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2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
A Review on Advanced Treatment of Pharmaceutical
Wastewater
Y Guo, P S Qi and Y Z Liu
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of
Technology, Heilongjiang, China
[email protected]
Abstract. The composition of pharmaceutical wastewater is complex, which is high
concentration of organic matter, microbial toxicity, high salt, and difficult to biodegrade. After
secondary treatment, there are still trace amounts of suspended solids and dissolved organic
matter. To improve the quality of pharmaceutical wastewater effluent, advanced treatment is
essential. In this paper, the classification of the pharmaceutical technology was introduced, and
the characteristics of pharmaceutical wastewater effluent quality were summarized. The
methods of advanced treatment of pharmaceutical wastewater were reviewed afterwards, which
included coagulation and sedimentation, flotation, activated carbon adsorption, membrane
separation, advanced oxidation processes, membrane separation and biological treatment.
Meanwhile, the characteristics of each process were described.
1. Introduction
In China, pharmaceutical technology can be classified by productive methods. First is
biopharmaceutical, which contains fermentation engineering, cell engineering, enzyme engineering
and genetic engineering. The most popular is fermentation engineering. It depends on activities of
microorganisms to ferment, filter and extract from organic raw materials, such as antibiotics, vitamins,
amino acids. Next is chemical pharmacy, which is synthesis using multilevel chemical reactions of
organic matter or inorganic matter. In addition, there is another kind of method by extracting from
plants and animals or directly, called Chinese patent medicine, also known as natural medicine.
In recent years, the fast development of pharmaceutical industry has become an important part of
China’s national economy. In 2014, the output of chemical original medicine had reached 3.034
million tons, rose by 15.2 %, compared to the same period in 2013. There are some characteristics of
the pharmaceutical industry in China, such as a multitude of enterprises and products with small scale,
scattered overall arrangement. By the end of 2014, the pharmaceutical enterprises have reached 7108
in China, which was 8.9 % higher than 2013. Only 1609 among them are large or medium-sized
enterprises.
However, with the development of pharmaceutical industry, the environmental pollution is
becoming more and more serious. Due to the variety of the pharmaceutical industry products, and the
difference of production scale and process, there are many kinds of pharmaceutical wastewater.
Biopharmaceutical wastewater is mainly generated by high-concentrated antibiotic wastewater, which
is characterized as strong fluctuation in quantity, low C/N, high SS concentration, high sulfate
concentration, complicated composition, biological toxicity and high chroma. The composition of
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2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
chemical pharmacy is single, leading to lack of nutrition. It also has high concentration and salt
content. And it is hard to biodegrade and toxicity to microbiology [1].
Along with the strict government standard, traditional treatment methods of pharmaceutical
wastewater are difficult to satisfy the demand. Therefore, advanced treatment of pharmaceutical
wastewater is essential.
The review aims to introduce the fundamental advanced treatment of pharmaceutical wastewater.
2. Characteristics of pharmaceutical wastewater
2.1. Characteristics of pharmaceutical wastewater
In general, the composition of pharmaceutical wastewater is complex, which has high concentration of
organic matter, microbial toxicity, high salt, and it’s hard to biodegrade [2,3]. In addition, most of
pharmaceutical factories are batch process, and there are different raw materials and production
process, which causes huge varieties in different wastewater [4]. Table1 provided a summary of the
characteristics of pharmaceutical wastewater [5].
Table 1. Common pharmaceutical wastewater physicochemical properties
COD BOD5 TN TP SS Chromaticity Temp.
pH
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (times) (℃)
1000-10000 500-2500 500-1500 50-250 200-500 500-1000 25-80 1-8
Otherwise, different kinds of pharmaceutical wastewater has different characteristics.
Biopharmaceutical wastewater is characterized as strong fluctuation in quantity, low C/N, high SS
concentration, high sulfate concentration, complicated composition, biological toxicity and high
chroma. Chemical pharmacy is lack of nutrition, hard to biodegrade and toxicity to microbiology, and
it also has high salt content. The characteristics of the wastewater of Chinese patent medicine is
containing sugar, glycosides, organic pigment, anthraquinone, tannins, Alkali content, cellulose, lignin
and other organic matter [6].
2.2. Characteristic of secondary effluent
Biological treatment is mainstream for pharmaceutical wastewater at home and abroad, which is the
most economical way to remove organic pollutants. Therefore, organic matter are the main pollutants
in pharmaceutical wastewater. Biological treatment technologies can be generally divided into aerobic
process, anaerobic process and combination of anaerobic-aerobic process [7]. After secondary
treatment, almost every kind of pollutants concentration are decline.
However, due to their own complex features of pharmaceutical wastewater, and discharge standard
is increasingly strict, the current methods are hard to satisfy the demand.
3. Methods of Advanced treatment of pharmaceutical wastewater
In recent years, the main emphasis of the scientific research and engineering application has shifted to
advanced treatment of pharmaceutical wastewater, which main method is physicochemical technology
[7]. It means that wastewater is treated by physical or chemical methods, like coagulation and
sedimentation, flotation, activated carbon adsorption, advanced oxidation processes, membrane
separation.
3.1. Coagulation and sedimentation
Coagulation is adding chemical agents to wastewater, dispersing by rapid mixing, then making stable
pollutants into unstable and precipitable matters. The mechanism of coagulating is complex. For
advanced treatment of pharmaceutical wastewater, the key is how to squeeze and remove bound water
round hydrophilic colloid. So the character of flocculent is important, which related to the effect of
coagulation. Inorganic metal salts and polymers are frequently used as flocculent. This method can
remove SS, chromaticity and toxic organic matter [8]. Meanwhile, it can improve the biodegradability
of pharmaceutical wastewater.
2
2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
Sedimentation is the most common method after coagulation. Under the gravity, pollutants can be
separated, which has greater density than wastewater.
Coagulation and sedimentation have some advantages, such as easy operation and mature
technology, but it is hard to remove dissolved organic matter.
3.2. Flotation
Except for sedimentation, flotation can also remove suspended solids of secondary effluent. The
technology characteristic is producing a large number of tiny bubbles by injecting air into wastewater,
forming floating floc with smaller density than wastewater. And it can float to the surface of
wastewater to separate.
3.3. Activated carbon adsorption
Activated carbon, as a kind of adsorbent, has many advantages. It has large specific surface area,
multilevel pore structure, high adsorption capacity and stable chemical property. Therefore, it is
widely used as adsorbent or catalyst carrier to remove pollutants [9,10]. In industrial effluents
treatment, activated carbon is used for effluent, which is toxic and hard to achieve discharge standard.
It is an important method of advanced treatment of pharmaceutical wastewater as well.
Activated carbon adsorption can be classified as physical adsorption and chemical adsorption.
Physical adsorption is reversible, and no selectivity to adsorbate. When activated carbon saturated by
adsorbates, it is easy to desorb. To the contrary, chemical adsorption adsorbs only one or several
specific adsorbates, which is irreversible and hard to desorption. For cyclic utilization, saturation of
activated carbon restores its adsorption property by regeneration.
This method is widely used for advanced treatment, because it can be recycled, its better treatment
effect and wide suitability. But there are some disadvantages, such as high costs relatively, low
efficiency of regeneration and complex operation, which limit application.
3.4. Advanced oxidation processes
Advanced oxidation processes (AOPs), which can oxidize pollutants by forming free radicals. Those
kinds of pollutants cannot be degraded by common oxidizing agent. There are many kinds of AOPs,
such as wet air oxidation, supercritical water oxidation, Fenton reagent, photocatalytic oxidation,
ultrasound oxidation, electrochemical oxidation and ozonation.
3.4.1. Wet air oxidation(WAO). WAO has been put forward by F. J. Zimmer Mann in 1958, which was
used for papermaking black liquid treatment. By using of air or oxygen as the oxidant, this method
decomposes organic matter into inorganic or small molecules at high temperature (150-350 ℃) and
high pressure (0.5-20 Mpa). WAO is generally used in pretreatment of wastewater advanced
treatment.
This method has wide range of applications, high efficiency of COD removal, which can even
reaches more than 90 % under appropriate conditions, low energy consumption, less secondary
pollution, and it is easy management.
3.4.2. Supercritical water oxidation(SCWO). SCWO is chemical reaction between dissolved oxygen
and organic pollutants in supercritical water. Organic matter, air, and supercritical water were
complete mixed at 24 Mpa pressure and 400 ℃ temperature, becoming homogeneous phase. Under
these conditions, organic compounds spontaneously initiate the oxidation reaction. With the increase
of the reaction temperature, 99.9 % or more of the organic matter is rapidly oxidized into simple
non-toxic small molecules in a period of time, achieving the purpose of removing pollutants.
SCWO has high oxidation efficiency, will not cause secondary pollution, organic can be oxidized
completely. However, this method has some shortcomings, such as it requires high operating
conditions and high cost.
3
2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
3.4.3. Fenton reagent. Fenton system was initially used in organic synthesis, with the deepening of
people's understanding of it, the system was gradually applied to industrial wastewater treatment.
Fenton reaction can be carried out under normal temperature and pressure, and less damage to the
environment [11]. It is an advanced oxidation method, which is simple, mild reaction conditions, and
high oxidation efficiency. However, the shortcomings of the Fenton reaction cannot be ignored. One is
due to free radical scavenging and decomposition of H2O2 itself, leading the loss of oxidant. The other
is the formation of iron mud in the neutral conditions, making it hard to the subsequent processing
[12].
3.4.4. Photocatalytic oxidation. Photochemical oxidation, also known as ultraviolet photocatalytic
oxidation, is a method combination of UV radiation and oxidant. In the excitation of ultraviolet light,
oxidative decomposition of oxidants produces stronger oxidative capacity of free radicals, which can
oxidize more difficult to decomposition of refractory organic pollutants with oxidants only.
According to the types of oxidants, photochemical oxidation can be divided into UV / O3, UV /
H2O, UV / H2O2 / O3 and so on. At present, the steps of the reaction process still can’t be described.
However, the effect of this method on the treatment of refractory organic matter is undeniable.
3.4.5. Ultrasound oxidation. Ultrasonic degradation of organic matter in wastewater is a physical and
chemical degradation process, mainly based on ultrasonic cavitation effect and the resulting physical
and chemical changes, which includes the following three ways: free radical oxidation, pyrolysis and
supercritical water oxidation.
There are many factors that affect the effect of ultrasonic degradation of organic pollutants in
wastewater. The main factors are ultrasound frequency, sound power, ultrasonic time, solution
temperature and pH, and the nature of organic matter.
3.4.6. Electrochemical oxidation. The use of electrochemical reaction to remove toxic and harmful
pollutants in the water, is known as the electrochemical method. Electrochemistry is a new method in
water treatment field. The principle of the method is as follow: in the electrochemical reaction process,
the reactant will lost electrons and be oxidized in the anode. Conversely, the reactant in the cathode
will lose electrons and be reduced. In general, the removal of refractory organic matter, mainly due to
the oxidation of the anode. Conventional electrochemical wastewater treatment processes includes:
electrolytic recovery, electrochemical oxidation, electrolytic air flotation, electrodialysis and
micro-electrolysis.
Electrochemical method is also known as "Environmentally Friendly" process, has a great
advantage compared with other methods. For example, the electrochemical method is generally carried
out under normal temperature and pressure and has high efficiency, can be used alone or in
combination with other processes, and it covers a small area and no secondary pollution, has relatively
high degree of automation. The main research direction of the electrochemical reaction in the future is
the research of the anode and electrochemical reactor [13].
3.4.7. Ozonation. For a long time, ozone is considered to be a very effective oxidant and disinfectant.
In acidic conditions, ozone is primarily an oxidant. But in neutral and alkaline conditions, it mainly
relys on free radical reactions. Table 2 shows the oxidation potential of various oxidants. It can be
seen that the oxidation capacity of ozone is significantly higher than other conventional oxidants.
Table 2. The oxidation potential of various oxidants
Oxidant Half-reaction Oxidation potential(V)
·OH ·OH + H+ + e → H2O 3.06
O3 O3+ 2H+ + 2e → O2 + H2O 2.07
H2O2 H2O2 + 2H+ + 2e → 2H2O 1.77
HClO 2HClO + 2H+ +2 e → 2Cl- + 2H2O 1.63
Cl2 Cl2 + 2H+ + 2e → 2Cl- 1.36
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2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
Ozone can quickly oxidize and decompose most of the organic matter in the water, which can
effectively remove pollutants in water. However, it is difficult to directly mineralize. Instead, a
product which is easily biodegradable can be produced. At the same time, it can also effectively
remove turbidity and pathogens in wastewater.
Ozone can be combined with other wastewater treatment technologies, forming ozone advanced
oxidation technology. This method has stronger oxidation ability and lower selectivity to reactants.
Such as O3 / H2O2, O3 / UV, etc.
3.5. Membrane separation
Under certain driving force across the membrane, a component in water selectively permeates it by
using permselective membrane separating media, which is called membrane separation. In this way,
achieve the separation, purification, concentration of the target substance from the mixture. There are
several membrane separation techniques in wastewater treatment. Such as microfiltration,
ultrafiltration, reverse osmosis and electrodialysis.
3.5.1. Microfiltration(MF). MF is based on static pressure as the driving force, and the separation
process is performed by the action of the sieve separation of the membrane, which principle is similar
to traditional filtration. The slight difference is that the pore size of MF is smaller. This method can
effectively remove SS and microorganisms in wastewater.
3.5.2. Ultrafiltration(UF). UF driving force is the pressure difference between the membranes on both
sides, the filter medium is the ultrafiltration membrane. Under certain pressure, when water passes
through the membrane surface, water, inorganic salts and small molecules penetrate, other
macromolecules are trapped.
This method is mainly used for the removal of macromolecules and colloids in wastewater. In the
application of this method, it should be ensured that the membrane has adequate membrane flux and is
easily disassembled, replaced, cleaned.
3.5.3. Reverse osmosis(RO). There are two categories of RO membrane, cellulose ester and aromatic
polyamide. Its component form includes tube, plate and frame, roll and hollow fiber type.
RO process can remove a wide range of impurities, dissolved inorganic salts and a variety of
organic matter. Meanwhile, it has a high efficiency of salt removal and water reuse rate. However, this
method requires a high pretreatment of the feed water. With the development of RO, nanofiltration
(NF) has been proposed as a new method.
3.5.4. Electrodialysis(ED). ED is a combination of electrolytic and dialysis diffusion process. Under
the action of the DC electric field, anions and cations of the dissolved salts in the wastewater are
moved to the anode and the cathode respectively. In this way, the concentration of anions and cations
in the intermediate compartment is gradually reduced, and the separation and recovery are achieved.
This method has many advantages, such as less energy and pharmaceutical consumption, less
environmental pollution, easy to operate and automate. But it can only remove the salt in water, and
desalination efficiency is lower than RO.
3.6. Biological treatment
In theory, after secondary treatment, pharmaceutical wastewater should not be treated by biological
methods, because of its poor biodegradability. However, we cannot ignore the advantages of
biological treatment, such as low cost, stable treatment effect. It can be used as a way of pretreatment
in advanced treatment.
5
2017 International Conference on Environmental and Energy Engineering (IC3E 2017) IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
63 (2017) 012025 doi:10.1088/1755-1315/63/1/012025
4. Conclusion
Due to the complexity of pharmaceutical processes, pharmaceutical wastewater has some
characteristics, such as poor biodegradability and high concentration. From these characteristics,
advanced treatment of pharmaceutical wastewater is very necessary. There are many kinds of
advanced treatment, each method has its own features. Through rational utilization of various methods,
can effectively improve the quality of pharmaceutical wastewater effluent.
5. Acknowledgments
During the writing of this paper, Prof. P S Qi and Mrs. Y Z Liu gave me great support and
encouragement, I would like to express my sincere thanks to them. And thanks to my classmates, B
Liu and L L Liu.
6. References
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South China University of Technology) pp 1-3
[2] Shubin X and Liren R 2009 J. Fine. Specialty. Chemicals. 3/4 16-8
[3] Huiqiang X, Liangjun L and Yuting H 2005 J. Environ. Sci. Techno. 28 92-3
[4] Wenxin M, Weizhong C, Jianjun R, Zhangqian W and Yueming L 2001 J. Environ.
Pollution. Control. 2 87-9
[5] Xin L and Guoyi L 2015 A Review: Pharmaceutical Wastewater Treatment Technology
and Research in China (Zhuhai: Asia-Pacific Energy Equipment Engineering
Research Conference) pp 345-7
[6] Yu Y 2013 Experimental on Pharmaceutical Tail Water before Biochemical Pretreatment
(Changchun: Jilin University) pp 12-9
[7] Liang W, Qi X and Wenfei Z 2015 J. Technology. Innovation. Application. 6 1-2
[8] Yiping G and Yu B 2010 Advanced Treatment and Recycling Technology of Wastewater
Treatment Plant (China Architecture Press) pp 198-206
[9] Bingyu M, Yubin T, Fangyan C and Tao W 2015 J. Chinese. J. Environ. Eng. 4 1863-4
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