The current situation of batteries used in China The most commonly used
industrial battery in China is lead-acid battery. Lead accounts for more than
50% of the total battery cost. It mainly uses fire method, hydrometallurgical
process and solid-phase electrolytic reduction technology. The shell is made of
plastic and can be recycled, basically achieving no secondary pollution.
Currently, the most commonly used small secondary batteries are nickel-cadmium,
nickel-hydrogen and lithium-ion batteries. The cadmium in nickel-cadmium
batteries is one of the heavy metal elements strictly controlled by
environmental protection. The organic electrolyte in lithium-ion batteries,
nickel-cadmium and nickel-hydrogen batteries The alkali in the battery and heavy
metals such as copper, an auxiliary material for making batteries, all
constitute environmental pollution. The total number of small secondary
batteries currently used in China is only a few hundred million, and most of
them are small in size. The utilization value of waste batteries is low, and
their use is scattered. Most of them are treated as domestic waste. There are
costs and management aspects to their recycling. There are also certain
technical problems in recycling. Civilian dry batteries are currently the most
widely used and most dispersed battery product, with an annual domestic
consumption of 8 billion units. There are mainly two series: zinc-manganese and
alkaline zinc-manganese, as well as a small amount of zinc-silver, lithium
battery and other varieties. Zinc-manganese batteries, alkaline zinc-manganese
batteries, and zinc-silver batteries generally use mercury or mercury compounds
as corrosion inhibitors. Mercury and mercury compounds are highly toxic
substances. When waste batteries are incinerated as domestic waste, some of the
heavy metals such as Hg, Cd, PB, and Zn in the waste batteries are discharged
into the atmosphere at high temperatures, and some become ash, causing secondary
pollution. There are generally three internationally accepted methods of
disposal of used batteries: solidification and deep burial, storage in waste
mines, and recycling.
1. Solidify, bury deeply, and store in abandoned mines. For example, a
factory in France extracts nickel and cadmium from it, then uses the nickel for
steelmaking, and the cadmium is reused for the production of batteries. The
remaining types of waste batteries are generally transported to special toxic
and hazardous landfills. However, this approach is not only too expensive but
also causes waste, because there are still many useful substances that can be
used as raw materials.
2. Recycling
(1) Heat treatment There are two factories in Switzerland that specialize
in processing and utilizing old batteries. The method adopted by Butterek
Company is to grind the old batteries and send them to the furnace for heating.
At this time, the volatilized mercury can be extracted. At higher temperatures,
zinc Also evaporates, it is also a precious metal. Iron and manganese fuse to
form the ferromanganese alloy required for steelmaking. The factory can process
2,000 tons of waste batteries a year, and can obtain 780 tons of manganese
ferroalloy, 400 tons of zinc alloy and 3 tons of mercury. Another factory
extracts iron directly from batteries and sells metal mixtures such as manganese
oxide, zinc oxide, copper oxide and nickel oxide directly as metal scrap.
However, the heat treatment method is more expensive, and Switzerland also
stipulates that each battery buyer charges a small fee for the processing of
waste batteries.
(2) "Wet treatment" A "wet treatment" device is being built in the suburbs
of Magdeburg. Here, except for lead-acid batteries, all types of batteries are
dissolved in sulfuric acid, and then various metals are extracted from the
solution with the help of ionic resins. The raw materials obtained in this way
are purer than heat treatment methods, so they sell for higher prices on the
market, and 95% of the various substances contained in the battery can be
extracted. Wet processing can eliminate the sorting process (because sorting is
a manual operation, which will increase costs). The Magdeburg unit has an annual
processing capacity of 7,500 tons. Although its cost is slightly higher than the
landfill method, precious raw materials will not be discarded and the
environment will not be polluted.
(3) Vacuum heat treatment method The vacuum heat treatment method developed
by the German Alt company is even cheaper, but it first needs to sort out the
nickel-cadmium batteries from the waste batteries. The waste batteries are
heated in a vacuum, and the mercury evaporates quickly, and they can be After
recycling, the remaining raw materials are then ground, a magnet is used to
extract the metallic iron, and nickel and manganese are extracted from the
remaining powder. The cost of processing one ton of waste batteries is less than
1,500 marks! View the article Waste Battery Recycling Methods of Waste Batteries
2007-01-2616:002.1 Current Situation of Waste Battery Recycling The most
commonly used industrial battery in China is lead-acid battery, and lead
accounts for the total number of batteries The cost is more than 50%, mainly
using fire method, hydrometallurgical process and solid-phase electrolytic
reduction technology. The shell is made of plastic and can be recycled,
basically achieving no secondary pollution. Currently, the most commonly used
small secondary batteries are nickel-cadmium, nickel-hydrogen and lithium-ion
batteries. The cadmium in nickel-cadmium batteries is one of the heavy metal
elements strictly controlled by environmental protection. The organic
electrolyte in lithium-ion batteries, nickel-cadmium and nickel-hydrogen
batteries The alkali in the battery and heavy metals such as copper, an
auxiliary material for making batteries, all constitute environmental pollution.
The total number of small secondary batteries currently used in China is only a
few hundred million, and most of them are small in size. The utilization value
of waste batteries is low, and their use is scattered. Most of them are treated
as domestic waste. There are costs and management aspects to their recycling.
There are also certain technical problems in recycling. Civilian dry batteries
are currently the most widely used and most dispersed battery product, with an
annual domestic consumption of 8 billion units. There are mainly two series:
zinc-manganese and alkaline zinc-manganese, as well as a small amount of
zinc-silver, lithium battery and other varieties. Zinc-manganese batteries,
alkaline zinc-manganese batteries, and zinc-silver batteries generally use
mercury or mercury compounds as corrosion inhibitors. Mercury and mercury
compounds are highly toxic substances. When waste batteries are incinerated as
domestic waste, some of the heavy metals such as Hg, Cd, PB, and Zn in the waste
batteries are discharged into the atmosphere at high temperatures, and some
become ash, causing secondary pollution. 2.2 Recycling Technology of Wasted Dry
Batteries a. Manual sorting and recycling technology generally involves
classifying dry batteries and then performing simple mechanical cuts to manually
separate zinc sheets, plastic covers, carbon rods, etc., and residual Mn02,
manganite and other mixtures Send it back to the brick kiln for calcination to
make dehydrated Mn02. This method is simple and easy to implement, but it takes
up a lot of labor and has little economic benefit. b. Fire recycling technology
generally classifies and crushes dry batteries and then sends them to a rotary
kiln. At a high temperature of 1100 to 1300 degrees Celsius, zinc and zinc
chloride are oxidized into zinc oxide and discharged with the flue gas, using a
cyclone dust collector. To recover zinc oxide, the remaining manganese dioxide
and manganite enter the residue, and then further recover manganese and other
substances. This method is simple and easy to implement. Generally, smelters can
recover zinc without adding additional equipment. c. Wet recycling technology is
based on the principle that zinc and manganese dioxide are soluble in acid.
After classifying and crushing used dry batteries, they are placed in a leaching
tank, and dilute sulfuric acid (100~120g/L) is added for leaching to obtain zinc
sulfate. Solution, metallic zinc can be obtained by electrolysis. After the
filter residue is washed and separated to separate the copper cap and carbon
rod, the remaining Mn02 and manganite are calcined to obtain Mn02. The methods
used include roasting-leaching method and direct leaching method. Compared with
the fire method, the wet method has the advantages of less investment, low cost,
fast factory construction, high profit, and flexible process, but it cannot
guarantee the complete recovery of harmful ingredients.
3. Prevention and control of secondary pollution during the recycling
process of waste batteries. The above three recycling methods are all simple and
easy to implement, but each has its own shortcomings, and there is the problem
of secondary pollution. Through a large number of experimental measurements, we
have obtained feasible methods for preventing and controlling secondary
pollution. method. First, the used dry batteries are classified, and after being
cut open mechanically, the copper caps and zinc sheets are separated, which can
be recycled separately. After magnetic separation to remove iron from the
remaining carbon bag material, it is soaked in water at a solid-liquid ratio of
1:4 for 1 hour. The supernatant liquid is taken for evaporation and
crystallization. The main components of the precipitate are Mn02, MnO(OH), and
acetylene black. , carbon rods and other substances are added to the rotary kiln
and refined to 600 degrees Celsius. The generated flue gas can be condensed to
obtain a condensate, which can be cleaned regularly to obtain pure mercury. It
also prevents mercury vapor from polluting the environment. During the
calcination process, a large amount of acetylene black and carbon in the mixture
reduce MnO2 to MnO. The reaction process is as follows: 2Mn02+C--->2MnO+C02.
Add this calcined product into a sulfuric acid solution with a concentration of
less than 2 mol/L at a solid-liquid ratio of 1:4, and soak it at a temperature
of 80°C for 1 hour. The following reaction occurs: MnO+H2S04--->MnS04+H20
obtains manganese sulfate salt solution. At the same time, other soluble heavy
metal sulfates will also be introduced. The obtained zinc skin, copper and other
metals can be directly remelted and utilized. Ammonium chloride can be made into
fertilizers or purified as chemical reagents. Manganese sulfate is a hormone
component for animal and plant growth and can be used as a drying agent for
paints and inks and in some organic synthesis reactions. As a catalyst, it is
also used as a reagent for the production of paper, ceramics, printing and
dyeing, and electrolytic manganese. Table 1 shows the composition of recyclable
materials from zinc-manganese dry batteries. This recycling method requires less
investment, uses simple equipment, and is easy to implement in small and
medium-sized cities, thus eliminating the problem of transporting used
batteries. The solution after recycling the used batteries is concentrated and
reacts with EDTA to form a metal complex, which can completely eliminate
secondary pollution. It has been determined that the amount of heavy metals
contained in the solution after recycling waste batteries complies with national
environmental protection standards. To separate these metals, they can be
classified based on their different stabilities. Table 2 shows the complexation
stability constants of metal ions and EDTA.
4. Problems and suggestions in the recycling process of used batteries
① Batteries cannot be disposed of after recycling and are generally piled.
Batteries may leak or toxic substances may spread during stacking.
② Due to the wide variety of batteries and many counterfeit products, it
also brings difficulties to battery recycling. Some batteries are
mercury-containing batteries, some are cadmium-containing batteries, some use
ammonium chloride as the electrolyte, and some use chloride. Zinc is an
electrolyte, so it is recommended that manufacturers use unified standards to
identify the type of battery and its main ingredients for recycling.
③ Strengthen the development of high-performance, environmentally friendly
batteries and achieve mercury-free batteries for ordinary civilian use.
④The state should provide policy support for the recycling and disposal of
waste batteries.
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