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Application of the combined ultrafiltration and reverse osmosis for refinery

wastewater reuse in Sinopec Yanshan Plant

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DOI: 10.5004/dwt.2011.1137

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 Desalination and Water Treatment 25 (2011) 133–142
January
www.deswater.com
1944-3994 / 1944-3986 © 2011 Desalination Publications. All rights reserved.
doi: 10.5004/dwt.2011.1137

Application of the combined ultrafiltration and reverse osmosis

for refinery wastewater reuse in Sinopec Yanshan Plant

Daxin Wanga*, Flora Tonga, Peter Aertsb

a
F8 Xueyuan International Tower, 1 Zhichun Road Haidian District, Beijing, 10083, China
The Dow Chemical (China) Company Limited, 24/F Aurora Plaza, 99 Fu Cheng Road , Shanghai 200120, China
Tel. +86 (21) 38511671; Fax +86 (21) 58954597; email: [email protected]
The Dow Chemical Company, DOW Water Solutions, Larkin Laboratory 120-3, 1691 N Swede Rd., Midland, MI 48674, USA
b

Received 16 January 2009: Accepted in revised form 29 June 2010

ab s t r ac t
The refinery wastewater reuse system of Sinopec Yanshan Plant in Beijing (China) has been in
operation for more than four years. The water reuse system combines biological treatment, media
filtration with a combination of ultrafiltration (UF) and reverse osmosis (RO). After more than
30 times of chemical cleaning, the current RO system salt rejection is still above 97% at 80% system
recovery. The normalized permeate flow of the three RO trains vary with the operation time but
after chemical cleaning, they recover to above the design flow of 100 m3/h. The data presented in this
study indicate the fouling nature of the RO feed water on the 1st stage RO. However, according to
the experience of Sinopec Yanshan Plant the output water quality meets the customer requirements.
This is one of the first publications which show that the combination of UF and RO technology can
be applied to reuse the refinery wastewater. The TOC rejection of the UF process is determined at
34%, which is highly dependent on the molecular weight of the organics. Low molecular weight
organics could pass the UF unit and foul the RO membrane surface, causing serious organic foul-
ing. Furthermore, the periodic pressure drop increase of the 1st stage RO system showed that there
was serious bio-fouling. Therefore, addition of other pretreatment technology before UF, such as
activated carbon cartridge filter and dosing non-oxidized biocides, are proposed alternatives that
could help to increase the life-span of UF and RO elements.
Keywords: Refinery wastewater; Water reuse; Membranes; Ultrafiltration; Reverse osmosis

1. Introduction mand) discharge volume in industrial wastewater was

5.4 million tons and the ammonia discharge volume was
The industrial growth in China over the last 15 years
425 thousand tons. The top five industries with the largest
has dramatically increased the discharge volumes of
discharge volume are pulp and paper, chemical, power,
wastewater from all industrial sectors. According to the
textile and metallurgy. The chemical manufacturing
China Environmental Statistic Report, in 2006 the total
industry mainly involves refineries and petrochemical
discharge volume of the industrial wastewater in China
industries.
was 24 billion tons [1]. The COD (chemical oxygen de-
The Chinese government is imposing increasingly
stringent restrictions to encourage industries to treat
* Corresponding author. and reuse their wastewaters. However, refinery and
134 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142

petrochemical wastewater is very complex and contains (polyaluminium chloride) and PAM (polyacrylamide),
both high levels of TOCs (total organic compounds) and respectively. SDI of the UF permeate was less than 3 and
TDS (total dissolved solids) and many kinds of soluble oil was less than 1 mg/L.
organic compounds, most of which are non-biodegrad- MBR (membrane bioreactor) technology has been
able. Therefore the reuse of refinery and petrochemical tested recently on a laboratory scale for re-use potential
wastewater is quite limited. Wastewater in the refinery of refinery wastewater. Hu [7] compared the removal
and petrochemical industries is currently treated by an efficiency of MBR and UF for turbidity, COD and SDI
ASP (active sludge process) using an oil/water separator of a petrochemical waste stream. The pilot test showed
as pretreatment. There are limited studies (both pilot that the permeate water quality of MBR and UF can both
and full scale) on the treatment and reuse of refinery and meet the feed water requirement of RO system (turbidity
petrochemical wastewater using advanced technology. < 1 NTU, SDI < 5, COD best < 10 mg/L for surface water,
Nevertheless, innovative technologies such as membrane COD tolerable < 40 mg/L for wastewater). The average
technology and more advanced degradation techniques level of COD, SDI and turbidity of the UF effluent were
like photo-catalytic degradation and advanced oxida- 22 mg/L, 2.5 and 0.18 NTU, respectively, while those of
tion process are required to comply with the tightening the MBR effluent were 20 mg/L, 2.2 and 0.14 NTU. Stabil-
wastewater discharge and water reuse regulations. ity of the turbidity and SDI of MBR effluent was better
In China, membrane technologies, including MF than that of the UF effluent and the authors concluded
(microfiltration), UF (ultrafiltration), NF (nanofiltration) that MBR can withstand much higher COD fluctuation
and RO (reverse osmosis), have been widely applied in compared to UF. In another bench scale study, an anoxic/
water treatment and wastewater reuse for power and aerobic concept MBR was tested under different condi-
metallurgy industry [2,3]. In refinery and petrochemical tions by Qi et al. [8]. The results showed the feasibility
industry, membrane technology is not widely applied to treat the refinery wastewater using MBR technology.
yet, with only few recent and successful cases in China. The sustainable membrane flux and applicable HRT (hy-
This paper, presents the oldest case history of refinery draulic retention time) of the process were obtained. The
wastewater reuse in China (Sinopec Yanshan Plant, treated water quality consistently met the requirements
Beijing) which has been operating for more than four for discharge while segregation of the streams with high
years. An overview of the operation and the performance TDS was required to reclaim the water for reuse. COD in
of the ultrafiltration and RO elements are discussed. the product was consistently less than 100 mg/L although
feed COD fluctuated from 700 to 2000 mg/L. This level
of COD removal efficiency (more that 93%) was also
2. Backgroud reported elsewhere [9] using cross-flow MBR to treat
2.1. Literature wastewater discharged by a petroleum refinery plant.
In the recent study of Viero et al. [10] it was proved that
Recently, some bench scale studies have been per- the membrane had a key role in the MBR process, since
formed with UF membrane systems to treat wastewater it improved COD and TOCs removal efficiencies by 17
contaminated by organic compounds from refinery or and 20%, respectively, in comparison with the results
petrochemical industries. UF and MF processes are be- obtained by the biological treatment only.
ing used as an alternative or as an additional step to the Since polymer membranes are sensitive to both polar
conventional clarification and filtration methods. and chlorinated solvents, as well as high oil fractions,
A laboratory scale study was conducted by Zhang et ceramic membranes are expected to have a wider ap-
al. [4] to investigate the effectiveness of UF technology plication range to treat refinery wastewater. Zhong et al.
for treatment of refinery wastewater using powdered ac- [11] reported that ceramic membranes, particularly the
tivated carbons and coagulant. Flux decline, cleanability zirconia membranes, show better separation performance
by backwashing and removal rates of TOCs were studied. such as higher flux, less fouling and higher oil rejection.
In this study, the removal rate of TOCs was reported at
more than 99%. Fang [5] applied the combined MMF
2.2 Case history of refinery and petrochemical wastewater
(multi-media filters) and UF technology to treat refinery
reuse in China
wastewater. COD rejection was about 50–70% and COD
of the UF permeate water was less than 32 mg/L. Both the In recent years, several refinery and petrochemical
turbidity and SDI (silt density index) of the UF permeate companies have begun to reuse their wastewater through
water met the pretreatment requirements and limits for a combined UF and RO membrane process. The wastewa-
RO feed water quality (Turbidity < 1 NTU, SDI < 5). Li ter reuse system of Sinopec Yanshan Plant, which is the
[6] applied a combined UF and RO membrane system earliest one (started operation in November 2004) and still
to reuse the petrochemical wastewater. The pretreat- the biggest, has been operating for more than four years.
ment before UF was contact oxidization and coagulation Table 1 [12–15] presents a list of the major petrochemical
settlement, and the coagulant and flocculant were PAC wastewater treatment projects (both discharge and reuse)
 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142 135

Table 1
Major refinery and petrochemical wastewater treatment projects applying membrane technology (MBR, UF and RO/NF)

Company name Capacity Treatment process Commission Reference

(m3/h) date
Kelamayi 170 Refinery wastewater + flotation + BAC + NF Jun. 2004 [13]
Yanshan 800 Petrochemical wastewater + pretreatment + disinfection + UF + RO Aug. 2004 [14]
Yanshan 410 Refinery wastewater + BAF + coagulation settlement + UF + RO Oct. 2004 [12]
Daqing 500 Refinery and petrochemical wastewater + coagulation + cartridge Oct. 2005 [14]
filter + UF + oxidization + ACF + RO
Jingmen 200 Petrochemical wastewater + BAF + MMF + UF 2006 [15]
Haerbin 130 Refinery wastewater + coagulation + sand filtration + MF + ACF + RO Mar. 2006 [14]
Qilu 150 Petrochemical wastewater + UF + RO Jun. 2006 [14]
Dagang 320 Refinery wastewater + BAC + UF + RO Nov. 2006 [14]
Jinan 230 Refinery wastewater + fiber filtration + BAC + electric flocculation + Dec. 2006 [14]
MMF + UF + RO
Jinzhou 600 Refinery wastewater + flotation + oxidization + BAC + UF + RO Jul. 2007 [14]
Dushanzi 200 Petrochemical wastewater + BAF + MMF + UF + RO Dec. 2007 [14]

which applied membrane technology in China. The earli- water which originates from the refinery process is treated
est adaptor to use UF and RO technology was Sinopec by a BAF (biological aerated filter) and coagulation settle-
Yanshan Plant in 2004. For reuse needs of wastewater, ment followed by chlorine treatment. Additionally, this
the combined UF and RO technology has been applied in water is treated by fibrous filtration (multimedia filter)
many cases. BAF (biological aerated filter) and MMF are and ACF (active carbon filter) to remove soluble organics
applied as the pretreatment of UF to protect both the UF prior to filtration with advanced filtration technologies
and RO systems. BAC (biological active carbon) and ACF for water reuse.
(active carbon filter) are also applied to remove organics The integrated membrane solution for this water
in the treatment process. reuse opportunity is a combination of outside-in pressur-
ized hollow fiber ultrafiltration (DOW UltrafiltrationTM
SFP2660) and spiral wound fouling resistant brackish
3. Wastewater reuse system design of Sinopec Yanshan
water membranes (Dow FILMTEC TM BW30-365 FR)
Plant
(Fig. 2). The characteristics of both products are presented
The wastewater reuse system in Sinopec Yanshan in Table 2. In total 600 UF elements are used with a total
Plant is presented in Figs. 1 and 2. Fig. 1 shows the process capacity of 560 m3/h. One train capacity of UF system is
flow of the refinery wastewater reuse system. The waste- 56 m3/h. Fouling resistant RO membranes are used in the

Fig. 1. Flowchart of the refinery wastewater reuse process.

136 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142

Table 2
Characteristics of SFP2660 and BW30-365 FR

DOW UltrafiltrationTM SFP2660 FILMTECTM RO BW30-365 FR

Base polymer PVDF Membrane type Polyamide (FTC)
Module surface area, m2 33 (355 ft2) Nominal active surface area, m2 34 (365 ft2)
Filtrate flux @ 25°C, lmh 40–120 Permeate flow rate, m3/h 860 (9500 gpd)
Diameter, cm 16.5 (6.5 inch) Feed spacer thickness, mm 0.864 (34 mil)
Nominal pore diameter, μm 0.3 Stabilized salt rejection, % 99.5

Table 3
UF and RO systems summary

Module model UF RO
Capacity, m /h
3
560 309
Number of skids 10 (8R/2S) 3
Number of modules per skid 60 138
Total number of modules 600 414
Capacity per skid, m3/h 70 103
Recovery >95% 80%
Design flux, l/m2h 37.2 22

Fig. 2. RO and UF system.

Table 4
Feed water quality of the refinery wastewater reuse system [12]
three RO trains with 270 elements in the first stage and pH 7.0~8.4
144 elements in the second stage. The capacity of one CODCr, mg/L 20–50
train of the RO system is 103 m3/h. A summary of the UF
NH3-N, mg/L 0–10
and RO systems is shown in Table 3. The UF permeate
TDS, mg/L 900–1400
water is pumped directly into the RO system by high
Hardness, mg/L 300–500
pressure pump after dosing scaling inhibitors (Flocon
Plus, BWATM), reducing agents (NaHSO3) and biocides Ca2+, mg/L 200–360
(Flocide 380, BWATM). Alkalinity, mg/L 50–150
Table 4 shows the feed water quality of the refinery Conductivity, us/cm 1400–1900
wastewater reuse system, which is the secondary effluent T, °C 25–38
of refinery wastewater [12]. The main characteristics are Turbidity, NTU 1–6
the high level of COD and the presence of some oil. The Cl–, mg/L 150–400
rejection of UF to COD is relatively low, thus the main SO42–, mg/L 150–360
problem of RO may be bio-fouling and organic fouling. Silica, mg/L 8–11
Oil, mg/L 0–1.2
4. Results and discussion Bacteria, unit 103–105
Total Fe, mg/L 0.5
4.1. UF system performance
The UF elements that are used can withstand a high
concentration of oxidants (max. 5000 ppm NaClO, nor- then air scoured with forward flush every 6 h for 60 s.
mal 2000 ppm NaClO cleaning) which is ideal to control No chemically enhanced backwash (CEB) or chlorine
bacteria growth [16]. The outside-in hollow fiber design was dosed during the backwash operation. Clean in
enables demanding cleaning conditions like high turbu- place (CIP) (0.2% NaClO at pH 12, 0.5% oxalic acid) was
lent air scouring. Table 5 shows the UF system operation performed every 2–5 months to remove the foulants from
process. The UF units were backwashed every 30 min for the fiber surface thoroughly. The UF system was operated
60 s, and air scoured with backwash every 6 h for 60 s, at a water recovery of 92–95%.
 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142 137

Table 5
UF system operation process

Serial No. Contents Frequency Duration Chemical consumption

1 Filtration 30 min
2 Upstream backwash After every filtration 30 s None
3 Downstream backwash After upstream backwash 30 s
4* Air scour with backwash 6h 60 s 768 Nm3/d
5* Air scour with forward flush 6h 60 s
6* Forward flush After backwash 30 s
7 CEB None None None
8 CIP 2–5 months 8h Acid: 0.5% oxalic
Alkaline: 0.2% NaClO at pH 12
* Repeat 4-5-6 several times per 12 h operation.

The UF units are used as a pretreatment to protect 4.2. RO system performance

the RO elements from suspended solids, colloids and
some large molecular weight organics. The SDI of the UF Fig. 4 shows the operation performance of the three
permeate was always below 3 (SDI unit). The turbidities RO trains in the refinery wastewater treatment plant in
of UF feed and permeate water are about 5 and 0.3 NTU recent four months, including feed pressure, permeate
respectively. Fig. 3 shows the trans-membrane pressure flow, and salt passage system. The system recoveries of
(TMP) and permeate flow of the UF units in 10 months. the three trains were all stable at 80%. The feed pressure
The average TMP was around 0.6 bar, which indicated increased with operation time but could be recovered
that the UF fouling was well managed. This UF system after chemical cleaning as is shown in Fig. 4. The permeate
has had 5 CIPs in the reported period, as indicated by flows of the three trains were all kept at about 100 m3/h.
the arrows in Fig. 3. In these 10 months of operation, The salt passages of three trains were very low and less
the highest TMP was about 1.6 bar and far away from than 3%.
the design limit of 2.5 bar [16]. The permeate flow was The operation data can only reflect the observed per-
around 60 m3/h, which is slightly higher than the design formance of the current RO systems, thus performance
flow 56 m3/h. normalization was also done to show any performance

Fig. 3. Trans-membrane pressure and permeate flow of the UF units. The arrow (↓) indicates a chemical cleaning.
138 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142

Fig. 4. Feed pressure, permeate flow, and salt passage of the three RO trains vs. operation time.

changes between day one and the actual date. Normaliza- varied with the operation time. After chemical cleaning,
tion is a comparison of the actual performance to a given they could be recovered to above 100 m3/h.
reference performance while the influences of operating Fig. 6 shows the pressure drop of the RO train C
parameters are taken into account (feedwater composi- changing with the operation time. The data show that the
tion, feed pressure, temperature and recovery). The refer- pressure drop of the 1st stage increased with the operation
ence performance may be the designed performance or time from 2 bar to 5 bar, then dropped back to 2 bar after
the measured initial performance. In this case, normaliza- chemical cleaning. The arrows in Fig. 6 indicate the time
tion was done on the basis of the system performance on of each chemical cleaning and show a cleaning frequency
the start-up date. Fig. 5 shows the normalized salt pas- of once per month. This indicates a serious fouling con-
sage of one of the RO trains. As shown in the figures, the cern in the 1st stage of the RO system. After the chemical
normalized salt passages were close to 1.5% and all less cleaning though, the pressure drop of stage one decreased
than 2%, and also shown a little bit increase over time. to the original level of 2 bar and the permeate flow also
The normalized permeate flows of the three RO trains increased. The pressure drop of the 2nd stage was about
 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142 139

Fig. 5. Normalized salt passage of RO A vs. operation time.

Table 6
UF Feed water, UF and RO permeate quality of the refinery
wastewater reuse system

Items Feed water UF permeate RO permeate

pH 7.42 7.39 5.99
HCO3–, mg/L 102.4 114 2.2
NO3–, mg/L 56 51 3.4
SO42–, mg/L 359 353 1.2
Cl–, mg/L 221.17 222.56 5.9
Ca2+, mg/L 146.7 156.5 1.0
Mg2+, mg/L 41.1 43.0 0.2
K+, mg/L 5.94 6.12 0.3
Na+, mg/L 168.8 176.6 5.4
Fig. 6. Pressure drops of RO train C vs. operation time. TOC, mg/L 10.63 7.00 1.1
TDS, mg/L 1197 1232 24

0.5–1.5 bar which was lower and much more stable than
that of the 1st stage.
the RO manufacturer to evaluate the fouling status of
4.3. Permeate water quality the RO system. The EPAS (element performance analysis
service) test of these two elements were done with the
Table 6 shows the UF feed water quality and the UF
standard test condition: 2000 ppm NaCl as test solution, at
and RO permeate water quality in one sampling process
225 psig (15.3 bar) operation pressure, 77°F (25°C), pH 8,
in 2009. The data shows that the rejection to TOC of UF
and 15% recovery. The results showed that the flow rates
membrane is about 34% and RO has about 84% rejection
of the two fouled elements were almost 30% lower than
to TOC. The salt rejection of RO is about 98% as shown
the standard flow rate and the pressure drops of a single
previously. For different ions, the lowest anion rejection is
element were also close to the limited condition (1 bar
nitrate which is about 93% and the lowest cation rejection
for single element), which indicated a serious blocking
is potassium which is about 95%. After more than four
of the feed channel. The first element in the first stage
years operation, the salt rejection of RO is still good and
showed more severe fouling than the last element in the
the TOC rejection of UF is also acceptable.
second stage, which was consistent with the observation
of the system pressure drops in Fig. 6. In order to have
4.4. RO fouling evaluation and cleaning protocol
more understanding of the membrane fouling, the first
Two elements (the first element in the 1st stage and element in the first stage was cleaned to help find the best
the last element in the 2nd stage) have been sent back to chemical cleaning method, while the last element in the
140 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142

second stage was autopsied to analyze the characteristic the chemical cleaning could only partially remove the fou-
of the foulant. lant attached to the feed-spacer and membrane surface.
More vigorous cleaning might be needed to peel it off.
4.4.1. Cleaning tests
4.4.2. Autopsy inspection and foulant ignition test
In each chemical cleaning, a caustic-acidic-caustic
cycle was performed and the cleaning conditions were Fig. 7 shows the photos of the fouled membrane sur-
described as below: face. It can be seen that the whole membrane leaves were
•• NaOH, pH 12, 35°C. Circulated for 60 min and flushed covered by brown and caramel colored foulant, which
for 30 min. also stuck to the feed spacer screen when the screen was
•• HCl, pH 2, 45°C. Circulated for 30 min and flushed removed from the membrane leaf. The foulant was easy
for 30 min. to smear from the membrane surface but hard to rinse
•• NaOH, pH 13, 35°C. Circulated for 60 min and flushed away by water. The acid and caustic drip tests showed no
for 30 min. reaction or effect to the foulant, which explained the poor
pressure drops decrease during chemical cleaning test.
In the two high pH caustic cleaning, the solutions were The foulant was scrubbed from the membrane and
both caramel colored, while the solution was clean after sent for loss of ignition test. The foulant was first dried
low pH acidic cleaning. The product flow rate increased at 110°C. The test results showed that dry substance
13% overall. The salt rejection was still between 99.35 to was 17.2% of the whole foulant, as shown in Table 7. A
99.43%. The cleaning results showed that high pH caustic number less than 20% typically indicated that the foulant
cleaning can partially remove the foulant from membrane was mainly composed of biofouling. The dry substance
surface and recover the product flow to a certain level, but was then dried at 550°C. This procedure destroys the
not to the initial value; low pH acidic cleaning almost had organic material in the foulant sample. In the test 100%
no effect on foulant removal. Salt rejection was not influ- of the dry substance was proved to be organics. It can be
enced by two high pH caustic cleaning and one low pH concluded that the foulant on the membrane surface was
acidic. However, the pressure drop of the element only bio-fouling and organics.
showed a little bit decrease after cleaning. It indicated that In order to address the issue of organic fouling and

Fig. 7. Photos of the fouled membrane surface.

 D. Wang et al. / Desalination and Water Treatment 25 (2011) 133–142 141

Table 7 of 80%. The normalized permeate flows of the three RO

Loss of ignition test results of the foulant trains vary with the operation time but can be recovered
fully after chemical cleaning, to above 100 m3/h. The pres-
3 samples average sure drop of the 1st stage increases with the operation
Dry substance, % 17.20 time from 2 bar to 5 bar, then drops back to 2 bar after each
Foulant distribution, g/m² 22.39 chemical cleaning. The pressure drop of the 2nd stage is
Inorganics, % 0.00 lower and much more stable than that of the 1st stage,
Inorganics distribution, g/m² 0.00 which is about 0.5–1.5 bar. This observation indicates a
Organics, % 100.00
serious fouling concern in the 1st stage RO.
UF could protect RO elements and remove suspended
Organics distribution, g/m² 22.39
solids, bacteria and colloids effectively. However, TOC
Sample surface area, m² 0.0232
rejection of UF was 34% in the case study presented here.
Other research showed that the COD rejection is highly
dependent on the molecular weight of the organics. The
biofouling, some actions have been taken to prevent rejection data that were obtained in the Sinopec Yanshan
bacteria growth. For example, NaClO was dosed in the Plant are in line with the 0~60% COD rejection observed
UF permeate pipes and keeping a 0.5 ppm free chloride by Wu et al. [17]. For refinery and petrochemical water
in the UF permeate tank. At the same time, nonoxidizing with high organic contaminants, coagulation/floccula-
biocides (such as DBNPA) were also dosed intermittently tion and multimedia filter can remove most of the large
prior to the RO unit. The amount of DBNPA used depends molecular weight organics, while active carbon filter as
on the severity of the biological fouling. 10–30 mg/L of the pretreatment before the UF can adsorb small molecular
active ingredient from 30 min to 3 h every 5 d is minimum weight organics. In the case study presented here, the
for this kind of feed water. Since reducing agents (sodium authors believe that some low molecular weight organ-
bisulfite) were used for chlorine removal, the concentra- ics could pass the UF unit and foul the RO membrane
tion of DBNPA should also be increased by 1 ppm of surface, causing serious organic fouling. For this reason,
active ingredient for every ppm of residual reducing some research institutes suggested to use ACF + UF as
agent in the RO feed water. To remove the dead biofilm, organic removal process [17] to increase the lifetime of
an alkaline cleaning is also recommended. Sometimes, the both the UF and RO elements.
end user applied two kinds of biocides in turn to destruct Furthermore, the periodical pressure drop increase of
the immunity of bacteria to one biocide. the 1st stage RO system strongly suggests that biofouling
The chemical cleaning procedure was adjusted ac- occurs. Element autopsy and foulant analysis further con-
cording to the lab cleaning test results. A caustic-acid- firmed the cause. This can be induced by the secondary
caustic approach was adopted, since caustic cleanings contamination of the pipes or water storage tanks. This
are needed both for organic removal and for dead biofilm problem can be solved by dosing NaClO in the UF perme-
removal. As indicated both by the pressure drop data ate pipes and keeping a 0.5 ppm free chloride in the UF
and membrane autopsy, the 1st RO stage was much more permeate tank. A precaution should be taken to add the
fouled than the 2nd stage, thus NaOH alkaline cleaning appropriate amount of reducing agent (NaHSO3) before
(pH = 12) was first performed in the 1st stage (recycling the RO operation to protect RO membranes from damage
2–4 h, soaking for 10 h). Then, acid cleaning (pH = 2) was by oxidation. Alternatively, non-oxidized biocides could
performed in two stages together to avoid any possible be dosed prior to the RO operation to reduce the bio-
scaling of insoluble salts (recycling 2~4 h, soaking for fouling on the RO elements and increase their life-span.
10 h). Finally, alkaline cleaning (pH = 12) was performed According to the experience of Sinopec Yanshan Plant,
again in two stages together to further clear the residue the combined and integrated use of UF and RO technol-
oragnics/biofilm (recycling 2–4 h, soaking for 10 h). The ogy suits their need to reuse wastewater. The output water
CIP frequency was kept within 1 month, which was ac- quality meets the customer requirements. However, some
ceptable by the end users. operational concerns like organic fouling and bio-fouling
of the RO elements demand the use of more stringent
5. Conclusions or alternative pretreatment of the membrane operation.
The refinery wastewater reuse system of Sinopec Yan-
shan Plant in Beijing has been in operation for more than References
four years. In the beginning, the RO cleaning frequency
[1] China Environmental Statistic Report, 2006, http://www.sdpc.
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Now the cleaning frequency is about once per month. [2] A. Yeung, R. Chu, S. Rosenberg and T. Tong, Integrated mem-
After more than 30 times of chemical cleaning, the current brane operations in difficult waters, commercial case studies
system rejection is still above 97% at a system recovery of UF + RO in China, Water Environment Federation Technical
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Exhibition and Conference (WEFTEC), 2008. Sant’Anna Jr, C.P. Borges and V.M.J. Santiago, The effects of long-
[3] E. Zhao, FR element combined with DBNPA in wastewater term feeding of high organic loading in a submerged membrane
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