Science of the Total Environment 633 (2018) 189–197

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Upgrading the Chinese biggest petrochemical wastewater treatment

plant: Technologies research and full scale application
Changyong Wu a,b, Yanan Li c, Yuexi Zhou a,b,⁎, Zhimin Li d, Siyu Zhang e, Hengming Liu c
a
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
b
Research Center of Water Pollution Control Technology, Chinese Research Academy of Environment Sciences, Beijing 100012, China
c
School of Marine Science and Technology and Environment, Dalian Ocean University, Dalian 116023, China
d
Jilin Petrochemical Wastewater Treatment Plant, Jilin Petrochemical Company of PetroChina, Jilin 132000, China
e
School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A combined process for the treatment of

petrochemical wastewater is proposed.
• Good organic micropollutants removal
can be achieved in the full-scale applica-
tion.
• The effluent shows low acute toxicity
and genotoxicity.
• Electricity need increases 44.1% for
elimination of organic micropollutants.

a r t i c l e i n f o a b s t r a c t

Article history: The components of petrochemical wastewater (PCWW) are very complex and it is one of the most important
Received 27 December 2017 sources of organic micropollutants (OMPs) in water bodies. To improve the effluent qualities of PCWW, the Chi-
Received in revised form 2 March 2018 nese government has promulgated a new Emission Standard of Pollutants for Petroleum Chemistry Industry.
Accepted 16 March 2018
More than 60 types of OMPs, most of which are toxic organics, are added and strictly limited in the standard.
Available online 21 March 2018
Based on the bench- and pilot-scale experiments, a pretreatment (microaerobic hydrolysis and acidification,
Editor: Zhen (Jason) He MOHA), biological (anoxic/oxic process, A/O) and advanced treatment (micro-flocculation dynasand filtration
and catalytic ozonation, MFDF-CO) integrated process is proposed. The full-scale application in the Chinese big-
Keywords: gest petrochemical wastewater treatment plant has demonstrated that the performance of the integrated pro-
Organic micropollutants (OMPs) cess is stable and it can significantly improve the effluent qualities. The effluent COD decreased from 84.7 to
Petrochemical wastewater (PCWW) 47.0 mg/L and most of the OMPs were removed. The EC50 of the effluent for luminescent bacteria assay, algal
Emission standard growth inhibition, Daphnia magna inhibition test and zebrafish eggs test are all higher than 100% and the

Abbreviations: A/O, anoxic/oxic process; AHA, anaerobic hydrolysis and acidification; AOPs, advanced oxidation process; BOD5, 5 d biochemical oxygen demand; CMA, China
Metrology Accreditation; CO, catalytic ozonation; COD, chemical oxygen demand; DO, dissolved oxygen; DOM, dissolved organic matter; EC50, the concentration for 50% of maximal effect;
EPS, extracellular polymeric substances; EU, European Union; FID, flame ionization detector; GC–MS, gas chromatography–mass spectrometer; HA, hydrolysis and acidification; HIS, hy-
drophilic substances; HOA, hydrophobic acids; HOB, hydrophobic bases; HON, hydrophobic neutrals; HRT, hydraulic retention time; IR, induction rate; LB-EPS, loosely bound extracellular
polymeric substances; LID, the lowest ineffective dilution; MFDF, micro-flocculation dynasand filtration; MLSS, mixed liquid suspended solids; MLSS, mixed liquor suspended solid;
MOHA, microaerobic hydrolysis and acidification; OMPs, organic micropollutants; ORP, oxidation-reduction potential; PAFC, poly aluminum ferric chloride; PCWW, petrochemical waste-
water; SOB, sulfate-oxidizing bacteria; SRB, sulfate-reducing bacteria; SS, suspended solids; SVOCs, semi-volatile organic compounds; TB-EPS, tightly bound extracellular polymeric sub-
stances; TN, total nitrogen; TOC, total organic carbon; VOCs, volatile organic compounds; WWTP, wastewater treatment plant.
⁎ Corresponding author at: State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China.
E-mail address: zhouyuexi@263.net (Y. Zhou).

https://doi.org/10.1016/j.scitotenv.2018.03.164
0048-9697/© 2018 Published by Elsevier B.V.
190 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197

Full-scale application induction rate (IR) for genotoxicity is only 0.76. The energy demand, however, with the electricity consumption
Carbon emission increase by 44.1%, is very high for OMPs removal, leading to high indirect carbon emission.
© 2018 Published by Elsevier B.V.

1. Introduction petrochemical industry, a new Emission Standard of Pollutants for Pe-

troleum Chemistry Industry (GB 31571-2015) was implemented in
The potential accumulation of OMPs in the aquatic environment July 1, 2017 to replace the implemented standard (GB 8978-1996)
may cause negative impact on human health and other environmental (MEPPRC, 2015). More than 60 types of OMPs, most of which are toxic
problems (Deblonde et al., 2011). Study on OMPs, concerning the mea- organics (EPA, 2000a, 2000b), are added into the new standard with
surement, removal, toxicity and health impact, is one of the focuses in strict discharge concentrations (See Supporting Information, SI).
the field of environmental engineering (Jiang et al., 2013). It is reported From 2012 to 2014, a series of bench-scale (2–10 L/h) and pilot-scale
that industries, such as petrochemical (Grandclément et al., 2017) and (1–2 m3/h) experiments, targeting at the OMPs control treating PCWW,
pharmaceutical (Kim et al., 2007), are the important sources of the have been finished (Yang et al., 2015; Wu et al., 2015a, 2015b, 2016a,
OMPs to the aquatic environment. In the last decade, the petrochemical 2016b; 2017). Based on the research achievements, a full-scale petro-
industry has developed very fast in China. The total business income chemical park WWTP, which is the biggest petrochemical WWTP in
was as high as 1.75 trillion dollars in 2015. There is a trend of gathering China, was upgraded in November 2014.
different producing plants, such as oil refining plants, petrochemical in- A few papers have been published so far to describe the full-scale ap-
termediates plants and synthesis material plants, into integrated petro- plication of OMPs removal in industrial wastewater treatment, espe-
chemical parks. In China, N390 petrochemical parks have been built and cially in PCWW. Most of the previous studies focus on the OMPs
2.66 × 109 t of PCWW is discharged per year (MEPPRC, 2014). removal efficiency and process-dependent performance in the ad-
The PCWW is characterized by high organic pollutants and sulfate vanced treatment of municipal WWTP (Hollender et al., 2009; Luo
concentration (Wu et al., 2016a), high toxicity (Liu et al., 2014) and et al., 2014; Mousel et al., 2017). Since the type and concentration of
low biodegradation (Yang et al., 2015). Due to the toxicity of the waste- pollutants in PCWW are obviously different from municipal wastewater
water, pretreatment is recommended during which HA is used as the and the OMPs removal is dependent on compound- and process-
most option (Wu et al., 2015a). HA can break macromolecular and par- specific factors (Luo et al., 2014). More detailed descriptions of the stan-
ticular organic compounds into micromolecular and simple soluble dard, technology investigation process, OMPs removal, toxicity varia-
compounds such as VFAs. Thus, it can enhance the treatability of the tion and energy distribution when upgrading petrochemical WWTP
PCWW (Bai et al., 2013). The sulfate content in the PCWW is relatively are lacking.
high (380–552 mg/L) (Yang et al., 2015). The high sulfate and its reduc- After upgrade, start-up and operation for more than one year, this
tion product of HS− or H2S during HA can cause toxic and inhibition ef- paper reflects not only on the performance, such as COD and OMPs re-
fect on biological process (Zhang et al., 2013a, 2013b), such as moval, but also on technology mechanism and investigation process, ef-
irreversible inhibition of the anaerobic digestion (Kanjanarong et al., fluent toxicity and especially design considerations. Furthermore, the
2017). To overcome the negative effect, some novelty technologies, full-scale application energy demand and distribution concerning the
such as acidification with Fe2O3 dosage, were proposed (Zhang et al., carbon emission is also discussed in detail. The technologies developed
2013a, 2013b). However, the Fe2O3 dosage obviously increases the op- by us have been recognized as a general upgrade technology for petro-
eration cost and its effect on the performance of following biological chemical WWTP, and it is now being recommended in China.
unit is unknown. Previous study has shown that the MOHA is an effec-
tive PCWW pretreatment technology (Wu et al., 2015a, 2015b). 2. Materials and methods
Many OMPs cannot effectively be removed by the conventional bio-
logical WWTP because some OMPs are not biological degradable (Luo 2.1. Description of the petrochemical WWTP
et al., 2014; Altmann et al., 2015; Grandclément et al., 2017). Upgrading
WWTP or adding additional process units are the essential options to The selected WWTP, located in the northeast of China, is the biggest
control the OMPs emission. Previous studies also has shown that petro- petrochemical WWTP in China. It is the centralized WWTP of a petro-
chemical secondary effluent treated by biological processes contains chemical park. The petrochemical park has N50 sets of petrochemical
some OMPs (Rubio-Clemente et al., 2015), even shows a certain degree production plants, including refinery plants, petrochemical intermedi-
of aquatic toxicity (Wu et al., 2015b). The advanced treatment technol- ates (such as ethylene, aromatics and acrylonitrile) production plants,
ogy is needed to develop. AOPs, such as CO, is used as the most option and petrochemical synthetic material (synthetic resins and rubbers)
for the advanced treatment (Giannakis et al., 2015). The SS of the petro- plants. The influent flowrate is about 5000 m3/h. The main processing
chemical secondary effluent is approximately 35 mg/L, which is obvi- units of the WWTP are AHA tank, A/O tank and the secondary clarifier
ously higher than that in municipal secondary effluent of 3.8–5.1 mg/L (Fig. S1). The volumes are 100,000, 120,000 and 19,500 m3 with the
as reported by Altmann et al. (2015). The wastewater particles ad- HRT of 20, 24 and 3.9 h, respectively. The MLSS in the A/O tank is
versely affect the ozonation efficiency (Zucker et al., 2015). To reduce 4000–6000 mg/L with the SRT of 17–24 d. The sludge recycle rate is
the invalid ozone consumption, high removal of SS is needed before cat- 100% as previously optimized (Wu et al., 2016a). The SVI of the sludge
alytic ozonation process. Previous study has proved that the MFDF is in A/O tank is 67–85 mL/g. The wastewater characteristics of influent
suitable as the pretreatment option for the CO for the advanced treat- and effluent are given in Table S2.
ment of petrochemical secondary effluent (Wu et al., 2016b). However,
the relationship between MFDF and CO, toxicity reduction and full-scale 2.2. Research reactor setups and operation
application are still needed to investigate.
To control the OMPs emission, many countries have released or re- The research plans of this study are shown in SI. The pretreatment
vised discharge standards, such as the Micropoll Strategy for and the advanced treatment of biological secondary effluent are the
Switzerland (Giannakis et al., 2015) and Contaminants of emerging con- focusses of the research. To investigate the pretreatment of PCWW
cern Decision 2015/495/EU in EU Environmental Quality Standards and the advanced treatment of biological secondary effluent, a serial
(Sousa et al., 2018). China has also revised many industrial wastewater of bench-scale (2–10 L/h) and pilot-scale (1–2 m3/h) experiments
emission standards to control the OMPs emission since 2008. For were carried out. The HRT of different experimental units is the same
 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197 191

as that in the WWTP while the MLSS is close to the corresponding tanks. TOC-VCPH/CPN analyzer (Shimadzu Corporation, Japan), while the DOC
To investigate the pretreatment technology of PCWW, MOHA was in- of HON was calculated by the difference of influent DOC and DOC sum
vestigated by bench-scale experiments. The reactor was operated for of HOA, HOB, HIS.
about one year. Based on the parameters got by the bench-scale exper-
iment, the pilot-scale combination of MOHA-A/O was operated. The re- 2.3.4. Wastewater toxicity assay
sults showed that advanced treatment unit was still needed (this will be The acute toxicity and genotoxicity are used to evaluate the OMPs
discussed in detail in 3.1.1). The pilot-scale advanced treatment unit reduction. The tests of acute toxicity used in this study are luminescence
was built to investigate the combination of the MOHA-A and O-MFDF- assay (Photobacterium phosphoreum T3 spp.), 72 h algal (FACHB-271
CO process. The commercial catalyst (Cathay Chemical (Dalian) Co., Selenastrum capricornutum) growth inhibition assay, 48 h mobility of
Ltd.) was used in the experiment and full-scale application (Table S3). Daphnia magna inhibition assay and 48 h zebrafish (Brachydanio rerio)
The experiments lasted about 7 months. To investigate the effect of SS eggs assay. In addition, the genotoxicity assay (Salmonella typhimurium
on CO process, the batch experiments were carried out (SI). The photos TA1535/pSK1002) was also conducted. The measurement process was
of the pilot-scale reactors are shown in the Fig. S3. carried out according to the ISO standard toxicity measurement proto-
cols (ISO 6341, 1982; ISO 11384, 1994; ISO 13829, 2000; ISO 9692,
2.3. Analytic items and methods 2004; ISO 15088, 2007) by a CMA testing organization. The concentra-
tion for EC50 and the LID are used as the parameters to evaluate the tox-
2.3.1. Wastewater samples icity of the wastewater (Wu et al., 2016a, 2016b).
Normally, the wastewater samples were taken once a day from the
bench- and pilot-scale experimental reactors during the operation. To 2.3.5. Other analysis
evaluate the upgrade of the WWTP, the samples were taken from differ- COD, BOD5, MLSS and other conventional wastewater qualities were
ent tanks of the WWTP once a day before and after the upgrade. The analyzed according to the Standard Methods (APHA, 2005). TN and TOC
sampling lasted for about two years. COD, NH+4 -N, TP and pH were mea- were analyzed by a TOC-VCPH/CPN analyzer (Shimadzu Corporation,
sured every day while the OMPs were measured every 30 d. Toxicity of Japan). Sulfate was measured by ion chromatography using a conduc-
the final effluent was measured twice. Two samples were taken before tivity detector (Dionex ICS-1000, Japan). DO and ORP were monitored
and after the upgrade during the steady state at day 300 and 600 during by a portable meter (WTW 340i, Germany). VFAs were analyzed by ti-
the investigation, respectively. tration method using WTW 340i pH meter (Feitkenhauer et al., 2002).
In addition, the plant operation ledger concerning COD and power con-
2.3.2. OMPs measurement sumption were taken from the WWTP. The floc size of the wastewater
According to our previous study, most of the OMPs in the PCWW are was measured by a particle size analyzer (Malvern Mastersizer 2000).
VOCs and SVOCs (Song et al., 2016). In fact, most of the organics listed in 1 L sample without setting was used for the measurement. Triplicate
the priority pollutant list of US EPA are also VOCs and SVOCs (EPA, measurements were conducted for each sample. The median volumet-
2000a, 2000b). VOCs and SVOCs were the measurement focus of this ric diameter (d50) was used in this study. EPS, LB-EPS and TB-EPS,
study. The VOCs were measured according to the method of EPA 524.2 were measured in the batch ozonation experiment. EPS was extracted
(EPA, 1995). Purge and trap with GC–MS (Agilent 7890/5975, USA) by the heating method described by Li and Yang (2007).
was used. The parameters of the measurement were the same as our
previous study (Wu et al., 2016a, 2016b). The organics identification 3. Results and discussion
was based on the NIST 05 mass spectral library database and organic
standards verification. GC-FID was used to determine the concentration 3.1. Bench- and pilot-scale experiments investigation
of each substance. The SVOCs were measured by dichloromethane
liquid-liquid extraction coupled with GC–MS (Agilent 7890/5975, 3.1.1. Biological treatment processes
USA) (Song et al., 2016). The purge and trap samples were used for ex- To overcome the inhibition of high sulfate to HA process, MOHA,
traction. The concentration factor of wastewater samples was 1000. The achieved by limiting the aeration supply, was investigated and devel-
GC–MS operation and parameters are the same as our previous study oped. The performance and operation parameters optimization of
(Wu et al., 2016a, 2016b). The identification of organics is also based MOHA have been reported in detail in our previous studies (Wang
on the NIST 05 mass spectral library database. According to the match et al., 2013, 2015; Wu et al., 2015a, 2015b; Yang et al., 2015). The
results, organic standards were used further to verify each organic. bench- and pilot-scale experiments showed that the optimized param-
The concentration determination is the same as VOCs by GC-FID. The eters for MOHA were: DO of 0.2 to 0.3 mg/L with ORP of −290 ± 71 mV
standards recovery and detection precision were carried out during and HRT of 12 h. On this condition, the BOD5/COD of influent was ap-
the measurement. The minimum detectable concentration of each com- proximately 0.23, and it could increase to approximately 0.43 while it
ponent ranged from 0.034 to 0.127 mg/L. The standards recovery rates was 0.42 obtained by AHA. The COD removal rate was approximately
were 82.3%–115.7%. The relative standard deviation of each sample 25% while the parallel AHA was lower than 11%. After pretreatment by
was lower than 5.00%. MOHA, the aerobic degradation of the PCWW improved obviously, as
shown in Fig. 1B. The reminded COD was higher than 100 mg/L for influ-
2.3.3. Resin fractionation of DOM ent after 72 h aerobic degradation, while it decreased to lower than
The resin fractionation of DOM was used to investigate the organics 80 mg/L after the treatment of MOHA. The MOHA also benefited the re-
removal of MFDF-OC and the relationship of different units. The waste- moval of toxic OMPs, such as benzene, toluene, ethylbenzene and xy-
water samples (5 L) were filtered through 0.45 μm cellulose acetate lenes, reducing the toxicity and improving the treatability of the
membrane and then adjusted pH to 7.0 before fractionation. Supelite PCWW (Wu et al., 2015a, 2015b). The MOHA has been proved to be
XAD-8 Macroporous Resin (Sigma-Aldrich Co. LLC) was used for frac- suitable for the pretreatment of high sulfate and toxicity PCWW.
tionation. The DOM in the wastewater can be divided into 4 constitu- We found the microaerobic condition could inhibit the reduction of
ents, namely HOA, HOB, HON and HIS (Wang et al., 2007). The pore sulfate during the HA process (Fig. 1A). In addition, the microbial com-
size of the resin is approximately 9 nm with the particle size ranged munity structure shifted with the application of microaerobic condition
from 40 to 60 mesh. The resins were fixed into a column with the (Wu et al., 2015a, 2015b). However, the mechanism is still unclear. For
inner diameter of 1.6 cm and the height of 20 cm. The detailed fraction- example, some previous studies showed that the microaerobic condi-
ation process was the same as the previous studies (Huang and Yeh, tion could not inhibit the activity of SRB. Some typical SRB, such as
1997). The DOC of influent, HOA, HOB and HIS were measured by a Sulfuritalea, Desulfobulbus, Desulfocapsa, Desulfococcus, Desulfofusti and
192 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197

Desulfomicrobium could be detected and enriched in MOHA (Yang et al., 80% of COD could be removed by the A/O unit. The effluent COD is nor-
2015). In addition, the SOB can co-exist with SRB (Okabe et al., 2005) mally lower than 80 mg/L (Fig. S4), which is lower than that before up-
and Celis-Garcia et al. (2008) also found the reduction and oxidation grade (Table S2). This also demonstrates the positive role of MOHA
of sulfate could take place in the same reactor. Klok et al. (2012) pro- compared to AHA process for biological treatment. However, the mea-
posed the metabolic pathways of sulfide oxidation on low DO condition. surement showed that there were still some OMPs in the biological ef-
Sulfide was sequentially oxidized to elemental sulfur and sulfate when fluent (Yang et al., 2015; Wu et al., 2016a). In addition, the effluent
O2/S2− b 1. SOB used coenzyme Q instead of O2 as the electron donor still showed low degree of acute ecotoxicity by luminescent bacteria
to reduce NAD+. Combined with the traditional HA process, the possi- assay (Wu et al., 2016a). Advanced treatment is still needed to develop.
ble metabolic pathways of MOHA treating PCWW is proposed in this
study, as shown in Fig. 2. 3.1.2. Advanced treatment of biological secondary effluent
The key of the MOHA is the proper O2 supply, as shown in Fig. 2. The The biodegradability of the biological secondary effluent is very low.
O2 can promote the circulation of S (reaction ② and ③), reducing the The BOD5/COD of it is approximately 0.06, indicating the main compo-
accumulation of S2− and the production of H2S. The production of nents are refractory organics. According to the wastewater qualities,
H2S: (a) is toxic to microbial metabolism including HA process (Wang we have investigated many advanced treatment processes (Fu et al.,
et al., 2014); (b) is dangerous to the WWTP operators; (c) is harmful 2016; Wu et al., 2016b). Based on the achievements and the previous
to the corrosion of concrete tank (Jiang et al., 2016). The S circulation studies, MFDF (filters are sand with the size of 0.5–1.2 mm) and CO is
provides an electronic transmission channel to promote acidification finally proposed and demonstrated as a suitable option according to
(reaction (2), (3) and (5)). Most of the hydrolysis acidification bacteria the bench- and pilot-scale experiments (Fig. S5). The optimized condi-
are facultative bacteria. They can survive in the anaerobic or aerobic tions were: coagulant PAFC, dosage 5–10 mg/L as product concentra-
condition (Zhang et al., 2012). However, excessive O2 will also consume tion, filtration speed 7 m/h, O3 dosage 30–40 mg/L, oxidization time
the new produced organic acids, resulting in the decrease of accumu- 1 h. More than 77% of SS could be removed in the MFDF and the final ef-
lated organic acids (reaction ④). We also found the BOD5/COD de- fluent SS was lower than 10 mg/L. The SS in the biological secondary ef-
creased when the DO was over 0.4 mg/L (Wang et al., 2013). fluent could adversely affect the CO process. According to the
The MOHA effluent was treated by A/O. A/O process is used as one of experimental statistics, the O3 consumption for removing per g COD in-
the most options in the biological wastewater treatment. In China, N1.5 creased with the increase of SS in the wastewater (Fig. 3). This is be-
× 107 m3/d wastewater is treated by A/O (Wu et al., 2016a). The bench- cause the biological flocs in the wastewater can react with O3 (Zucker
and pilot-scale experiments demonstrated that the optimized condi- et al., 2015), thereby increase the invalid O3 consumption. The high re-
tions were: sludge recycle ratio 100%, HRT approximately 20 h, SRT ap- moval of SS from the biological secondary effluent is essential for the CO
proximately 20 d, and DO 2.0–3.0 mg/L (Wu et al., 2016a). More than unit.
To furtherly investigate the adverse effect, the batch experiment was
carried out by the O3 dosage varying from 10 to 40 mg/L. Overall, the
concentration (Fig. S6) and particle size (d50) (Fig. 4A) decreased with
the increase of O3 dosage. This is because the flocs can react with O3.
This is consistent with previous study (Zucker et al., 2015). And
Zucker et al. (2015) has proved that particle formation/aggregation
and particle disintegration occurs simultaneously during wastewater
ozonation. Unexpectedly, the particle size almost was unchanged
when the O3 dosage was lower than 10 mg/L. It can be speculated that
the DOC in the bulking solution has higher reaction coefficient than
flocs, therefore, most of the dissolved O3 exhausted by DOC. Low

Fig. 1. The performance of pilot-scale MOHA experiment (n = 180 for A and n = 3 for B). Fig. 2. The possible metabolic pathways of MOHA treating petrochemical wastewater.
 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197 193

residual O3 cannot break the structure of the flocs and it also cannot de-
crease the SS concentration. However, it can change the ratio of LB- and
TB-EPS, as shown in Fig. 4B. The TB-EPS is firstly converted into LB-EPS,
and then LB-EPS is oxidized by CO process with the increase of O3 dos-
age. This can decrease the flocs size and the SS concentration, as demon-
strated by the experimental data.
The MFDF has another important role for the pretreatment of CO
process as reported by our previous study (Wu et al., 2017). Most of
the removed organics by MFDF are macromolecular organics (molecu-
lar weight higher than 3 k) with strong hydrophobicity, such as HOA
and HON, which are relatively difficult to be oxidized by CO process.
So the MFDF and catalytic ozonation are coupled in the removal of or-
ganics. The final effluent COD was lower than 50 mg/L (Fig. S5B) and
most of the influent OMPs cannot be detected in the effluent
(Table S4). Though the main active component of the catalyst is Cu,
the effluent Cu2+ is always lower than 0.03 mg/L, which can meet the
new standard.

3.2. Full-scale application, OMPs and toxicity reduction

Based on the research results of different units, the upgrade pro-

cesses were finally determined. The order of the main processing units
is as follows: MOHA → A/O → MFDF → CO. The positive results from
both the bench- and pilot-scale experiments led to the approval and up-
grade of the petrochemical WWTP. The whole upgrade, consisting of
modification of AHA to MOHA (gas to water ratio of 0.25–0.5:1) and
new construction of MFDF and CO tanks (the fill rate of catalyst is ap-
proximately 75%), was finished after 8 months (Fig. 5; Fig. S7).
The modification of MOHA is a challenge to design consideration be-
cause it is very difficult to maintain the low DO and good mixture of
sludge to wastewater in such large plug flow tanks (100,000 m3). To
overcome the conflict, aeration and mechanical mixing devices are in-
terval placed (Fig. S8). Then the mathematical model (Modeling by
Gambit 2.4 and calculated by Fluent 6.3) was used to simulate the
sludge mixture and the sedimentation of the MOHA tank (Fig. S9). The
aeration intensity, angle and depth of mechanical mixing devices were
optimized before modification. The mathematical simulation will not
be discussed in detail here. Finally, the air to water ratio of 0.25:1 was
applied in the MOHA tank. To prevent VOC pollution, the MOHA tanks Fig. 4. The effect of ozonation on the floc size and EPS.
are covered with gas collection and biological oxidation treatment sys-
tems which can remove N97% of off-gas VOC.
The average effluent COD before upgrade was 84.7 ± 20.9 mg/L.
10.1 mg/L during the steady period and it can meet the new standard
When it was upgraded, the average effluent COD decreased to 47.0 ±
of GB 31571-2015 (Fig. 6). The integrated process has strong ability
withstanding shock loadings, as shown in Fig. 6. When the influent
COD suddenly increased to as high as 1800 mg/L, the final effluent
was still near to 60 mg/L. The COD reduction of the upgraded WWTP
is over 1400 t/y. It is noteworthy that the start-up and shut-down of
the different operational plants in the park can cause the fluctuation
of influent qualities, thereby affect the effluent qualities. To guarantee
the final effluent qualities, pretreatment of some high toxic wastewaters
in the park, such as trimethylolpropane, acetaldehyde and 2-butenal
wastewaters, are recommended. In addition, it is needed to increase
the ozone dosage of catalytic ozonation unit if the biological effluent
COD increases. According to the operation experience, the increased
ozone can be determined by the ratio of 1.5 g O3/g increased COD.
The aim of the upgrade is to reduce the OMPs. The OMPs removal of
the petrochemical WWTP before and after the upgrade is summarized
in Table 1. The upgrade of WWTP had significant improvement in the
OMPs removal. More than 10 types of OMPs could not be detected
after upgrade. 30 types of OMPs had the removal rate higher than 90%.
After upgrade, the highest concentration of OMPs in the effluent was
lower than 30 μg/L, and the annual reduction of OMPs was up to
95.5 t/y. The OMPs concentration in the effluent can meet the new Emis-
sion Standard of Pollutants for Petroleum Chemistry Industry (GB
Fig. 3. The effect of SS on the consumption of O3 for COD removal. 31571-2015) after upgrade.
194 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197

Fig. 5. Panoramic view of the upgraded petrochemical WWTP.

The acute toxicity and genotoxicity of the effluent are shown in 3.3. Energy distribution and carbon emissions analysis
Table 2. It can be seen that the biological effluent shows acute
ecotoxicity (luminescent bacteria assay). It can be classified as moder- It is known that processes eliminating OMPs would increase energy
ately toxic level II because its value is lower than 75% (Bulich and demand during which power is the major source of carbon emissions in
Isenberg, 1981). However, all the indexes are lower than the values pro- WWTP (Mousel et al., 2017). There are direct and indirect carbon emis-
posed by FMENCUS (2004) for chemical industrial effluent. When the sions in WWTP (Wang et al., 2016). The COD reduction per year after
upgrade was applied, the toxicity of the effluent reduced furtherly, as the upgrade is 1400 t. According to the theory calculation, the direct
shown in Table 2. The EC50 for luminescent bacteria assay decreased CO2 production due to the organic pollutants oxidation is appropriate
from 68.01% to higher than 100% and the IR for genotoxicity decreased 1925 t/y. The increased electricity use, which is mainly from the ozone
from 1.50 to 0.76. LID is the dilution factor for the maximum concentra- generator, is 0.30 kW·h/m3 with the increased rate of 44.1% (Fig. 7).
tion group where no inhibition is observed. The higher the LID is, the The electricity used for organic pollutants (in terms of COD) removal
higher the toxicity is for the wastewater (ISO 11348, 1998). The LID in MOHA, A/O and MFDF-CO are 0.09, 1.20 and 9.38 kW·h/kg COD, indi-
for luminescent bacteria decreased from 3 to 1 with upgrade applied. cating that more and more energy is needed in the next level of process
In Federal Ministry for the Environment (FMENCUS, 2004), the LID for for the removal of organic pollutants. The energy demand for the OMPs
luminescent bacteria and algal inhibition of chemical industrial effluent elimination is very huge. The added power consumption is 1.314
are 32 and 16. To fully evaluate the OMPs and toxicity reduction, the × 107 kW·h/y in the upgraded WWTP. According to the previous stud-
chronic and accumulative toxicity are more recommended than acute ies, the CO2 emission factor is 1.17 kg CO2e/kW·h (Wang et al., 2016).
toxicity.

Fig. 6. The COD variations of influent and effluent before and after upgrade.
 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197 195

Table 1
The main OMPs detected in the effluent before and after the upgrade of the petrochemical WWTP (two years data, measure times n = 24, interval = 30 d).

No. OMPs name CAS No. Before upgrade (μg/L) After upgrade (μg/L)

1 1,3-Dioxolane 646-06-0 11.30 ± 3.04 0.23 ± 0.20

2 Trichloromethaneb 67-66-3 25.90 ± 2.94 0.11 ± 0.09
3 1,2-Dichloro-ethaneb 107-06-2 11.31 ± 4.03 0.05 ± 0.04
4 3-Methyl-2-butanone 563-80-4 244.5 ± 35.1 1.24 ± 1.02
5 2,3-Butanedione 431-03-8 428.1 ± 90.3 2.38 ± 0.98
6 Benzeneb 71-43-2 5.12 ± 1.61 NDa
7 3-Methyl-2-Butenal 107-86-8 19.52 ± 4.78 0.14 ± 0.07
8 2-Ethylacrolein 922-63-4 12.41 ± 2.94 0.06 ± 0.04
9 2,2′-Azobis[2-methyl]-propanenitrile 78-67-1 25.66 ± 8.65 0.23 ± 0.16
10 2-Pentanone 107-87-9 11.33 ± 3.04 2.35 ± 1.78
11 1-Chloro-3-methyl-2-butene 503-60-6 3.12 ± 0.97 ND
12 1,4-Dioxane 123-91-1 15.57 ± 2.50 0.05 ± 0.04
13 Methyl isobutyl ketone 108-10-1 75.36 ± 50.38 0.11 ± 0.06
14 2-Methyl-(E)-2-butenal 497-03-0 22.15 ± 3.10 ND
15 Tolueneb 108-88-3 9.94 ± 2.40 ND
16 1,3,5-Cycloheptatriene 544-25-2 5.18 ± 1.61 ND
17 2-Chloro-2-methyl-butane 594-36-5 11.34 ± 3.07 0.03 ± 0.02
18 Paraldehyde 123-63-7 70.83 ± 15.67 0.09 ± 0.07
19 2-Hexanol 626-93-7 2.71 ± 0.91 1.23 ± 1.02
20 1H-Pyrazole 288-13-1 10.27 ± 3.22 0.12 ± 0.08
21 4-Hydroxy-4-methyl-2-pentanone 123-42-2 11.45 ± 3.59 0.25 ± 0.22
22 Chloro-benzeneb 108-90-7 6.06 ± 1.18 1.01 ± 0.99
23 2-(Chloromethyl)-1,3-dioxolane 2568-30-1 362.7 ± 94.22 12.03 ± 7.89
24 1,2-Dichloro-, trans-cyclopentane 14376-81-9 24.72 ± 6.98 ND
25 3-Pyridinecarbonitrile 100-54-9 4.85 ± 1.56 ND
26 Tetramethylbutanedinitrile 3333-52-6 112.9 ± 12.32 28.03 ± 10.68
27 N,N-Dimethyl-benzenemethanamine 103-83-3 8.14 ± 2.57 0.12 ± 0.05
28 Acetophenone 98-86-2 7.67 ± 1.35 0.05 ± 0.04
29 Ethyl ester 2,4-hexadienoic acid 2396-84-1 22.24 ± 5.76 7.73 ± 2.39
30 Triethyl phosphate 78-40-0 7.23 ± 1.29 ND
31 2,5-Bis(1,1-dimethylethyl)-phenol 5875-45-6 37.83 ± 5.59 0.17 ± 0.12
32 2,4-Bis(1,1-dimethylethyl)-phenol 96-76-4 56.09 ± 6.42 0.45 ± 0.34
33 Butylated hydroxytoluene 128-37-0 3.97 ± 1.26 2.19 ± 1.27
34 Diethyl phthalate 84-66-2 4.65 ± 1.47 ND
35 6-Chloro-N-ethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4-diamine 1912-24-9 5.74 ± 0.93 0.19 ± 0.13
36 Propazine 139-40-2 30.43 ± 14.78 1.82 ± 1.26
37 Terbuthylazine 5915-41-3 8.46 ± 3.86 0.25 ± 0.21
38 Ipazine 1912-25-0 30.45 ± 8.33 2.34 ± 1.22
39 1,2,3,4,5,6,7,8-Octahydro-acridine 1658-08-8 9.57 ± 3.00 0.78 ± 0.43
40 Bis(2-methylpropyl) ester-1,2-benzenedicarboxylic acid 84-69-5 0.43 ± 0.12 ND
41 2-Chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide 34256-82-1 7.18 ± 1.79 0.33 ± 0.22
42 1,2-Benzenediacetonitrile 613-73-0 398.5 ± 103.6 17.56 ± 10.33
43 Hexadecane 544-76-3 0.24 ± 0.06 ND
44 2-Ethyl-9,10-anthracenedione 84-51-5 5.57 ± 1.16 0.23 ± 0.12
45 Heptadecane 629-78-7 3.68 ± 1.14 ND
46 (Z)-9-octadecenamide 301-02-0 27.94 ± 8.89 3.56 ± 1.79
47 Tetracosane 646-31-1 6.88 ± 2.14 0.66 ± 0.53
48 Eicosane 112-95-8 11.34 ± 3.04 0.21 ± 0.11
49 Octadecane 593-45-3 16.34 ± 5.06 0.27 ± 0.15
a
ND means not detected.
b
Listed in new standard GB 31571-2015.

Therefore, the indirect CO2 emission due to the increased electricity significant carbon emission. Does the strict OMPs controlling protect
consumption is about 15,374 t/y as N75% electricity is generated by the water environment or deteriorate the whole environment? It
coal in China. The data calculation process can be checked in the carbon needs deep thinking for every one of us. Not just in China, but in the
emission calculation (SI). Obviously, the reduction of OMPs can lead to whole world because controlling emissions of OMPs from WWTP by

Table 2
The toxicity of the effluent before and after the upgrade.

Index Before upgrade After upgrade

Luminescent Algal Daphnia Zebrafish Genotoxicity Luminescent Algal Daphnia Zebrafish Genotoxicity
bacteria (Selenastrum magna eggs (umu) bacteria (Selenastrum magna eggs (umu)
(Photobacterium capricornutum) inhibition (Brachydanio (Photobacterium capricornutum) inhibition (Brachydanio
phosphoreum T3 growth test (48 rerio) test phosphoreum T3 growth test (48 rerio) test
spp.) assay inhibition (72 h) (48 h) spp.) assay inhibition (72 h) (48 h)
h) h)

EC50 (%) 68.01 N100 N100 N100 – N100 N100 N100 N100 –
LID 3 3 1 1 – 1 3 1 1 –
Induction – – – – 1.50 – – – – 0.76
rate (IR, %)

– Not measured or calculated.

196 C. Wu et al. / Science of the Total Environment 633 (2018) 189–197

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