Desalination 351 (2014) 213219

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Desalination
journal homepage: www.elsevier.com/locate/desal

Inhibition of scale buildup during produced-water reuse: Optimization of

inhibitors and application in the eld
Gang Li a, Shuhai Guo a,, Jiangwei Zhang a,b, Yu Liu a
a
b

Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, PR China

University of Chinese Academy of Sciences, Beijing 100039, PR China

H I G H L I G H T S
Formation mechanism of bedding scale from produced water is hypothesized and proved.
Anti-corrosion, crude oil dispersing and Ca2 + chelation are essential for scale inhibition.
The compound (PBTCA, HEDP and ATMP) achieves desired effect of scale inhibition.

a r t i c l e

i n f o

Article history:
Received 9 April 2014
Received in revised form 1 August 2014
Accepted 2 August 2014
Available online 15 August 2014
Keywords:
Produced-water
Reuse
Scale buildup
Compound inhibitor
Optimization

a b s t r a c t
Inhibition of scale buildup and optimization of the selected compound inhibitor were investigated during the
recycling and reuse of oileld produced-water. Particular attentions were paid to the factors of scale inhibition,
and the changes of scale phase composition and morphology. The results showed that the addition of Zn2+
ions can effectively inhibit the process of corrosion, and then reduce scale growth. A dispersing agent was required to buffer against the adhesion of crude oil with the precipitates. The compound inhibitor (ratio of
PBTCA, HEDP and ATMP, 2:2:1) achieved a higher efciency of scale inhibition (97.34%) than any of the inhibitors
individually. Moreover, structural anomalies of the crystals also revealed signicant differences in the presence
and absence of the compound inhibitor. The results proved that the pipelines rst corrode, then, mechanical impurities, residual petroleum hydrocarbons and calcium scale gradually attach to the corrosion point to form a dirt
scale layer. After n periods, a bedding black-and-white scale layer forms. During the eld trial, it was found that
dosing the compound inhibitor at 70 ppm results in a 92.46% inhibition efciency (IEs) at 85 C. Therefore, the
compound inhibitor could be applied to prevent the buildup of scale during produced-water reuse.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Oileld produced-water is co-produced during oil extraction, and is
considered to be the largest stream of waste, in terms of volume generated during the processes of petroleum exploration and production. To
reduce the excessive consumption of clean water resources and protect
the water environment, it is necessary to nd an effective way to reuse
these wastewaters, especially in water-scarcity regions. During the process of high pour-point crude oil or heavy oil exploitation, producedwater can be used to transport crude oil after heating in the petroleum
pipeline [1]. The benets of recycling and reusing produced-water include not only a saving of vast quantities of fresh water, but also an absolute recovery of the thermal energy. However, in contrast to fresh
water, produced-water contains abundant organic substrates and inorganic ions, despite processing in the form of oatation and ltration
Corresponding author. Tel./fax: +86 024 83970449.
E-mail address: shuhaiguo@iae.ac.cn (S. Guo).

http://dx.doi.org/10.1016/j.desal.2014.08.003
0011-9164/ 2014 Elsevier B.V. All rights reserved.

treatment before reuse [2]. Generally, the process of reuse leads to

scale accumulation in pipelines and heat-transfer equipment, which
makes the effective inner diameters of pipelines smaller and causes a reduction in the efciency of processing equipment [3,4]. This represents
a signicant threat to safe operation and also leads to huge economic
losses. Thus, the term inhibiting scale in the petroleum industry has
become important, with three types of direct benet recognized:
decreased fresh water consumption, thermal energy recovery, and
cost saving related to periodical pipeline cleaning.
It is interesting that the scale in transmission pipelines of high pourpoint crude oil is different to ordinary calcium carbonate scale or silicate
scale in the case of water-based cooling systems [5]. Fig. 1 shows a section of a high pour-point crude oil pipeline. It can be seen that the scale
is composed of impurities mixed with petroleum hydrocarbon, and bedding is an obvious structural feature. Therefore, based on existing
knowledge, we hypothesize that the process of scale formation occurring in the transmission pipeline at high temperatures (80 C90 C)
might take place as follows: Pitting corrosion of the pipeline steel is

214

G. Li et al. / Desalination 351 (2014) 213219

Fig. 1. Schematic diagram of scale formation in a pipeline during the recycling and reuse of high pour-point oil produced-water.

rst caused by dissolved oxygen, Cl and SO2

4 in the reused producedwater. The coarse and irregular surface of the pipeline as a result of the
corrosion then provides a base for crude oil and suspended particles to
adhere to. Meanwhile, precipitation of dissolving salt naturally occurs
on the surface of the crude oil and impurity mixture, forming a layer
of white salt scale. Finally, over time (n periods in Fig. 1), a blackand-white scale layer forms. Although the mechanisms of mineral
scale formation and inhibition in other cases have been studied previously [6,7], there has been little research aiming at elucidating the
main factors involved in these processes during produced-water reuse
at the higher temperatures in pipelines for the transmission of high
pour-point crude oil.
Many scale inhibitors have been applied successfully in oilelds to
prevent the growth of carbonate and sulfate scale [8]. However, less is
known about scale inhibitors for produced-water reuse of high pourpoint crude oil, especially under high temperature conditions. In fact,
the effect of temperature on calcium carbonate scale formation is always important [911]. When the temperature is higher than 80 C,
the scale inhibition efciencies of many chemical inhibitors decrease.
This is because high temperature water not only accelerates the hydrolysis of the inhibitors, but also promotes the formation of scale. In addition, higher temperatures decrease the solubility of dissolved salts to
promote a rapid upward tendency of scaling. Meanwhile, the abundances of dissolved and suspended solids play important roles during
scale formation in the transmission system. Previous literatures have reported that some inhibitors such as pteroyl-L-glutamic acid [12], maleic
acid-ortho toluidine (MA-OT) copolymer [13] and synthesized anhydride based polymers [14] can signicantly improve the efciency of
scale inhibition. However, they have not been applied to the type of
scale mixed with the impure admixture that forms the focus of the present study. Thus, it is important to develop compound inhibitors suitable
for high temperature produced-water. In this study, the selection of
anti-scaling and corrosion inhibitors was considered not only for the effects of pitting corrosion protection but also for the effects of impurities
dispersion, calcium and magnesium ions chelating at high temperature.
Therefore, zinc salt, dispersant and scale inhibitors with better high
temperature resistance were selected.
The main aim of the current research is to investigate the various factors affecting inhibition of scale buildup during produced-water reuse.
Experiments were designed to test the hypothesized mechanism of
scale formation and identify the optimum compound inhibitor. From
the results, the optimal techniques of scale inhibition would be
employed for the reuse of produced water from high pour-point crude
oil. The study investigates the inuence of Zn2+ ions on the surface of
stainless steel, the effect of dispersing agents on crude oil and
suspended solids, and the performance of the compound inhibitor
under high temperature conditions. The samples of inhibited scale
mass were further characterized through X-ray power diffractometer
(XRD) and scanning electron microscopy (SEM) to investigate the
crystal morphology of the scale. In addition, a eld trial was designed
to verify the effect of the compound inhibitor.

2. Materials and methods

2.1. Materials
The produced-water and scale samples were collected from the 5th
Metering Station, Shenyang oileld, which is the largest production
base of high pour-point oil in world. The properties of produced-water
from high pour-point crude oil are listed in Table 1, and pH of the
water is 8.5. The test scales were obtained from the internal surface of
steel pipes used as the watered transmission pipelines. The analysis results of the scale samples are listed in Table 2. As can be seen, calcium
oxide and loss on ignition (LOI) are the two key parameters.
Zinc sulfate, 1-Hydroxy Ethylidene-1, 1-Diphosphonic Acid
(HEDP), and Amino Trimethylene Phosphonic Acid (ATMP), 2Phosphonobutane-1,2,4-Tricarboxylic Acid (PBTCA), well known antiscaling and corrosion inhibitors, were selected for investigation in this
study [15,16]. The HEDP, ATMP and PBTCA used were industrial grade.
And other reagents were analytical grade in the study. OctaphenylPolyoxyethylene-15 (OP-15) dispersant is a kind of octyl phenol
polyoxyethylene ether, which contains 15 ethoxy. Its molecular weight
is 871. It has a good ability in emulsication, dispersion, wetting and
cleaning.
During the static jar tests, in order to reduce the disturbance, all the
produced-water and inhibitor solutions were ltered through 0.45-m
lter paper before use. Standard coupon I (20# carbon steel sheets,
size: 50 25 2 mm) for the weight loss tests had a composition of
(wt.%): 0.22 C, 1.4 Mn, 0.35 Si, 0.05 S, 0.045 P. And the remainder was Fe.
The specimens were immersed in petroleum ether for 5 min after
cleaning with lter paper. They were dewatered and degreased by absolute alcohol for 5 min. After drying in cold air, they were covered with
lter paper and kept in desiccators.
2.2. Experiment design
In order to test the hypothesis of scale formation process during
produced-water recycling and reuse of high pour-point crude oil,
three batch experiments were designed as follows: 1) Dosages of the

Table 1
Analysis results of produced-water samples.
Parameter

Concentration (mg/L)

Mg2+
HCO
3
SO2
4
Ca2+
Cl
Oil
Total alkalinity
Total mineralization
Total dissolved solids
Total residue

2.31
23.04
47.19
94.37
1159.43
28.53
2014
2349
2559
2825

G. Li et al. / Desalination 351 (2014) 213219

A eld trial test was constructed at the 5th Metering Station of the
Shenyang Production Plant, Liaohe Oileld, China, in which the optimum compound inhibitor was used in the oileld produced-water
recycling system. A control pipe and a treated pipe were established
to compare the efciencies of the inhibitors. After a 90-day test, the control pipes and the treated pipes were treated according to the steel specimen treatment process. The corrosion rate (R) and the corrosion
inhibition efciency (IEc%) were calculated using Eqs. (2) and (3). And
the scale inhibition efciency (IEs%) was calculated using Eq. (1).

Table 2
Analysis results of scale samples.
Parameter

wt.%

Moisture content
Acid non-soluble substance
Fe
Crude oil
Loss on ignition
CaO

0.78
0.90
1.32
4.71
35.60
50.82

inhibitors were sufcient, but the dosage of ZnSO4 was changed to

investigate its effect on the formation of corrosion pitting and scale. Inhibitor dosage was set at 50 ppm, while ZnSO4 varied at 5, 10, 15, 20, 25,
30 and 35 ppm; 2) Total dosages of the anti-scale/corrosion inhibitors
and dispersant were xed, the effect of crude oil content on the scale inhibition efciency was observed, and then the dosage of the dispersing
agent OP-15 was varied to investigate the effect of the dispersing agent
on scale inhibition; 3) Desired dosages of the individual inhibitors
(PBTCA, HEDP and ATMP) and the compound inhibitor (ratio of
PBTCA, HEDP and ATMP was 2:2:1) were designed to investigate the optimum compound inhibitor for application during produced-water
reuse.
Static jar tests with different inhibitors were conducted at a high
temperature (85 C) of pour-point oil transmission system. Standard
corrosion coupons after pretreatment were weighed accurately, and
hung in a beaker with 1000 ml produced-water. The beaker was placed
in a constant temperature bath. Dynamic simulation experiments were
conducted at a constant speed of 120 rpm. During the experimental process, deionized water was added in the beaker every 4 h to compensate
the loss of water via evaporation and maintain the concentrations of different ions and reagents in the water samples. After 24 h of processing,
the coupons were carefully removed to prevent any detachment of
scale, immersed in absolute alcohol to dewater immediately, dried in
the oven at 100 C105 C and weighted after cooling. Then, the coupons were cleaned in a compound of hydrochloric acid and hexamethylenetetramine, and the weight was recorded again after dewatering by
absolute alcohol and drying in the oven. The water samples obtained
were used to analyze the contents of calcium and magnesium ion by
atomic absorption spectrometry, and the efciency of calcium carbonate inhibition was calculated. In addition, after a 24-h test period,
aliquots were ltered through 0.45-m lter paper and analyzed immediately for residual calcium in solution using Ethylenediaminetetraacetic Acid (EDTA) titration. The percentage inhibition efciency (IEs%)
was determined following Eq. (1).

2.3. Analysis methods

The analysis of water sample followed the standard method used in
China and the practice for analysis of oileld waters [17]. The chemical
composition analysis of scale samples references the paper [18].
Changes in scale crystal morphology were examined using an SSX-550
scanning electron microscope (SEM). X-ray diffraction patterns were
recorded in an XRD with Cu K radiation ( = 0.154 nm). Analytical
instruments during tests included a pH meter (PHS-3C, Shanghai), a
UV-2100 ultraviolet spectrophotometer (Unico, Beiijing), an electronic
analytical balance (AEL-200, Xiangyi), and an infrared oil measuring instrument (JDS-106U, Jilin).
3. Results and discussion
3.1. Factors of scale inhibition and inhibitor optimization
3.1.1. Effect of Zn2+ on corrosion and scale inhibition
Corresponding to our hypothesis, ZnSO4 was applied as an external
anti-corrosion coating agent. Zn2+ is used extensively as an anodic inhibitor for metallic corrosion protection [19]. The variation in appearance of carbon steel coupons in the presence and absence of Zn2 + is
shown in Fig. 2. The coupon in the blank test had a large area of
yellow-brown rust, and the surface appeared black. The coupon with
the compound inhibitor action retained its original bright color between
the parallel tests (tests 1 and 2). The main reason was that a layer of protective lm formed on the surface due to role of zinc salts. Therefore,
ZnSO4 can improve the inhibition efciency signicantly when applied
with the compound inhibitor [20]. Previous studies have pointed to a
synergistic action of Zn2 +explained predominantly on the basis of
controlling the anodic reaction and forming a protective lm on the metallic surface [21,22]. Moreover, a reduction of rust particles (major

a
IEs % G0 G=G0   100

215

where G0 is the scale weight of the control sample, and G is the scale
weight of the treated sample.
The weight loss measurement was tested to verify anti-corrosion
performance of the agents in the static jar tests. It was performed with
carbon steel specimens for 24 h at 85 C. Prior to all measurements,
the steel samples were washed thoroughly with double-distilled
water, degreased with ethanol and acetone, then dried at room temperature and accurately weighed. After the test, the steel samples were
carefully washed in double-distilled water, dried and weighed again.
The corrosion rate (R) and the corrosion inhibition efciency (IEc%)
were calculated using Eqs. (2) and (3):
R W=At

IEc % R0 R=R0   100

where W is the weight loss, is the density of carbon steel, A is the total
area, t is the immersion time, R0 and R are the values of the corrosion
rate, respectively.

A
a

B
Fig. 2. Carbon steel coupons in the presence and absence of Zn2+: (A), coupons after the
24-h jar test; (B), coupons cleaned by hydrochloric acid. In each panel, coupon (a) is the
blank test,(b) is test 1, and (c) is test 2.

G. Li et al. / Desalination 351 (2014) 213219

nucleating sites for scale crystals) in the produced-water system may

help to reduce scale deposition.
In addition, the effect of Zn2+ on scale inhibition and anti-corrosion
efciency was investigated quantitatively. The concentration of the
compound inhibitor was set at 50 ppm, while the ratio of ZnSO4 to compound inhibitor was changed from 10% to 70%. The results are shown in
Fig. 3. It can be seen that by increasing the dosage of zinc salts, there was
a similar trend between scale inhibition and anti-corrosion rate along
the ratio axis. In other words, the anti-corrosive effect and scale inhibition should be considered simultaneously to achieve the desired objectives. The results also indicate that consideration must be given to both
the inhibition of scale and corrosion, and the ratio of ZnSO4 to the compound inhibitor should be selected at between 30% and 40%. When the
ratio of Zn2+ was above 40%, there was a little decrease in inhibition efciency percentage. The inhibitors, especially HEDP and PBTCA, have an
excellent chelating ability at the presence of Ca2 +, Mg2 + and Zn2 +.
Once excess Zn2+ consumed the inhibitors, the calcium scale will increase. In addition, the high value of turbidity and suspended solids of
the produced water facilitated zinc precipitation, and maybe form a
new zinc scale. In a word, it is necessary to add ZnSO4 into the compound inhibitor because some organic agents are not appropriate for
exclusive use as a corrosion inhibitor, especially under high temperature conditions [23].

80

70

40

80

120

160

200

240

Concentration of crude oil (mg/L)

Fig. 4. Effect of crude oil concentration on the scale inhibition efciency in the absence of
the dispersing agent (temperature, 85 C; pressure: 1.013 105 Pa).

temperature of 85 C. The good emulsication, dispersion, wet and

cleaning ability of OP-15 can bring better dispersion effect for crude
oil and suspended solids. Fig. 5 shows the results of adding different
dosages of the dispersing agent on scale inhibiting. It can be seen that
the efciency of scale inhibition was improved signicantly by adding
only 2 ppm OP-15. This indicates that deposition and adsorption properties of crude oil were changed by the emulsion-dispersion means,
which is conductive to decrease the precipitation of dissolving salts.
When the dosage of the dispersing agent was 6 ppm, the efciency of
scale inhibition reached its highest levels. When its dosage was over
6 ppm, the more dispersing agent added, the lower the efciency of
scale inhibition. It is possible that an excess addition of the dispersing
agent reduced the efciency of the compound inhibitor. The main reason is attributed to the fact that the ratio of scale inhibitor to the dispersing agent decreased with the xed total dosages of the anti-scale/
corrosion inhibitors and dispersant.
3.1.3. Effect of the individual and compound inhibitors on scale formation
and corrosion inhibition
During high pour-point oil exploration, the uids hinder the pipeline
easily because of high wax content and high solidication point properties [26]. High temperature is an important factor, which must be considered during the recycling and reuse of produced water in high
pour-point oil transmission systems for preventing crude oil solidication. In this study, we carried out static jar tests at 85 C to compare
the performance of all the inhibitors. The performances of the individual
inhibitors (ATMP, HEDP, PBTCA) and the compound inhibitor were
assessed and the results are shown in Fig. 6. The data indicate an obvious increase of scale inhibition efciency for all inhibitor dosages from
0 to 70 ppm, which then plateaued at 79%, 81%, 88% and 97%, respectively. Furthermore, the compound inhibitor showed a higher efciency

100

100

90
80
70
60
50
40
IEs

30
20

Compound inhibitor
PBTCA
HEDP
ATMP

90

60

Scale inhibition efficiency (%

Efficiency of antiscale and corrosio

inhibition (%)

3.1.2. Effect of dispersing agent on scale formation

The inuence of crude oil on the scale inhibition efciency of inhibitors and the effect of the dispersing agent are shown in Figs. 4 and 5.
The results indicate that crude oil in the produced-water has a signicant effect on scale formation. In Fig. 4, at a temperature of 85 C, the
dosage of inhibitors was set at 50 ppm, and the efciency of scale inhibition decreased obviously with increasing the crude oil concentration.
The effects of the three single agents and the compound inhibitor were
all reduced. Usually, scaling is thought to result from the formation of
precipitates adhering to surrounding surfaces [24]. In this study, crude
oil in the water could not be dispersed. Therefore, it can cause an adsorption inhibitor effect. On the other hand, crude oil droplets were dissolved in salt water to provide attachment points, and this accelerated
the crystallization of dissolved salt precipitation. Excess crude oil has
some unfavorable effect on the chelating of Ca2+, due to the fact that
the scale inhibitor can be soluble incrude oil. In addition, some aggregates, formed by the crude oil droplets and suspended solids (SS), can
be adsorbed on the surface of the pipeline to accelerate the formation
of scale. As previous work reported, the micrographs of the suspended
solids showed that most of the crude oil droplets and SS formed some
aggregates, and the small SS were adsorbed on the surface of oil droplets, making them difcult to coalesce and be separated [25].
In order to reduce the negative inuence of crude oil, OP-15
was added into the produced-water as a dispersing agent at a test

100

Scale inhibition efficiency (%

216

10

20

30

40

50

IEc
60

70

80

2+

Ratio of Zn (%)
Fig. 3. Efciencies of scale and corrosion inhibition with different ratios of Zn2+ to compound agents (compound inhibitor at 50 mg/L).

95

20 mg/L
40 mg/L
60 mg/L
80 mg/L
100 mg/L

90

85

10

Concentration of dispersing agent (mg/L)

Fig. 5. Effect of dispersing agent (OP-15) on the formation of scale with different crude oil
content (temperature, 85 C; pressure: 1.013 105 Pa).

G. Li et al. / Desalination 351 (2014) 213219

217

Fig. 6. Inuence of inhibitors concentration on scale inhibition performance (the composition and constituents of compound inhibitor: PBTCA:HEDP:ATMP, 2:2:1; Zn2+, 30%
ratio of compound inhibitor; OP-15, 4 mg/L).

than each of individual inhibitor and plateaued at 97.34% at the dosage

of 70 ppm. Among the individual inhibitors, the scale inhibition efciency of PBTCA was higher than that of either ATMP or HEDP. This is likely
because PBTCA is known to be effective in reducing the formation of
CaCO3 crystals in pipelines [27]. However, the compound inhibitor
showed better inhibition efciency compared to each single inhibitor
at 85 C. It is possible a synergistic effect of the active groups in the
three individual scale inhibitors played an important role in the dispersion of CaCO3 [28]. According to the previous reports [2932], HEDP
contains two phosphate group and one alcoholic hydroxyl group. The
alkyl group part in the molecule is of certain hydrophobicity. Meanwhile, HEDP can form stable adducts with the compounds containing
reactive oxygen species, and has the ability of absorption of oxygen.
So the effect of isolating oxygen by HEDP reduces the surface corrosion
of the pipeline. It can act as surface active component and can form a
protective layer on the substrate which modies the properties of the
surface. ATMP, containing three phosphate groups, is not easy to be hydrolyzed. It has the better scale inhibiting ability under 200 C. In general, it was used as an excellent anti-scale and corrosion inhibitor in
oilelds. In chemical structure of PBTCA, there are three carboxyl groups
and one phosphate group. C-P bond connects directly, which cause the
higher chemical and thermal stability. Therefore, it is more suitable for
the scale inhibition of high temperature, hardness and alkalinity water
comparing to ATMP and HEDP.
The corrosion rate (R) and corrosion inhibition efciency (IEc%) of
steel in a supersaturated solution test were determined after 24-h of immersion at 85 C and at an inhibitor dosage of 70 ppm. The results are
given in Table 3. It can be seen that the R of steel with the compound inhibitor was lower than that of steel with any single inhibitor, and the
IEc% of the compound inhibitor reached 97.95%. In addition, the dosage
of the compound inhibitor will need to change depending on the temperature of the produced-water. Plummer and Busenberg showed the
general behavior of CaCO3 solubility as a function of temperature [33].
Calcium carbonate becomes less soluble as temperature increases.
Therefore, higher dosages of inhibitor are required at higher temperatures to prevent CaCO3 precipitation of the test solution.

Fig. 7. SEM images of scale: (A) blank and (B) in the presence of compound inhibitor.

3.1.4. Comparison of SEM and XRD results in the presence and absence of
compound inhibitor
Panels of Fig. 7A and B are SEM images of the scale crystals deposited
on the stainless steel surface. It can be seen that, in the absence of
inhibitor, all of the crystal growth was normal, exhibiting regular
rhombohedrum shapes. The crystal-shaped blocks are typical of calcite
formation [34]. The blank test showed that only one homogeneous
layer of cubic crystals was smaller than 0.1 m. After treatment with
the inhibitor, the edges of scale crystals disappeared and were more
spherical in shape. This is because the inhibitor adsorbed onto the active
growth sites of the crystal surfaces and inhibited the regular outgrowth
of scale crystals during the crystal growth process. Also, the modication of crystal morphology could affect the adherence of CaCO3 on the
stainless steel surface. The morphological study of the scale crystals

Table 3
Corrosion rate and corrosion inhibition efciency of inhibitors.
Inhibitor

IEc (%)

R (mm/a)

Blank
Compound inhibitor
PBTCA
HEDP
ATMP

97.95
88.32
85.59
87.67

1.84
0.02
0.21
0.26
0.23

Fig. 8. XRD images of scale: (A) blank and (B) in the presence of compound inhibitor.

218

G. Li et al. / Desalination 351 (2014) 213219

Acknowledgment

Table 4
Corrosion rate, scale and corrosion inhibition efciency in the oileld.
Pipe

IEs (%)

IEc (%)

R (mm/a)

Control pipe 1#
Treated pipe 1#

92.46

95.12

1.019
0.037

This study was supported by the National High Technology Research

and Development Program of China (No. 2012AA063401) and Liaoning
BaiQianWan Talents Program. The authors thank the Ministry of
Science and Technology, China, for partially funding this study.
References

indicated that the tested inhibitor appeared to interfere with or block

the growth process of the growing crystals. Thus, the inhibition of
scale formation may involve an irreversible adsorption of the inhibitor
at the active growth site of crystals, resulting in their complete blockage
[35].
Fig. 8 shows the XRD patterns of precipitated scale products in the
absence and presence of 70 ppm of compound inhibitor. The sharp reection point almost coincides with that of the CaCO3 standard substance. This suggests that CaCO3 was the main crystalline component
of scale in the blank test sample. Especially, it can be seen that calcite
is the dominant carbonate mineral in the scale. However, there were
fewer fraction peaks of scale in the XRD image for the absence of inhibitors. Without considering the interference of other impurities, the arrangement of crystal takes on irregularity clearly. This indicates that
the scale was in a substantially amorphous state, and CaCO3 crystallized
substances had been controlled by the chelation, low threshold inhibition, and lattice distortion of the compound inhibitor according to the
three points coinciding with the CaCO3 standard diffraction.
3.2. Field trial test
The compound inhibitor was applied in a eld trial test, in which the
dosage of the inhibitor was controlled at 70 ppm by a metering pump.
The results of the eld trial test are given in Table 4. The efciencies of
scale and corrosion inhibition reached 92.46% and 95.12%, respectively.
The result indicates the compound inhibitor can solve the scaling problem at Shenyang oil eld.
It was found that the compound inhibitor of scale can be successfully
applied for the reuse of produced-water at high temperature, and Zn2+
can be applied to form a protective lm in order to inhibit corrosion of
the pipeline. After that process, residual crude oil and mechanical impurities left in the treated produced-water can be dispersed using OP-15.
The calcium and magnesium scale can be inhibited by using the compound of PBTCA, HEDP, and ATMP. The inhibition process is promising
for real applications in produced-water reuse and may be competitive
with other processes such as anti-scale magnetic separation and acid
cleaning [36,37], due to its low cost requirements and high temperature
tolerance.
4. Conclusions
The compound inhibitor comprising PBTCA, HEDP, ATMP and Zn2+
seems to have performed as well as we hoped in reuse of high temperature produced water from high pour-point crude oil. The results show
that the inhibitor has high IEs% (97.34) and IEc% (97.95) at 70 ppm. In
eld trial test, the efciencies of scale and corrosion inhibition reached
92.46% and 95.12%, respectively. Meanwhile, the study also elaborated
specic characteristics of the scale formed in produced water pipeline
under high temperature conditions. The mechanisms of scale inhibition
could be attributed to the fact that the agents inhibit crystal growth. In
addition, because produced water contains many organic agents that
have been used in oil exploration, comprehensive research is ongoing
to characterize the effects of ooding agents as well as to identify the
necessary ratio of the compound inhibitor. Meanwhile, with the development of green chemistry, researchers should nd an environmentally
friendly and efcient reagent that can overcome both corrosion and
scale problems.

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