CN104109766B - Technology for separating and purifying bismuth from lead-bismuth alloy - Google Patents
Technology for separating and purifying bismuth from lead-bismuth alloy Download PDFInfo
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Abstract
The invention discloses a technology for separating and purifying bismuth from lead-bismuth alloy. The technology comprises the following steps: continuously carrying out vacuum distillation by adopting a vacuum distillation furnace system to separate and purify bismuth, wherein the vacuum distillation furnace consists of a melting furnace, a siphon tank and a vacuum distillation furnace; firstly continuously conveying the lead-bismuth alloy into a melting furnace body, melting, then conveying into the vacuum distillation furnace, carrying out vacuum distillation so as to separate and purify the bismuth. The purity of bismuth obtained by separation can achieve more than 99.9%, the produced lead alloy has no bismuth residues, and the continuous separation of bismuth in the lead-bismuth alloy can be realized; the technology is low in cost, low in energy consumption and environment-friendly, thus meeting the industrial production requirements.
Description
Technical field
The present invention relates to a kind of technique of separating-purifying bismuth from lead bismuth alloy, belong to bismuth and smelt purification technique field.
Background technology
Bismuth (bismuth), ordination number 83, silvery white or blush, have metalluster.Mainly for the manufacture of fusible alloy, for scolding tin, safety fuse, fire protection system, automatic water sprayer, boiler safety plug etc.Meanwhile, bismuth alloy has non-shrinking characteristic when solidifying, for casting printing type and high precision casting mold.In addition, bismuthyl carbonate and bismuthyl nitrate are used for the treatment of skin injury and gastroenteropathy.
Lead bismuth alloy, in nonferrous smelting or iron work, many times occur with byproduct, its economic worth, use value are all little, need be isolated, purify, become lead bullion, smart bismuth, its use value of competence exertion and economic worth, through the long-felt of scientific worker and technical specialist, current domestic lead, bismuth isolation technique are mainly based on chlorination process and electrolytic process.This method of chlorination process uses more in Large scale nonferrous metals smeltery.Its production process is melted by lead bismuth alloy, and logical people's chlorine in melt, preferentially plumbous and chlorine chemical combination forms chlorination lead skim (plumbous Cl2), is removed by chlorination lead skim, thus reaches separation of lead bismuth.The bismuth separated, again through pyrogenic attack, obtains smart bismuth.Meanwhile, chlorination lead skim otherwise processed, output lead bullion.Advantage: (1) this method is fairly simple, is applicable to scale operation.Shortcoming: (1) this method cost is higher, need form large-scale production and just produce economic worth.(2) when content≤12% of bismuth in alloy, this method cost can be very high, and industrial production is applied.(3) operational requirement is strict, and easy contaminate environment, environment toxic is large.(4), after chlorination, bismuth and lead all need again to smelt, and cause total cost to rise, and continue to cause environmental pollution.Electrolytic process, after alloy dissolves, after the certain mother liquor of adapted, according to plumbous, bismuth standard potential difference take electrolytic process.Under the conditions such as certain electrolysis voltage, lead in alloy anode plate forms ion and dissolves in electrolytic solution, and subsequently on lead electrode plate reduction separate out electric plumbous product, general plumbous >=99.5%; And bismuth has more positive polarity than lead, there is not electrochemical solution and form anode sludge enrichment, general bismuth >=95%, be i.e. thick bismuth.Thick bismuth just can obtain smart bismuth with pyrorefining again.Advantage: (1) advantage of lower cost.(2) equipment investment is relatively less.Shortcoming: (1) mother liquor selection and comparison is crucial, otherwise easily causes electric plumbous foreign matter content to increase, the low grade of electrolytic efficiency thus cause sepn process not reach requirement.(2) owing to being electrolysis, its energy consumption is relatively high.(3) bismuth also needs further processing after forming the anode sludge, causes follow-up environmental pollution.(4) due to the water pollutions of electrolysis waste solution, could discharge after need dealing with.(5) electrolytic process is applicable to the lower alloy of bismuth-containing amount.
Summary of the invention
For the defect existed in the technology of chlorination process in prior art and electrolytic process separation of lead and bismuth, the object of the invention is to be to provide a kind of technique being continuously separated high purity bismuth of purifying out by simple process from lead bismuth alloy, this technique low cost, less energy-consumption, environmental protection, meet demand of industrial production.
The invention provides a kind of technique of separating-purifying bismuth from lead bismuth alloy, this technique adopts vacuum distilling furnace system to carry out continous vacuum fractionation by distillation purification bismuth to lead bismuth alloy, described vacuum distilling furnace system comprises smelting furnace, siphon groove and vacuum distillation furnace, and vacuum distillation furnace comprises body of heater and inner bag, smelting furnace bottom is provided with discharge nozzle, and discharge nozzle one end is stretched in siphon groove, is provided with siphon pipe between siphon groove and vacuum distillation furnace, and siphon pipe one end is stretched into bottom siphon groove, and the other end stretches into vacuum distillation furnace furnace interior upper end, the top of described inner bag is provided with metal reservoir, and the middle part in inner bag is provided with multilayer distillation tray, is provided with groove bottom lower floor's distillation tray, and bottom portion of groove is connected with the plumbous collector that goes out of body of heater outside by pipeline, and the bottom in inner bag is provided with out bismuth pipe, when carrying out lead bismuth alloy fractionation by distillation purification bismuth, open vacuum pump and heating system, make vacuum distilling furnace interior be negative pressure state, the temperature of smelting furnace and siphon groove is elevated to 500 ~ 550 DEG C, and the temperature of distillation tray is elevated to 1550 ~ 1600 DEG C, now, lead bismuth alloy is sent in smelting furnace body of heater continuously and melts, fusing gained molten metal flows in siphon groove, under the low pressure effect of molten metal in siphon groove in vacuum distillation furnace, the metal reservoir injecting inner bag top is siphoned in vacuum distillation furnace by siphon pipe, entering inner bag inside again flows on the distillation tray of upper strata, and from upper strata distillation tray successively to lower floor's distillation tray flowing, maintain vacuum distillation furnace internal vacuum < 8Pa, bismuth seethes with excitement and evaporates in each layer distillation tray, after bismuth vapour encounters inner bag inwall, condensation is gathered into liquid state, collection is discharged in time by the bismuth pipe that goes out bottom inner bag, and comprise plumbous high boiling point alloyed metal liquid along the distillation tray successively dirty groove entered into bottom distillation tray always, enter plumbous collector by bottom portion of groove pipeline again to collect, complete vacuum distilling from lead bismuth alloy and isolate pure bismuth.
The technique of separating-purifying bismuth from lead bismuth alloy of the present invention also comprises following preferred version:
In preferred scheme, the temperature of distillation tray is 1550 ~ 1575 DEG C; Most preferably be 1550 DEG C.
In preferred scheme, the temperature of smelting furnace and siphon groove maintains 520 ~ 540 DEG C; Most preferably be 520 DEG C, to keep the liquid phase of the best of molten metal.
In preferred scheme, vacuum distillation furnace bottom of furnace body is provided with upflow tube; Molten metal excessive for vacuum distilling furnace interior can be discharged by upflow tube in time, protection body of heater.
Be provided with aperture in preferred scheme bottom metal reservoir to be communicated with inner bag inside.
When in the metal reservoir at inner bag top during molten metal overfill in preferred scheme, overflow to the bottom in body of heater, discharge body of heater from upflow tube.
Go out bismuth pipe in preferred scheme and connect vacuum collector in vacuum distillation furnace outside.
In preferred scheme, side wall of inner is provided with vacuum-pumping tube, and vacuum-pumping tube is connected with the vacuum pump of body of heater outside.
In preferred scheme, distillation tray is set to 3 ~ 8 layers, most preferably is 3 ~ 5 layers.
Beneficial effect of the present invention: the present invention designs a kind of by vacuum distillation furnace system and device first, and goes out to be separated by vacuum distilling the technique of high purity metal bismuth of purifying out from plumbous bismuth metal in conjunction with this apparatus design.Technique hinge structure of the present invention has the following advantages: 1, simple for process, can carry out continuous seepage; 2, less, energy consumption is low, with low cost for equipment and input; 3, environmental pollution is little, does not almost have waste gas, does not produce waste water, and waste residue is few; 3, good separating effect, isolated bismuth purity >=99.9%, processes without the need to follow-up refining, is separated in the metallic lead obtained and remains without bismuth.
Accompanying drawing explanation
[Fig. 1] is lead content in bismuth of the present invention and distillation temperature graph of relation.
[Fig. 2] is vacuum distillation furnace structure of system equipment sketch; 1 is smelting furnace, and 2 is refractory brick, and 3 is nichrome wire, and 4 is entrance of cooling water, 5 is base, and 6 is stirring rake, and 7 is cooling water outlet, and 8 is discharge nozzle valve, 9 is discharge nozzle, and 10 is siphon groove, and 11 is siphon pipe, and 12 is siphon pipe valve, 13 is vacuum distilling furnace body, and 14 is vacuum distilling furnace internal-lining, and 15 is distillation tray, and 16 is electrode, 17 is upflow tube valve, and 18 for going out bismuth tube valve, and 19 is upflow tube, 20 for going out bismuth pipe, and 21 is plumbous collector, and 22 is vacuum-pumping tube; 23 is groove, and 24 is metal reservoir.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Embodiment 1
Adopt lead bismuth alloy derive from Jiangxi smeltery, wherein Fe, Cu, As and Cd content below 0.3wt%, Sb content at below 0.5wt%, Ag content within 2wt%.Atomic absorption spectrometry is adopted to detect; Detecting instrument: atomic absorption spectrophotometer (hydrogeneous compound producer), AA320N.
Vacuum distilling tripping device system with reference to accompanying drawing 2 carries out lead bismuth alloy fractionation by distillation purification bismuth.Described vacuum distilling furnace system comprises smelting furnace, siphon groove and vacuum distillation furnace, and vacuum distillation furnace comprises body of heater and inner bag; Smelting furnace bottom is provided with discharge nozzle, and the discharge nozzle the other end stretches in siphon groove, is provided with siphon pipe between siphon groove and vacuum distillation furnace, and siphon pipe one end is stretched into bottom siphon groove, and the other end stretches into vacuum distillation furnace furnace interior upper end; The top of described inner bag is provided with metal reservoir, middle part in inner bag is provided with 3 ~ 5 layers of distillation tray, groove is provided with bottom lower floor's distillation tray, bottom portion of groove is connected with the plumbous collector that goes out of body of heater outside by pipeline, bottom in inner bag is provided with out bismuth pipe, goes out bismuth pipe and connects vacuum collector in vacuum distillation furnace outside; Described vacuum distillation furnace bottom of furnace body is provided with upflow tube; Molten metal excessive for vacuum distilling furnace interior can be discharged by upflow tube in time, protection body of heater; Be provided with aperture bottom described metal reservoir to be communicated with inner bag inside; In the metal reservoir at inner bag top during molten metal overfill, overflow to the bottom in body of heater, discharge body of heater from upflow tube; Described side wall of inner is provided with vacuum-pumping tube, and vacuum-pumping tube is connected with the vacuum pump of body of heater outside.
Material is sent in fusing body of heater with the speed of 5.2 ~ 5.8kg/h by loading hopper, open vacuum pump and heating system, when the vacuum tightness < 20Pa of vacuum distilling furnace interior, by smelting furnace temperature to 520 DEG C, the temperature of siphon groove also maintains 520 DEG C simultaneously, the temperature of distillation tray is elevated to 1550 DEG C, and lead bismuth alloy is melted in smelting furnace, and fusing gained molten metal flows in siphon groove, under the low pressure effect of molten metal in siphon groove in vacuum distillation furnace, the metal reservoir injecting inner bag top is siphoned in vacuum distillation furnace by siphon pipe, entering inner bag again flows on the distillation tray of upper strata, and from upper strata distillation tray successively to lower floor's distillation tray flowing, maintain vacuum distillation furnace internal vacuum < 8Pa, bismuth seethes with excitement and evaporates in each layer distillation tray, after bismuth vapour encounters inner bag inwall, condensation is gathered into liquid state, in time discharge out of the furnace to be collected by vacuum collector by the bismuth pipe that goes out bottom inner bag, and comprise plumbous high boiling point alloyed metal liquid along the distillation tray successively dirty groove entered into bottom distillation tray always, enter plumbous collector by bottom portion of groove pipeline again to collect, complete vacuum distilling from lead bismuth alloy and isolate pure bismuth.
Isolated bismuth metal and lead metal are detected, purity >=99.9% of bismuth; And in lead, can't detect bismuth metal.
The temperature of distillation tray in vacuum distilling body of heater is repeated above-mentioned experiment every 5 DEG C of values between 1550 ~ 1655 DEG C, and the purity of bismuth metal and lead metal is detected, plumbous purity is substantially constant, and the purity of bismuth as shown in Figure 2, within the scope of 1550 ~ 1575 DEG C, the purity of bismuth is all more than 99.9%; And in the scope of 1575 ~ 1600 DEG C the purity of bismuth all more than 99.8%; And within the scope of 1600 ~ 1625 DEG C the purity drop of bismuth to 99.6 ~ 99.7% between; Illustrate that distillation temperature is too high, cause plumbous in bismuth product (mainly plumbous) impurity significantly higher.
Test in addition and also find, when temperature is lower than 1550 DEG C, it yields poorly, and has the hidden danger causing the plumbous discharging mouth of pipe to block.And smelting temperature is too low, slowly even there is non-fusible phenomenon in the fusing of test interalloy; Smelting temperature is too high, then cause part metals volatilization loss in raw material to fall, too increase energy consumption simultaneously.For certain lead bismuth alloy raw material, wherein bismuth 63wt%, plumbous 35wt%, gold and silver 1.7wt%, other below metal 0.3wt%, when smelting temperature is too low, during lower than 325 DEG C, because the fusing point of lead is 327.3 DEG C, there will be part material non-fusible; When temperature is too high, during higher than 765 DEG C, because in raw material, part metals boiling point is lower, there will be part metals (as cadmium, potassium etc.) and vapor away, the too high corresponding energy consumption of simultaneous temperature too increases.Therefore smelting temperature is unsuitable too high, also unsuitable too low, through test of many times, smelting temperature be 400 ~ 700 DEG C comparatively suitable, temperature is better at 475 ~ 525 DEG C.
Claims (10)
1. the technique of a separating-purifying bismuth from lead bismuth alloy, it is characterized in that, adopt vacuum distilling furnace system to carry out continous vacuum fractionation by distillation purification bismuth to lead bismuth alloy, described vacuum distilling furnace system comprises smelting furnace, siphon groove and vacuum distillation furnace, and vacuum distillation furnace comprises body of heater and inner bag, smelting furnace bottom is provided with discharge nozzle, and discharge nozzle one end is stretched in siphon groove, is provided with siphon pipe between siphon groove and vacuum distillation furnace, and siphon pipe one end is stretched into bottom siphon groove, and the other end stretches into vacuum distillation furnace furnace interior upper end, the top of described inner bag is provided with metal reservoir, and the middle part in inner bag is provided with multilayer distillation tray, is provided with groove bottom lower floor's distillation tray, and bottom portion of groove is connected with the plumbous collector that goes out of body of heater outside by pipeline, and the bottom in inner bag is provided with out bismuth pipe, when carrying out lead bismuth alloy fractionation by distillation purification bismuth, open vacuum pump and heating system, make vacuum distilling furnace interior be negative pressure state, the temperature of smelting furnace and siphon groove is elevated to 500 ~ 550 DEG C, and the temperature of distillation tray is elevated to 1550 ~ 1600 DEG C, now, lead bismuth alloy is sent in smelting furnace body of heater continuously and melts, fusing gained molten metal flows in siphon groove, under the low pressure effect of molten metal in siphon groove in vacuum distillation furnace, the metal reservoir injecting inner bag top is siphoned in vacuum distillation furnace by siphon pipe, entering inner bag inside again flows on the distillation tray of upper strata, and from upper strata distillation tray successively to lower floor's distillation tray flowing, maintain vacuum distillation furnace internal vacuum < 8Pa, bismuth seethes with excitement and evaporates in each layer distillation tray, after bismuth vapour encounters inner bag inwall, condensation is gathered into liquid state, collection is discharged in time by the bismuth pipe that goes out bottom inner bag, and comprise plumbous high boiling point alloyed metal liquid along the distillation tray successively dirty groove entered into bottom distillation tray always, enter plumbous collector by bottom portion of groove pipeline again to collect, complete vacuum distilling from lead bismuth alloy and isolate pure bismuth.
2. technique as claimed in claim 1, it is characterized in that, the temperature of described distillation tray is 1550 ~ 1575 DEG C.
3. technique as claimed in claim 2, it is characterized in that, the temperature of described distillation tray is 1550 DEG C.
4. technique as claimed in claim 1, it is characterized in that, described smelting furnace and the temperature of siphon groove maintain 520 ~ 540 DEG C.
5. technique as claimed in claim 4, it is characterized in that, described smelting furnace and the temperature of siphon groove maintain 520 DEG C.
6. technique as claimed in claim 1, it is characterized in that, described vacuum distillation furnace bottom of furnace body is provided with upflow tube.
7. technique as claimed in claim 1, is characterized in that, is provided with aperture and is communicated with inner bag inside bottom described metal reservoir.
8. technique as claimed in claim 6, is characterized in that, in the metal reservoir at inner bag top during molten metal overfill, overflow to the bottom in body of heater, discharges body of heater from upflow tube.
9. technique as claimed in claim 1, is characterized in that, goes out bismuth pipe and connects vacuum collector in vacuum distillation furnace outside.
10. technique as claimed in claim 1, it is characterized in that, described side wall of inner is provided with vacuum-pumping tube, and vacuum-pumping tube is connected with the vacuum pump of body of heater outside.
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| CN105779790A (en) * | 2016-04-12 | 2016-07-20 | 永兴佳盛有色金属再生利用有限责任公司 | Method for removing lead and purifying bismuth from lead-bismuth material through vacuum distillation |
| CN106048243B (en) * | 2016-08-11 | 2018-06-05 | 永兴佳盛环保科技有限责任公司 | A kind of method that high bismuth crude tin alloy vacuum distillation depth removes bismuth |
| CN111504924A (en) * | 2020-04-23 | 2020-08-07 | 中国原子能科学研究院 | Method for removing lead and bismuth in lead-bismuth alloy and method for measuring cadmium in lead-bismuth alloy |
| CN115491509A (en) * | 2022-08-31 | 2022-12-20 | 永兴县鸿福金属有限公司 | Vacuum purification method for multi-stage extraction of refined bismuth |
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| CN101696469A (en) * | 2009-10-29 | 2010-04-21 | 昆明理工大学 | Method for separating multi-element alloy of lead, bismuth, gold, silver and copper |
| CN102586627B (en) * | 2012-02-14 | 2013-12-11 | 蒙自矿冶有限责任公司 | Method for recovering bismuth from bismuth slag |
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