CN104357682B - The method of the efficient copper removal of a kind of thick bismuth bismuth kettle refining - Google Patents

Abstract

The invention discloses the method for the efficient copper removal of a kind of thick bismuth bismuth kettle refining, be characterized in adding in sulphur copper removal process, the ratio being 1:0.4 in sulphur and wood chip mass ratio adds wood chip, wood chip is as raising agent, and select water and its mixing and stirring, boiling point due to water is 100 DEG C, effectively can extend the duration of contact of sulphur and melt; Adding the sulphur after puddling can effective implemention copper removal from bismuth liquation, because wood chip plays a part raising agent, stop because sulphur is formed spherical with the defect such as bismuth liquation contact area is little, and effectively improve sulphur utilization ratio, solve and add that sulphur in sulphur copper removal process directly burns, the low problem of sulphur utilization ratio, effectively improve the direct yield of bismuth simultaneously.

Description

The method of the efficient copper removal of a kind of thick bismuth bismuth kettle refining

Technical field

The present invention relates to metallurgical technology technical field, the method for the efficient copper removal of a kind of thick bismuth bismuth kettle refining specifically.

Background technology

The domestic bismuth element that reclaims from lead anode slurry mainly adopts bismuth kettle refining to obtain smart bismuth product at present, in bismuth kettle refining process, most of producer all adopts and adds sulphur copper removal, because sulphur belongs to inflammable substance, add bismuth pot directly to float over afterwards on bismuth molten surface, cause sulphur directly to burn and sulphur adds pot floats on liquid level in bulk afterwards, focus under stirring and stir arbor place, form bulk, easily adhesion parcel is carried out to bismuth, cause except bi content in copper ashes is more than 20%.Meanwhile, sulphur utilization ratio low, increase bismuth production cost, extend the copper removal cycle.

Summary of the invention

The object of the invention is to overcome above-mentioned prior art Problems existing, and the method for the efficient copper removal of a kind of thick bismuth bismuth kettle refining is provided, this method technical process is short, easy to operate, effectively can improve copper removal effect, shorten bismuth refining cycle, reduce production cost and labour intensity, effectively improve bismuth direct yield.

In order to achieve the above object, the present invention is achieved in that the method for the efficient copper removal of a kind of thick bismuth bismuth kettle refining, and it comprises following processing step:

A, thick bismuth add in bismuth pot, be warming up to 530-550 DEG C, thick bismuth is melted completely, drag for the scum silica frost in clean bismuth pot;

B, to puddle in sulphur and the appropriate clear water of wood chip mass ratio 1:0.4 ratio, after stirring, water content is 20-25%, control bismuth pot temperature at 530-550 DEG C, while stirring, by the sulphur for preparing in batches, each add-on is about 12kg, adds in bismuth pot, under braking whipping appts stirs, carry out reaction copper removal;

C, wood chip all burnt to be added, sulphur all becomes coccoid, and surface adhesion is when slag, illustrate that this batch of sulphur reacts completely, pull out with strainer, in time dragging for clean, sulphur copper removal is added for the second time again by above step, when in solution, copper content is down to < 0.005%, copper removal is complete, enters next process;

D, be warming up to 600-650 DEG C, iron pipe inserted in liquation, pass into pressurized air and carry out oxidation except antimony, arsenic, tellurium, control compressed air pressure 0.2-0.25MPa, air quantity 1.5-1.8m ³/ min, when smoke which obviously reduces, point adds solid sodium hydroxide tablet four times, per hourly adds once, a 10kg, and drags for most scum silica frost, except antimony, arsenic, tellurium are complete;

E, next pot will be imported except liquid after antimony, arsenic, tellurium, control temperature 450-500 DEG C, and adopt Glass tubing to insert in liquation and carry out logical chlorine deleading, require that chlorine gas pressure controls at 0.15-0.2MPa, flow control 0.2-0.25m ³/ min, when lead content is less than 0.05%, stop logical chlorine, now, deleading is complete;

F, cool the temperature to 300 DEG C, add spelter, according to silver content in bismuth liquid, in zinc: silver=3:1 ratio adds spelter, divide and add for three times, first add 1/3rd of spelter, when temperature rises to 450 DEG C, stop heating up, when spelter fusing is complete, open braking whipping appts, stir two hours, stop stirring, decrease temperature crystalline, when temperature is down to 350 DEG C, strainer is adopted to drag for slag, wait to drag for clean slag by above step add second time spelter, third time spelter, add third time spelter and drag for slag clean after, desilver is complete;

G, adopt bismuth pump to squeeze in next pot liquid after f step, between control temperature 350-450 DEG C, pass into chlorine, require that chlorine gas pressure controls at 0.15-0.2MPa, flow control 0.2-0.25m ³/ min, after logical chlorine 2h, stop logical chlorine, control temperature 600-650 DEG C, passes into pressurized air, controls compressed air pressure 0.2-0.25MPa, air quantity 1.5-1.8m ³/ min, when bismuth liquid surface smokelessly produces, stop logical chlorine, bismuth refining completes.

The method of the efficient copper removal of a kind of thick bismuth bismuth of the present invention kettle refining, use wood chip as raising agent, and adopt water and its mixing and stirring, boiling point due to water is 100 DEG C, effectively can extend the duration of contact of sulphur and melt, control temperature 550 DEG C, adding the sulphur after puddling can effective implemention copper removal from bismuth liquation, because wood chip plays a part raising agent, stop because sulphur is formed spherical with the defect such as bismuth liquation contact area is little, and effectively improve sulphur utilization ratio, solving to add in sulphur copper removal process causes sulphur directly to burn, low and the sulphur of sulphur utilization ratio adds pot and floats on liquid level in bulk afterwards, focus under stirring and stir arbor place, form bulk, easily adhesion parcel is carried out to bismuth, cause except bi content in copper ashes is more than 20%, the copper removal cycle is long, production cost is high, the problems such as bismuth direct yield is low.

Compared with the prior art the method for the efficient copper removal of a kind of thick bismuth bismuth of the present invention kettle refining has outstanding substantive distinguishing features and marked improvement, and 1, the configuration of the method processing unit is simple, easy to operate, be convenient to control; 2, effectively improve sulphur utilization ratio, reduce sulphur usage quantity, shorten the copper removal cycle, reduce production cost; 3, reduce the amount of pulling out of slag, and in slag, bismuth-containing amount is down to less than 5%, improves bismuth direct yield; 4, overcome the low problem causing affecting the batch production of smart bismuth of copper removal efficiency, improve process stream adaptability.

Embodiment

In order to Comprehension and Implementation better, describe the present invention in detail below in conjunction with embodiment.

Case study on implementation 1: thick bismuth is for containing, for example lower element, and its constituent content is as table 1:

Table 1

Take following processing step:

1, the thick bismuth of 3.5t adds in bismuth pot through driving, ventilates, logical oil, controls Wind-oil ratio 1:0.02(volume ratio), fully emerging without opium with diesel combustion and be advisable, guarantee that temperature reaches more than 500 DEG C, when reaching after 530 DEG C of bismuths melt completely, dragging for clean scum silica frost;

2, puddle by 50kg sulphur and 20kg wood chip, and add 15L clear water hold not water outlet after stirring, control temperature is at 540 DEG C, under churned mechanically effect, divided by the sulphur prepared 7 times (each add-on is about 12kg) to add in bismuth pot, stop adding sulphur when copper is down to and is less than 0.005%;

3, be warming up to 650 DEG C, iron pipe inserted in liquation, pass into pressurized air and carry out oxidation except antimony, arsenic, tellurium (control compressed air pressure 0.2MPa, air quantity 1.5m ³/ min), when smoke which obviously reduces, point to add solid sodium hydroxide tablet (per hour add once, a 10kg) for four times, and drag for most scum silica frost, except antimony, arsenic, tellurium are complete;

4, next pot will be imported except liquid after antimony, arsenic, tellurium, control temperature 500 DEG C, and carry out logical chlorine deleading in employing Glass tubing insertion liquation and (require that chlorine gas pressure controls at 0.15MPa, flow control 0.2m ³/ min), when lead content is less than 0.05%, stop logical chlorine, now, deleading is complete;

5,300 DEG C are cooled the temperature to, add spelter, according to silver content in bismuth liquid, in zinc: silver=3:1 ratio adds spelter, i.e. spelter 470kg, divide and add for three times, first add 150kg, when temperature rises to 450 DEG C, stop heating up, when spelter fusing is complete, open braking whipping appts, stir two hours, stop stirring, decrease temperature crystalline, when temperature drops to 350 DEG C, adopt strainer to drag for slag, wait that dragging for clean slag adds second time spelter 150kg, third time spelter 170kg by above step, add third time spelter and drag for slag clean after, desilver is complete;

6, adopt bismuth pump to squeeze in next pot liquid after desilver, control temperature 450 DEG C, passes into chlorine, requires that chlorine gas pressure controls at 0.15MPa, flow control 0.2m ³/ min, after logical chlorine 2h, stops logical chlorine.Control temperature 650 DEG C, passes into pressurized air and (controls compressed air pressure 0.2MPa, air quantity 1.5m ³/ min), when bismuth liquid surface smokelessly produces, stop logical chlorine, bismuth refining completes.

Through experiment, this is except process for copper is than existing technique saving sulphur usage quantity 51%, and the copper removal cycle foreshortened to 3 days by 5-7 days, and bismuth direct yield reaches 91%.

Claims (1)

1. a method for the efficient copper removal of thick bismuth bismuth kettle refining, is characterized in that it comprises following processing step:

A, thick bismuth add in bismuth pot, be warming up to 530-550 DEG C, thick bismuth is melted completely, drag for the scum silica frost in clean bismuth pot;

B, to puddle in sulphur and the appropriate clear water of wood chip mass ratio 1:0.4 ratio, after stirring, water content is 20-25%, control bismuth pot temperature 530-550 DEG C, while stirring, the sulphur prepared is added in batches in bismuth pot, each add-on is about 12kg, under braking whipping appts stirs, carry out reaction copper removal;

C, wood chip all burnt to be added, sulphur all becomes coccoid, and surface adhesion is when slag, illustrate that this batch of sulphur reacts completely, pull out with strainer, in time dragging for clean, sulphur copper removal is added for the second time again by above step, when in solution, copper content is down to < 0.005%, copper removal is complete, enters next process;

D, be warming up to 600-650 DEG C, iron pipe inserted in liquation, pass into pressurized air and carry out oxidation except antimony, arsenic, tellurium, control compressed air pressure 0.2-0.25MPa, air quantity 1.5-1.8m ³/ min, when smoke which obviously reduces, point adds solid sodium hydroxide four times, per hourly adds once, a 10kg, and drags for most scum silica frost, except antimony, arsenic, tellurium are complete;

E, will import in next pot except liquid after antimony, arsenic, tellurium, control temperature 450-500 DEG C, and adopt Glass tubing to insert in liquation and carry out logical chlorine deleading, require that chlorine gas pressure controls at 0.15-0.2MPa, flow control 0.2-0.25m ³/ min, when lead content is less than 0.05%, stop logical chlorine, now, deleading is complete;

F, cool the temperature to 300 DEG C, add spelter, according to silver content in bismuth liquid, in zinc: silver=3:1 ratio adds spelter, divide and add for three times, first add 1/3rd of spelter, when temperature rises to 450 DEG C, stop heating up, when spelter fusing is complete, open braking whipping appts, stir two hours, stop stirring, decrease temperature crystalline, when temperature is down to 350 DEG C, strainer is adopted to drag for slag, wait to drag for clean slag by above step add second time spelter, third time spelter, add third time spelter and drag for slag clean after, desilver is complete;

G, adopt bismuth pump to squeeze in next pot liquid after f step, between control temperature 350-450 DEG C, pass into chlorine, require that chlorine gas pressure controls at 0.15-0.2MPa, flow control 0.2-0.25m ³/ min, after logical chlorine 2h, stop logical chlorine, control temperature 600-650 DEG C, passes into pressurized air, controls compressed air pressure 0.2-0.25MPa, air quantity 1.5-1.8m ³/ min, when bismuth liquid surface smokelessly produces, stop logical chlorine, bismuth refining completes.