CN201038237Y - Selective volatilization recovery system for waste zinc-manganese battery - Google Patents

Abstract

The utility model relates to a selective volatilization recovery system for waste zinc-manganese batteries, which comprises classification conveying equipment, a liquid filter, a battery shell breaker, a water washing tank, a selective volatilization roasting furnace, a condensation recovery device, Acid-dissolving tank, heating concentrator; Among them, the battery breaking machine carries out axial breaking of the waste battery; the water washing tank performs energy-enhancing rinsing; the roasting furnace conducts staged heating and fractionation to obtain flue gas at different temperature ranges; the condensation recovery device conducts condensation Ammonium chloride particles and zinc/zinc oxide powder are obtained respectively; acid dissolution and alkali precipitation are carried out in an acid-dissolving tank; liquid filter is used for filtration and purification; a heating concentrator heats and concentrates the purified acid-dissolving tank solution to obtain purified manganese sulfate particles. The recovery system of the utility model can comprehensively recover bulk content in the zinc-manganese battery, and the recovered product has high purity, and the recovery operation and related equipment are relatively simple, and basically no secondary pollution is generated.

Description

Selective Volatility Recovery System for Waste Zinc-Manganese Batteries

technical field

The utility model relates to environmental protection and resource recovery equipment, more specifically, the utility model relates to a recycling equipment system for waste chemical power sources.

Background technique

Modern society has entered the electronic age, and there are more and more types of mechanical and electrical products and electronic equipment in modern society, and the quantity is getting larger and larger. Among these products/equipment, the chemical power source-battery, which is convenient to carry and mobile use, is widely used . Among them, the commonly used batteries in people's common appliances and vehicles mainly include primary batteries represented by zinc-manganese batteries. The zinc-manganese battery includes the following coating surface material and electrochemically active content, wherein the coating surface material includes: iron casing, sealing material asphalt, plastic, paper and other materials; the electrochemically active content includes positive electrode active material, Negative active material, electrolyte, and among them, the positive active material is mainly manganese dioxide, and the rest are carbon rods, acetylene black, graphite, etc.; the negative active material is mainly zinc, and the rest is added to reduce the corrosion rate of the zinc electrode A small amount of mercury, cadmium, lead; electrolyte, for neutral zinc-manganese batteries, the electrolyte solution is ammonium chloride and zinc chloride, for alkaline zinc-manganese batteries, the electrolyte solution is potassium hydroxide.

Hundreds of thousands of tons of waste zinc-manganese batteries are discarded in my country every year. Most of the above-mentioned organic and inorganic substances containing heavy metals such as zinc, mercury, cadmium, copper, manganese and ammonium salts contained in waste zinc-manganese batteries are difficult for the natural environment. Degradation, if it is discarded at will, it is easy to cause serious damage to the environment. For example, heavy metals such as mercury remaining in it will gradually accumulate in natural water bodies and biological chains and pollute the environment. On the contrary, if all these substances can be recycled, tens of thousands to hundreds of thousands of tons of manganese, zinc, copper, etc. can be regenerated, which are considerable resources. However, recycling technology is the key issue. If the recycling technology is not good, it will not be able to eliminate pollution or economical operation, and if it is not handled properly, it may cause secondary environmental pollution and cause waste of resources.

There is a Chinese patent application document with the application number 200410026573.8 disclosing a method for extracting zinc and manganese dioxide from waste dry batteries. The method includes: (A) pretreatment of waste dry batteries, which includes the following steps: (A1 ) Waste dry batteries are subjected to anaerobic pyrolysis in a pyrolysis furnace to decompose organic matter and reduce the manganese dioxide in the battery to low-valent oxides that are easily acid-soluble and extracted. The pyrolysis temperature is 450°C to 550°C, and the pyrolysis time 1.5-3.5 hours; (A2) crushing of waste dry batteries and magnetic selection of iron; (B) acid dissolution and purification of waste dry batteries after the above-mentioned pretreatment; (C) electrolysis of the above-mentioned purified acid solution, using zinc-manganese The same tank electrolysis method, the cathode current density is 250-1200A/m ² , and the anode current density is 30-100A/m ² . The method and its equipment system have the following disadvantages: the use of electrolysis methods and electrolysis equipment to recover and extract zinc and manganese in waste alkali-manganese batteries consumes a lot of electricity, which is not suitable for the overall economic situation of domestic power shortages, and the method uses strong acid electrolysis Liquid, the preparation process is more complicated, the working conditions are worse, and it will cause secondary pollution of acid mist.

Contents of the invention

In view of the above-mentioned shortcomings of the prior art, the purpose of this utility model is to provide a selective volatilization recovery system for waste zinc-manganese batteries, which has the following advantages: it can fully recover the bulk content in the zinc-manganese batteries, and the recovery can be obtained The purity of the product is high, and the recovery operation and related equipment are relatively simple, and there is basically no secondary pollution.

For this reason, the technical solution of the utility model is a selective volatilization recovery system for waste zinc-manganese batteries, which includes classification conveying equipment and a liquid filter, and the recovery system includes a battery breaking machine installed according to the following procedure , water washing tank, selective volatilization roaster, condensation recoverer, acid soluble tank, heating concentrator; wherein, the battery breaking machine includes a battery through-hole with a wall blade and a battery pusher, which carries out the waste battery to break the shell; the washing tank is equipped with a water body energizer, which energizes and rinses the surface and contents of the battery after the shell is broken; the roasting furnace divides the washed battery surface and contents into sections Heating and fractional distillation to obtain flue gas at different temperature sections; the condensation recoverer condenses the flue gas at each temperature section to obtain ammonium chloride particles and zinc/zinc oxide powder respectively; The solid residue in the furnace is acid-dissolved and alkali-precipitated; the liquid filter is used to filter and purify the bath liquid in the washing tank and the alkali-precipitation solution in the acid-dissolving tank; the heating concentrator heats the purified acid-dissolving tank solution Concentrate to obtain purified manganese sulfate particles.

In the selective volatilization recovery system of the present utility model, firstly use a battery breaking machine with a wall blade to axially break the waste battery; then thoroughly clean the electrochemically active content in the battery with a water washing tank, so that the The alkaline electrolyte with complex components is basically left in the cleaning liquid, which greatly simplifies the components of the solid electrochemical active content into three main types: inorganic carbon and carbon-containing organic matter, zinc and zinc compounds, and manganese oxides; then the components The simplified solid electrochemical active content is placed in a selective volatilization roaster for staged temperature recovery/extraction. In a properly closed furnace at a high temperature range of 1000°C, among the three main battery components, (1) inorganic carbon and carbon-containing organic matter can be burned Release chemical energy, can produce carbon-containing reducing furnace atmosphere, and carbon-containing furnace gas reducibility can vary with temperature and air volume, correspondingly change the reducing strength of the furnace atmosphere, this adjustable The reducing atmosphere will have a positive effect on the extraction of zinc and manganese compounds in the furnace; (2) the evaporation temperature of elemental zinc is 419°C, and its boiling temperature is not very high at 910°C; the original zinc compound ZnCl2 After the water washing step, it will be hydrolyzed into attached solid Zn(OH) ₂ , Zn(OH)2 can be converted into ZnO at a relatively low temperature (100-200°C) in the furnace, and ZnO can be converted into ZnO in a reducing atmosphere. Converted to metallic zinc, ZnO or Zn can be volatilized into a gaseous state at high temperature, and can be condensed at a lower temperature of 100-300°C to obtain high-purity ZnO or Zn powder products; (3) The main 2 and 4 of manganese Under the reducing atmosphere in the selective volatilization roaster, all or most of the 4-valent oxides of manganese will be converted into 2-valent oxides of manganese, which will facilitate the subsequent acidification of them. Dissolution and recovery, the divalent manganese oxide powder is acid-dissolved and alkali-precipitated in an acid-dissolving tank, filtered and clarified by a liquid filter to obtain a purified manganese sulfate solution, and then dried to obtain a pure manganese sulfate particle product, and (4) For remaining The main substance NH ₄ Cl in the cleaning liquid, the process method of the present utility model also borrows the easy-to-obtain medium-temperature heat source in the same roasting furnace to sublimate in the range of 340-390°C to obtain pure ammonium chloride gas, and the chlorine Ammonium chloride gas is collected by cooling or liquid absorption to obtain high-purity ammonium chloride solution and even crystallization.

In addition, although the country has increasingly strict control over mercury-based hazardous substances added to batteries, considering that some small battery factories may still produce mercury-containing zinc-manganese batteries or cannot completely eliminate the application of mercury, in order to strictly protect the environment and maximize For the sake of benefit, the utility model system can also use selective volatilization roaster, condensation recoverer, etc. to carry out the following operations: firstly, the temperature in the roaster is controlled within the range of 50-600°C, and the surface layer and the contents of the obtained Medium-temperature dry distillation, the distilled medium-temperature gas is sequentially passed through the condensation recovery device, the cyclone separator, and the bag filter for gravity separation and filtration, and the mercury liquid is collected to prevent mercury pollution.

It can be seen from the above analysis that the process of the utility model adopts five main equipments such as improved battery breaking machine, water washing tank, selective volatilization roaster, condensation recovery device, acid soluble tank, liquid filter, etc. The bulk waste materials are completely extracted for recycling. Among them, the roaster is the main energy-consuming equipment. In addition to being conducive to the comprehensive and high-purity recovery of bulk waste materials and improving the efficiency of subsequent dissolution and separation, compared with electrolytic cells, roasting The furnace can adopt electric auxiliary heating and coal coke or oil gas heating in multiple ways. The energy substitution is flexible and can well adapt to the domestic energy industry policy. The unit operations of the whole process are carried out in an alkaline environment or alkaline products can be obtained quickly, and Properly closed roasters have comparative advantages for energy saving and avoiding secondary pollution, which can greatly improve the separation effect and reduce energy consumption and secondary pollution.

The specific structural improvement of the utility model also includes:.

In order to improve the washing efficiency of the water washing tank and promote the optimization of the subsequent treatment, the water washing tank includes one or more of heat exchanger coils for applying heat energy, ultrasonic vibrators, and mechanical stirrers.

In order to improve the energy efficiency, operating flexibility, degree of automation, and environmental protection of the main energy-consuming and volatile gas equipment in this system, the roaster includes a combustion chamber that generates high-temperature flue gas or is also equipped with an electric heater, which is set horizontally and sequentially A connected medium temperature chamber, a high temperature chamber, a cooling chamber and a tubular material passage running through each chamber. There are partitions between the chambers and they are properly closed to the outside of the furnace body and are not directly connected. In the material passage It contains a series of material pushing boats and their vibrating propulsion devices. In each chamber, there are high-temperature smoke inlets, air inlets, exhaust outlets, temperature detection devices and air duct systems. The air duct system includes fans. and a control valve, the cooling chamber is provided with a cooling heat exchanger, the cooling heat exchanger includes a gas pipe heat exchanger for preheating the intake air and a liquid medium heat exchanger for heating the liquid medium, at the air inlet of each chamber Gas sensors for detecting gas components are respectively arranged at the exhaust ports, and the output lines of the gas sensors are connected with secondary instruments and control circuits.

As the system’s important equipment for recovering relatively high-purity products and preventing secondary pollution, the condensate recoverer includes the gas inlet, gas outlet, and cooler coils distributed along the wall of the folded plate in a vertically folded plate type settling chamber. , the settling chamber includes a plurality of upper folded plates and lower folded plates arranged alternately, the folded plates are hollow structures, the inner wall of the folded plates is closely distributed with cooler coils, and the upper folded plate is arranged below the upper folded plate It is the collection port of the settling chamber, and the gas outlet of the condensation recovery device is connected to the bag type and/or electrostatic and/or cyclone type dust collector.

In order to improve the recovery efficiency of the system, the purity of recovered products, and prevent secondary pollution, the condensation recovery device includes an ammonium chloride condensation recovery device for condensing and separating ammonium chloride particles, residual mercury liquid, zinc/zinc oxide powder, and mercury liquid Condensation recovery device, zinc-containing powder condensation recovery device, wherein, the air inlet of the ammonium chloride condensation recovery device and mercury liquid condensation recovery device is connected to the exhaust port of the medium temperature chamber of the roaster, and the zinc-containing powder The gas inlet of the condensation recoverer is connected to the exhaust port of the high temperature chamber of the roaster.

In order to save energy for the system, reduce pollution, and increase recycling varieties, the inlet and outlet of the heat exchanger coil in the water washing tank are connected to the liquid-medium heat exchanger set in the cooling chamber of the roasting furnace.

In order to save energy for the system, reduce pollution, and increase the operating flexibility of the roaster, the gas outlets of the condensation recovery device are all connected to the air inlet of the gas pipe heat exchanger set in the cooling chamber of the roaster, and the air pipe heat exchanger The air outlet is connected to the air inlet of each chamber of the roasting furnace through the air duct system. The air duct system includes a circulation input pipeline connected to the gas outlet of the condensate recoverer and a circulation output pipeline connected to the exhaust port of the roaster, and its circulation control device includes a gas sensor, a secondary instrument, a control circuit and a control valve .

In order to save energy and reduce pollution of the system, the heating concentrator includes a heat exchanger coil for applying heat energy, and the inlet and outlet of the heat exchanger coil are connected to the liquid-medium heat exchanger provided in the cooling chamber of the roaster.

In order to improve system efficiency, the liquid filter includes an alkali filter for separating and filtering the tank liquid in the washing tank and filtering the alkali precipitation solution, and an acid filter for filtering the acid-soluble solution; between each main equipment The above-mentioned sorting conveying equipment is provided.

The utility model will be further described below in conjunction with the accompanying drawings and specific embodiments.

Description of drawings

Fig. 1 is a structural schematic diagram of an embodiment of the recovery system of the present invention.

Detailed ways

FIG. 1 is a schematic structural view of an embodiment of a selective volatilization recovery system for waste zinc-manganese batteries of the present invention. It includes the classified conveying equipment (not shown in detail) set up between the main equipment, the alkali filter for filtering the alkali precipitation solution, and the acid filter for filtering the acid solution (not shown in detail), and the The recovery system also includes a battery breaking machine 100, a water washing tank 110, a selective volatilization roaster 120, a condensation recoverer 150, an acid-dissolving tank 180, and a heating concentrator 190 installed according to the following procedures; wherein, the battery breaking The machine 100 includes a battery through hole 102 with a wall blade 101 and a battery pusher (not shown in detail), which axially cracks the waste battery Bt; the water washing tank 110 has a heat exchanger coil 113, an ultrasonic Vibrator 112, mechanical agitator 111 and other water body energizers, which energize and rinse the surface and contents of the battery Bt after the shell is broken; the roasting furnace 120 divides the washed battery surface and contents into sections Heating and fractional distillation to obtain flue gas at different temperature sections; one or more condensation recoverers 150 condense the flue gas at each temperature section to obtain ammonium chloride particles and zinc/zinc oxide powder respectively; the acid-dissolving tank 180 will undergo high temperature The solid residue left in the roaster by fractional distillation is acid-dissolved and alkali-precipitated; the liquid filter filters and purifies the bath liquid in the washing tank and the alkali-precipitated solution in the acid-dissolving tank; the heating concentrator 190 utilizes volatile roasting The waste heat from the furnace 120 heats and concentrates the solution in the acid-dissolving tank 180 after purification to obtain purified manganese sulfate particles.

The heating concentrator 190 heats and concentrates the purified acid solution to obtain purified manganese sulfate particles. The heating concentrator 190 includes a jacketed heat exchanger coil 191 for applying heat energy, and the inlet and outlet of the heat exchanger coil 191 are connected to the liquid medium heat exchanger 136 set in the cooling chamber 124 of the roasting furnace 120 .

The air duct system includes a circulation input pipeline 141 connected to the gas outlet of the condensation recoverer 150 and a circulation output pipeline 142 connected to the exhaust port 131 of the roaster, and its circulation control device includes a gas sensor 137 and a secondary instrument 138 , a control circuit and a control valve 134 .

The roasting furnace 120 puts the washed battery surface and contents in the material pushing boat 127 for staged temperature rise and fractionation to obtain flue gas at different temperature sections; the roasting furnace 120 includes a combustion chamber 121A for generating high-temperature flue gas and an attached An electric heater 121B, a medium temperature chamber 122, a high temperature chamber 123, a cooling chamber 124, and a tubular material channel 125 that are arranged horizontally and communicated in sequence, and there are partitions 126 between the chambers and are connected to the furnace. The outside of the body is properly closed and not directly connected. A series of material push boats 127 and its vibrating propulsion device 128 are accommodated in the material passage 125. High-temperature smoke inlets 129 and air inlets are provided in each chamber. 130, exhaust port 131, temperature detection device 132 and air duct system, this air duct system includes blower fan 133 and control valve 134, is provided with cooling heat exchanger in described cooling chamber 124, and cooling heat exchanger includes preheating inlet The tracheal heat exchanger 135 of gas and the liquid medium heat exchanger 136 of heating liquid medium are also respectively provided with the gas sensor 137 that detects gas composition at the air inlet of each chamber, the exhaust port place, the output line of gas sensor 137 (indicated by a dotted line, and the dotted line also indicates a control circuit) is connected to the secondary instrument and the control circuit 138 .

The condensation recovery device 150 includes an ammonium chloride condensation recovery device that condenses and separates ammonium chloride particles, a mercury liquid condensation recovery device that condenses and separates residual mercury liquid, and a zinc powder condensation recovery device that condenses and separates zinc/zinc oxide powder (only One of them is illustrated), wherein, the gas inlet of the ammonium chloride condensate recovery device and the mercury liquid condensate recovery device is connected to the exhaust gas of the medium temperature chamber 122 of the roaster 120 through a pipeline controlled by an electric valve. The air inlet of the zinc-containing powder condensation recovery device is connected to the exhaust port of the high-temperature chamber 123 of the roasting furnace 120, and the flue gas in each temperature section is condensed to obtain ammonium chloride particles, zinc/zinc oxide Powder; the gas outlet of the condensate recoverer 150 is connected to the gas inlet of the gas pipe heat exchanger 135 provided in the cooling chamber 124 of the roasting furnace 120 through gas/solid or gas/liquid separation, and the gas pipe heat exchange The air outlet of device 135 is communicated with the air inlet of each chamber of described roasting furnace 120 through air duct system. Each condensate recoverer 150 comprises a vertical folded-plate settling chamber 151, comprising a plurality of upper folded plates 153 and lower folded plates 154 arranged alternately in the settling chamber 151, the folded plates 153, 154 are hollow structures, and the folded plates Cooler coils 152 are distributed close to the inner walls of 153 and 154, and the collection port 155 of the settling chamber is located below the upper flap 153. The air outlet of the condensation recovery device 150 is connected to the cyclone type dust collector 171 and the electrostatic type dust collector. Dust collector 172.

Claims (10)

1. The utility model provides a selective volatilization recovery system of abandonment zinc-manganese dioxide battery, its characterized in that including categorised conveying equipment, liquid filter: the recovery system comprises a battery shell breaking machine, a washing tank, a selective volatilization roasting furnace, a condensation recoverer, an acid dissolving tank and a heating concentrator which are arranged according to the following procedures; the battery shell breaking machine comprises a battery through hole with a wall surface blade and a battery propeller, and is used for axially breaking the shells of the waste batteries; the washing tank is provided with a water energizer which is used for energizing and rinsing surface materials and contents after the battery is broken; the roasting furnace carries out sectional heating and fractionation on the washed battery surface layer objects and the washed battery contents to obtain flue gas with different temperature sections; the condensation recoverer condenses the flue gas of each temperature section to respectively obtain ammonium chloride particles and zinc/zinc oxide powder; the acid dissolving tank is used for carrying out acid dissolving and alkali precipitation on solid residues which are subjected to high-temperature fractionation and left in the roasting furnace; the liquid filter is used for filtering and purifying the bath solution of the rinsing bath and the alkali precipitation solution in the acid dissolving bath; and the heating concentrator heats and concentrates the purified acid solution in the dissolution tank to obtain purified manganese sulfate particles.

2. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 1, wherein: the rinsing bath comprises one or more than one of a heat exchanger coil pipe applying heat energy, an ultrasonic vibrator and a mechanical stirrer.

3. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 1, wherein: the roasting furnace comprises a combustion chamber for generating high-temperature flue gas or is additionally provided with an electric heater, a middle-temperature chamber, a high-temperature chamber, a cooling chamber and a tubular material channel communicated with the chambers in sequence, wherein the chambers are horizontally arranged, the middle-temperature chamber, the high-temperature chamber, the cooling chamber and the tubular material channel are properly sealed and not communicated with the outside of the furnace body, a series of material pushing boats and vibrating propelling devices thereof are accommodated in the material channel, a high-temperature flue gas inlet, a high-temperature flue gas outlet, a temperature detection device and an air pipe system are arranged in each chamber, the air pipe system comprises a fan and a control valve, a cooling heat exchanger is arranged in the cooling chamber, the cooling heat exchanger comprises an air pipe heat exchanger for preheating inlet air and a liquid medium heat exchanger for heating liquid medium, gas sensors for detecting gas components are respectively arranged at the air inlet and the air outlet of each chamber, and the output circuit of the gas sensors is connected with a secondary instrument and a control circuit.

4. The system for selective recovery of spent zinc manganese dioxide batteries of claim 1, further comprising: the condensation recoverer comprises a gas inlet, a gas outlet and cooler coils, wherein the cooler coils are distributed along the wall surface of a vertical folded plate type settling chamber, the settling chamber comprises a plurality of upper folded plates and lower folded plates which are arranged alternately, the folded plates are of hollow structures, the cooler coils are distributed on the inner wall surfaces of the folded plates in a clinging mode, a collecting port of the settling chamber is arranged below the upper folded plates, and the gas outlet of the condensation recoverer is communicated with a bag type and/or electrostatic and/or cyclone dust collector.

5. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 2, wherein: and the inlet and the outlet of a heat exchanger coil in the rinsing bath are connected with a liquid medium heat exchanger arranged in a cooling chamber of the roasting furnace.

6. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 3, wherein: the condensation recoverer comprises an ammonium chloride condensation recoverer, a mercury liquid condensation recoverer and a zinc-powder-containing condensation recoverer, wherein the ammonium chloride condensation recoverer and the mercury liquid condensation recoverer are respectively used for condensation separation of ammonium chloride particles, residual mercury liquid and zinc/zinc oxide powder, air inlets of the ammonium chloride condensation recoverer and the mercury liquid condensation recoverer are connected with an air outlet of a medium-temperature cavity of the roasting furnace, and an air inlet of the zinc-powder-containing condensation recoverer is connected with an air outlet of a high-temperature cavity of the roasting furnace.

7. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 3, wherein: the gas outlets of the condensation recoverers are communicated with gas inlets of gas pipe heat exchangers arranged in the cooling chambers of the roasting furnace, and the gas outlets of the gas pipe heat exchangers are communicated with gas inlets of the chambers of the roasting furnace through a gas pipe system.

8. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 3, wherein: the air pipe system comprises a circulating input pipeline communicated with the air outlet of the condensation recoverer and a circulating output pipeline communicated with the air outlet of the roasting furnace, and the circulating control device comprises a gas sensor, a secondary instrument, a control circuit and a control valve.

9. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 3, wherein: the heating concentrator comprises a heat exchanger coil for applying heat energy, and an inlet and an outlet of the heat exchanger coil are connected with a liquid medium heat exchanger arranged in a cooling chamber of the roasting furnace.

10. The system for selectively volatilizing and recovering the discarded zinc-manganese battery as recited in claim 1, wherein: the liquid filter comprises an alkali liquid filter for separating and filtering the bath solution in the rinsing bath, filtering the alkali precipitation solution and an acid liquid filter for filtering the acid dissolution solution; the sorting and conveying equipment is arranged among the main equipment.

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