Hazardous Wastewater

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With the development of industrialization, hazardous wastes are generated in large quantities. According to the definition of the "Hazardous Waste Identification Standards," Hazardous waste refers to corrosive, toxic, flammable, reactive, infectious, etc., listed in the national list of hazardous wastes or identified according to the national dangerous waste identification standards and identification methods. One or more dangerous characteristics and solid waste with the above hazardous characteristics are not excluded. Hazardous waste mainly comes from the mining industry, mechanical processing, petrochemical industry, automobile manufacturing industry, pharmaceutical industry, electronics industry, and scientific research experiments.

Different industries have different types and properties of hazardous waste, so the disposal methods are also different. Integrated dangerous waste disposal plants usually receive dozens of harmful wastes. Therefore, comprehensive hazardous waste disposal plants will set up different disposal lines to dispose of hazardous wastes of various properties and types. A large amount of production wastewater will be generated during the hazardous waste disposal process. The water quality of hazardous waste production wastewater is complex, and it is difficult to choose a disposal method.

Table of contents（Click to go to where you want to see）

3.1 Hazardous waste pretreatment technology

3.1.1 Curing and stabilization treatment

3.2 Chemical technology

3.3 Biotechnology

4. What are the sources of wastewater from hazardous waste treatment plants ?

4.1 Laboratory drainage、Car wash drainage、Wash bucket drainage、Initial rain etc.

4.2 Emulsion wastewater

4.3 Acid and alkali wastewater

5. How to treat wastewater from hazardous waste treatment plants?

5.1 The role of air flotation in hazardous wastewater treatment ( Our company’s main products and cases)

5.2 Emulsion wastewater treatment technology

5.3 Acid-base wastewater treatment technology

5.4 Flue gas scrubbing wastewater treatment technology

5.5 Fly ash washing wastewater treatment technology

5.6 Disposal of other wastewater

What are the sources of hazardous wastewater ?

Hazardous waste includes industrial, medical, and other dangerous waste, mainly from printing and dyeing, medicine, chemical industry, metallurgy, electroplating industry, food, mining, mechanical processing, daily chemical, and other industries.

According to different production sources, hazardous wastes can be divided into industrial and social sources. Hazardous waste can be divided into inorganic, petroleum, organic, and other dangerous solid waste according to its components. There are many types of hazardous wastes; their compositions are complex, and their treatment and disposal methods vary greatly. The final products and by-products are also different. If they are not appropriately handled, secondary pollution problems can quickly occur.

To centrally treat hazardous wastewater, the wastewater generated by dangerous comprehensive waste treatment plants is also the primary source of hazardous wastewater.

What does hazardous waste include?

1. Corrosive solid waste and hazardous materials with one or more hazards such as flammability and reactivity.
Solids with hazardous characteristics or liquid waste in containers;

2. Solids and waste liquids in containers that have dangerous characteristics on the environment or human body and may cause harmful effects.
Hazardous waste treatment and disposal usually uses incineration, stable solidification, and physicochemical treatment methods. A certain amount of wastewater will be produced during the treatment and disposal. If this part of wastewater is not treated correctly, it will easily cause secondary environmental pollution.

What are the methods for municipal sewage treatment?

Hazardous waste pretreatment technology

Curing and stabilization treatment

Solidification and stabilization to fix or wrap the harmful substances in hazardous wastes in an inert solid matrix, which chemically inerts or encapsulates the polluting components of dangerous wastes, reduces the toxicity and migration of solid wastes, improves the objects' engineering properties and facilitates transportation and disposal.

The solidification process is mainly used to treat hazardous waste and solid waste residues that are unsuitable for incineration. Such as containing asbestos, acid-base sludge, incineration residue, etc. Commonly used methods: plasticity, cement, polymer, lime, melt solidification, etc. Other physical techniques for solidification and stabilization include filtration, dialysis, centrifugal flocculation, sedimentation, etc.

Chemical technology

Chemical methods are mainly used for the disposal of inorganic solid waste. Commonly used technologies primarily include redox, acid-base neutralization, and coagulation precipitation. The valence state of some pollutants in wastewater is converted through oxidation-reduction reactions, turning them into easily handled forms.

A comprehensive acid-base reaction is the most economical and effective way to deal with waste acid and alkali. However, due to the industrial characteristics of various regions, waste acid and alkali often cannot be balanced. Chemical raw materials such as sulfuric acid and caustic soda must be introduced to achieve relevant treatment.

The sedimentation method is a conventional physical and chemical treatment process. By adding flocculants and coagulants to the wastewater, the suspended solids and colloids collide and aggregate under a specific external force to form large particle flocs, thereby causing the pollutants to be absorbed. Floc adsorption is removed by precipitation.

This treatment method has low investment and can effectively remove suspended solids in wastewater and reduce COD and color.
Simple chemical treatment methods can often achieve better treatment results, but they will still form a large amount of wastewater. The salt content in this part of the wastewater is usually high, and a unique desalination process is required for pretreatment before entering the sewage station for unified treatment; at the same time, this method requires Adding a large amount of chemicals, which will result in higher processing costs.

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Biotechnology

Biodegradation of organic matter in hazardous waste is often used to treat machine waste liquids and wastewater. Main methods: anaerobic, aerobic, and facultative anaerobic processes, etc. Specifically, it includes activated sludge, AO, AAO, compost treatment, biological filter, stabilization pond, etc.

Anaerobic biological treatment

It mainly includes the anaerobic activated sludge method (UASB, IC), anaerobic biofilm method (filter, oxygen fluidized bed, etc.), and two-stage method (acid production section and gas production section).

Anaerobic biological treatment of wastewater refers to the conversion of various organic molecules in wastewater into methane, carbon dioxide, and other substances through the action of anaerobic organisms (including facultative organisms) under conditions without molecular oxygen. Under anaerobic conditions, anaerobic bacteria in sewage decompose organic matter, such as carbohydrates, proteins, and fats, into organic acids. Under the action of methanogens, they are further fermented to form methane, carbon dioxide, and hydrogen, thereby purifying sewage.

Compared with aerobics, anaerobics do not require blast aeration, and the electricity consumed by the aeration fan is a significant expense in sewage treatment. At the same time, the biogas generated anaerobically has recycling value. It can be used to supplement energy to supply production and living needs in the factory to a certain extent. However, the wastewater after anaerobic treatment still has high COD. A combination of back-end aerobic and aerobic treatment can result in a better treatment effect.
Contact oxidation method

Biological contact oxidation evolves by combining the characteristics of biological filters and aeration processes, and it is a biologically fixed treatment method.

Biological contact fillers are arranged in the pool, the sewage is wholly immersed in the fillers, and a specific flow rate is formed on the filler surface to wash away the filler surface. On the surface of the filler, under the action of the metabolic function of biofilm microorganisms, organic pollutants in the sewage are removed, and the sewage is purified.
Activated sludge process

A typical activated sludge process comprises aeration, sedimentation, sludge return, and excess sludge removal. Sewage and return activated sludge enter the front end of the aeration tank to form a mixed liquid. The air is dispersed through the aerator at the bottom of the aeration tank. It enters the sewage in tiny bubbles, supplying the oxygen required for the normal metabolism of microorganisms. At the same time, the contact between mud and water is promoted through air stirring in the tank. Dissolved oxygen, activated sludge, and sewage are mixed and fully contacted so the activated sludge reaction can proceed normally.

Features of the activated sludge method: good treatment effect, suitable for treating sewage with a high degree of purification and stability; the degree of sewage treatment can be flexibly adjusted according to specific circumstances; when the inlet water load increases, the sludge return ratio can be increased way to solve it.

Disadvantages of the activated sludge method: the aeration tank has a large volume, covers a large area, and requires a lot of infrastructure investment to prevent the mixed liquid at the head end of the aeration tank from being in an an anoxic or anaerobic state, the organic load of the incoming water cannot be too high, so the aeration The volumetric load of the tank is generally low; the oxygen supply rate may be greater than the oxygen demand rate at the end of the aeration tank, resulting in greater power consumption; and the ability to adapt to impact loads is poor.

What are the sources of wastewater from hazardous waste treatment plants?

Cleaning wastewater from solid waste transport vehicles, temporary storage warehouses, ground flushing water in the incineration workshop, production drainage from the test building, initial rainwater in the polluted areas, etc., the water quality fluctuates wildly. The pollution components are complex due to the pretreatment facilities of the wastewater treatment station and the duplication of the physical and chemical workshops.

To improve the utilization rate of treatment equipment, reduce the usage of chemicals and duplicate configuration of certain substances, and save equipment investment and later operating costs, the wastewater generated above is sent to the physical and chemical workshop for pretreatment before entering the treatment station for processing.

Laboratory drainage

Due to the laboratory's characteristics, the laboratory's water body is complex and changeable, and the concentration of pollutants is high. The contaminants in the wastewater are mainly COD, heavy metals, petroleum, viral substances, etc.

The laboratory wastewater is collected and entered into the pretreatment unit, where it is pretreated and reused with heavy metal waste liquid, leachate, and other sewage.
Car wash drainage

Hazardous waste transport vehicles must be flushed accordingly after unloading before being discharged. Therefore, the wastewater generated by transport truck washing mainly contains petroleum, suspended solids, organic matter, and viruses.
Wash bucket drainage

The pollutants in wastewater are mainly COD, heavy metals, petroleum, viral substances, etc. The water used for washing the barrels can be flushed with recycled water produced by the pretreatment system.
Initial rain

Since a lot of hazardous waste is scattered in the disposal site, the toxic and harmful substances in the dangerous waste, after being poured by rainwater, are transferred to the initial rainwater through soaking. Therefore, according to relevant regulations, the initial rainwater in the disposal site must be treated accordingly， Efflux.

An initial rainwater collection pipe and an initial rainwater collection tank are set up on the site, and the rainwater is collected and processed. This part of the sewage contains a large amount of suspended solids.
Treating Process Drainage

Equipment cleaning water (such as solidification equipment) and some waste oil are naturally stored and discharged after stratification. The discharged water is collected in the collection tank and sent to the sewage treatment station.
Drainage of stored materials

Improper packaging or storage of incoming materials can easily cause spillage of wastewater. The quality and quantity of this part of water vary greatly, and the concentration is high.

Set up corresponding collection pools in the semi-solid and liquid hazardous waste storage areas for collection, and then send the collected water to the physical and chemical workshops for corresponding treatment. This part of drainage is greatly affected by the composition of materials and often has the characteristics of high concentration, high toxicity, and small water volume. It is the key to the success or failure of hazardous waste disposal wastewater treatment.
Foreign waste liquid
For some wastewater dominated by heavy metal pollution, petroleum pollutants, and low-concentration organic pollutants, this part of the water is first sent to the physical and chemical processing workshops, where the heavy metal wastewater is solidified separately. Wastewater is sent to a sewage treatment station for treatment.

To summarize the waste liquid, the main categories are as follows:
1. Waste acid and alkali: liquid waste acid and alkali containing impurities;
2. Waste oil-water mixture: wastewater produced by corresponding treatment processes such as demulsification. Although this wastewater contains high oil content, it cannot be directly incinerated;
3. Organic wastewater: wastewater containing organic matter and other impurities;
4. Wastewater containing heavy metals: Wastewater containing various types of heavy metals produced in the heavy metal treatment section.
This part of wastewater often has the characteristics of large water volume, high salt content, and complex pollutant components. Effective pretreatment and desalination are the keys to affecting the discharge of hazardous waste treatment wastewater.
Domestic sewage

Wastewater generated in living areas includes drainage from offices, shower rooms, toilets, and employee dormitories.

The main pollutants are organic pollutants. The volume of domestic sewage is generally small, but its biochemical properties are good, and it is a good nutrient in the system to improve the biochemical properties of wastewater.
Incinerator exhaust gas absorption produces wastewater

The wastewater produced by absorbing the flue gas generated after hazardous waste incineration has the following characteristics:

Instability, imbalance, and uncertainty: the pollutants generated depend on the solid waste incineration and incineration conditions, mainly acidic components (SO₂, NO_x, HC1, HF, CO), smoke, volatile heavy metals, dioxin-like substances, etc.

The source analysis of each pollutant component is as follows:

1. Acid gas
HC1: formed by the incineration of chlorine-containing organic matter.
HF: Incineration of fluorocarbons.
SO₂: Incineration of natural gas and sulfur-containing compounds.
NO_x mainly comes from the combustion of nitrogen-containing compounds and the thermal combustion of air nitrogen.
CO: Carbon decomposition of organic matter and incomplete combustion of carbon-containing compounds.

2. Heavy metal

Heavy metals undergo gaseous transformation under high temperatures, and heavy metal pollutants are transferred to the water phase when the flue gas is absorbed.

3. Dioxins

Sources of dioxins produced by incineration are solid waste itself, high temperature inside the furnace, and low temperature outside the furnace, and then they are synthesized.

Emulsion wastewater

Generally, mineral oil, vegetable oil, surfactants, admixtures, and water constitute emulsion wastewater. There are many types of emulsions. According to the existing form of oil in water, emulsions can be divided into dispersed oil, floating oil, dissolved oil, and emulsified oil. As shown in the table below, various oil droplets have different particle sizes.

The qualities of different kinds of oils
Oil type	oil slick	Dispersed oil	Emulsified oil	Dissolve oil
Oil droplet size	＞100μｍ	10-100μm	0.1-10μm	0.1nm-0.1μm
Characteristic	Easily floats on the surface of water to form an oil layer or film	Oil in this state is unstable and is easily stimulated by external conditions or becomes floating oil if left standing for a long time.

The waste emulsion produced by the mechanical processing industry contains emulsifiers, mineral oil, preservatives, metal shavings, etc. It is a high-concentration organic wastewater that is difficult to degrade.

At home and abroad, waste emulsions with COD mass concentrations in the range of 1000~50000mg/L are commonly treated with chemical agents, demulsification, electrolysis, ultrafiltration and other methods. The demulsification methods are divided into acid demulsification, alkali demulsification, Demulsification by heating, demulsification by cooling, etc.

Acid and alkali wastewater

Waste alkali liquid mainly comes from waste alkali liquid produced by waste production units for cleaning petrochemical plant waste alkali liquid and other purposes. Its main components are about 11% alkali (calculated as NaOH) and the washed dissolved alkali liquid. 8% waste oil and a small amount of mechanical impurities.

The waste acid liquid mainly comes from waste acid production units that use acid liquid to clean metal surfaces and for other purposes. It is mainly sulfuric acid waste liquid, and the impurities contained in it are metal ions and other mechanical impurities.

Comprehensive wastewater treatment

Comprehensive wastewater treatment mainly focuses on the treatment of organic matter. With the development and application of membrane materials in recent years, membrane bioreactors (MBR) have become more and more widely used. The MBR process is suitable for all types of industrial wastewater. This process replaces the secondary sedimentation tank in the form of a membrane module, thereby achieving a higher activated sludge concentration in the biochemical treatment system and reducing the floor space. The sludge concentration in the MBR can reach 8~10g/L, and the sludge age can reach more than 30 days. It has good treatment effect on high-concentration industrial wastewater, high-ammonium nitrogen wastewater, and high-concentration surfactant wastewater.

How to treat wastewater from hazardous waste treatment plants ?

Wastewater disposal methods can be divided into the following two types:

In combined treatment, the wastewater generated by each hazardous waste disposal line is collected centrally and discharged to the sewage station in the plant for treatment, and the treated effluent is reused at various water points;
For diversion treatment, the wastewater generated by each treatment line will be further processed and reused in the workshop first, and the remaining reused water will be transported to other water points.

Since the quality of wastewater from each disposal line varies greatly, the use of "combined disposal" may affect the stability of the operation of sewage treatment facilities.

Since various pollutants may restrict each other during the treatment process, a set of sewage treatment facilities cannot remove all pollutants at the same time. Therefore, using the "diversion treatment" method, different treatment processes can be used to produce wastewater of different water quality and sources, thereby ensuring the stable operation of sewage treatment facilities.

The role of air flotation in hazardous wastewater treatment

Dissolved Air flotation technology is important in hazardous waste (hazardous waste) wastewater treatment. Its functions include but are not limited to the following aspects:

Solid-liquid separation: Air flotation technology injects bubbles to cause suspended solid particles, pigments, grease, and other substances in the wastewater to float to the water surface under the lift of the bubbles, thereby achieving solid-liquid separation. This helps remove suspended solids and solid particles from wastewater and improves water quality.

Removal of grease and suspended solids: Hazardous wastewater often contains many oily substances and suspended solids, such as grease, paint, pigments, and glue. Air flotation technology can effectively separate these greases and suspended solids from the water and form scum for subsequent follow-up. Processing and recycling.

Removal of heavy metals and pollutants: Air flotation technology can also remove heavy metal ions, organic pollutants, discarded drugs, and other hazardous substances in hazardous wastewater, helping to purify water quality and reduce environmental risks.

Pre-treatment: In the process of hazardous wastewater treatment, air flotation technology is usually used as the pre-treatment stage, which can effectively reduce the load of subsequent treatment devices, improve treatment efficiency, and extend the life of treatment equipment.

Air flotation technology plays an important role in hazardous wastewater treatment, mainly including solid-liquid separation, removal of grease and suspended solids, and water purification. Through the effective application of air flotation technology, efficient treatment of hazardous wastewater can be achieved and the environment and human health can be protected.

Application case(Preprocessing-physical method)

Case Studies-Resin Material Recycling Project

This project case introduces that the wastewater discharged by HANGZHOU ELECTROCHEMICAL NEW MATERIAL CO., LTD. during the production of PVC raw materials also contains a small amount of PVC fine particles. After the wastewater is pH-adjusted, coagulated, and flocculated, the fine particles are aggregated into larger flocs and recycled using high-efficiency dissolved air flotation, achieving good results.

Case Studies-Composite Wastewater Treatment

In this case, Jiangsu Fengmang Compound Material sewage treatment project, we used the high-efficiency dissolved air flotation produced by our factory to remove most of the suspended impurities, and the effluent was sent to biochemical treatment, achieving good results.

Suma Park North Wastewater Treatment Plant Project.jpg

Case Studies-Suma Park North Wastewater Treatment Plant Project

This case introduces the Suma Park North Wastewater Treatment Plant Project, which uses a C-AAO combined biochemical pool + micro-flocculation filtration process, and the drainage complies with the town Class A standard. The raw water is treated with high-efficiency dissolved air flotation produced by our plant to remove more than 90% of SS. The reduced concentration of suspended solids can reduce the treatment load of the combined biochemical pool and improve the treatment efficiency.

Case Studies-Recycling And Recycling of Lithium Batteries

This case study presents the success of Zhejiang New Era Zhongneng Technology in recycling lithium batteries wastewater. They achieved their goal with the help of our factory's high-efficiency dissolved air flotation technology.

Emulsion wastewater treatment technology

Emulsions are mainly used in metal processing for cooling, surface cleaning, and lubrication. The main ingredients are water, mineral oil, emulsifier, lubricating oil agent, extreme pressure agent, surfactant, anti-rust agent, anti-fungal agent, defoaming agent, etc. Due to the uniquemulsion's e electric double-layer structure, the oil is highly dispersed in the water, making the emulsion relatively stable.

Usually, the oil content of emulsion wastewater can reach up to 20,000~30,000 mg/L, and the chemical oxygen demand can reach up to 50,000~100,000mg/L. Therefore, making the emulsion lose its stability and achieving oil-water separation is the key to emulsion wastewater disposal.

Electric flotation can use emulsion wastewater as an electrolyzable medium to achieve the purpose of demulsification through the action of positive and negative currents and consumes fewer chemicals during operation.

However, demulsification is only the pretreatment stage of emulsion wastewater disposal. If the effluent needs to be reused, chemical treatment, biological treatment, reverse osmosis depth treatment, etc., will be required after demulsification.

The picture shows a typical emulsion wastewater treatment process flow chart. The emulsion wastewater is first pre-treated by demulsification and air flotation to separate most of the oil; then biochemical treatment or chemical treatment is performed to remove dissolved organic matter; emulsion wastewater usually Contains 1000~5000mg/L dissolved salt, and finally performs reverse osmosis desalination and treats the effluent for reuse.

Emulsion wastewater treatment process flow chart

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Acid-base wastewater treatment technology

Acid-base wastewater comes from the electronics industry, steel industry and aerospace industry. The composition of acid-base wastewater is complex and contains Na⁺, H⁺, OH^-, SO_4^2-, NO^_3-, F^- and heavy metals.
There are two main ways to dispose of acid-base wastewater: comprehensive utilization of resources and harmless disposal. Among them, the extensive utilization of resources mainly includes the recovery of precious metals and the recovery of acids and alkalis.

Harmless disposal mainly includes neutralizing waste acid and alkali and recycling treated effluent. Use carbide slag to replace lime to neutralize the titanium dioxide wastewater from the sulfuric acid process. Adding dried carbide slag neutralizes the wastewater and removes COD, which has the same effect as adding lime.

The picture shows a typical acid-base wastewater treatment process flow chart. Waste acid and waste alkali first reduce the concentration through dilution; then waste acid and waste alkali form salts and water through a neutralization reaction; finally, the neutralized effluent enters the flocculation sedimentation tank to remove colloidal substances. , the sediment produced in the neutralization reaction tank and the coagulation sedimentation tank enters the filter press to form a filter cake.

However, incineration may be considered if acid-base wastewater has a complex composition or contains high concentrations of organic matter, which is not conducive to resource recovery and acid-base neutralization disposal.

Acid-base wastewater treatment process flow chart

Flue gas scrubbing wastewater treatment technology

In the wet deacidification process of hazardous waste incinerators, a large amount of flue gas scrubbing wastewater will be generated by neutralizing the HCl acid gas in the flue gas with NaOH solution.

Flue gas scrubbing wastewater has a high salt content, usually between 1 and 10%. The main salt types are NaC1, and there are also small amounts of Ca²⁺, Mg²⁺, SO₄²⁺, HCO₃^-, NO₃^-, etc.
Due to the complex types of hazardous wastes being incinerated, there may be a small amount of organic matter that is not decomposed by the high temperature of the incinerator and enters the subsequent treatment unit, so there will be a small amount of organic matter in the flue gas scrubbing wastewater.

In current research, few reports exist on disposing of hazardous waste, such as flue gas scrubbing wastewater. Hazardous waste flue gas scrubbing wastewater is a typical high-salt organic wastewater unsuitable for ordinary RO processes. Considering the heat source conditions in the dangerous comprehensive waste disposal plant, consider using multi-effect or MVR evaporation technology. The distillate is collected and reused in the process. Considering the composition of the evaporation product, consider comprehensive utilization of resources or safe landfill disposal.

Flue gas scrubbing wastewater treatment process flow chart

For the flue gas scrubbing wastewater quenching and recycling device, the quenching tower and the alkali washing tower are the core process units. The higher temperature and pH of the flue gas scrubbing wastewater may affect the quenching effect of the acidic flue gas, and the higher salt content may cause blockage of the quenching tower pipeline. These factors must be comprehensively considered in actual engineering applications.

Fly ash washing wastewater treatment technology

Fly ash water washing is the primary means of fly ash pretreatment. Most Na, K, Ca, and Cl can be removed through water washing, thereby increasing the comprehensive utilization of fly ash. The main components of fly ash washing wastewater are NaC1, KC1, CaCl2, and heavy metals. The salt content is usually 5~10%. The heavy metals are mainly Pb, Zn, Cu, Mn, Cd, Cr, etc. This is the flow chart of the fly ash washing pretreatment process.

Fly ash washing pretreatment process flow chart

The primary process of fly ash washing pretreatment is thoroughly cleaned according to a certain water-cement ratio, washing time, and washing times, and the washed fly ash is separated from solid and liquid.

The fly ash washing wastewater undergoes physical and chemical pretreatment and then enters the MVR to evaporate the final product. The crystallized salt reduces part of the cost through comprehensive utilization of resources. After solid-liquid separation, the fly ash is dried and then comprehensively utilized.

Disposal of other wastewater

The cleaning wastewater generated from the cleaning of waste storage containers can be disposed of by incineration due to its high organic content.

The sewage produced by the backwash of the boiler water softener has high salt content and low organic matter content. Evaporation treatment can be considered.

Due to the lower salt and organic matter content, the sewage generated by the fixed-discharge boiler can be reused after RO treatment, or discharged into domestic sewage treatment facilities for combined disposal.

Conclusion and recommendations

The salt content and organic matter content in hazardous waste production wastewater are the main pollutant indicators that affect the selection of disposal processes. Reasonable processes must be selected based on water quality conditions.

In addition, front-end process control must be strengthened to reduce the production of production wastewater and reduce water treatment costs; reduce fluctuations in water quality, and ensure stable operation of water treatment facilities.

The production wastewater disposal system is the terminal environmental protection facility of the comprehensive hazardous waste disposal plant and is the guarantee for the stable operation of other disposal systems. Therefore, when it comes to process selection, priority should be given to stable treatment processes.

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