阅读说明：本技术 一种降低碱渣品位锑精炼的方法 (Refining method for reducing grade antimony in alkaline residue ) 是由 刘进先 欧阳景权 胡忠 谢勇 曹军 刘锐 于 2020-12-07 设计创作，主要内容包括：本发明提供一种降低碱渣品位锑精炼的方法。所述降低碱渣品位锑精炼的方法,包括以下步骤：S1、首先将锑氧、10％的白煤以及1％-2％纯碱放入反射炉炉膛中,利用反射炉火膛内部的高温对锑氧进行熔炼,通过白煤将氧化锑还原成锑水。本发明提供一种降低碱渣品位锑精炼的方法,该锑精炼的方法通过在还原锑水工序上加入1％-2％纯碱,利用纯碱的除杂效果,能够在还原锑水的同时进行除杂处理,实现边还原边除渣效果,对锑水进行一次除杂操作,不仅可以缩短单炉熔炼的时间,而且在后续除杂操作时,可以大大减少纯碱及片碱的投入量,减少了重复添加纯碱及片碱的操作,在除杂时,只需要两部操作,便可以将锑水中的杂质去除至符合国标,使得锑精炼时间有效缩短。(The invention provides a refining method for reducing the grade of antimony in alkaline residue. The method for refining the antimony with reduced alkaline residue grade comprises the following steps: s1, firstly, placing antimony oxide, 10% of white coal and 1% -2% of soda ash into a hearth of a reverberatory furnace, smelting the antimony oxide by utilizing high temperature in the hearth of the reverberatory furnace, and reducing antimony oxide into antimony water by the white coal. The invention provides a method for refining antimony with reduced grade of caustic sludge, which is characterized in that 1% -2% of soda ash is added in a process of reducing antimony water, impurity removal treatment can be carried out while reducing the antimony water by utilizing the impurity removal effect of the soda ash, the effect of removing slag while reducing is realized, and one-time impurity removal operation is carried out on the antimony water, so that the time of single-furnace smelting can be shortened, the input amount of the soda ash and flake caustic soda can be greatly reduced in the subsequent impurity removal operation, the operation of repeatedly adding the soda ash and flake caustic soda is reduced, and the impurities in the antimony water can be removed to meet the national standard by only two operations during impurity removal, so that the antimony refining time is effectively shortened.)

1. The method for refining antimony with reduced alkaline residue grade is characterized by comprising the following steps:

s1, firstly, placing antimony oxide, 10% of white coal and 1% -2% of soda ash into a hearth of a reverberatory furnace, smelting the antimony oxide by utilizing high temperature in the hearth of the reverberatory furnace, and reducing antimony oxide into antimony water by the white coal;

s2, when the antimony oxide in the S1 is about to be reacted, repeatedly adding the antimony oxide, 10% of white coal and 1% -2% of soda ash until the reduced antimony water reaches the required liquid level, stopping smelting, and keeping the obtained antimony water for later use;

s3, filtering the antimony water in the S2 to remove residues generated in the antimony water;

s4, adding NaOH and Na into the antimony water in S3₂CO₃The temperature of the mixed solvent is controlled to be 1073-1123 ℃, wind pressure is introduced into the antimony water, the calcined soda and the caustic soda flakes are stirred and mixed to promote the mutual reaction of the substances, and the antimony water is filtered again to remove arsenic-alkali residue in the antimony water;

s5, adding Na into the antimony water in S4₂CO₃Introducing a solvent, introducing wind pressure into the antimony water, blowing air for oxidation, stirring the antimony liquid, removing sodium selenate slag generated in the antimony water, and cooling to obtain antimony ingots meeting the national standard;

and S6, putting the residues in the S3, the S4 and the S5 into an air blowing system, and recycling the metal in the residues by using the air blowing system.

2. The method for refining antimony with reduced alkaline residue grade as claimed in claim 1, wherein the ratio of antimony oxide, 10% white coal and 1% -2% sodium carbonate added into S1 is 1:1.5:0.6, and the melting temperature of the reverberatory furnace hearth is 1273-.

3. The method for refining antimony with reduced soda ash residue grade according to claim 1, wherein 1% -2% of soda ash is added into S1, so that antimony oxide can be removed while reduction is carried out, and the time of single-furnace smelting can be shortened.

4. The method for refining antimony of reduced soda residue grade according to claim 1, wherein the amount of antimony oxide, 10% of white coal and 1% -2% of soda ash added in each time in S2 is kept consistent for statistics and reaction stability.

5. The method for refining antimony of reduced caustic sludge grade according to claim 1, wherein NaOH and Na are contained in S4₂CO₃The ratio of the two in the mixed solvent is 1:2, NaOH and Na are added₂CO₃After the solvent is mixed, the reaction is carried out for 20-30 minutes, and the arsenic alkali residue in the antimony water can be completely produced.

6. The method for refining antimony with reduced caustic sludge grade as claimed in claim 1, wherein Na in S5 is contained in the S5₂CO₃The solvent amount is 0.12 times of the total mass of the antimony water, and the antimony water is placed in a room at the temperature of 22-25 ℃ during cooling.

7. The method for refining antimony with reduced soda residue grade according to claim 1, wherein the reverberatory furnace for reducing antimony water in S1 comprises a furnace body, wherein a supporting base is fixedly connected to each side of the bottom of the furnace body, two telescopic slots are formed in the bottom of the supporting base, and two movable slots are formed in each side of the bottom of the supporting base.

8. The method for reducing alkaline residue grade antimony refining according to claim 7, wherein an electric telescopic rod is fixedly connected to the top of the inner surface of the telescopic groove, rolling wheels are fixedly connected to the bottom end of the electric telescopic rod, a support rod is movably connected to the inside of the movable groove, a support block is fixedly connected to the bottom end of the support rod, and a support spring is sleeved on the outer surface of the support rod and located outside the support block.

9. The method for reducing alkaline residue grade antimony refining according to claim 7, characterized in that a feed hopper is fixedly connected to the top of the furnace body, the right side of the top of the furnace body is communicated with a smoke exhaust pipe, the left side of the inner wall of the furnace body is provided with a flame injection piece, and the right side and the bottom of the furnace body are respectively communicated with a residue discharge pipe and a metal liquid discharge pipe.

Technical Field

The invention relates to the field of antimony refining, in particular to a method for reducing the grade of alkaline residue for antimony refining.

Background

Antimony refining refers to a metallurgical process for removing crude antimony impurities and producing refined antimony, is an important component of an antimony metallurgy process, the content of crude antimony impurities prepared by different smelting methods is greatly different, for example, crude antimony produced by precipitation smelting of antimony sulfide concentrate is high in iron content, the crude antimony refining method comprises a fire method and an electrolysis method, the antimony fire refining is a refining method widely adopted in industry, and is mainly carried out in a reverberatory furnace and a short-drum rotary furnace, the antimony electrolysis refining comprises two methods of aqueous solution electrolysis refining and molten salt electrolysis refining, the aqueous solution electrolysis refining is commonly used for refining crude antimony containing precious metals to recover gold and silver, and the molten salt electrolysis refining is always in the semi-industrial and industrial test stages from the 20 th century and the 70 th century, and is a new method with a great development prospect.

In the antimony fire refining, antimony oxide produced by a blast furnace is used as a raw material, a certain amount of white coal (reducing agent) is added into the antimony oxide, the antimony oxide is reduced into elemental antimony, the antimony oxide is a reduction smelting process, and after reduction, a refining deslagging process is started, namely impurity elements such as arsenic, lead and the like with more than specified content in antimony water are removed to achieve the standard operation process of national standard antimony ingots.

Therefore, it is necessary to provide a method for refining antimony with reduced grade of alkaline residue to solve the above technical problems.

Disclosure of Invention

The invention provides a method for refining antimony for reducing the grade of alkaline residue, which solves the problems that the required amount of an impurity removing agent is large, the operation is complicated and the time consumption for removing the impurity is long in the conventional antimony fire refining method during impurity removal.

In order to solve the technical problem, the method for refining the antimony with reduced grade of the caustic sludge provided by the invention comprises the following steps:

s1, firstly, placing antimony oxide, 10% of white coal and 1% -2% of soda ash into a hearth of a reverberatory furnace, smelting the antimony oxide by utilizing high temperature in the hearth of the reverberatory furnace, and reducing antimony oxide into antimony water by the white coal;

s2, when the antimony oxide in the S1 is about to be reacted, repeatedly adding the antimony oxide, 10% of white coal and 1% -2% of soda ash until the reduced antimony water reaches the required liquid level, stopping smelting, and keeping the obtained antimony water for later use;

s3, filtering the antimony water in the S2 to remove residues generated in the antimony water;

s4, adding NaOH and Na into the antimony water in S3₂CO₃The temperature of the mixed solvent is controlled to be 1073-1123 ℃, wind pressure is introduced into the antimony water, the calcined soda and the caustic soda flakes are stirred and mixed to promote the mutual reaction of the substances, and the antimony water is filtered again to remove arsenic-alkali residue in the antimony water;

s5, adding Na into the antimony water in S4₂CO₃Introducing a solvent, introducing wind pressure into the antimony water, blowing air for oxidation, stirring the antimony liquid, removing sodium selenate slag generated in the antimony water, and cooling to obtain antimony ingots meeting the national standard;

and S6, putting the residues in the S3, the S4 and the S5 into an air blowing system, and recycling the metal in the residues by using the air blowing system.

Preferably, the ratio of the antimony oxide, 10% of white coal and 1% -2% of soda ash added into the S1 is 1:1.5:0.6, and the smelting temperature of the reverberatory furnace hearth is 1273-.

Preferably, 1% -2% of soda ash is added into S1, so that the antimony oxide can be subjected to deslagging during reduction, and the time of single-furnace smelting can be shortened.

Preferably, the amount of each addition of antimony oxide, 10% of white coal and 1% -2% of soda ash in S2 is kept consistent, so that statistics and reaction stability are convenient to obtain.

Preferably, NaOH and Na in S4₂CO₃The ratio of the two in the mixed solvent is 1:2, NaOH and Na are added₂CO₃After the solvent is mixed, the reaction is carried out for 20-30 minutes, and the arsenic alkali residue in the antimony water can be completely produced.

Preferably, Na in S5₂CO₃The solvent amount is 0.12 times of the total mass of the antimony water, and the antimony water is placed in a room at the temperature of 22-25 ℃ during cooling.

Preferably, it is as described.

Compared with the related technology, the method for reducing the grade antimony in the caustic sludge refining has the following beneficial effects:

the invention provides a method for refining antimony with reduced grade of caustic sludge, which is characterized in that 1% -2% of soda ash is added in a process of reducing antimony water, impurity removal treatment can be carried out while reducing the antimony water by utilizing the impurity removal effect of the soda ash, the effect of removing slag while reducing is realized, and one-time impurity removal operation is carried out on the antimony water, so that the single-furnace smelting time can be shortened, the input amount of the soda ash and flake caustic soda can be greatly reduced in the subsequent impurity removal operation, the operation of repeatedly adding the soda ash and flake caustic soda is reduced, and the impurities in the antimony water can be removed to meet the national standard only by two operations in the impurity removal process, so that the antimony refining time is effectively shortened, the production cost is reduced, the yield of the caustic sludge is reduced to a certain extent, the content of the antimony in the caustic sludge is reduced, the yield of the single-furnace antimony water can be directly increased, and the direct yield is improved.

Drawings

FIG. 1 is a schematic structural view of a reverberatory furnace according to the present invention;

fig. 2 is an enlarged schematic view of a portion a shown in fig. 1.

Reference numbers in the figures: 1. the device comprises a furnace body, 2, a supporting base, 3, a telescopic groove, 4, a movable groove, 5, an electric telescopic rod, 6, a rolling wheel, 7, a supporting rod, 8, a supporting block, 9, a supporting spring, 10, a feeding hopper, 11, a smoke exhaust pipe, 12, a flame injection piece, 13, a residue discharge pipe, 14 and a metal liquid discharge pipe.

Detailed Description

The invention is further described with reference to the following figures and embodiments.

Please refer to fig. 1 and fig. 2 in combination, wherein fig. 1 is a schematic structural diagram of a reverberatory furnace according to the present invention; fig. 2 is an enlarged schematic view of a portion a shown in fig. 1. The method for refining antimony with reduced alkaline residue grade comprises the following steps:

s1, firstly, placing antimony oxide, 10% of white coal and 1% -2% of soda ash into a hearth of a reverberatory furnace, smelting the antimony oxide by utilizing high temperature in the hearth of the reverberatory furnace, and reducing antimony oxide into antimony water by the white coal;

s2, when the antimony oxide in the S1 is about to be reacted, repeatedly adding the antimony oxide, 10% of white coal and 1% -2% of soda ash until the reduced antimony water reaches the required liquid level, stopping smelting, and keeping the obtained antimony water for later use;

s3, filtering the antimony water in the S2 to remove residues generated in the antimony water;

s4, adding NaOH and Na into the antimony water in S3₂CO₃The temperature of the mixed solvent is controlled to be 1073-1123 ℃, wind pressure is introduced into the antimony water, the calcined soda and the caustic soda flakes are stirred and mixed to promote the mutual reaction of the substances, and the antimony water is filtered again to remove arsenic-alkali residue in the antimony water;

s5, adding Na into the antimony water in S4₂CO₃Introducing a solvent, introducing wind pressure into the antimony water, blowing air for oxidation, stirring the antimony liquid, removing sodium selenate slag generated in the antimony water, and cooling to obtain antimony ingots meeting the national standard;

and S6, putting the residues in the S3, the S4 and the S5 into an air blowing system, and recycling the metal in the residues by using the air blowing system.

The proportion of antimony oxide, 10 percent of white coal and 1 to 2 percent of soda ash added into the S1 is 1:1.5:0.6, and the smelting temperature of the firebox of the reverberatory furnace is 1273-.

1% -2% of soda ash is added into S1, so that the antimony oxide can be removed while being reduced, and the time of single-furnace smelting can be shortened.

The amount of the added antimony oxide, 10% of white coal and 1% -2% of soda ash added in each time in the S2 needs to be kept consistent, so that statistics and reaction stability are convenient to calculate.

NaOH and Na in the S4₂CO₃The ratio of the two in the mixed solvent is 1:2, NaOH and Na are added₂CO₃After the solvent is mixed, the reaction is carried out for 20-30 minutes, and the arsenic alkali residue in the antimony water can be completely produced.

Na in S5₂CO₃The solvent amount is 0.12 times of the total mass of the antimony water, and the antimony water is placed in a room at the temperature of 22-25 ℃ during cooling.

The prior antimony refining method mainly comprises two working procedures, namely: a reduction smelting process, wherein a reverberatory furnace hearth adopts bituminous coal/lump coal as fuel, heat generated in the combustion process of the fuel moves a high-temperature area backwards through an exhaust fan at the rear end, high temperature is fed into a hearth by utilizing the principle of furnace top reflection, antimony oxide and white coal are added into the hearth in batches, the proportion of the white coal is generally 10%, the white coal has the main function of reducing antimony oxide into antimony, the process is a repeated process, the white coal and the antimony oxide are continuously added, and the first operation process can be stopped until reduced antimony water reaches a certain liquid level;

the second procedure: refining and deslagging, namely, after antimony oxide is reduced into antimony water, starting a deslagging process, removing arsenic and lead in the antimony water, wherein the arsenic in front of a furnace is generally 1.5 percent, the lead in front of the furnace is 0.13 percent, the arsenic removal operation is to add a certain amount of soda ash and caustic soda flakes into the antimony water to achieve the arsenic removal effect, at least three arsenic removal operations are needed to meet the national standard requirements, compressed air is introduced into the antimony water in the deslagging process to play a role in reaction and stirring, the deslagging process effect is related to three major elements, the air pressure, the reaction time and the reaction temperature are needed, deslagging operation is needed after each arsenic removal operation, the alkaline slag is mainly antimony material with higher arsenic content, namely, the arsenic in the antimony water is solidified in the alkaline slag and then manually pulled out, and the antimony slag is placed into a warehouse for stacking;

compared with the method for refining antimony provided by the invention, 1% -2% of soda ash is added in the process of reducing antimony water, the impurity removal effect of the soda ash is utilized, the impurity removal treatment can be carried out while reducing the antimony water, the slag removal effect is realized while reducing, one-time impurity removal operation is carried out on the antimony water, the time of single-furnace smelting can be shortened, the input amount of the soda ash and flake caustic soda can be greatly reduced in the subsequent impurity removal operation, the operation of repeatedly adding the soda ash and flake caustic soda is reduced, only two operations are needed during impurity removal, the impurities in the antimony water can be removed to meet the national standard, the antimony refining time is effectively shortened, the production cost is reduced, the yield of alkali slag is reduced to a certain extent, the content of the antimony in the alkali slag is reduced, the yield of the antimony water in a single furnace can be directly increased, the direct yield is improved, and the calculation is carried out according to 50 tons of refined antimony after the operation of the method of the invention is used, the arsenic content in the front of the furnace can be controlled to 0.8% by only adding 500kg of soda ash, the national standard requirements can be met by only carrying out one-to-two arsenic removal procedures, the mixed slag generated in the reduction smelting process directly enters a blast furnace system and is recycled again, the metal amount is recycled, and 169 tons of recoverable metal amount in the whole year are estimated.

The reverberatory furnace for reducing the antimony water in the S1 comprises a furnace body 1, wherein two supporting bases 2 are fixedly connected to two sides of the bottom of the furnace body 1, two telescopic grooves 3 are formed in the bottoms of the supporting bases 2, and two movable grooves 4 are formed in two sides of the bottom of the supporting bases 2.

The telescopic trough is characterized in that an electric telescopic rod 5 is fixedly connected to the top of the inner surface of the telescopic trough 3, rolling wheels 6 are fixedly connected to the bottom end of the electric telescopic rod 5, a supporting rod 7 is movably connected to the inside of the movable trough 4, a supporting block 8 is fixedly connected to the bottom end of the supporting rod 7, and a supporting spring 9 is sleeved on the outer surface of the supporting rod 7 and located outside the supporting block 8.

The top fixedly connected with feeder hopper 10 of furnace body 1, the right side at furnace body 1 top communicates with the pipe 11 of discharging fume, the left side of furnace body 1 inner wall is provided with flame injection spare 12, the right side of furnace body 1 and bottom communicate respectively with residue discharge pipe 13 and metal liquid discharge pipe 14.

The two supporting bases 2 are respectively positioned at the left side and the right side of the bottom of the furnace body 1 and provide support for the furnace body 1, the electric telescopic rod 5 is externally connected with a power supply, the operation of the electric telescopic rod is controlled by an external switch, the supporting rod 7 can move up and down in the movable groove 4, the supporting spring 9 provides elastic support for the supporting rod 7, the supporting spring 9 can be simultaneously extruded when the supporting block 8 moves up, when the reverberatory furnace needs to be moved, the electric telescopic rod 5 is controlled to extend downwards, and then the rolling wheels 6 can be driven to extend downwards, so that the rolling wheels 6 gradually lift the supporting bases 2, the bottoms of the supporting bases are separated from the ground until the electric telescopic rod 5 extends to the maximum state, at the moment, the rolling wheels 6 are contacted with the ground, the supporting bases 2 are directly contacted, the rolling mode is changed, the furnace body 1 can be easily pushed to move, compared with the traditional reverbera, become more convenient when removing, it is lighter, simultaneously when removing to suitable position, control electric telescopic handle 5 shortens, make roll wheel 6 inside to flexible groove 3, when roll wheel 6 contracts to flexible groove 3 completely inside, supporting shoe 8 receives the action of gravity this moment, at the inside rebound of activity groove 4, and extrude supporting spring 9 simultaneously, cooperation through supporting shoe 8 and supporting spring 9, in the twinkling of an eye that roll wheel 6 packed up, play the buffering guard action to the bottom that supports base 2, avoid its direct and ground contact, probably lead to supporting base 2 to receive the damage.

The working principle of the refining method for reducing the grade of the antimony in the caustic sludge provided by the invention is as follows:

s1, firstly, placing antimony oxide, 10% of white coal and 1% -2% of soda ash into a hearth of a reverberatory furnace, adding the antimony oxide, 10% of white coal and 1% -2% of soda ash in a ratio of 1:1.5:0.6, smelting the antimony oxide by utilizing the high temperature in the hearth of the reverberatory furnace, wherein the smelting temperature of the hearth of the reverberatory furnace is 1273-;

s2, when the antimony oxide in the S1 is to be reacted, repeatedly adding the antimony oxide, 10% of white coal and 1% -2% of soda ash until the reduced antimony water reaches the required liquid level, stopping smelting, and keeping the obtained antimony water for later use, wherein the amount of the added antimony oxide, 10% of white coal and 1% -2% of soda ash added each time needs to be kept consistent, so that statistics and reaction stability are facilitated;

s3, filtering the antimony water in the S2 to remove residues generated in the antimony water;

s4, adding NaOH and Na into the antimony water in S3₂CO₃The temperature of the mixed solvent is controlled to be 1073-1123 ℃, wind pressure is introduced into the antimony water, the calcined soda and the flake caustic soda are stirred and mixed to promote the mutual reaction of the substances, the antimony water is filtered again to remove arsenic caustic sludge, NaOH and Na in the antimony water₂CO₃The ratio of the two in the mixed solvent is 1:2, NaOH and Na are added₂CO₃After the solvent is mixed, the reaction is carried out for 20-30 minutes, and the arsenic alkali residue in the antimony water can be completely produced;

s5, adding Na into the antimony water in S4₂CO₃Solvent, introducing wind pressure into the antimony solution, blowing air to oxidize and stir the antimony solution, removing sodium selenate slag generated in the antimony solution, and cooling to obtain antimony ingots and Na meeting the national standard₂CO₃The dosage of the solvent is 0.12 times of the total mass of the antimony water, and the antimony water is placed indoors at the temperature of 22-25 ℃ during cooling;

and S6, putting the residues in the S3, the S4 and the S5 into an air blowing system, and recycling the metal in the residues by using the air blowing system.

Compared with the related technology, the method for reducing the grade antimony in the caustic sludge refining has the following beneficial effects:

according to the antimony refining method, 1% -2% of soda ash is added in the antimony reduction water process, the impurity removal effect of the soda ash is utilized, impurity removal treatment can be carried out while antimony reduction water is reduced, the slag removal effect is achieved while reduction is carried out, one-time impurity removal operation is carried out on the antimony water, the time of single-furnace smelting can be shortened, the input amount of the soda ash and flake caustic soda can be greatly reduced during subsequent impurity removal operation, the operation of repeatedly adding the soda ash and flake caustic soda is reduced, only two operations are needed during impurity removal, impurities in the antimony water can be removed to meet the national standard, the antimony refining time is effectively shortened, the production cost is reduced, the yield of alkali slag is reduced to a certain extent, the content of antimony in the alkali slag is reduced, the yield of the single-furnace antimony water can be directly increased, and the direct yield is improved.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.