydrogen electrode.

In the actual operation process, the present invention is with the concentrate containing semiconductor element, secondary material, smeltery and chemical plant By-product, the cinder of coal-fired plant and the thick simple substance of cigarette ash, semiconductor element are raw material, by producing electrolyte, optical electro-chemistry deposition It is realized with three steps of subsequent processing and extracts semiconductor element simple substance.

In the actual operation process, the principle of electrolyte produced are as follows: semiconductor element is with all or part of oxidation state The dispersion of form stable in the electrolytic solution, in the electrolyte concentration of semiconductor element be 1~9000mmol/L, preferably 50 ~5000mmol/L, further preferably 100~3000mmol/L.The producing mainly of electrolyte has three ways, such as following:

1. directly with joined additive (lithium chloride, sodium chloride, potassium chloride, ammonium chloride, iron chloride, lactic acid, vulcanized sodium, Ammonium sulfide, Beta Naphthol 99MIN, cresol sulfonic acid) concentrate (earth of positive pole, flue dust, coal ash) and metallurgical by-product/intermediate product (tellurium is white) leach Liquid is electrolyte.

2. dissolving out the thick simple substance of semiconductor element, and as electrolyte with solution such as acid, alkali, chlorates.3. to be not easy It is molten

It is used as solute in the metallurgical extraction intermediary or refining process intermediate (chloride, the silicon chloride of germanium) of water, it will Its is molten

Solution is in organic matter or ionic liquid as electrolyte.

In the actual operation process, the operation of optical electro-chemistry deposition process are as follows:

After metallurgical raw material is configured to electrolyte, using three electrodes or two electrode systems as optical electro-chemistry sedimentary system, inertia Electrode stainless steel, titanium sheet, transparency conducting layer or pure is partly led either using the identical thick simple substance of deposited semiconductor element as anode Body simple substance is cathode, and reference electrode chooses according to electrolyte system, and in cathode applies illumination or simultaneously on cathode and anode Apply illumination, then applies voltage to promote the semiconductor element in electrolyte to deposit on cathode, to reach the mesh of extraction 's.

It is required to make cathode product reach sale, according to the purity of cathode semiconductor-on-insulator, impure situation and form Difference carries out the process means of the processing such as secondary light electrorefining, zone refining, thermal distillation or ingot casting.

The cathode production that ingot casting is spare, does not reach requirement to impurity content is carried out to the cathode product that impurity content reaches requirement Object carries out the further ingot casting again after purification such as electrorefining, zone refining, gasification, distillation condensation.Zone refining is referred to light The cathode semiconductor high frequency sense furnace that electrochemical deposition obtains should heat, and by impurity enriched in the end of melting zone.Gasification rises The techniques such as China's condensation then refer to the difference using element and its melting point compound, boiling point and sublimation point, in certain atmospheric condition Under, by the heating of cathode that optical electro-chemistry deposits to achieve the purpose that separate impurity, the atmosphere can be inert atmosphere, S atmosphere, Cl₂Atmosphere, O₂It is carried out under one or more of atmosphere or CO atmosphere atmosphere.Electrorefining is primarily referred to as with photoelectrochemical The anode that the secondary cathode obtained after deposition is deposited as optical electro-chemistry is learned, to contain the conducting liquid of semiconductor element to be refined As electrolyte, electrorefining is carried out by said extracted technique.In the electrolyte, semiconductor element to be refined is with whole or portion Divide the dispersion of the form stable of oxidation state in the electrolytic solution.

The present invention can be used for the preparation of classes of semiconductors element, as silicon, germanium, boron, selenium, tellurium, carbon, iodine, phosphorus, tin, arsenic, The elements such as antimony, bismuth, sulphur.Most prominent advantage be the method be advantageously implemented semiconductor element simple substance process it is short, it is low loss, it is low Cost is extracted.

Principle and advantage

The present invention is based on semiconductor principles, optical electro-chemistry principle, provide a kind of optical electro-chemistry metallurgical extraction semiconductor element Method, be stimulated under light conditions using semiconductor element and generate the feature of electron-hole pair, develop one kind be suitble to it is low The technique of cost, the optical electro-chemistry metallurgical extraction semiconductor element of low pollution.On the one hand photoexcited electron-hole is to can be enhanced The electric conductivity of semiconductor can not carry out the predicament of electrochemical deposition metallurgical extraction to solve most semiconductors, still further aspect this A little photo-generate electron-holes are to can also be separated by semiconductor/electrolyte interface potential barrier and to participate in electrode reaction heavy to strengthen Product process.This be not only avoided that pyrometallurgical smelting it is existing the device is complicated, it is with high costs, generate the deficiencies of exhaust gas residue contamination, Impurity content caused by capable of effectively overcoming conventional wet process soda acid to be used alternatingly increases, reagent consumption increases, waste water and dregs are difficult The problems such as processing.Its mechanism is briefly described as below:

Based on optical electro-chemistry principle, semiconductor can generate photoelectricity when being greater than the illumination that its characteristic absorption limits by frequency Lead the redistribution of effect and carrier.Photoconductive effect can substantially reduce ohmmic drop, this helps to solve electrochemistry metallurgy nothing Method extracts the problem of low conductivity semiconductor；The carrier that the redistribution of carrier can form high concentration in space charge layer is poly- Ji Qu, to change semiconductor surface energy state, the change of this energy state will promote the separation of electron-hole pair, most The process that reinforcing electrode process and semiconductor element are leached from mineral eventually.On the other hand, shape of the light as a kind of energy transmission Formula, illumination can promote the migration and diffusion of reactive ion, to promote the process of electrochemical reaction, according to theoretical calculation, to tin, Antimony, bismuth are deposited using photoelectricity, and current density promotes 1-5 times；Tellurium, germanium, selenium, silicon are deposited using photoelectricity, current density Promote 10-100 times；When especially tellurium, selenium carry out photoelectricity deposition in same system, current density is promoted just more obvious.

The present invention is when semiconductor element to be deposited is present in electrolyte in the form of cation or simple substance, semiconductor element Element is driven by electric field force, is reduced or is adsorbed on cathode, to realize that cathode deposits, when semiconductor element to be deposited In the presence of acid group or other anionic forms, the ion containing semiconductor element is driven by diffusion, and (proper time can be with Stirring is added), it completes to deposit in cathode.

In the extractive technique of semiconductor element, electro-deposition, such as tellurium, tin, antimony, bismuth have just been used in the extraction of some elements Element, but more or less there are some problems in this electrolysis process, as current density and efficiency are more low.Of the present invention half In conductor element simple substance, the band gap of Se is 1.6eV, and the band gap of Te is 0.34eV, and the band gap of Ge is 0.67eV, α-Sn's (gray tin) Band gap is that 0.075~0.094eV can be excited when illuminated as this kind of elements, as previously mentioned, this light swashs The breaking-out development for being beneficial to optical electro-chemistry metallurgical extraction technique.

In conclusion technical solution of the present invention is simple and convenient to operate, not only solve existing for pyrometallurgical smelting it is at high cost, The problems such as seriously polluted, the problems such as also capable of effectively overcoming conventional wet process pharmaceutical use big.It is simultaneously electrochemistry metallurgy skill Art extracts semiconductor element and provides an effective scheme, is conducive to large-scale industry and promotes and apply.

Detailed description of the invention

Attached drawing 1 is that the embodiment of the present invention 1 is strong with illumination is applied at about 2220s during Conventional electrochemical metallurgy method extraction Se Degree is 5mW/cm²Daylight light irradiation (illumination) when cathode-current density variation；

Attached drawing 2 is that the embodiment of the present invention 1 is strong with illumination is applied at about 1285s during Conventional electrochemical metallurgy method extraction Se Degree is 100mW/cm²Xenon lamp irradiation (illumination) and about 1298s at closing illumination (no light) when cathode-current density variation；

Attached drawing 3 is the selenium simple substance that the embodiment of the present invention 1 is obtained on cathode with optical electro-chemistry metallurgy method extractive technique；

It is 100mW/cm that attached drawing 4, which is the embodiment of the present invention 3 applying intensity of illumination,²Xenon lamp irradiation when optical electro-chemistry metallurgy Extract the cathode-current density of Te (curve 2) and Conventional electrochemical metallurgical extraction Te (curve 1)；

Attached drawing 5 is black gray expandable selenium-tellurium mixture that the embodiment of the present invention 4 is extracted with optical electro-chemistry metallurgy method；

It is 100mW/cm that attached drawing 6, which is the embodiment of the present invention 5 applying intensity of illumination,²Incandescent lamp irradiation when, optical electro-chemistry The cathode-current density of metallurgical extraction Ge (curve 2) and Conventional electrochemical metallurgical extraction Ge (curve 1)；

Attached drawing 7 is the embodiment of the present invention 6 during optical electro-chemistry metallurgy method extracts Si, closes light at about 748s respectively It is 100mW/cm according to intensity is applied at (no light) and about 753s²Daylight light irradiation (illumination) when, the change of cathode-current density Change situation；

Attached drawing 8 is the embodiment of the present invention 7 during Conventional electrochemical metallurgy method extracts Sn, applies light at about 2090s It is 100mW/cm according to intensity²Daylight light irradiation (illumination) and about 2110s at close illumination (no light) when cathode-current density Situation of change；

It will be seen from figure 1 that electrochemistry metallurgy method applies intensity of illumination during extracting Se as 5mW/cm²Fluorescent lamp shine When penetrating, cathode-current density has obtained obvious reinforcement, i.e. deposition is strengthened, and we can also have found with illumination Continue, deposition is further promoted.Under this illumination condition, with constantly thickening for electrode semiconductor-on-insulator, electrode Electric conductivity gradually reducing, the photoresponse of film is but further strengthening on electrode, and final cathode-current density is up to one A stationary value speculates that the theoretical current density value of cathode SEDIMENTARY SELENIUM is 65-85A/m under this condition according to theory²。

Figure it is seen that electrochemistry metallurgy method is applying intensity of illumination during extracting Se as 100mW/cm²Xenon lamp When illumination, depositing current density rapid increase, under illustrating that deposition process is strengthened, and cathode-current density is quick when no light Drop, illustrate selenium will receive inhibition when being electrochemically-deposited in no light.Under this illumination condition, with electrode semiconductor-on-insulator It constantly thickens, the electric conductivity of electrode is gradually reducing, and the photoresponse of film is but further strengthening on electrode, final cathode current Density is up to a stationary value, is speculated according to theory, and the theoretical current density value of cathode SEDIMENTARY SELENIUM is 145- under this condition 155A/m²。

From figure 3, it can be seen that the selenium simple substance that optical electro-chemistry metallurgy method extractive technique obtains on cathode has certain thickness Degree, it was demonstrated that optical electro-chemistry extracts the feasibility of semiconductor element selenium.

It is as can be seen from Figure 4 100mW/cm applying intensity of illumination²Xenon lamp irradiation when optical electro-chemistry metallurgical extraction Te The cathode-current density of (curve 2) is 0.5 times higher than the cathode-current density of electrochemistry metallurgical extraction Te (curve 1), illustrates photoelectricity Chemical extraction is conducive to the efficient production of electrochemistry Te metallurgy.

Optical electro-chemistry metallurgy method extractive technique obtains black gray expandable selenium-tellurium mixture on cathode and has as can be seen from Figure 5 Certain thickness, it was demonstrated that optical electro-chemistry extracts semiconductor element selenium-tellurium mixture feasibility.

It is as can be seen from Figure 6 100mW/cm applying intensity of illumination²Xenon lamp irradiation when optical electro-chemistry metallurgical extraction Ge Cathode-current density of the cathode-current density of (curve 2) than electrochemistry metallurgical extraction Ge (curve 1) is high, illustrates that optical electro-chemistry mentions Take the efficient production for being conducive to electrochemistry Ge metallurgy.We are also found that as time increases simultaneously, and Conventional electrochemical is heavy The cathode-current density of product Ge has a declining tendency, and the cathode-current density of optical electro-chemistry deposition Ge has the tendency that rising, says Bright to generate on cathode with semiconductor, the lower conductivity of Ge hinders the progress of deposition process, and the introducing of illumination but can be with Solve conductivity semiconductor it is low and caused by react passivation phenomenon, the program is conducive to the electrochemical extraction of Ge.

It is as can be seen from Figure 7 100mW/cm applying intensity of illumination²Daylight light irradiation under conditions of carry out it is photoelectrochemical Cathode-current density rapid decrease when disconnecting illumination (no light) during metallurgy method extracts Si is learned, illustrates that the electrochemistry of Si is heavy Product will receive inhibition when there is no light, and applying intensity of illumination again at this time is 100mW/cm²Daylight light irradiation (illumination) when, yin Pole depositing current density rapid increase, illustrates that deposition process is strengthened.

Applying intensity of illumination during electrochemistry metallurgy method extracts Sn as can be seen from Figure 8 is 100mW/cm²Daylight When light irradiation (illumination), depositing current density rapid increase illustrates that deposition process is strengthened, and cathode current is close when no light Rapid decrease is spent, illustrate selenium will receive inhibition when being electrochemically-deposited in no light.

Specific embodiment

Below with reference to embodiment, invention is further described in detail,

Embodiment 1

It takes appropriate selenium cigarette ash leachate and HCl is added thereto, make [the H of leachate after mixing⁺] reach 1.0mol/ L, the concentration of Se is 1.3mol/L, is added to using the leachate prepared as electrolyte spare in three-electrode system.With stainless steel Plate is cathode, and graphite is anode (spacing between cathode and anode is 8mm), and saturated calomel electrode is reference electrode.Control electricity Solving liquid temperature is 70 DEG C,

Following experiments are carried out according to above-mentioned condition

A1 uses xenon lamp to introduce intensity of illumination toward cathode as 100mW/cm²Irradiation light (intensity of illumination be introduce Intensity of the Cathode illumination light in cathode surface), when control cathode deposition potential is -0.1V (vs NHE), tank voltage 0.9V, yin Pole reduction current density is in 57~63A/m²；The deposition that is powered 2h, takes out cathode and cleans up and dry, in deposition process first Red Se is precipitated on cathode, is transformed into black as the carry out Se of extraction process gradually agglomerates.Specific reaction equation is as follows:

H₂SeO₃+4e^-+4H⁺=3H₂O+Se(S)

Weight of the products therefrom on unit area on cathode is detected, specific testing result is shown in Table 1；

A2 other conditions and A's is consistent, when control cathode deposition potential is -0.3V (vs NHE), tank voltage 1.3V, and yin Pole reduction current density is in 73~80A/m², detect weight of the products therefrom on unit area on cathode, specific testing result It is shown in Table 1；

B1 introduces light source, intensity of illumination 100mW/cm as cathode using sunlight², control cathode deposition potential When for -0.1V (vs NHE), tank voltage 0.9V, cathodic reduction curent density is in 59~66A/m², detect gained on cathode and produce Weight of the object on unit area, specific testing result are shown in Table 1；

B2 other conditions and B1's is consistent, when control cathode deposition potential is -0.3V (vs NHE), tank voltage 1.3V, Cathodic reduction curent density is in 75~83A/m², detect weight of the products therefrom on unit area on cathode, specific detection knot Fruit is shown in Table 1；

C1 introduces light source, intensity of illumination 100mW/cm as cathode using LED light², control cathode deposition potential be- When 0.1V (vs NHE), tank voltage 0.9V, cathodic reduction curent density is in 52~59A/m², detect products therefrom on cathode and exist Weight on unit area, specific testing result are shown in Table 1；

C2 other conditions and C1's is consistent, when control cathode deposition potential is -0.3V (vs NHE), tank voltage 1.3V, Cathodic reduction curent density is in 70~76A/m², detect weight of the products therefrom on unit area on cathode, specific detection knot Fruit is shown in Table 1；

D1 introduces light source, intensity of illumination 5mW/cm as cathode using fluorescent lamp², control cathode deposition potential be- When 0.1V (vs NHE), tank voltage 0.9V, cathodic reduction curent density is in 19~26A/m²；Products therefrom exists on detection cathode Weight on unit area, specific testing result are shown in Table 1；

D2 other conditions and D1's is consistent, when control cathode deposition potential is -0.3V (vs NHE), tank voltage 1.3V, Cathodic reduction curent density is in 42~46A/m², detect weight of the products therefrom on unit area on cathode, specific detection knot Fruit is shown in Table 1；

E1 is under non-illuminated conditions, when control cathode deposition potential is -0.1V (vs NHE), tank voltage 0.9V, and cathode Reduction current density is in 13~16A/m²；Weight of the products therefrom on unit area on cathode is detected, specific testing result is shown in Table 1；

E2 other conditions and E1's is consistent, when control cathode deposition potential is -0.3V (vs NHE), tank voltage 1.3V, Cathodic reduction curent density is in 37~39A/m², detect weight of the products therefrom on unit area on cathode, specific detection knot Fruit is shown in Table 1；

In above-mentioned experiment, when using the sun as light source, photon reaches cathode by the reflection of reflecting mirror, the refraction of electrolyte On；When using xenon lamp and LED light as light source, it can place it near cathode, at this point, photon is merely through transparent electrolytic bath and electrolysis Cathode surface is reached after the refraction of liquid.

Table 1 is the weight that gained cathode product Se is respectively tested in embodiment 1 on unit area

As can be known from the above table, the optical power density the big more is conducive to the extraction of the optical electro-chemistry of selenium, under same optical power density, hot spoke It penetrates irradiation of the light source compared to cold light lamp source and is conducive to optical electro-chemistry and extract selenium (extraction rate high), the potential the negative also more to be conducive to The optical electro-chemistry of selenium is extracted.

Under the conditions of attached drawing 1 gives E2, during electricity consumption chemical metallurgy method extracts selenium simple substance at -0.3V (vs NHE), Applying (on) and disconnecting (off) intensity of illumination is 5mW/cm²The situation of change of cathode-current density when daylight light irradiation.Attached drawing 2 To apply (on) under equal conditions and disconnecting (off) 100mW/cm²The situation of change of cathode-current density when xenon lamp irradiates.Attached drawing 3 provide be A2 under the conditions of, photoelectrochemical method extracts the photo obtained when selenium simple substance 40min, it can be found that obtained selenium is in ash Color, uniform fold, has certain thickness on the electrode.Illustrate that the present invention solves Conventional electrochemical and extracts selenium to will receive selenium blunt Change the problem of film prevents reaction from carrying out.In the reduction process of the present embodiment technique, the reduction rate of selenium is 99.54%, gained selenium powder In containing selenium more than 99%.

Test proves that the present invention is by that can extract selenium from selenium leachate using optical electro-chemistry Extraction metallurgy technology Element, obtained selenium is (more than 99%) with high purity, and the present invention extracts the technology of selenium at low cost, the rate of recovery is high, technical process Be easy to control, light source choose type it is wide, make full use of the features such as clean energy resource, only enterprise does not realize mentioning for economic benefit High, the energy the sustainable use, also reduces solid waste and toxic gas SO₂Pollution.

Embodiment 2

Take appropriate metallurgical intermediary tellurium dioxide TeO₂NaOH solution is added and dissolves, to the alkali soluble for having dissolved tellurium dioxide The sodium sulfide solution of 0.7g/L is added to remove the foreign metal ion in solution in liquid, and prepared solution is that optical electro-chemistry mentions The electrolyte (wherein tellurium content be 100~120g/L, NaOH70~120g/L, Se < 0.3g/L, Pb < 0.3g/L) taken, by itself plus Enter spare into two electrode systems.Using stainless steel as cathode, copper plate is that (spacing between cathode and anode is anode 20mm), control electrolyte temperature is 10 DEG C, and the cathode-current density for controlling reduction system is 270A/m², controlling tank voltage is 2.5V, with 100mW/cm²Sunlight passes through on electrolyte vertical irradiation cathode as light source.Keep cathode sedimentation time be 120h then takes out cathode and cleans up simultaneously ingot casting, smart tellurium block purity > 99.9% obtained after founding, this scheme prepares smart tellurium Energy consumption low compared with conventional method energy consumption 40%, deposition efficiency is increased to the hydrometallurgy that original 180% is a kind of low energy consumption Technique.

Embodiment 3

The tellurium powder for taking appropriate sodium sulfite to restore, and alkali oxide leaching is carried out, obtained leachate is as electricity It solves liquid (pH value 12.8, the concentration of tellurium are 5.1mol/L), adds it to spare in three-electrode system.With transparent SnO₂It is conductive Glass is cathode, and thick tellurium is anode (spacing between cathode and anode is 30mm), and reference electrode is saturated calomel electrode, 50mW/cm²Xenon lamp stablizes irradiation and is used as light source, and photon passes through transparent SnO₂The transmission of electro-conductive glass reaches cathode surface after penetrating, control Electrolyte temperature processed is 30 DEG C, and control cathode electrode potential is -0.3V (vs NHE), and control tank voltage is that 1.7V makes Reduction Body The cathode-current density of system is 95~110A/m².Sedimentation time stops reaction after reaching 260h, takes out cathode and cleans up and cast Ingot, smart tellurium block purity > 99.9% obtained after founding.

Attached drawing 4 is shown within 0~1500s of the present embodiment, in 100mW/cm²Optical electro-chemistry metallurgical extraction when xenon lamp irradiates The cathode-current density of Te (curve 2) and electrochemistry metallurgical extraction Te (curve 1).It is apparent that illumination obviously promotes electricity The current density of chemical metallurgy extraction Te.

In addition, our potentiostatic polarization curves in prolonged deposition process it can be found that after depositing to 5h In, as time increases, the trend that the cathode-current density of Conventional electrochemical deposition Te decreased significantly, and optical electro-chemistry is heavy The cathode-current density of product Te still slowly rises, and illustrates to generate on cathode with semiconductor, and the lower conductivity of Te hinders The progress of deposition process, the introducing of illumination but can solve conductivity semiconductor it is low and caused by react passivation phenomenon, the party Case is conducive to the electrochemical extraction of Te.

Embodiment 4

Take the earth of positive pole containing tellurium and selenium in right amount, and carried out oxidizing acid leaching, obtained leachate as electrolyte, Electrolysis cycle liquid or water dilution are added in leachate, pH is made to reach 0 or so (concentration of the concentration 2mol/L of tellurium, selenium at this time Optical electro-chemistry extraction is carried out for 2.1mol/L), extraction time is 48 hours, and the mixing of the tellurium and selenium of black is precipitated on cathode Object.

When carrying out optical electro-chemistry extraction, with transparent SnO₂Electro-conductive glass is cathode, and graphite is anode (between cathode and anode Spacing be 40mm).Control tank voltage is 2.1V, control electrolyte temperature is 60 DEG C；Control the cathode electricity of electrolytic deposition system Current density is 210A/m², cathode is taken out after depositing 48 hours and is cleaned up and is dried.In different light source and intensity of illumination Under, photon reaches cathode surface, the cathode product ingredient and quality test knot that optical electro-chemistry is extracted after the refraction of electrolyte Fruit such as table 2:

The test result of 2 embodiment of table, 4 cathode deposition constituent content and quality

Light conditions	Cathode contains Se%	Cathode contains Te%	1m²The quality g of upper extract
				Xenon lamp 900mW/cm²	45.07	51.70	3824.52
Metal halogen lamp 100mW/cm²	45.11	50.14	2365.34
				Mercury lamp 100mW/cm²	46.26	49.69	2427.47
330nm wavelength laser 5mW/cm²	43.07	45.85	175.68
				No light	40.5	59.5	114.53

As a result similar to Example 1, optical electro-chemistry, which is extracted, changes different from, tool with optical power density and the type of light source Body shows themselves in that optical power is big, and extraction rate is high；Light source color temperature is high, and extraction rate is fast, and on the whole optical electro-chemistry extracts tellurium and selenium The rate of mixture is faster than the rate that optical electro-chemistry extracts selenium simple substance.Therefore it can be extracted after tellurium and selenium again simultaneously with optical electro-chemistry Solve the problems, such as that selenium electrochemical extraction rate is low through distillation separation selenium.

Attached drawing 5 gives in SnO₂It in cathode-current density is 210A/m with optical electro-chemistry metallurgy method on electro-conductive glass²Under The photo obtained when extracting selen-tellurjum mixture 20min uniformly covers on the electrode it can be found that obtained mixture is in black gray expandable Lid, it is opaque, there is thicker thickness.Illustrate the present invention suitable for from solution while extracting selenium and tellurium.

Thermal distillation purifying is carried out to photocathode, vapo(u)rizing temperature is 300 DEG C, and condensation temperature is 220 DEG C.Condense obtained smart selenium Purity is 99.98% or more, and cathode purity containing Te after purification is 99.96% or more.The present invention is conducive to semiconductor element It extracts simultaneously, reduces pharmaceutical use and slag and effluent generates, the semiconductor simple substance extracted is with high purity, energy consumption is small, without dirt Dye, is a kind of efficient clean metallurgical extraction process.

Embodiment 5

Using the stronger metallurgical intermediate germanium tetrachloride of volatility as solute, under argon gas protective atmosphere by its with from Sub- liquid (such as -3 methylimidazole of chlorination 1- hexyl) is dissolved, and the electrolyte extracted as optical electro-chemistry, and wherein the concentration of germanium is 3mol/L.Using titanium plate as cathode, Pt ring is the reference electrode subject to Ag to electrode (spacing between cathode and anode is 19mm), Using incandescent lamp as light source, photon reaches cathode surface, intensity of illumination 100mW/cm by the refraction of electrolyte², with PAR273A electrochemical workstation is deposition process controller, and holding cathode potential is that -1.1V (vs NHE) carries out permanent potential also Original, at this point, cathode-current density is 18~27A/m², control tank voltage is 2.9V, and control solution temperature is 70 DEG C, extraction time It is 430 hours, after the time for reaching requirement, stops reaction, take out cathode and clean up and dry, it can be seen that sinks on cathode Product goes out the germanium of metallic luster.

Attached drawing 6 is originally to apply example in 100mW/cm²Incandescent lamp irradiates time electrochemistry metallurgical extraction Ge (curve 2) and tradition electricity Chemical metallurgy extracts the cathode-current density situation of Ge (curve 1).It is apparent that in the 800~2400s range for extracting Ge Interior, the cathode-current density of optical electro-chemistry metallurgical extraction Ge (PED) deposits the cathode electricity of Ge in the case where being apparently higher than no light Current density, and the cathode-current density of optical electro-chemistry metallurgical extraction Ge (PED) is continuously increased, and Conventional electrochemical metallurgical extraction The cathode-current density of Ge (CED-Te) is gradually reduced.This explanation under non-illumination conditions, the Ge semiconductor that is generated on electrode The progress of electrochemical extraction process is really inhibited, and the effect of illumination will significantly reduce the generation of this inhibitory effect, and And the progress that illumination can also promote electrodeposition to react.

The germanium high production efficiency that the present invention extracts, energy consumption is small, is a kind of convenient germanium metallurgical extraction technique of letter.

Embodiment 6

In argon gas protective atmosphere by silicon metallurgical process silicon chlorizate trichlorosilane and silicon tetrachloride be dissolved in Bis- (trifluoro methylsulfonyl) inferior amine salts of ionic liquid 1- butyl -1- crassitude, and as optical electro-chemistry deposition Electrolyte (concentration of silicon is 2mol/L in electrolyte at this time).Using high purity graphite as cathode, Pt ring is to electrode (cathode and anode Between spacing be 5mm), reference electrode subject to Ag, with 100mW/cm²Fluorescent lamp passes through the folding of electrolyte as light source, photon It is mapped to up to cathode surface, using PAR273A electrochemical workstation as deposition process controller, holding cathode potential is -1.8V (vs NHE), at this point, cathode-current density is 13~15A/m², control tank voltage is 3.7V, and control solution temperature is 80 DEG C, in three electricity Permanent potential reduction is carried out in polar body system, the recovery time is 430 hours, after the time for reaching requirement, stops reaction, takes out cathode simultaneously It cleans up and dries, it can be seen that its purity of the silicon of precipitating metal gloss is greater than 99.9% on cathode.

Attached drawing 7 is originally to apply example to disconnect (off) during optical electro-chemistry metallurgy method extracts Si and apply (on) 100mW/cm² The situation of change of cathode-current density when daylight light irradiation.

Embodiment 7

Using the solution system of sulfuric acid dissolution chemistry pure tin powder as optical electro-chemistry deposited electrolyte, and guarantee there is tin in solution Simple substance is slightly excessive (electrolyte composition is shown in Table 3).Using refined tin as cathode, thick tin of casting is that (Sn content is 96%, Pb content to anode For 1%, Bi content be 0.5%, Cu content be 0.1%, Fe content be 0.1%, As content be 0.2%, Sb content be 2%), with The sun reaches cathode surface after the reflection of reflecting mirror, the refraction of electrolyte, reaches the light of cathode surface as light source, photon It is 120mW/cm according to intensity², using two electrode systems as optical electro-chemistry sedimentary system, interpolar is away from being 10 centimetres, electrolyte pH =1, electrolysis temperature is 40 DEG C, and retention groove pressure is that 0.3V carries out permanent potential optical electro-chemistry deposition, at this point, cathode-current density is 200~208A/m², after being powered 200 hours, take out cathode and anode and clean up and dry.Every 10 hours in deposition process Anode is taken out, surface anode mud is removed.

The ingredient (g/l) of liquid is solved in 3 embodiment 7 of table

Ingredient	Sn²⁺	Sn⁴⁺	H₂SO₄	Cr⁶⁺	NaCll	Latex	Beta Naphthol 99MIN	Cresol sulfonic acid
									Content	36	3	65	2.5	3	1.4	0.2	17

Table 4 gives optical electro-chemistry deposition (PED) and the major technique economy of Conventional electrochemical refining techniques (CED) refers to Mark, the energy consumption of present invention extraction tin is small as can be seen from Table 4, and current efficiency is high, other economic indicators are also slightly promoted.

The major economic indicators of table 4 embodiment of the present invention 7 (PED) and traditional technology (CED) refined tin

Deposition method	Current efficiency/%	Smelting recovery/%	Direct current consumption/KWh
				CED	78	99.5	180
PED	88	99.8	120

Table 5 gives the cathode tin (electric tin) of optical electro-chemistry deposition (PED) and Conventional electrochemical refining techniques (CED) output Ingredient illustrates that the present invention is conducive to the product purity for further promoting tin refining, reduces the content of impurity element.

5 cathode tin of table (electric tin) chemical component (mass fraction/%)

Deposition method	Sn	Pb	Bi	Fe	Cu	As	Sb
								CED	99.94	0.015	0.004	0.006	0.007	0.014	0.014
PED	99.98	0.005	0.001	0.001	0.001	0.006	0.006

Attached drawing 8 is originally to apply example to apply (on) during electrochemistry metallurgy method extracts Sn and disconnect (off) 120mW/cm²Too The situation of change of cathode-current density when sunlight irradiates.Since tin has the characteristics such as low conductivity, the high current response of semiconductor, In the case where the light source of the condition irradiates for a long time, due to the synergistic effect of these characteristics, final cathode-current density is up to one Stationary value speculates that the theoretical current density value of cathode deposition tin is about 210A/m under this condition according to theory²。

Embodiment 8

A certain amount of active bismuth meal and ammonium sulfide solution are added in ferric trichloride-salt Ore Leaching bismuth mineral solution system, To reduce influence of the foreign ion to subsequent optical electrochemical deposition, the stablizing solution system prepared in this way is heavy as optical electro-chemistry Product electrolyte.Using stainless steel as cathode, sponge bismuth ingot casting is as anode.Using the LED light that uninterruptedly flashes as light source, photon warp The intensity of cathode surface is reached after crossing the refraction of electrolyte as 450mW/cm², using with diaphragm, (such as aperture is about 15 microns micro- Hole plastic plate) two electrode systems as optical electro-chemistry sedimentary system, interpolar is away from (diaphragm is away from anode and cathode point for 14.5 centimetres Wei not be 6 centimetres and 8.5 centimetres), leachate is added in cathodic region, and batch catholyte of test discharge, galvanization is added in anode region In in cathodic region be continuously added leachate (keep the two poles of the earth liquid level poor < 10mm), Bi ion concentration is about in catholyte 44g/L, HCl concentration are 45g/L, Fe²⁺Concentration is 2.9g/L.Keeping electrolyte temperature is 55 DEG C, cathode-current density 260A/ m², slot pressure be 1.4~1.6V, under conditions of carry out optical electro-chemistry galvanostatic deposition.After being powered 15 hours, anode region solution can be with All or part of discharge takes out cathode and cleans up and dry.Cathode efficiency be greater than 97%, direct current consumption be 0.85 degree/ Kilogram bismuth.

Cathode deposition bismuth is heated to 300 DEG C in the sodium hydroxide of melting, bismuth melts and aggregation of sinking, to prevent The oxidation of bismuth, while oxide in bismuth and impurity are soluble in sodium hydroxide, the bismuth ingot purity that final founding obtains > 99.8%.

Embodiment 9

With akali sulphide (Na₂S and NaOH) leach antimony concentrate solution as optical electro-chemistry deposited electrolyte (54g/L containing antimony, Tin 16g/L, vulcanized sodium 48g/L, sodium hydroxide 61g/L, sodium sulphate 26g/L, sodium carbonate 63g/L, sodium thiosulfate 53g/L).Yin Pole and anode all use stainless steel material, with 70mW/cm²Mercury lamp as light source, photon reaches after the refraction of electrolyte Cathode surface, using two electrode systems as optical electro-chemistry sedimentary system, interpolar carries out under the conditions of 55 DEG C of temperature away from for 190mm Optical electro-chemistry deposits, and it is 290A/m that cathodic reduction curent density is kept in galvanization²Constant-current electrolysis deposition is carried out, slot pressure is 0.5~0.6V after being powered 24 hours, takes out cathode and cleans up and dry.Obtained cathode antimony purity > 99.8%, other Impurity is mainly sulphur (about 0.02%), As (about 0.02%), bismuth (about 0.01%), lead (about 0.1%).The cathode antimony of this method production It can get purity after melting and be higher than country 1^#The standard of business star metal.

The throughput rate that the present invention extracts antimony is high, compared with 1.6 times of high production efficiency of traditional soda electro-deposition antimony, energy consumption 260 KWh/ton antimony, is the 70% of traditional soda electro-deposition antimony total energy consumption, is a kind of simply and easily antimony metallurgical extraction technique.

Embodiment 10

It takes appropriate selenium bone coal leachate and HCl is added thereto, dilute after mixing, the pH of leachate is made to reach 4.3, The concentration of Se is 0.1mol/L, is added to using the leachate prepared as electrolyte spare in three-electrode system.With stainless steel plate For cathode, graphite is anode (spacing between cathode and anode is 20mm), and saturated calomel electrode is reference electrode.With Metal halogen lamp For light source, 150mW/cm is introduced toward cathode²Irradiation light, control electrolyte temperature be 60 DEG C, control cathode deposition potential be -1V When (vs NHE), tank voltage 2.8V, cathodic reduction curent density is in 110~120A/m²；Deposition 100 hours, in unit square The quality that high purity selenium (>=99%) is obtained on the cathode plate of rice and flour product is 5.17kg.

Embodiment 11

It takes appropriate selenic acid mud leachate to dilute, [the H of leachate is made after dissolution sufficiently⁺] concentration that reaches 10mol/L, Se is 3mol/L is added to spare in three-electrode system using the leachate prepared as electrolyte.Using stainless steel plate as cathode, graphite is Anode (spacing between cathode and anode is 100mm), saturated calomel electrode is reference electrode.Using tungsten halogen lamp as light source, toward yin Pole introduces 50mW/cm²Irradiation light, control electrolyte temperature is 20 DEG C, when control cathode deposition potential is -3V (vs NHE), Tank voltage is 5V, and cathodic reduction curent density is in 305~320A/m²；Deposition 50 hours, in the cathode plate of unit square rice and flour product On obtain high purity selenium (>=99%) quality be 6.4kg.

Embodiment 12

It takes and HCl is added in the earth of positive pole containing tellurium copper of appropriate oxidizing roasting, make [the H of leachate after mixing⁺] reach 0.1mol/L, into solution, the sodium sulfide solution of addition 0.7g/L is prepared molten to remove the foreign metal ion in solution Liquid is the electrolyte (wherein tellurium content is 50mmol/L, Se < 0.3g/L, Cu < 0.3g/L) that optical electro-chemistry is extracted, and is added into It is spare into two electrode systems.Using titanium plate as cathode, copper plate is anode (spacing between cathode and anode is 230mm), Controlling electrolyte temperature is 10 DEG C, and the cathode-current density for controlling reduction system is 50A/m², control tank voltage is 1.1V, ether Sun be used as light source, by electrolyte vertical irradiation cathode, toward cathode on introduce intensity of illumination be 300mW/cm²Irradiation light.It protects Holding cathode sedimentation time is 50h, then takes out cathode and cleans up simultaneously ingot casting, smart tellurium block purity > 99.9% obtained after founding.

Embodiment 13

It takes the baked earth of positive pole containing tellurium lead of moderate amount of sulfuric acidization that NaOH solution is added and dissolves, prepared solution is light The electrolyte (wherein tellurium content is 3.7mol/L, NaOH70~120g/L, Se < 0.3g/L, Pb < 0.3g/L) of electrochemical extraction, It adds it to spare in two electrode systems.Using stainless steel as cathode, copper plate is the anode (spacing between cathode and anode For 300mm), controlling electrolyte temperature is 80 DEG C, and the cathode-current density for controlling reduction system is 430A/m², control tank voltage For 3.7V, using mercury lamp as light source, by electrolyte vertical irradiation cathode, toward cathode on to introduce intensity of illumination be 30mW/cm²'s Irradiation light.Holding cathode sedimentation time is 320h, then takes out cathode and cleans up, on the cathode plate of unit square rice and flour product The quality for obtaining tellurium is 53.17kg, smart tellurium block purity > 99.9% that will be obtained after cathode tellurium founding.

Embodiment 14

The copper anode mud containing tellurium and selenium in right amount is taken, and is carried out oxidizing acid leaching, obtained leachate is as electrolysis Electrolysis cycle liquid or water dilution are added in leachate, pH is made to reach 1.1 or so (concentration 50mmol/L, the selenium of tellurium at this time for liquid Concentration be 75mmol/L) carry out optical electro-chemistry extraction, optical electro-chemistry extract when, using transparent stainless steel as cathode, graphite be sun Pole (spacing between cathode and anode is 30mm).Using halogen gold lamp as light source, introducing intensity of illumination toward cathode is 430mW/cm²'s Irradiation light, control tank voltage is 8V, control electrolyte temperature is 60 DEG C；Control electrolytic deposition system cathode-current density be 430A/m², cathode is taken out after depositing 1 hour and is cleaned up and is dried to obtain the tellurium of black and the mixture of selenium.

Embodiment 15

It, will under argon gas or nitrogen protective atmosphere using the stronger metallurgical intermediate germanium tetrachloride of volatility as solute It uses ionic liquid (bis- (trifluoro methylsulfonyl) inferior amine salts of such as 1- butyl -1- crassitude) dissolution to be electrolysed as optical electro-chemistry The electrolyte of extraction, the concentration of germanium are 100mmol/L.Using pure germanium as cathode, Pt ring is to electrode (between cathode and anode Away from for 25mm), reference electrode subject to Ag, using incandescent lamp as light source, photon reaches cathode surface by the refraction of electrolyte, Intensity of illumination is 85mW/cm², using PAR273A electrochemical workstation as deposition process controller, holding cathode potential is -1.8V (vs NHE) carries out permanent potential reduction, at this point, cathode-current density is 140~154A/m², control tank voltage is 5.0V, control Solution temperature is 50 DEG C, extraction time is 2 hours, after the time for reaching requirement, stops reaction, takes out cathode and cleans up simultaneously Drying, it can be seen that the germanium that metallic luster is deposited on cathode is detected its purity > 99.9%.

Embodiment 16

Using the stronger metallurgical intermediate germanium tetrachloride of volatility as solute, under nitrogen protective atmosphere by its with from Sub- liquid (such as -3 methylimidazole bromine ammonia of 1- ethyl) dissolves the electrolyte as optical electro-chemistry electroextraction, and the concentration of germanium is 1mol/L.Using red copper as cathode, Pt ring is the reference electrode subject to Ag to electrode (spacing between cathode and anode is 25mm), Using LED light as light source, photon reaches cathode surface, intensity of illumination 230mW/cm by the refraction of electrolyte², with PAR273A electrochemical workstation is deposition process controller, and holding cathode potential is that -3V (vs NHE) carries out permanent potential reduction, At this point, cathode-current density is 285~310A/m², control tank voltage is 8.0V, and control solution temperature is 50 DEG C, extraction time It is 200 hours, after the time for reaching requirement, stops reaction, take out cathode and cleans up and dry, the yin in unit square rice The quality that metallic luster germanium is deposited on extremely is about 9.3kg.

Embodiment 17

Metallurgical grade silicon chlorizate silicon tetrachloride is dissolved in ionic liquid 1- butyl -1- first in nitrogen protective atmosphere Bis- (trifluoromethanesulfonic acid) inferior amine salts of base pyrrolidines, and as the electrolyte of optical electro-chemistry deposition (at this time in electrolyte The concentration of silicon is 100mmol/L).Using titanium sheet as cathode, Pt ring is to electrode (spacing between cathode and anode is 20mm), Ag Subject to reference electrode, using halogen gold lamp as light source, photon reaches cathode surface by the refraction of electrolyte, and intensity of illumination is 980mW/cm², using PAR273A electrochemical workstation as deposition process controller, holding cathode potential is -4V (vs NHE), this When, cathode-current density is 240~255A/m², control tank voltage is 10V, and control solution temperature is 80 DEG C, in three-electrode system The permanent potential reduction of middle progress, the recovery time is 60 hours, after the time for reaching requirement, stops reaction, takes out cathode and cleans dry Only it and dries, it can be seen that the silicon of precipitating metal gloss on cathode is detected its purity greater than 99.9%, obtained on unit square rice The siliceous amount obtained is about 3.3kg.

Embodiment 18

Metallurgical grade silicon chlorizate silicon tetrachloride is dissolved in ionic liquid 1- butyl -3- first in nitrogen protective atmosphere Base limidazolium hexafluorophosphate, and (concentration of silicon is in electrolyte at this time as the electrolyte of optical electro-chemistry deposition 3mol/L).Using high purity graphite as cathode, Pt ring is to electrode (spacing between cathode and anode be 7mm), and reference is electric subject to Ag Pole, using common fluorescent lamp as light source, photon reaches cathode surface by the refraction of electrolyte, with PAR273A electrochemical operation Standing is deposition process controller, and holding cathode potential is -1V (vs NHE), at this point, cathode-current density is 6~7.5A/m², control Tank voltage processed is 2.6V, and control solution temperature is 35 DEG C, carries out permanent potential reduction in three-electrode system, and the recovery time is 80 small When, after the time for reaching requirement, stop reaction, takes out cathode and simultaneously clean up and dry, it can be seen that on unit square rice The silicon that siliceous amount is about 0.2kg precipitating metal gloss is obtained on cathode, purity is greater than 99.99%.

Embodiment 19

Using suitable recycling tin as raw material and with alkali soluble solution, Sn content is that 1.3~1.5%, NaOH contains in the solution of acquisition Amount is 5~6%, Na₂CO₃It is 3%, optical electro-chemistry extraction is carried out using this solution system as optical electro-chemistry deposited electrolyte.With essence Tin is cathode, and thick tin of casting is that (it be 0.1%, Bi content is that 0.2%, Cu content is that Sn content is 96%, Pb content to anode 1.1%, Fe content are that 2.1%, As content is 0.3%, Sb content for 0.2%), using 540nm laser as light source, photon passes through Cathode surface is reached after the reflection of reflecting mirror, the refraction of electrolyte, the intensity of illumination for reaching cathode surface is 550mW/cm², adopt Use two electrode systems as optical electro-chemistry sedimentary system, for interpolar away from being 50 centimetres, electrolyte pH=14, electrolysis temperature is room temperature, Retention groove pressure is that 3V carries out permanent potential optical electro-chemistry deposition, at this point, cathode-current density is 320A/m², after being powered 50 hours, take Cathode is cleaned up and is dried out.The tin quality obtained on unit square rice is about 26kg, through the pure of detection purity >=99.98% Tin.

Embodiment 20

The solution system of thick tin is dissolved as optical electro-chemistry deposited electrolyte using fluosilicic acid, and (concentration of tin is in electrolyte 8.5mol/l).Using refined tin as cathode, thick tin of casting is that (Sn content is that 98%, Pb content is that 0.9%, Bi content is to anode 0.4%, Cu content be 0.2%, Fe content be 0.1%, As content be 0.2%, Sb content be 0.2%), using xenon lamp as light Source, photon converge to cathode surface after the reflection of reflecting mirror, the refraction of electrolyte, and the intensity of illumination for reaching cathode surface is 450mW/cm², using two electrode systems as optical electro-chemistry sedimentary system, for interpolar away from being 6 centimetres, electrolyte pH=3, electrolysis is warm Degree is room temperature, and retention groove pressure is that 0.2V carries out permanent potential optical electro-chemistry deposition, at this point, cathode-current density is 110A/m², it is powered After 100 hours, takes out cathode and anode and clean up and dry.The cathode tin quality that average every square meter obtains is 21kg, is obtained To cathode tin through detecting, the pure tin of purity >=99.98%.

Embodiment 21

Using sodium bismuthate as electrolyte, it is yin with titanium sheet that the concentration of bismuthic acid root, which is 4.3mol/l, pH=10, in electrolyte Pole, sponge bismuth ingot casting is as anode, and interpolar is away from being 48 centimetres.Using LED light as light source, photon arrives after the refraction of electrolyte Intensity up to cathode surface is 50mW/cm², keeping electrolyte temperature is 30 DEG C, cathode-current density 670A/m², slot pressure is Optical electro-chemistry galvanostatic deposition is carried out under conditions of 7.1V.After being powered 5 hours, takes out cathode and clean up and dry.Direct current Consumption is 0.92 degree/kilogram bismuth.

Embodiment 22

Using sulfate-ammino-complex-electrolysis of fluorides liquid system as optical electro-chemistry deposited electrolyte (antimony ion concentration For 230g/L, fluorinion concentration 70g/L, sulfate concentration 348g/L, ammonia root concentration is 75g/L, pH=5.4).Cathode and Anode all uses stainless steel material, with 260mW/cm²Halogen gold lamp as light source, photon reaches yin after the refraction of electrolyte Pole surface, using two electrode systems as optical electro-chemistry sedimentary system, interpolar carries out light under the conditions of 55 DEG C of temperature away from for 260mm Electrochemical deposition, it is 530A/m that cathodic reduction curent density is kept in galvanization²Constant-current electrolysis deposition is carried out, slot pressure is 5.5V after being powered 12 hours, takes out cathode and cleans up and dry.The cathode antimony that unit square rice obtains is 18kg.

Claims

1. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element, it is characterised in that: in electrodeposition groove, shone with light Cathode is penetrated, is deposited by optical electro-chemistry, semiconductor is obtained on cathode；Being electrolysed electrolyte used is the conduction containing semiconductor element Liquid；The semiconductor element includes tellurium, germanium, selenium, silicon, tin, antimony, at least two in bismuth；It irradiates in the light of cathode and contains Energy is more than or equal to the photon of institute's deposited semiconductor band gap width；

Simultaneously when two or more semiconductor element of electrolytic deposition, control cathodic reduction curent density is 1~800A/m², control Bath voltage processed is 0.1~12V, and control cathode deposition potential is 0~-5V, and control electrolytic deposition is 1~500 hour；Electrolysis When deposition, the reference system of the cathode deposition potential is hydrogen electrode.

2. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: electrolysis Diaphragm is equipped between yin-yang the two poles of the earth of dislodger, having on the diaphragm can be by the pore of semiconductor element to be deposited.

3. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: irradiation The intensity of the light of cathode is 1~9000mW/cm²。

4. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: partly lead Element of volume with the dispersion of oxidation state and/or the form stable of simple substance in the electrolytic solution；Semiconductor element is total in the electrolyte Concentration is 1~9000mmol/L.

5. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: described Cathode is selected from one of stainless steel, titanium sheet, red copper, transparency conducting layer, semiconductor simple substance to be deposited.

6. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: anode Selected from one of inert electrode, the conductive material containing semiconductor element to be deposited.

7. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 6, it is characterised in that: work as sun When conductive material extremely containing semiconductor element to be deposited, anode is irradiated with light, is irradiated big containing energy in the light of anode In or equal in anode semiconductor element simple substance or its compound band gap width to be deposited photon；Irradiate the light of anode Intensity is 1~9000mW/cm²。

8. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: described The pH value of electrolyte is -1~14.

9. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: electrolysis When deposition, the temperature for controlling electrolyte is 10~95 DEG C.

10. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: adopt Electrolytic deposition is carried out with constant voltage or constant current or pulse current.

11. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: yin Spacing between pole and anode is 5~500mm.

12. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element described in any one according to claim 1~11, Be characterized in that: the light of irradiation cathode and/or anode is provided by one of stable light source, light-pulse generator, fluctuation light source.

13. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 12, it is characterised in that: mention The sun, xenon lamp, tungsten halogen lamp, Metal halogen lamp, incandescent lamp, fluorescent lamp, LED are selected from for the light source of irradiation cathode and/or the light of anode At least one of lamp, mercury lamp, laser.

14. a kind of method of optical electro-chemistry metallurgical extraction semiconductor element according to claim 1, it is characterised in that: same When electrolytic deposition tellurium selenium when, control cathodic reduction curent density be 1~500A/m², control bath voltage is 0.1~8V, control Cathode deposition potential processed is 0~-5V, and the control electrolytic deposition time is 1~360 hour.