CN113131031B - A method of recycling waste batteries to prepare ultra-low mercury catalyst - Google Patents

Abstract

The invention discloses a method for preparing an ultra-low mercury catalyst by recycling waste batteries. The battery powder obtained by dismantling the used batteries is used as the raw material, and extracted with dilute hydrochloric acid under the condition of oxidation to obtain an extract; by weight, an adjusting agent is added to adjust the main elements of mercury, zinc, manganese, copper, and copper in the extract. The ratio of cadmium, nickel and cobalt is 3-5: 2-6: 2-6: 1-5: 1-5: 0.1-2: 0.1-2, to adjust the solution, add activated carbon to soak and dry to obtain vinyl chloride Ultra-low mercury catalyst for synthetic catalysis. By separating the valuable metal elements in the waste battery, the vinyl chloride synthesis catalyst is prepared, and the recycling and utilization of the waste battery is realized.

Description

A method of recycling waste batteries to prepare ultra-low mercury catalyst

technical field

The invention relates to a method for recycling waste batteries to prepare ultra-low mercury catalysts, and belongs to the technical field of waste battery recycling.

Background technique

China is the world's largest battery producer and consumer. The output of primary batteries has far surpassed that of the United States and Japan, ranking first in the world; the output of secondary batteries is also ranked third in the world after Japan and South Korea. In 2011, my country's battery output reached about 37.266 billion, including 34.16 billion primary batteries and secondary batteries (140 million lead-acid batteries and 2.966 billion lithium-ion batteries). With the wide application and technological update of secondary batteries in industries such as smart phones, digital cameras, and new energy vehicles, waste batteries will inevitably be generated. Therefore, the recycling of waste batteries is particularly important.

At present, the recycling of waste batteries is usually roasting and reducing the elemental valuable metals therein, such as the method for recovering metal elements in waste nickel-hydrogen batteries of Chinese patent CN103031441B. The method for recovering metal elements in waste nickel-hydrogen batteries includes reduction roasting, recycling Rare earth elements, recovery of manganese, recovery of nickel and cobalt, etc. Chinese patent CN101451246B discloses a method for recovering metals in waste nickel-cadmium batteries. The method comprises combining waste residues obtained by removing organic substances in waste nickel-cadmium batteries with a metal that can fully dissolve metals in waste residues into ionic states. contacting the solution so that the metal in the waste residue exists in the form of ions; then filtering to obtain a filtrate, wherein the method further comprises electrolyzing the filtrate under the condition that the current density is 80-120A/m , and the pH value is below 2, Get metal cadmium. For the recycling of used batteries, there are problems such as single recovery of valuable metals, insufficient utilization rate and high cost.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for recycling waste batteries to prepare ultra-low mercury catalysts. By separating the valuable metal elements in the waste battery, the vinyl chloride synthesis catalyst is prepared, and the recycling and utilization of the waste battery is realized.

Technical scheme of the present invention:

A method for recycling waste batteries to prepare ultra-low mercury catalysts, extracting and separating valuable elements from battery powder obtained by dismantling waste batteries, and preparing vinyl chloride synthesis ultra-low mercury catalysts, comprising the following steps:

S1, stirring and extracting the battery powder obtained from dismantling the waste battery and dilute hydrochloric acid, and taking the extract;

S2, after the extraction liquid is filtered and separated, analyze the mercury, zinc, manganese, copper, cadmium, nickel and cobalt content in the extraction liquid, add a regulator by weight, adjust the mercury, zinc, manganese, The ratio of copper, cadmium, nickel and cobalt is 3-5:2-6:2-6:1-5:1-5:0.1-2:0.1-2, and the solution must be adjusted;

S3, adding activated carbon to the adjustment solution for soaking and drying to obtain an ultra-low mercury catalyst.

The aforementioned method of recycling waste batteries to prepare ultra-low mercury catalyst, the step s1 is to add battery powder and dilute hydrochloric acid into a stirring tank, and at 40°C-70°C, dropwise add hydrogen peroxide to stir and react for 20-120 minutes, and the concentration of hydrochloric acid is 0.3- 1mol/L, until the battery powder is no longer dissolved, take the supernatant, add calcium carbonate powder to remove sulfate ions, and obtain an extract.

The aforementioned method of recycling waste batteries to prepare an ultra-low mercury catalyst, the step s1 is to add battery powder and dilute hydrochloric acid into a stirring tank, and at 50°C-60°C, dropwise add hydrogen peroxide to stir and react for 40-100 minutes, and the concentration of hydrochloric acid is 0.5-100 minutes. 0.8mol/L.

In the aforementioned method of recycling waste batteries to prepare an ultra-low mercury catalyst, the adjusting agents are mercuric chloride, zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.

Aforesaid method for preparing ultra-low mercury catalyst by recycling waste batteries, the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjustment solution is 3-4:3-5:3-5:2-4 : 2-4: 0.5-1.5: 0.5-1.5.

In the aforementioned method for preparing an ultra-low mercury catalyst by recycling waste batteries, the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjustment solution is 4:5:5:3:3:1:1.

Beneficial effects:

The current battery powder obtained by dismantling and recycling waste batteries contains: Mn 10-12%; Ni 32-35%; Co10-20%; in addition, it also contains copper, cadmium, mercury and other heavy metal elements and other impurity elements. The cost of recycling a single metal is very high and not economical. The applicant's previous research found that the metal elements in the recycled waste batteries can be used to prepare ultra-low mercury catalysts for the synthesis of vinyl chloride after chlorination and extraction.

Vinyl chloride is the monomer of polyvinyl chloride (PVC), one of the five major synthetic resins in the world, and is mainly produced by the calcium carbide acetylene method and the petroleum ethylene method. China's energy structure is "rich in coal, lean in oil, and less in gas", which determines that for a long time in the future, the calcium carbide acetylene process will continue to be the main process for the production of vinyl chloride in my country, that is, mercury chloride catalyzes the reaction of acetylene and hydrogen chloride to generate vinyl chloride . Restricted by the International Convention on the Limitation of Mercury, it is necessary to develop new and efficient ultra-low mercury catalysts to replace traditional mercury chloride catalysts.

The applicant's research found that the metal elements in the battery powder obtained by dismantling and recycling waste batteries can be used to prepare multi-metal composite ultra-low mercury catalysts for vinyl chloride catalysts. There is also a certain difference in the content of each element, so the present invention mixes battery powder and dilute hydrochloric acid, adds hydrogen peroxide, stirs, and extracts to obtain a metal ion extract containing mercury, zinc, manganese, copper, cadmium, nickel and cobalt. The content of each ion in the extract is adjusted by adding a regulator to adjust the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the extract to prepare an ultra-low mercury catalyst catalyst, which can be used for vinyl chloride synthesis.

In order to further prove the catalytic effect of the catalyst prepared by the present invention, the inventor adjusted the solution with the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt as 4:5:5:3:3:1:1, A batch of 5 tons of ultra-low mercury catalysts was prepared, which was tested on the 66# converter of Inner Mongolia Yihua Chemical Co., Ltd. (Example 2 in Table 1), and 10 tons of ultra-low mercury catalysts were prepared with other ratios of adjustment solutions, The results of tests on 56# and 68# converters of Inner Mongolia Yihua Chemical Co., Ltd. (Examples 1 and 3 in Table 1) show that: the vinyl chloride synthesis catalyst prepared by the battery powder obtained by disassembling the battery of the present invention, when synthesizing vinyl chloride, The reaction temperature is 110-150°C, the yield is 65-98%, the purity of vinyl chloride is 96.7-97.2%, and the selectivity of vinyl chloride is 96-100%; the purity of the crude vinyl chloride product after rectification reaches 99.99V/%. It can meet the production requirements of vinyl chloride.

The detection result of table 1 vinyl chloride synthesis test

Through the analysis of the results of the vinyl chloride synthesis test in Table 1, it can be seen that the ultra-low mercury catalyst prepared by recycling waste batteries in the present invention produces vinyl chloride, the reaction temperature is 110-150 ° C, the yield is 65-98%, the purity of vinyl chloride is 96.7-97.2%, the chlorine The selectivity of ethylene reaches 96-100%; the purity of the crude vinyl chloride product after rectification reaches 99.99V/%. It can meet the production requirements of vinyl chloride.

The technical scheme of the present invention proposes a process method for preparing vinyl chloride catalyst from battery powder, and a catalyst ratio with high catalytic efficiency. The comprehensive recovery and efficient utilization of metal elements in battery powder are realized.

Detailed ways

The present invention will be further described below in conjunction with the examples, but not as a basis for limiting the present invention. For structures or processes that are not specified in particular, they are all conventional prior art in the art.

Embodiment: The method for reclaiming waste battery to prepare ultra-low mercury catalyst, to extract and separate valuable elements from the battery powder obtained by dismantling the waste battery, to prepare vinyl chloride synthesis ultra-low mercury catalyst, comprising the following steps:

S1, stirring and extracting the battery powder obtained from dismantling the waste battery and dilute hydrochloric acid, and taking the extract;

S2, after the extraction liquid is filtered and separated, analyze the mercury, zinc, manganese, copper, cadmium, nickel and cobalt content in the extraction liquid, add a regulator by weight, adjust the mercury, zinc, manganese, The ratio of copper, cadmium, nickel and cobalt is 3-5:2-6:2-6:1-5:1-5:0.1-2:0.1-2, and the solution must be adjusted;

S3, adding activated carbon to the adjustment solution for soaking and drying to obtain an ultra-low mercury catalyst.

In the step s1, the battery powder and dilute hydrochloric acid are added into the stirring tank, and at 40°C-70°C, hydrogen peroxide is added dropwise for a stirring reaction for 20-120 minutes, the concentration of hydrochloric acid is 0.3-1mol/L, and calcium carbonate powder is added to remove sulfate ions. Get the extract.

The step s1 is to add battery powder and dilute hydrochloric acid into a stirring tank, and at 50°C-60°C, dropwise add hydrogen peroxide for stirring reaction for 40-100 minutes, and the concentration of hydrochloric acid is 0.5-0.8 mol/L.

The adjusting agents are mercuric chloride, zinc chloride, manganese chloride, cupric chloride, cadmium chloride, nickel chloride and cobalt chloride.

Preferably, the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjustment solution is 3-4:3-5:3-5:2-4:2-4:0.5-1.5 : 0.5-1.5. The optimum ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjustment solution is 4:5:5:3:3:1:1.

The following embodiments are provided below in conjunction with specific circumstances

Example 1.

A method for recycling waste batteries to prepare ultra-low mercury catalysts, extracting and separating valuable elements from battery powder obtained by dismantling waste batteries, and preparing vinyl chloride synthesis ultra-low mercury catalysts, comprising the following steps:

S1, stirring and extracting the battery powder obtained from dismantling the waste battery and dilute hydrochloric acid, and taking the extract;

S2, after the extraction liquid is filtered and separated, analyze the mercury, zinc, manganese, copper, cadmium, nickel and cobalt content in the extraction liquid, add a regulator by weight, adjust the mercury, zinc, manganese, The ratio of copper, cadmium, nickel and cobalt is 4:2:2:1:1:0.1:0.1, and the solution must be adjusted;

S3, adding activated carbon to the adjustment solution for soaking and drying to obtain a catalyst.

The step s1 is to add battery powder and dilute hydrochloric acid into a stirring tank, and at 50°C-60°C, dropwise add hydrogen peroxide for stirring reaction for 40-100 minutes, and the concentration of hydrochloric acid is 0.5-0.8 mol/L. Add calcium carbonate powder to remove sulfate ions to obtain an extract.

The adjusting agents are mercuric chloride, zinc chloride, manganese chloride, cupric chloride, cadmium chloride, nickel chloride and cobalt chloride.

Example 2.

A method for recycling waste batteries to prepare ultra-low mercury catalysts, extracting and separating valuable elements from battery powder obtained by dismantling waste batteries, and preparing vinyl chloride synthesis ultra-low mercury catalysts, comprising the following steps:

S1, stirring and extracting the battery powder obtained from dismantling the waste battery and dilute hydrochloric acid, and taking the extract;

S2, after the extraction liquid is filtered and separated, analyze the mercury, zinc, manganese, copper, cadmium, nickel and cobalt content in the extraction liquid, add a regulator by weight, adjust the mercury, zinc, manganese, The ratio of copper, cadmium, nickel and cobalt is 4:5:5:3:3:1:1, and the solution must be adjusted;

S3, adding activated carbon to the adjustment solution for soaking and drying to obtain a catalyst.

In the aforementioned method of recycling waste batteries to prepare ultra-low mercury catalyst, the step s1 is to add battery powder and dilute hydrochloric acid into a stirring tank, and at 60°C, dropwise add hydrogen peroxide to stir and react for 70 minutes, and the concentration of hydrochloric acid is 0.7mol/L. Add calcium carbonate powder to remove sulfate ions to obtain an extract.

The adjusting agents are mercuric chloride, zinc chloride, manganese chloride, cupric chloride, cadmium chloride, nickel chloride and cobalt chloride.

Example 3.

A method for recycling waste batteries to prepare ultra-low mercury catalysts, extracting and separating valuable elements from battery powder obtained by dismantling waste batteries, and preparing vinyl chloride synthesis ultra-low mercury catalysts, comprising the following steps:

S1, stirring and extracting the battery powder obtained from dismantling the waste battery and dilute hydrochloric acid, and taking the extract;

S2, after the extraction liquid is filtered and separated, analyze the mercury, zinc, manganese, copper, cadmium, nickel and cobalt content in the extraction liquid, add a regulator by weight, adjust the mercury, zinc, manganese, The ratio of copper, cadmium, nickel and cobalt is 3:6:6:5:5:1:1, and the solution must be adjusted;

S3, adding activated carbon to the adjustment solution for soaking and drying to obtain a catalyst.

In the step s1, the battery powder and dilute hydrochloric acid are added to the stirring tank, and at 60° C., hydrogen peroxide is added dropwise for a stirring reaction for 80 minutes, and the concentration of hydrochloric acid is 0.6 mol/L. Add calcium carbonate powder to remove sulfate ions to obtain an extract.

The adjusting agents are mercuric chloride, zinc chloride, manganese chloride, cupric chloride, cadmium chloride, nickel chloride and cobalt chloride.

Claims (6)

1. A method for preparing ultra-low mercury catalyst by recycling waste batteries is characterized by comprising the following steps: the method for preparing the chloroethylene synthesized ultra-low mercury catalyst by extracting and separating valuable elements from battery powder obtained by disassembling waste batteries comprises the following steps:

s1, stirring and extracting battery powder obtained by disassembling the waste batteries and dilute hydrochloric acid, and taking extract liquor;

s2, after the extraction liquid is filtered and separated, analyzing the content of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the extraction liquid, adding a regulator according to the weight, and regulating the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the extraction liquid to be 3-5: 2-6: 1-5: 0.1-2 to obtain a regulating solution;

and S3, adding activated carbon into the adjusting solution, soaking and drying to obtain the ultra-low mercury catalyst.

2. The method for preparing ultra-low mercury catalyst by recycling waste batteries according to claim 1, which is characterized in that: and step s1, adding the battery powder and dilute hydrochloric acid into a stirring tank, dropwise adding hydrogen peroxide at 40-70 ℃, stirring and reacting for 20-120 minutes until the battery powder is not dissolved any more, taking supernatant, and adding calcium carbonate powder to remove sulfate ions to obtain extract, wherein the concentration of the hydrochloric acid is 0.3-1 mol/L.

3. The method for preparing the ultra-low mercury catalyst by recycling the waste batteries according to claim 2, which is characterized in that: and step s1, adding the battery powder and dilute hydrochloric acid into a stirring tank, dropwise adding hydrogen peroxide at 50-60 ℃, stirring and reacting for 40-100 minutes, wherein the concentration of hydrochloric acid is 0.5-0.8 mol/L.

4. The method for preparing ultra-low mercury catalyst by recycling waste batteries according to claim 1, which is characterized in that: the regulator is mercury chloride, zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.

5. The method for preparing ultra-low mercury catalyst by recycling waste batteries according to claim 1, which is characterized in that: the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjusting solution is 3-4: 3-5: 2-4: 0.5-1.5.

6. The method for preparing ultra-low mercury catalyst by recycling waste batteries according to claim 5, which is characterized in that: the ratio of mercury, zinc, manganese, copper, cadmium, nickel and cobalt in the adjusting solution is 4: 5: 3: 1.