阅读说明：本技术 一种回收氧化铅用络合液提纯回用方法 (Method for purifying and recycling complexing liquid for recycling lead oxide ) 是由 张克军 于 2020-11-16 设计创作，主要内容包括：本发明提供一种回收氧化铅用络合液提纯回用方法,其包括沉淀反应工序、压滤工序、第一漂洗工序、第二漂洗工序、第三漂洗工序、提纯工序及回用工序,其通过利用多次压滤逐级提升滤液内络合液浓度的原理,将含低浓度络合液的滤液用于漂洗带有络合液的沉淀物,漂洗后再经过压滤,提升滤液内络合液的浓度,最后利用加热装置对沉淀物与滤液进行同步进行加热,使沉淀物分解形成氧化铅与沉淀剂,沉淀剂回收进行循环回用,滤液蒸发提纯形成高浓度的络合液进行回收循环回用,解决了含低浓度络合液溶液提纯回用的技术问题,实现了络合液的经济回用,降低了氧化铅回用的成本。(The invention provides a method for purifying and recycling complexing liquid for recovering lead oxide, which comprises a precipitation reaction process, a filter pressing process, a first rinsing process, a second rinsing process, a third rinsing process, a purification process and a recycling process, according to the principle of gradually increasing the concentration of the complexing liquid in the filtrate by utilizing multiple times of filter pressing, the filtrate containing the low-concentration complexing liquid is used for rinsing precipitates with the complexing liquid, the precipitates are rinsed and then subjected to filter pressing to increase the concentration of the complexing liquid in the filtrate, finally the precipitates and the filtrate are synchronously heated by utilizing a heating device, so that the precipitates are decomposed to form lead oxide and a precipitating agent, the precipitating agent is recovered for recycling, the filtrate is evaporated and purified to form the high-concentration complexing liquid for recycling, the technical problem of purifying and recycling the solution containing the low-concentration complexing liquid is solved, the economic recycling of the complexing liquid is realized, and the cost of the lead oxide recycling is reduced.)

1. A method for purifying and recycling complexing liquid for recovering lead oxide is characterized by comprising the following steps:

a. a precipitation reaction process, namely conveying the complex lead solution into a carbonization reaction kettle (10), introducing a precipitator, and carrying out precipitation reaction on the precipitator and the complex lead solution to obtain a precipitate;

b. a filter pressing step, wherein the precipitate is led into a first filter press (11) in the rinsing device (1) and is subjected to filter pressing by the first filter press (11) to obtain a solution a and first filter residue, the solution a is directly output for reuse, and the first filter residue falls into a filter pressing tank (12);

c. a first rinsing process, namely dropping the first filter residue in the filter-pressing tank (12), introducing a solution c into the first solution tank (13a), driving a stirring roller (122) to stir the first filter residue in the filter-pressing tank (12) by a stirring motor (121), introducing the stirred first filter residue into the first filter press (11), performing filter pressing by the first filter press (11) to obtain a solution b and a second filter residue, introducing the solution b into a purification area (21) of the purification device (2), and dropping the second filter residue into the filter-pressing tank (12);

d. a second rinsing step, in which second filter residue falling into the filter-pressing tank (12) is introduced into a solution d from a second solution tank (13b), the stirring motor (121) drives the stirring roller (122) to stir the second filter residue in the filter-pressing tank (12), the stirred second filter residue is introduced into the first filter press (11) and is subjected to filter pressing by the first filter press (11), so that a solution c and third filter residue are obtained, the solution c is introduced into the first solution tank (13a) for storage, and the third filter residue falls into the filter-pressing tank (12);

e. a third rinsing step, in which third filter residue falling into the filter-pressing tank (12) is introduced with deionized water from a third solution tank (13c), the stirring motor (121) drives the stirring roller (122) to stir the mixture in the filter-pressing tank (12), the mixture is stirred and introduced into the first filter press (11), the first filter press (11) performs filter pressing to form a solution d and fourth filter residue, the solution d is introduced into the second solution tank (13b) for storage, the fourth filter residue falls into the filter-pressing tank (12), and the third solution tank (13c) introduces deionized water again to the filter-pressing tank (12) to obtain slurry a;

f. a purification step, wherein the solution b introduced into a purification area (21) of the purification device (2) is heated and evaporated and purified by a heating area (22) on the purification device (2), so that the solution b is purified to form the solution a and water vapor;

g. and a recycling process, wherein the purified solution a is output for recycling through a material conveying pipeline (211), and the water vapor is condensed, purified and recycled to the third solution tank (13c) through a water vapor recycling device (4).

2. The method for purifying and recycling complex liquid for recycling lead oxide according to claim 1, wherein in the step a, the precipitator is CO₂。

3. The method as claimed in claim 1, wherein the complexing solution added to the complexing lead solution in step a is one or more selected from ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, aspartic acid, alanine, valine, glutamic acid, proline, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine, methionine, ornithine, acetic acid, and sodium, potassium and ammonium salts and quaternary ammonium salts thereof corresponding to the above substances, imidazole, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, and triethanolamine.

4. The method for purifying and recycling complexing liquid for recovering lead oxide according to claim 1, wherein in the step b, the obtained solution a contains complexing liquid in a percentage of 80% to 90%, in the step c, the obtained solution b contains complexing liquid in a percentage of 65% to 70%, in the step d, the obtained solution c contains complexing liquid in a percentage of 40% to 55%, and in the step e, the obtained solution d contains complexing liquid in a percentage of 15% to 30%.

5. The method for purifying and recycling complexing liquid for recovering lead oxide according to claim 1, wherein the first filter residue in the step c is rinsed from the solution c obtained in the step d.

6. The method for purifying and recycling complexing liquid for recovering lead oxide according to claim 1, wherein the second filter residue in the step d is rinsed from the solution d obtained in the step c.

7. The method for purifying and recycling complex liquid for recovering lead oxide according to claim 1, wherein the purifying device (2) in the step f comprises:

the ball milling device comprises a ball milling roller (23), wherein a ball milling drying area (24) is formed inside the ball milling roller (23), and a feeding channel (241) and a discharging channel (242) are arranged at two ends of the ball milling roller;

the jacket (25) is sleeved outside the ball milling roller (23), the purification zone (21) is arranged in the jacket (25), and a heating zone (22) is formed between the inner wall of the jacket and the outer wall of the ball milling roller (23).

8. The method for purifying and recycling complexing liquid for recycling lead oxide according to claim 7, wherein a blowing device (231) is disposed on the feeding channel (241), and the blowing device (231) is switchably connected to the feeding channel (241) through a switching guide mechanism (2315);

the discharging channel (242) is provided with a control device (232) for controlling the opening and closing of the discharging channel, the discharging channel (242) is further provided with a vacuum dehumidifying device (233), and the vacuum dehumidifying device (233) is used for carrying out vacuum dehumidifying on the ball milling drying area (24).

9. The method for purifying and recycling complexing liquid for recovering lead oxide as claimed in claim 8, wherein said vacuum dehumidifying device (233) comprises a vacuum pump (2331) and a sealing cover (2332), said vacuum pump (2331) is located above said discharging channel (242) and is in sealed communication with said control device (232), said sealing cover (2332) is detachably mounted on the end of said feeding channel (241) and is used for controlling the opening and closing of said feeding channel (241).

10. The method for purifying and recycling complexing liquid for recovering lead oxide according to claim 1, wherein a filter pressing device (3) is further arranged between the rinsing device (1) and the purifying device (2), and the filter pressing device (3) comprises:

a track (31), the track (31) being arranged in parallel between the rinsing device (1) and the purifying device (2);

second pressure filter (32), second pressure filter (32) slide set up in on track (31), its face one side of purification device (2) is provided with discharge gate (321), this discharge gate (321) with feedstock channel (241) movable switches over the connection, second pressure filter (32) are right the thick liquid a that rinsing device (1) a lot of rinsing obtained carries out the filter-pressing and obtains filter residue a to carry out heating decomposition and obtain gas product and solid product in ball-milling drying zone (24) with this filter residue a automatic input through discharge gate (321).

Technical Field

The invention relates to the technical field of lead-acid battery material recovery, in particular to a method for purifying and recycling complexing liquid for recovering lead oxide.

Background

The method for recycling lead oxide by the atomic economy method is a brand-new recycling method which is completely different from the heat treatment and the wet treatment of the waste lead-acid battery at home and abroad at present. The method converts waste lead-acid batteries into lead oxide powder which can be directly utilized by a chemical method through an atomic economic reaction, has no emission of dust, waste gas and waste water in the treatment process, has the advantages of high efficiency, high cleanness, low energy consumption, low cost and the like, and has the advantages of high recovery rate of 99 percent, and is a great revolutionary innovation for thoroughly changing dirty, messy and poor appearance of the global lead-acid battery recovery industry.

Chinese patent No. CN104789776A discloses a method for recovering lead oxide from lead oxide-containing waste, which is a method for recovering lead oxide powder by an atomic economic method, and the method comprises contacting the lead oxide-containing waste with a complexing solution, performing solid-liquid separation on the contacted mixture, performing precipitation treatment on the separated solution, and performing high-temperature ball-milling roasting to obtain PbO.

Disclosure of Invention

Aiming at the problems, the invention provides a method for purifying and recycling complexing liquid for recovering lead oxide, which uses the filtrate containing low-concentration complexing liquid to rinse precipitates with complexing liquid by utilizing the principle of gradually increasing the concentration of the complexing liquid in the filtrate by utilizing multiple times of filter pressing, then carries out filter pressing after rinsing to increase the concentration of the complexing liquid in the filtrate, and finally carries out evaporation purification and heating decomposition on the precipitates and the filtrate by utilizing a heating zone simultaneously, thereby solving the technical problem of purifying and recycling the solution containing the low-concentration complexing liquid, realizing the economic recycling of the complexing liquid and reducing the recycling cost of the lead oxide.

In order to achieve the purpose, the invention provides the following technical scheme:

a method for purifying and recycling complexing liquid for recovering lead oxide comprises the following steps:

a. a precipitation reaction step, namely conveying the complex lead solution into a carbonization reaction kettle, introducing a precipitator, and carrying out precipitation reaction on the precipitator and the complex lead solution to obtain a precipitate;

b. a filter pressing process, wherein the precipitate is led into a first filter press in a rinsing device and is subjected to filter pressing by the first filter press to obtain a solution a and first filter residue, the solution a is directly output for reuse, and the first filter residue falls into a filter pressing tank;

c. a first rinsing process, namely, dropping the first filter residue in the filter pressing tank, introducing a solution c into the first solution tank, driving a stirring roller to stir the first filter residue in the filter pressing tank by a stirring motor, introducing the stirred first filter residue into the first filter pressing machine, performing filter pressing by the first filter pressing machine to obtain a solution b and a second filter residue, introducing the solution b into a purification area of a purification device, and dropping the second filter residue into the filter pressing tank;

d. a second rinsing step, namely dropping the second filter residue in the filter pressing tank, introducing a solution d into the second filter residue by a second solution tank, driving the stirring roller to stir the second filter residue in the filter pressing tank by the stirring motor, introducing the stirred second filter residue into the first filter pressing machine, and performing filter pressing by the first filter pressing machine to obtain a solution c and a third filter residue, introducing the solution c into the first solution tank for storage, and dropping the third filter residue into the filter pressing tank;

e. a third rinsing step of dropping a third filter residue in the filter pressing tank, introducing deionized water into the third solution tank, driving the stirring roller to stir the mixture in the filter pressing tank by the stirring motor, stirring and introducing the mixture into the first filter pressing machine, performing filter pressing by the first filter pressing machine to form a solution d and a fourth filter residue, introducing the solution d into the second solution tank for storage, dropping the fourth filter residue into the filter pressing tank, and introducing deionized water into the third solution tank again to obtain slurry a;

f. a purification step, wherein the solution b introduced into the purification zone of the purification device is heated and evaporated by a heating zone on the purification device for purification, so that the solution b is purified to form the solution a and water vapor;

g. and a recycling procedure, wherein the solution a formed by purification is output and recycled through a material conveying pipeline, and the water vapor is condensed, purified and recycled to the third solution tank for recycling through a water vapor recycling device.

As an improvement, in the step a, the precipitator is CO₂。

In the step a, the complexing solution added to the complexing lead solution is one or more of ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, aspartic acid, alanine, valine, glutamic acid, proline, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine, methionine, ornithine, acetic acid, and sodium salts, potassium salts, and ammonium salts and quaternary ammonium salts corresponding to the above substances, imidazole, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, and triethanolamine.

As an improvement, in the step b, the obtained solution a contains the complexing solution by a percentage of 80% to 90%, in the step c, the obtained solution b contains the complexing solution by a percentage of 65% to 70%, in the step d, the obtained solution c contains the complexing solution by a percentage of 40% to 55%, and in the step e, the obtained solution d contains the complexing solution by a percentage of 15% to 30%.

As a modification, the first filter residue in step c is rinsed from the solution c obtained in step d.

As an improvement, the second filter residue in step d is rinsed from the solution d obtained in step c.

As a refinement, the purification apparatus in step f includes:

the ball milling device comprises a ball milling roller, a ball milling drying area, a feeding channel and a discharging channel, wherein the ball milling drying area is formed inside the ball milling roller, and the two ends of the ball milling roller are provided with the feeding channel and the discharging channel;

the jacket is sleeved outside the ball milling roller, the purification area is arranged in the jacket, and a heating area is formed between the inner wall of the jacket and the outer wall of the ball milling roller.

As an improvement, a blowing device is arranged on the feeding channel and is in switchable connection with the feeding channel through a switching guide mechanism;

the discharging channel is provided with a control device for controlling the opening and closing of the discharging channel, and the discharging channel is further provided with a vacuum dehumidifying device which is used for carrying out vacuum dehumidifying on the ball milling drying area.

As an improvement, the vacuum dehumidifying device comprises a vacuum pump and a sealing cover, the vacuum pump is located above the discharge channel and is hermetically communicated with the control device, and the sealing cover is detachably mounted at the end part of the feed channel and is used for controlling the opening and closing of the feed channel.

As an improvement, a filter pressing device is further arranged between the rinsing device and the purifying device, and comprises:

the rails are arranged between the rinsing device and the purifying device in parallel;

and the second filter press is arranged on the track in a sliding manner, a discharge hole is formed in one side of the purification device, the discharge hole is connected with the movable switching of the feeding channel, the second filter press is used for carrying out filter pressing on the slurry a obtained by rinsing the rinsing device for multiple times to obtain filter residue a, and the filter residue a is automatically input into the ball-milling drying area through the discharge hole to be heated and decomposed to obtain a gas product and a solid product.

The invention has the beneficial effects that:

(1) according to the invention, by utilizing the principle of increasing the concentration of the complexing liquid in the complexing liquid filtrate step by step through multiple filter pressing, the filtrate containing the low-concentration complexing liquid is used for rinsing precipitates with the complexing liquid, and then is subjected to filter pressing after rinsing, so that the concentration of the complexing liquid in the filtrate is increased, and finally, the filtrate is evaporated and purified by utilizing the waste heat generated during roasting and ball milling of the precipitates, so that the economic recycling of the low-concentration complexing liquid solution is realized, and the recycling cost of lead oxide is reduced;

(2) when a second rinsing device is arranged to rinse the precipitate with complexing liquid, the low-concentration complexing liquid solution generated in the last rinsing is adopted to rinse the next precipitate with complexing liquid, and the concentration of the low-concentration complexing liquid solution is gradually increased;

(3) when the low-concentration complexing solution is purified in the purification area, the steam evaporated by the low-concentration complexing solution is condensed and recovered by the condensing mechanism, the purity of the distilled water obtained after condensation is higher than that of deionized water, and the distilled water is recycled into the rinsing device, so that the residual complexing solution on the precipitate is effectively removed;

(4) when the purification zone and the ball milling zone are heated, the heating zone is arranged between the purification zone and the ball milling zone, so that heat in the heating zone can heat the pure zone and the ball milling zone simultaneously, the heat utilization rate is high, natural gas is used as an energy source in the heating zone, and carbon dioxide and water vapor generated by combustion are purified and recycled;

(5) when the waste gas product after natural gas combustion is purified, the deionized water in the third solution tank is used as a coolant to cool the water vapor in the waste gas, and meanwhile, the temperature of the deionized water in the third solution tank is increased, so that the solubility of the deionized water to the complexing liquid is improved when the complexing liquid carried on the precipitate is cleaned.

In conclusion, the method has the advantages of high-efficiency purification of the low-concentration complexing liquid, reduction of the recovery cost of the lead oxide and the like, and is particularly suitable for the technical field of purification of the complexing liquid in the recovery of the lead oxide by the atomic economy method.

Drawings

FIG. 1 is a schematic flow chart of the method of the present invention

FIG. 2 is a first perspective view of the present invention;

FIG. 3 is a schematic perspective view of the second embodiment of the present invention;

FIG. 4 is a schematic perspective cross-sectional view of a rinsing apparatus according to the present invention;

FIG. 5 is a schematic sectional view of a first embodiment of the purification apparatus of the present invention;

FIG. 6 is a schematic sectional view of a purification apparatus according to the present invention

FIG. 7 is a schematic perspective view of a purification apparatus according to the present invention;

FIG. 8 is a schematic view showing a part of the structure of a purification apparatus according to the present invention;

FIG. 9 is a schematic cross-sectional view of a filter press apparatus according to the present invention;

FIG. 10 is a schematic cross-sectional view of the water and gas recovery device of the present invention;

FIG. 11 is a schematic sectional view of the purification apparatus of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

The first embodiment is as follows:

a method for purifying and recycling complexing liquid for recovering lead oxide comprises the following steps:

a. a precipitation reaction step, namely conveying the complex lead solution into a carbonization reaction kettle 10, introducing a precipitator, and carrying out precipitation reaction on the precipitator and the complex lead solution to obtain a precipitate;

b. a filter pressing step, wherein the precipitate is led into a first filter press 11 in the rinsing device 1 and is subjected to filter pressing by the first filter press 11 to obtain a solution a and first filter residue, the solution a is directly output for reuse, and the first filter residue falls into a filter pressing tank 12;

c. a first rinsing step of introducing the first filter residue falling into the filter-press tank 12 into a solution c from a first solution tank 13a, driving a stirring roller 122 by a stirring motor 121 to stir the first filter residue in the filter-press tank 12, introducing the stirred first filter residue into the first filter press 11, and performing filter pressing by the first filter press 11 to obtain a solution b and a second filter residue, introducing the solution b into the purification zone 21 of the purification device 2, and introducing the second filter residue into the filter-press tank 12;

d. a second rinsing step of introducing a second filter residue into the pressure filtration tank 12, introducing a solution d into the second solution tank 13b, driving the stirring roller 122 by the stirring motor 121 to stir the second filter residue in the pressure filtration tank 12, introducing the stirred second filter residue into the first filter press 11, and performing filter pressing by the first filter press 11 to obtain a solution c and a third filter residue, introducing the solution c into the first solution tank 13a for storage, and introducing the third filter residue into the pressure filtration tank 12;

e. a third rinsing step of introducing deionized water into the third filter residue dropped into the filter-press tank 12 from a third solution tank 13c, driving the stirring roller 122 by the stirring motor 121 to stir the mixture in the filter-press tank 12, introducing the mixture into the first filter press 11 while stirring, and performing filter pressing by the first filter press 11 to form a solution d and a fourth filter residue, introducing the solution d into the second solution tank 13b for storage, introducing the fourth filter residue into the filter-press tank 12, and introducing deionized water into the third solution tank 13c again to obtain a slurry a;

f. a purification step of purifying the solution b introduced into the purification zone 21 of the purification apparatus 2 by heating the solution b in a heating zone 22 of the purification apparatus 2 to evaporate and purify the solution b into the solution a and water vapor;

g. and a recycling process, wherein the purified solution a is output for recycling through a material conveying pipeline 211, and the water vapor is condensed, purified and recycled to the third solution tank 13c through the water vapor recycling device 4 for recycling.

Wherein, in the step a, the precipitator is CO₂。

In the step a, the complexing solution added to the complexing lead solution is one or more of ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, aspartic acid, alanine, valine, glutamic acid, proline, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine, methionine, ornithine, acetic acid, and sodium salts, potassium salts, and ammonium salts and quaternary ammonium salts, imidazole, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, and triethanolamine corresponding to the above substances.

Furthermore, in the step b, the obtained solution a contains the complexing solution by a percentage of 80% -90%, in the step c, the obtained solution b contains the complexing solution by a percentage of 65% -70%, in the step d, the obtained solution c contains the complexing solution by a percentage of 40% -55%, and in the step e, the obtained solution d contains the complexing solution by a percentage of 15% -30%.

Furthermore, the first filter residue in step c is rinsed from the solution c obtained in step d.

And rinsing the second filter residue in the step d from the solution d obtained in the step c.

The slurry a obtained in the third rinsing step is subjected to pressure filtration to obtain PbCO-containing slurry a₃The precipitate is conveyed into a ball milling drying area 24 to be subjected to a ball milling drying process, and the ball milling drying process and the purification process are carried out synchronously.

Further illustrated is the CO-containing CO produced by the combustion of natural gas in the heating zone 22₂And after the waste gas of the water vapor is discharged, a condensation recovery procedure is carried out, which utilizes the distilled water generated in the recycling procedure to condense the waste gas and remove the water vapor, thereby removing CO₂And recycling the purified waste water for reuse.

It is worth noting that in the purification process and the ball-milling drying process, heat generated by combustion of the heating zone 22 supplies heat to the purification process balls and the ball-milling drying process, and waste gas generated by combustion of the heating zone 22 also wraps the outside of the ball-milling drying zone 24 in the ball-milling drying process, so that the effect of the ball-milling drying process is ensured.

Example two:

as shown in fig. 2, fig. 3, fig. 5 and fig. 6, the system for purifying and recycling complex liquid for recovering lead oxide by using a matched atomic economic method comprises:

a rinsing device 1, wherein the rinsing device 1 comprises a first filter press 11, a filter press tank 12 and a plurality of solution tanks 13; the pressure filtration tank 12 is positioned right below the first pressure filter 11, and the upper end thereof is provided with an opening and is communicated with the feeding end of the first pressure filter 11 through a pipeline assembly; the first filter press 11 rinses precipitates obtained by a precipitation reaction of the carbonization reaction kettle 10 for multiple times to obtain a solution a, a solution b, a solution c, a solution d and a slurry a in sequence, the solution a is output and recycled through a pipeline, the solution c and the solution d are respectively stored in the solution tank 13, filtrate obtained by rinsing precipitates to be rinsed next time is introduced into a tank body containing the solution c obtained by rinsing last time through the solution d, the solution b is obtained by rinsing the precipitates to be rinsed next time through the solution c, and the solution b is introduced into a purification device for purification; and

the purifying device 2 is arranged at the rear side of the rinsing device 1, and comprises a purifying area 21 and a heating area 22, the purifying area 21 is arranged at the outer side of the heating area 22, the heating area 22 supplies heat to purify a solution b obtained by rinsing the rinsing device 1 to obtain a solution a, the bottom of the purifying area 21 is provided with a conveying pipeline 211, the top of the purifying area is provided with a water vapor discharge pipe 212, the bottom of the heating area 22 is provided with a burner 221, and the top of the purifying area is provided with an exhaust gas pipe 222.

The solution a, the solution b, the solution c and the solution d all contain complexing liquid and deionized water, and the concentration of the complexing liquid is reduced in sequence.

It should be noted that the working principle of the atomic economic method for recovering lead oxide is as follows:

the waste lead plaster mainly comprises PbO, Pb and PbO₂、PbSO₄Mixing the prepared NaOH solution with the waste lead plaster according to the ratio of 1:2, and reacting the waste lead plaster with the NaOH solution to obtain PbO and Pb (OH)₂And NaSO₄A mixture of (a).

Then to PbO, Pb (OH)₂And NaSO₄The mixture of (A) is subjected to pressure filtration to dissolve NaSO in water₄The solution is filtered off and the NaSO filtered off₄The solution is collected and cooled to separate out NaSO₄The crystal is collected as an excellent industrial chemical, and PbO, Pb (OH)₂Filtering out solid particles, and rinsing with deionized water for 2-3 timesAdding complexing liquid with general formula of P/S to make PbO, Pb (OH)₂The complex dissolution reaction with P/S is shown as the following reaction formula:

PbO+P/S+H₂O＝Pb(P/S)²⁺+2OH^-

Pb(OH)₂+P/S＝Pb(P/S)²⁺+2OH^-

as can be seen from the above reaction principle, the PbO component in the lead oxide-containing waste can be dissolved by the complexation of the P/S complexing solution, and OH is generated at the same time^-In the reaction formulas 1 and 2, at this time, solid-liquid separation is carried out to remove insoluble filter residues to obtain an alkaline lead-containing solution, the filter residues are subjected to complexation dissolution reaction by using a complexation solution again, and the solution is input into a carbonization reaction kettle 10 and added with a precipitator to carry out precipitation reaction.

It should be noted that the complexing solution in this embodiment is one or more of ethylenediamine diacetic acid, propylenediamine tetraacetic acid, nitrilotriacetic acid, aspartic acid, alanine, valine, glutamic acid, proline, sarcosine, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine, methionine, ornithine, acetic acid, and sodium, potassium, and ammonium salts and quaternary ammonium salts corresponding to the above substances, imidazole, ethanolamine, phenylacetic acid, methylamine, ethylamine, ethylenediamine, propylenediamine, and triethanolamine.

The precipitating agent is preferably CO₂，CO₂And carrying out precipitation reaction with the solution, wherein the reaction formula is shown as follows:

CO₂+2OH^-＝CO₃ ^2-+H₂O (3)

Pb(P/S)²⁺+CO₃ ^2-＝PbCO₃+P/S (4)

as can be seen from the above reaction principles, the solution enables CO₂Conversion to CO₃ ^2-Ions. Due to PbCO₃Has a small solubility, and the Ksp constant of the complex is generally only 7.4 multiplied by 10^-14At this time, the lead complex ion is easily reacted with CO₃ ^2-Combine to form more insoluble PbCO₃The precipitate is formed by the precipitation of the mixture,releasing the complexing liquid P/S.

It should be noted that the kind of the precipitating agent in this embodiment is not particularly limited as long as it can generate at least one precipitating substance of lead carbonate, lead sulfite, lead sulfate and corresponding precipitates thereof with the soluble lead salt, and for example, the precipitating agent may be selected from carbon dioxide, sulfur dioxide, an aqueous solution of sulfur trioxide corresponding to the above substances, and an alkali metal acid salt, and one or more of ammonium sulfate, ammonium oxalate and ammonium carbonate. Wherein, specific examples of the alkali metal acid salt include, but are not limited to: one or more of sodium carbonate, potassium carbonate, sodium sulfate and potassium sulfate.

After the precipitate was stirred and cooled, the precipitate was introduced into the rinsing apparatus 1, and the complexing solution P/S in the mixture a11 was rinsed and removed several times, and the collected complexing solution P/S was returned to the concentration and subjected to classification treatment.

To complete the rinsing of PbCO₃Adding deionized water into the precipitate again, mixing to form a mixture, performing filter pressing separation, and separating out PbCO₃Roasting, decomposing and ball milling to form PbO powder.

Further, the percentage of the solution a, which is firstly press-filtered by the rinsing device 1, containing P/S reaches 80% -90%, so that the solution a can be directly recycled for participating in the complex dissolution reaction, the filter residue is rinsed for 3 times to respectively form a solution b containing 65% -70% of P/S, a solution c containing 40% -55% of P/S and a solution d containing 15% -30% of P/S, the solution d needs to be purified because the percentage of P/S is low, the solution b is conveyed into the purifying device 3 for evaporation and purification to form a solution a, which is recycled for participating in the complex dissolution reaction, and the solution c and the solution d are stored as a rinsing precipitate PbCO of the next batch₃The solution of (1).

The invention needs complexing liquid and precipitant in the reaction process, but the whole reaction process for recovering PbO can basically reach the condition of no consumption of complexing liquid and precipitant, thus meeting the requirements of atom economic reaction and saving the cost for recovering PbO.

It is to be noted that, in the present invention,the heating means 221 at the bottom of the heating zone 22 is preferably heated by open flame heating using natural gas, and the heated product CO is₂After the water vapor can be purified, CO is removed₂Used as a precipitant to be reused in the precipitation reaction.

It is further explained that the conveying pipeline 211 is used for inputting the complexing liquid into the purification area 21 and outputting the purified complexing liquid to the complexing and dissolving equipment for recycling.

As shown in fig. 4, as a preferred embodiment, a stirring motor 121 is disposed on the top of the filtration tank 12, a motor shaft of the bottom of the stirring motor 121 is coaxially connected to a stirring roller 122, and the stirring roller 122 is inserted into the filtration tank 12.

It should be noted that, after the first filter press 11 performs filter pressing on the precipitate, the formed filter residue directly falls into the filter press tank 12, and various solutions are introduced into the dropped filter residue to rinse the filter residue, and in the rinsing process, the stirring roller 122 needs to be driven by the stirring motor 121 to stir and mix the filter residue, so that the P/S contained in the filter residue is dissolved in the solution.

As shown in fig. 3, as a preferred embodiment, the number of the solution tanks 13 in this embodiment is preferably 3, and the solution tanks include a first solution tank 13a for storing a solution c, a second solution tank 13b for storing a solution d, and a third solution tank 13c for storing deionized water, discharge ends of the first solution tank 13a, the second solution tank 13b, and the third solution tank 13c are respectively disposed to communicate with the filtering press tank 12, and feed ends of the first solution tank 13a and the second solution tank 13b are disposed to communicate with a discharge end of the first filter press 11.

After the solution c stored in the first solution tank 13a is input into the filter-pressing tank 12, the solution b is formed by filter-pressing and separation by the first filter press 11, and the solution b is input into the purification area 21;

after the solution d stored in the second solution tank 13b is input to the filter-pressing tank 12, the solution d is filter-pressed and separated by the first filter press 11 to form the solution c, and the solution c is input to the first solution tank 13 a; and

after the deionized water stored in the third solution tank 13c is input to the filter-pressing tank 12, the deionized water is filter-pressed and separated by the first filter press 11 to form the solution d, and the solution d is input to the second solution tank 13 b.

It should be noted that, since the complexing solution P/S cannot be completely separated by performing one-time filter pressing on the precipitate, after the first filter pressing is completed in the filter press 11, the formed solution a is directly collected and recycled to participate in the complexing dissolution reaction, and the filter residue also contains a large amount of P/S, the filter residue is rinsed by using the solution c generated in the rinsing process of the previous batch, and is filter-pressed again after rinsing, the P/S in the solution c is lifted into the solution b, which can be transported into the purification area 21 for purification, and is upgraded into the solution a for collection and recycling, then, the filter residue is rinsed again by using the solution d with a lower P/S percentage, the formed solution c after filter pressing is stored in the first solution tank 13a for rinsing the precipitate of the next batch, and is finally rinsed by using deionized water, and the formed solution d after filter pressing is stored in the second solution tank 13b, and (4) rinsing the precipitate of the next batch, wherein after rinsing is completed, the P/S content of filter residue is less than 1%.

As shown in fig. 5, 6, 7, 8 and 9, as a preferred embodiment, the purification apparatus 2 includes:

the ball milling device comprises a ball milling roller 23, wherein a ball milling drying area 24 is formed inside the ball milling roller 23, and a feeding channel 241 and a discharging channel 242 are arranged at two ends of the ball milling drying area;

the jacket 25 is sleeved outside the ball milling roller 23, the purification zone 21 is arranged in the jacket 25, and a heating zone 22 is formed between the inner wall of the jacket 25 and the outer wall of the ball milling roller 23.

Wherein, the feeding channel 241 is provided with an air blowing device 231, and the air blowing device 231 blows air and discharges the ball milling drying area 24;

the discharging channel 242 is provided with a control device 232 for controlling the opening and closing of the discharging channel 242, the discharging channel 242 is further provided with a vacuum dehumidifying device 233, the vacuum dehumidifying device 233 comprises a vacuum pump 2331 and a sealing cover 2332, the vacuum pump 2331 is positioned above the discharging channel 242 and is hermetically communicated with the control device 232, and the sealing cover 2332 is detachably mounted at the end of the feeding channel 241 and is used for controlling the opening and closing of the feeding channel 241.

The control device 232 is in close communication with the discharge channel 242, and includes a material conveying pipe 2321 vertically communicated with the discharge channel 242 and an electric ball valve 2322 installed at the end of the material conveying pipe 2321, the electric ball valve 2322 is communicated with the powder collecting pipe 62 of the collecting tank 61, the exhaust pipe 63 of the collecting tank 61 is communicated with the blowing device 231, the discharge channel 242 is provided with an air outlet channel 2421, and the air outlet channel 2421 is communicated with the carbonization reaction kettle 10;

the blowing device 231 includes a support 2311 fixedly installed on the purification device 2, an air inlet pipe 2312 is provided at one end of the support 2311 corresponding to the feeding channel 241, the air inlet pipe 2312 is hermetically connected with an air supply pipe 2314 of an external blower 2313, and a switching guide 2315 installed on the support frame 2311 for quick docking of the air supply pipe 2314 with the feeding passage 241, the switching guide 2315 comprises a transverse guide assembly 23151 fixedly mounted on the support frame 2311 and a longitudinal guide assembly 23152 slidably arranged above the transverse guide assembly 23151, wherein a limit block a23153 and a limit block b23154 are respectively and correspondingly arranged on the outer side ends of the transverse guide assembly 23151 and the longitudinal guide assembly 23152, the lateral guide assembly 23151 comprises a second driving device 23155 fixed on the supporting frame 2311 for driving the lateral guide assembly 23151 to slide back and forth along a direction perpendicular to the axial direction of the purifying device 2; the longitudinal guide assembly 23152 comprises a third driving device 23156 which is slidably arranged on the longitudinal guide assembly 23152 and used for driving the blowing device 231 to slide in a reciprocating manner relative to the feeding channel 241, the third driving device 23156 is slidably arranged on the longitudinal guide assembly 23152 through a fixed seat 23157, and a blocking air cylinder 23158 is further arranged on one side of the fixed seat 23157, which is opposite to the limit block 23158.

It should be noted that, by arranging the vacuum pump 2331 at the upper end of the discharge channel 242, the vacuum pump 2331 pumps the water vapor in the ball milling drum, and the water vapor is discharged into the vacuum pump 2331, so that the ball milling drum is kept in a vacuum state, thereby accelerating the ball milling treatment in the ball milling drum, and in addition, because the heat in the ball milling drum is not easily dissipated in a closed state, the temperature in the ball milling drum is constant, and the drying operation can be completed when the temperature heated by the gas burner 221 reaches about 60 ℃, thereby saving energy, and improving the operability and the working efficiency of the equipment; the traditional drying and ball milling processes are finished in a ball milling roller, the whole ball milling time is controlled to be about 1 hour, and the heating temperature is controlled by using a gas burner 221; meanwhile, a sealing cover 2332 which is detachably connected is arranged at the feeding channel 211, and two working states of ball milling and air supply are achieved by manually detaching the sealing cover 2332; in addition, the three-station multidirectional cutting is performed by arranging the switching guide mechanism 2315, after the ball milling operation is finished, the electric ball valve 2322 is used for pressure relief, and air is supplied into the air supply pipe 2314 by matching with the blower 2313 so as to blow out the PbO powder after the ball milling roasting operation is finished.

Further, after the vacuum pumping is completed, the gas burner 221 is continuously heated to raise the temperature to 580-650 ℃, and the PbO powder is obtained by roasting and ball milling for 2 hours, and PbCO is added₃The conversion efficiency of the method reaches more than 99.9 percent.

It is worth noting that, when vacuum drying is carried out, since the heating temperature is only about 60 ℃, PbCO is adopted₃The thermal decomposition reaction did not start.

In the technical scheme, the feeding channel 241 is respectively matched and connected with the filter pressing device 3, the sealing cover 2332 and the blowing device 231, automatic switching can be realized according to different stages of ball-milling roasting reaction, and the automatic continuous production of PbO powder by thermal decomposition is ensured under the matching action of the vacuum pump 2331 and the electric ball valve 2322.

Further illustrated is the completion of the precipitate PbCO in the ball mill drying zone 24₃After the decomposition, PbO powder and precipitant are obtained, the electric ball valve 2322 is used for pressure relief, air is blown into the air blowing pipe 2314 by matching with the blower 2313, the PbO powder and the precipitant after the ball-milling roasting are blown out are output into the powder collection tank 61 through the powder collection pipe 62, then the powder collection tank 61 adopts the principle of cyclone dust removal to settle and collect the PbO powder, and the precipitant CO is generated in the collection process to ensure that the precipitant CO is generated₂Gas passing throughThe exhaust pipe 63 circulates and flows back to the ball milling drying area 24 again through the external blower 2313, and after the PbO powder is collected, the electric ball valve 2322 is closed, and the air outlet channel 2421 is opened to enable the precipitating agent CO to flow back to the ball milling drying area 24₂The gas is directly recycled into the carbonization reaction kettle 10 through a pipeline.

As shown in fig. 9, further, a filter pressing device 3 is further disposed between the rinsing device 1 and the purifying device 2, and the filter pressing device 3 includes:

rails 31, the rails 31 being disposed in parallel between the rinsing device 1 and the purifying device 2;

second pressure filter 32, second pressure filter 32 slide set up in on the track 31, its face purification device 2's one side is provided with discharge gate 321, this discharge gate 321 with incoming channel 241 movable switches over the connection, second pressure filter 32 is right slurry a that rinsing device 1 multiple rinsing obtained carries out the filter-pressing and obtains filter residue a to through discharge gate 321 with this filter residue a automatic input to ball-milling drying zone 24 in heat and decompose and obtain gaseous product and solid-state product.

Example three:

FIG. 10 is a schematic structural diagram of a second embodiment of the system for purifying and recycling complex liquid for recovering lead oxide by an atomic economic method according to the present invention; referring to fig. 7, wherein the same or corresponding components as those in the first embodiment are designated by the same reference numerals as those in the first embodiment, only the differences from the first embodiment will be described below for the sake of convenience, and the second embodiment is different from the first embodiment shown in fig. 1 in that:

as shown in fig. 3 and 10, the moisture discharge pipe 212 communicates with the moisture recovery device 4, and the moisture recovery device 4 includes:

the first condensation absorption tank 41, the first condensation absorption tank 41 is communicated with the moisture discharge pipe 212, deionized water is filled in the first condensation absorption tank, the moisture discharge pipe 212 is located at one end of the first condensation absorption tank 41, and is inserted into the deionized water, and the bottom of the first condensation absorption tank is communicated with the third solution tank 13c through a pipeline;

and a second condensation absorption tank 42, wherein the second condensation absorption tank 42 is communicated with the first condensation absorption tank 41 through a pipeline, and the second condensation absorption tank 42 is filled with deionized water.

It should be noted that, during the purification process of the complexing liquid, a large amount of water vapor is generated, and since the water vapor is condensed, a large amount of distilled water is formed, the purity of the distilled water is higher than that of the deionized water, and the PbCO-containing solution is subjected to the purification process of the PbCO-containing solution₃When rinsing with the mixture of complexing liquid, can effectual absorption complexing liquid, consequently through utilizing aqueous vapor recovery unit 4 to carry out the condensation absorption to it, input and store in third solution tank 13c after the absorption, and pipeline 211 can be linked together with the device that carries out the complexation reaction of dissolving, directly carries the solution a after the purification to carry out the device that carries out the complexation reaction of dissolving and participates in the reaction.

Example four:

fig. 11 is a schematic structural diagram of a third embodiment of the complex liquid purification and recycling system for recovering lead oxide by an atomic economic method according to the present invention; referring to fig. 8, wherein the same or corresponding components as those in the first embodiment are designated by the same reference numerals as those in the first embodiment, only the differences from the first embodiment will be described below for the sake of convenience, and the third embodiment is different from the first embodiment shown in fig. 1 in that:

as shown in fig. 3 and 11, the exhaust pipe 222 communicates with the purification apparatus 5, and the purification apparatus 5 includes:

a condensation pipe 51, wherein the condensation pipe 51 is communicated with the waste gas pipe 222, and the other end of the condensation pipe passes through the third solution tank 13 c;

the purification tank 52 is communicated with the condensation pipe 51, deionized water is contained in the purification tank 52, and the condensation pipe 51 is inserted into the deionized water;

and the gas storage tank 53 is communicated with the purification tank 52, and is used for storing the gas purified by the purification tank 52.

It is noted that heating zone 22, when heating zone 21 by burning natural gas, produces a product containing primarily CO₂The exhaust gas is discharged from the exhaust gas outlet 222 together with the water vapor, the discharged exhaust gas is condensed by the deionized water in the third solution tank 13c through the condenser pipe 51, the condensed exhaust gas is condensed into liquid water, the liquid water is introduced into the purification tank 52, and the CO is discharged from the purification tank 52₂The CO is purified by the purification tank 52 and then is conveyed to the gas storage tank 53 to be stored as a spare precipitator, and when the precipitator needs to be supplemented in the precipitation reaction, the CO in the gas storage tank 53₂Can be supplemented at any time.

It is further stated that no additional CO is required in the precipitation reaction₂When the exhaust gas is replenished, the exhaust gas outlet 222 is opened at the top by rotating the rotary closing plate 223, so that the exhaust gas is discharged to the air.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.