CN218596477U

CN218596477U - System for utilize arsenic sulfide sediment preparation arsenic trioxide

Info

Publication number: CN218596477U
Application number: CN202222451783.8U
Authority: CN
Inventors: 秦海辰
Original assignee: Linxi Jinyilai Arsenic Industry Co ltd
Current assignee: Linxi Jinyilai Arsenic Industry Co ltd
Priority date: 2022-09-15
Filing date: 2022-09-15
Publication date: 2023-03-10
Anticipated expiration: 2032-09-15

Abstract

The utility model discloses a system for preparing arsenic trioxide by utilizing arsenic sulfide slag, which comprises leaching equipment, a first filter press, a reduction reactor, a second filter press, a washing machine, an esterification reactor, an impurity removal reactor, a third filter press, a hydrolysis reactor, a fourth filter press, a three-section counter-flow washing machine and a drying machine; the utility model provides a system for utilize arsenic sulfide sediment preparation arsenic trioxide, it is not high, the cost is lower to the equipment requirement, is fit for large-scale industrial production, can effectually obtain high-purity arsenic trioxide product with the preparation of the discarded arsenic sulfide sediment.

Description

System for preparing arsenic trioxide by utilizing arsenic sulfide slag

Technical Field

The utility model relates to a system for utilize arsenic sulfide sediment preparation arsenic trioxide.

Background

The non-ferrous metal smelting ore is mainly sulfide ore, a large amount of flue gas containing sulfur dioxide is generated in the pyrometallurgy process, and the smelting flue gas is mainly used for preparing sulfuric acid; meanwhile, smoke dust is also carried in the smoke gas, and impurities such as the smoke dust and the like must be removed from the smoke gas in order to ensure the quality of the sulfuric acid. The flue gas is treated by combining a dry method and a wet method, the wet dust collection makes the flue gas and water fully contact, and impurities such as arsenic-containing dust, sulfur trioxide, fluorine, chlorine and the like in the flue gas enter the water to generate a large amount of acidic heavy metal wastewater (waste acid wastewater). The waste acid water is strong acid, the concentration of sulfuric acid is between 4% and 11%, wherein, in the waste acid water produced by smelting copper, nickel and lead, pollutants have the highest arsenic concentration and the greatest harm, and meanwhile, the waste acid water also contains heavy metal ions such as lead, cadmium, zinc, copper and the like, and the waste acid water needs to be treated. At present, the waste acid water is mainly treated by a vulcanization method, a large amount of arsenic sulfide slag is generated in the vulcanization treatment process, the arsenic content is up to 20% -50%, and the waste acid water also contains heavy metal ions such as copper, mercury and the like, so that the waste acid water belongs to dangerous solid waste with high toxicity, and if the waste acid water is directly stacked without being treated, serious harm risk exists to the surrounding ecological environment. Therefore, the arsenic sulfide slag is converted into high-purity arsenic trioxide through resource utilization, so that the environmental risk can be eliminated, and the method is a potential way for resource utilization of arsenic.

At present, the method for preparing arsenic trioxide by using arsenic sulfide slag mainly comprises the following two methods: (I) The method has the advantages of mature technology, short flow and the like, but has the defects of serious environmental pollution, high investment cost and the like, and is basically eliminated at present (CN 201611246172.2); (II) wet treatment, wherein the wet treatment in the prior art mainly comprises a copper sulfate replacement method (CN 201811055026.0) and an oxygen pressure leaching method

(CN 201510526952.1), an alkali leaching method (CN 201710500670.3), a sulfuric acid high-iron method (CN 201910712441.7) and the like, but the methods still have a plurality of defects, such as large copper powder consumption, large copper recovery difficulty and high cost in a copper sulfate replacement method.

In view of the above, there is a need to provide a system for preparing arsenic trioxide from arsenic sulfide slag to solve the above technical problems.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide an utilize system of arsenic sulfide sediment preparation arsenic trioxide, this system require not high, the cost is lower to equipment, is fit for extensive industrial production, can obtain high-purity arsenic trioxide product with the preparation of abandonment arsenic sulfide sediment.

The utility model provides a system for preparing arsenic trioxide by utilizing arsenic sulfide slag, which comprises leaching equipment, a first filter press, a reduction reactor, a second filter press, a washing machine, an esterification reactor, an impurity removal reactor, a third filter press, a hydrolysis reactor, a fourth filter press, a three-section counter-flow washing machine and a drying machine;

the discharge port of the leaching equipment is connected with the feed port of the first filter press, the filtrate outlet of the first filter press is connected with the feed port of the reduction reactor, the discharge port of the reduction reactor is connected with the feed port of the second filter press, the discharge port of the second filter press is connected with the feed port of the washing machine, the discharge port of the washing machine is connected with the feed port of the esterification reactor, the discharge port of the liquid-phase product of the esterification reactor is connected with the feed port of the impurity removal reactor, the discharge port of the impurity removal reactor is connected with the feed port of the third filter press, the filtrate outlet of the third filter press is connected with the feed port of the hydrolysis reactor, the discharge port of the hydrolysis reactor is connected with the feed port of the fourth filter press, the discharge port of the fourth filter press is connected with the feed port of the three-section counter-flow type washing machine, and the discharge port of the three-section counter flow type washing machine is connected with the feed port of the drying machine.

Preferably, the leaching equipment is an atmospheric leaching tank.

Preferably, the first filter press, the second filter press, the third filter press and the fourth filter press are any one of a plate-and-frame filter press, a box filter press, a vertical filter press and a belt filter press.

Preferably, the reduction reactor is a sealed reaction kettle provided with a gas inlet.

Preferably, the impurity removal reactor is a reaction kettle provided with a stirring mechanism.

Preferably, the hydrolysis reactor is a reaction kettle provided with a stirring mechanism.

Preferably, the esterification reactor adopts an esterification-rectification coupled reactor or an esterification-distillation coupled reactor.

Preferably, the dryer is a forced air drying oven or a vacuum drying oven.

The utility model has the advantages of:

the utility model provides a system for preparing arsenic trioxide by using arsenic sulfide slag, to

The method has low equipment requirement and low cost, is suitable for large-scale industrial production, and can effectively prepare the waste arsenic sulfide slag into high-purity arsenic trioxide products.

Drawings

Fig. 1 is a schematic diagram of the connection of the device of the present invention.

Fig. 2 is a working principle diagram of the present invention.

Wherein: 1-leaching equipment; 2-a first filter press; 3-a reduction reactor; 4-a second filter press; 5-a washing machine; 6-esterification reactor; 7-impurity removal reactor; 8-a third filter press; 9-a hydrolysis reactor; 10-a fourth filter press; 11-three-stage countercurrent scrubber; 12-a dryer.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present invention based on the embodiments of the present invention.

The utility model provides a system for utilize arsenic sulfide sediment preparation arsenic trioxide, as shown in figure 1, including leaching equipment 1, first pressure filter 2, reduction reactor 3, second pressure filter 4, washing machine 5, esterification reactor 6, edulcoration reactor 7, third pressure filter 8, hydrolysis reactor 9, fourth pressure filter 10, three-section counter-current scrubber 11 and desiccator 12;

a discharge hole of the leaching equipment 1 is connected with a feed hole of a first filter press 2, a filtrate outlet of the first filter press 2 is connected with a feed hole of a reduction reactor 3, a discharge hole of the reduction reactor 3 is connected with a feed hole of a second filter press 4, a discharge hole of the second filter press 4 is connected with a feed hole of a washing machine 5, a discharge hole of the washing machine 5 is connected with a feed hole of an esterification reactor 6, a discharge hole of a liquid-phase product of the esterification reactor 6 is connected with a feed hole of an impurity removal reactor 7, a discharge hole of the impurity removal reactor 7 is connected with a feed hole of a third filter press 8, a filtrate outlet of the third filter press 8 is connected with a feed hole of a hydrolysis reactor 9, a discharge hole of the hydrolysis reactor 9 is connected with a feed hole of a fourth filter press 10, a discharge hole of the fourth filter press 10 is connected with a feed hole of a three-section counter-flow type washing machine 11, and a discharge hole of the three-section counter flow type washing machine 11 is connected with a feed hole of a drying machine 12;

specifically, three sections of counter-flow washers are adopted, the third washing water is pure water, the third washing wastewater enters the second washing procedure as the second washing water, the second washing wastewater enters the first washing procedure as the first washing water, the washing is continuously carried out in a reverse order, and finally the washing wastewater flows out of the lower portion of the first washing machine and enters the wastewater storage tank.

In this example, the leaching apparatus 1 is an atmospheric leaching tank.

In this embodiment, the first filter press machine 2, the second filter press machine 4, the third filter press machine 8, and the fourth filter press machine 10 are plate-and-frame filter presses, respectively.

In the present embodiment, the reduction reactor 3 is a sealed reaction vessel provided with a gas inlet.

In this embodiment, the impurity removal reactor 7 is a reaction kettle provided with a stirring mechanism.

In this embodiment, the hydrolysis reactor 9 is a reaction kettle provided with a stirring mechanism.

In this example, the esterification reactor 6 is an esterification-rectification coupled reactor.

In this embodiment, the dryer 12 is a vacuum drying oven.

As shown in fig. 2, the working process of the present invention is:

step one, adding arsenic sulfide slag into leaching equipment 1 at normal temperature and normal pressure, adding water for slurrying, adding sulfuric acid and sodium chlorate, controlling the mass concentration of the sulfuric acid to be 30%, controlling the liquid-solid mass ratio to be 5:1, controlling the addition of the sodium chlorate to be 0.1% of the mass of the arsenic sulfide slag, and performing filter pressing on the leached mixed slurry by using a first filter press 2 to obtain high-valence arsenic-rich solution and leaching slag, wherein the leaching slag is returned to a pyrometallurgical process for smelting and recovering copper and mercury;

secondly, adding the high-valence arsenic-rich solution into a reduction reactor 3, introducing sulfur dioxide for reduction, cooling and crystallizing after reduction, and treating by a second filter press 4 and a washing machine 5 in sequence to obtain a crude arsenic trioxide product;

step three, crushing the crude arsenic trioxide product, adding the crushed crude arsenic trioxide product into an esterification reactor 6, adding a n-butyl alcohol-water mixed solution, carrying out an esterification reaction in a boiling state to generate a liquid-phase product, namely alkoxy arsenic, evaporating a byproduct generated in the reaction process to enter a gas phase, and separately recovering the gas-phase product;

step four, adding the liquid-phase product obtained in the step three into an impurity removal reactor 7, then adding activated carbon to remove impurities, and performing solid-liquid separation through a third filter press 8 to obtain refined alkoxy arsenic;

adding the refined alkoxy arsenic into a hydrolysis reactor 9, performing hydrolysis reaction with water at the temperature of 60 ℃ for 8 hours to generate arsenic trioxide crystals and alcohol, and sequentially treating the arsenic trioxide crystals and the alcohol by a fourth filter press 10, a three-section counter-current washer 11 and a dryer 12;

wherein the washing treatment specifically comprises the following steps: conveying the arsenic trioxide crystals to a washer, washing for three times in a reverse washing mode, wherein the washing water for the third time is pure water, the washing wastewater for the third time enters a second washing procedure as the washing water for the second time, the washing wastewater for the second time enters a first washing procedure as the washing water for the first time, continuously washing in a reverse order in such a way, finally, the washing wastewater flows out of the lower part of the first washing machine and enters a wastewater storage tank, and after the intermediate product is washed to be qualified, carrying out filter pressing to obtain a pressed intermediate product;

the drying treatment specifically comprises the following steps: the pressed and dried intermediate product is sent into a vacuum drier for drying, the drying temperature is 120 ℃, and the drying time is 6 hours; cooling, mixing and packaging to obtain the high-purity arsenic trioxide product with the purity of more than 99.99999 percent.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A system for preparing arsenic trioxide by using arsenic sulfide slag is characterized by comprising leaching equipment (1), a first filter press (2), a reduction reactor (3), a second filter press (4), a washing machine (5), an esterification reactor (6), an impurity removal reactor (7), a third filter press (8), a hydrolysis reactor (9), a fourth filter press (10), a three-section counter-flow washing machine (11) and a drying machine (12);

the discharge hole of the leaching equipment (1) is connected with the feed hole of the first filter press (2), the filtrate outlet of the first filter press (2) is connected with the feed hole of the reduction reactor (3), the discharge hole of the reduction reactor (3) is connected with the feed hole of the second filter press (4), the discharge hole of the second filter press (4) is connected with the feed hole of the washing machine (5), the discharge hole of the washing machine (5) is connected with the feed hole of the esterification reactor (6), the discharge hole of the liquid-phase product of the esterification reactor (6) is connected with the feed hole of the impurity removal reactor (7), the discharge hole of the impurity removal reactor (7) is connected with the feed hole of the third filter press (8), the filtrate outlet of the third filter press (8) is connected with the feed hole of the hydrolysis reactor (9), the discharge hole of the hydrolysis reactor (9) is connected with the feed hole of the fourth filter press (10), the discharge hole of the fourth filter press (10) is connected with the feed hole of the three-section counter-flow type washer (11), and the discharge hole of the three-section counter-flow type washer (11) is connected with the feed hole of the dryer (12).

2. The system for preparing arsenic trioxide from arsenic sulfide slag according to claim 1, wherein the leaching device (1) is an atmospheric pressure leaching tank.

3. The system for preparing arsenic trioxide from arsenic sulfide slag according to claim 1, wherein the first filter press (2), the second filter press (4), the third filter press (8) and the fourth filter press (10) are any one of a plate-and-frame filter press, a box filter press, a vertical filter press and a belt filter press.

4. The system for preparing arsenic trioxide by using arsenic sulfide slag according to claim 1, wherein the reduction reactor (3) is a sealed reaction kettle provided with a gas inlet.

5. The system for preparing arsenic trioxide by using the arsenic sulfide slag as claimed in claim 1, wherein the impurity removing reactor (7) is a reaction kettle provided with a stirring mechanism.

6. The system for preparing arsenic trioxide by using the arsenic sulfide slag as claimed in claim 1, wherein the hydrolysis reactor (9) is a reaction kettle provided with a stirring mechanism.

7. The system for preparing arsenic trioxide by using arsenic sulfide slag as claimed in claim 1, wherein the esterification reactor (6) is an esterification-rectification coupled reactor or an esterification-distillation coupled reactor.

8. The system for preparing arsenic trioxide by using arsenic sulfide slag according to claim 1, wherein the dryer (12) is an air blast drying oven or a vacuum drying oven.