Article

Cite This: Energy Fuels 2019, 33, 228−237 pubs.acs.org/EF

Study of Novel Aromatic Aminomethylenephosphonates as Oilfield

Scale Inhibitors
Mohamed F. Mady,*,†,‡ Synnøve Fevang,† and Malcolm A. Kelland†
†
Department of Chemistry, Bioscience and Environmental Engineering, Faculty of Science and Technology, University of Stavanger,
N-4036 Stavanger, Norway
‡
Department of Green Chemistry, National Research Centre, Dokki, Cairo 12622, Egypt

ABSTRACT: Nonpolymeric phosphonates are well-known scale inhibitors in the upstream oil and gas industry because they
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afford several advantages over other classes of inhibitors. But few of these phosphonates show good environmental properties as
Downloaded via UNIV FED DO RIO DE JANERIO on September 5, 2019 at 19:00:03 (UTC).

well as good thermal stability for high-temperature squeeze applications. Given the known high seawater biodegradability of
benzoic acid, we have synthesized and tested several easily accessible monoaromatic phosphonates. The tests include dynamic
tube-blocking experiments for both calcite and barite scaling, thermal stability, calcium compatibility, and seawater
biodegradation according to the OECD 306 protocol. The new aromatic inhibitors were compared to known
aminophosphonate scale inhibitors including the aromatic amino acid derivative, phenylalanine diaminomethylenediphosph-
onate. The results indicate that improved performance can be obtained together with good thermal stability for the phenolic
derivatives, but too much aromatic ring substitutions lead to lower biodegradation.

1. INTRODUCTION polyacrylates, polymaleates, and polysulphonates and their

Oilfield scaling is a common problem in the oil and gas industry. copolymers, as well as nonpolymeric phosphonates.4
Problems with scale cost the industry millions of dollars in Organic phosphonic acid compounds contain C−PO(OH)2
damage and lost production. Scale is one of the leading causes of moieties.5,6 These compounds and their salts, phosphonates,
production decline. It is considered together with corrosion and have a wide field of application in agriculture, chemical, and
hydrates as one of the biggest water-related operational pharmaceutical industries.7−11 Organophosphonic acid and
challenges in the oil industry.1 Scale can deposit on almost their salts are a widely used class of SIs used for scale in the
any surface. Once scale has formed, the layer will continue to get oil industry.12−18 Some of the SIs in this class are small
thicker unless it is treated. If scale forms in the near-wellbore nonpolymeric SI molecules with just a few phosphonate groups,
region or in the well, it can block the pore throats and cause whereas others are polymeric molecules, some of which have
damage and loss in production.2 It was well known that the four higher amounts of phosphonate groups attached and some of
most common scale formations in the oilfield are the divalent which are only end-capped with phosphonates. 4 The
salts: calcium carbonate (calcite and aragonite) and sulfate salts phosphonate is often connected to an aminomethylenephosph-
of calcium (gypsum), strontium (celestite), and barium onate group. The amine group in this molecule acts like a Lewis
(barite).1 base ligand, which helps the inhibition process by increasing the
Deployment of a scale inhibitor (SI) is the most common chelate effect on the divalent scaling cations.
method for preventing scale formation in the oil industry.3 SIs Besides the scale inhibition effect, the phosphonate group has
are generally used to avoid nucleation and/or crystal growth of other advantages. For example, phosphorus in a phosphonate
the scale. The concentration of SIs is in the range 1−500 ppm. group is easily detected, which can be helpful for determining
The SI concentration must be above a certain threshold in order the concentration of the SI in the produced water. The number
to prevent scale formation completely. In the field, operators of phosphonate groups in the SI gives an indication of when it is
often refer to the minimum inhibitor concentration (MIC), needed to resqueeze a well, to maintain complete scale
which prevents scale formation. The SIs are often used in a inhibition. Phosphonates also adsorb strongly to formation
downhole squeeze treatment or by continuous injection at the rocks, giving long squeeze lifetimes, which saves the operator
wellhead, but other deployment methods are possible. A squeeze time and money by reducing the downtime for well treatments.
treatment is a method where an SI solution is pumped directly The main problem of many commercial phosphonate SIs is
into a formation, usually through the production well. An that they are generally not readily biodegradable.4 As environ-
overflush of available water (e.g., seawater) is used to push the mental concerns become more important, production chemicals
inhibitor further into the formation and into a region around the such as SIs are increasingly scrutinized and legislated. Several
production well.4 The SI is absorbed or deposited on the attempts have been reported to provide more environmentally
formation rock in the near-well area. When the well is put on friendly biodegradable SIs.4 Development of products posing
production, SI desorbs and becomes dissolved into the
produced water, where it is available for preventing scale Received: October 9, 2018
formation during production. Commercial SIs for carbonate and Revised: November 29, 2018
sulfate scaling can be polymeric, such as polyphosphonates, Published: December 1, 2018

© 2018 American Chemical Society 228 DOI: 10.1021/acs.energyfuels.8b03531

Energy Fuels 2019, 33, 228−237
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Figure 1. Some of the promising novel aminobismethylenephosphonate-based scale inhibitors developed by our group.20,21

relatively little harm to the environment (specifically the marine inhibition using a classic dynamic tube-blocking equipment at
environment), as determined by the Oslo and Paris Commission approximately 80 bar and 100 °C. In addition, we also reported
(OSPARCOM), is very attractive to oil companies operating in studies of the biodegradability, thermal stability, and calcium
regions with strict environmental regulations.19 Very recently, compatibility activities for the new SIs, as well as commercial SIs
we have reported a new class of polycarbonate polymer with for comparison.
pendant anionic functional groups (carboxylate and phospho-
nate) as green SI as presented in Figure 1.20 In addition, we have 2. EXPERIMENTAL SECTION
investigated a series of biodegradable bisphosphonate SIs for
2.1. Chemicals. All chemicals and solvents for synthesis were
carbonate and sulfate scales, as also shown in Figure 1.21
purchased from VWR, Nippon Chemical Industrial Co., Ltd., Tokyo
Attempts to make more environmentally friendly SIs Chemical Industry Co., Ltd., and Sigma-Aldrich (Merck). The sodium
including phosphonic acid groups have been investigated.22 salts of diethylenetriaminepentakis(methylenephosphonic acid)
One of these attempts to afford more biodegradable SIs includes (DTPMP) and aminotris(methylenephosphonic acid) (ATMP) were
the phosphonation of amino acids. Devaux et al. have reported a obtained from Solvay. Phenylalanine diaminomethylenephosphonates
Moedritzer−Irani reaction for a series of amino acids. For (PADMP) was prepared according to the literature method (Figure
example, L-phenylalanine was functionalized with amino- 2).23,24
methylenephosphonate groups as shown in Figure 2.23,24 This 2.2. Characterization of Scale Inhibitors. To characterize the
target chemicals, and to verify the reactions, NMR spectroscopy was
used. The NMR spectra were recorded on a 400 MHz Bruker NMR
spectrometer in deuterium oxide (D2O) with two drops of sodium
deuteroxide solution. 1H NMR and 31P NMR chemical shifts were
obtained in D2O. All reactions were monitored by thin-layer
chromatography using Fluka GF254 silica gel plates with detection
under UV light at 254 and 360 nm.
2.3. Synthesis of New Scale Inhibitors (SIs). 2.3.1. Synthesis of
Phenolic α-Amino Acid, 2-((2-Aminoethyl)amino)-2-(2-
hydroxyphenyl)acetic Acid (5), Which is the Key Intermediate for
Figure 2. Phosphonation of L-phenylalanine via the Moedritzer−Irani the Subsequent Phosphonation Reaction. In a 50 mL two-necked
reaction as a biodegradable SI. Erlenmeyer flask, phenol (25.0 g, 256.6 mmol) was melted and stirred
at 50 °C. After complete melting, NaOH (50% w/w, 0.64 g, 7.97 mmol)
was added dropwise to the mixture. The temperature was then
study indicates that some amino acid alkyl phosphonates exhibit decreased to 30−35 °C. N-(2-Aminoethyl)acetamide (1.08 g, 10.62
improved good scale inhibition performance and thermal mmol) was added to the mixture simultaneously, at which time
stability properties. Some products are claimed to possess glyoxylic acid (50%, 1.57 g, 10.62 mmol) was added dropwise into the
advantages over existing phosphonates in that they exhibit good solution while keeping the temperature below 40 °C. The mixture was
biodegradation by the method OECD 306.23,24 They also offer kept at 75 °C overnight and then collected and kept at room
low toxicity to marine life.25 temperature for 30 min. After the addition of 60 mL of water, the
mixture was extracted with methyl tertiary butyl ether (3 × 20 mL).
The motivation for this study was the knowledge of the high Then, the water phase was removed under reduced pressure to yield
seawater biodegradation of sodium benzoate.26 Benzoate 97% of amide 4 as a solid. The hydrolysis of the acetamido group 4 was
degrades rapidly by attaching on the ring carboxylate by the carried out by reflux with HCl (37%, 60 mL) overnight. The solvent of
seawater bacteria. We reasoned that if benzoate and related the mixture was removed under reduced pressure to afford phenolic α-
aromatics could be part of a new aromatic phosphonate, we amino acid 5 (80% yield) as a yellow solid.31
might get an SI with high biodegradation. 2.3.1.1. 2-((2-Acetamidoethyl)amino)-2-(2-hydroxyphenyl)acetic
We looked for benzoic acid derivatives that were easily Acid 4. 1H NMR (D2O) δ ppm: 7.26−7.15 (m, 2H, ArH), 6.90−6.77
accessible and contained substituents that could be easily (m, 2H, ArH), 4.70 (s, 1H, CH), 3.34−30 (m, 2H, CH2), 2.90−2.84
(m, 1H, CH2), 2.74−2.68 (m, 1H, CH2), 1.91 (s, 3H, CH3).
modified to scale inhibitor functional groups, particularly 2.3.1.2. 2-((2-Aminoethyl)amino)-2-(2-hydroxyphenyl)acetic Acid
phosphonate. para-Aminobenzoic acid (PABA) has attracted 5. 1H NMR (D2O) δ ppm: 7.33−7.24 (m, 2H, ArH), 6.95−6.87 (m,
significant interest for the preparation of analogues of numerous 2H, ArH), 4.94 (s, 1H, CH), 3.37−3.20 (m, 4H, 2CH2).
medical and industrial applications, such as food sources, 2.3.2. Synthesis of 2-((2-(Bis(phosphonomethyl)amino)vinyl)-
biodegradable pesticides, an ingredient for many different (phosphonomethyl)amino)-2-(2-hydroxyphenyl)acetic Acid (SI-1)
cosmetics, and sunscreens as a UV filter.27−30 We have reported via the Moedritzer−Irani Reaction. To a 50 mL two-necked
Erlenmeyer flask fitted with a thermometer and an additional funnel
phosphonation of PABA by the introduction of phosphonic acid
and a magnetic stirring bar were placed appropriate phenolic α-amino
onto amino group by a one-pot Moedritzer−Irani reaction acid 5 (3.0 g, 27.49 mmol), phosphorous acid (H3PO3, 4.51 g, 54.98
affording SI-3 in a good yield. Moreover, we have synthesized for mmol), and HCl (5.42 g, 148.61 mmol) in deionized water (20 mL),
the first time a novel aminobismethylenephosphonate-based flushed with nitrogen for at least 15 min. The reaction mixture was kept
phenolic α-amino acid as a building block. All new SIs were under nitrogen and then allowed to heat stepwise from room
evaluated for calcium carbonate and barium sulfate scale temperature to 100 °C, at which time HCHO 37% (4.90 g, 163.47

229 DOI: 10.1021/acs.energyfuels.8b03531

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Figure 3. Synthesis of phenolic α-amino acid 5, functionalization of phenolic α-amino acid with phosphonate groups to afford phenolic α-amino acid-
PO3H2 (SI-1).

mmol) was then added dropwise into the solution while stirring and method to determine the relative performance of scale inhibitors used
heating at 110 °C. The reaction was then left overnight at 110 °C. Then, in oilfield applications. The main reason to use the high-pressure
the mixture was cooled to room temperature, and the solvent of the dynamic tube-blocking test, compared to static, is that it emulates the
mixture was removed under reduced pressure. The new amino- downhole conditions in a production tubing during production. The
methylenephosphonate was recrystallized from water and methanol to apparatus can provide a wide range of pressures and temperatures.21
give aminomethylenephosphonates SI-1 in 60% yield (Figure 3). The results from this test give a good estimate of the minimum inhibitor
2.3.2.1. 2-((2-(Bis(phosphonomethyl)amino)vinyl)- concentration (MIC) for the SIs. An acceptable value of MIC is from 1
(phosphonomethyl)amino)-2-(2-hydroxyphenyl)acetic Acid (SI-1). to 100 ppm, but the target is between 1 and 5 ppm.4 The test can be
1
H NMR (D2O, 400 MHz) δ ppm: 6.93−6.79 (m, br, 2H, ArH), 6.44− used to evaluate the performance of the SI for calcium carbonate and
6.30 (m, br, 2H, ArH), 4.76 (s, 1H, CH), 3.40−3.12 (m, br, 6H, 3CH2), barium sulfate scales. Dynamic tube-blocking tests to determine relative
2.57−2.13 (m, 4H, 2CH2); 31P NMR (D2O, 162.00 MHz) δ ppm: SI performance were carried out on an automated rig (built by Scaled
17.00. Solutions Ltd., Scotland). The scale rig consists of three pumps that
2.3.3. General Procedure for the Synthesis of Methylenephosph- pump fluids up to 10.00 mL/min through a 3.00 meter microbore coil
onate-Based Aromatic Amino Compounds via the Moedritzer−Irani made of 316 steel with a diameter of 1 mm. The coil is placed in an oven,
Reaction. In a 50 mL two-necked Erlenmeyer flask, a mixture of which in this experiment is set to 100 °C. The pressure in the tube was
appropriate aromatic amines 8−10 (1.0 equiv), H3PO3 (2.0 equiv), and 80.0 bar.25 The three pumps are marked with the numbers 1, 2, and 3.
HCl (2 equiv) was dissolved in deionized water (20 mL) and flushed Pump 1 is pumping brine 1 (scaling cations), pump 2 is pumping
with nitrogen for at least 15 min. Under the protection of nitrogen, the brine 2 (scaling anions), and pump 3 is pumping the scale inhibitor
reaction mixture was allowed to heat stepwise from room temperature solution (SI) as presented in Figure 5.
to 110 °C, at which time HCHO 37% (2 equiv) was added dropwise. The scale rig is set up to automatically test the inhibitors. It is
The reaction mixture was stirred at 110 °C overnight. Thin-layer programmed to complete four stages in each experiment:
chromatography analysis monitored completion of the reaction. The 1. First blank test with no scale inhibitor.
mixture was cooled to room temperature, and the solvent of the mixture 2. A set of tests with different concentrations of SIs is run for 1 h
was removed under reduced pressure. The crude phosphonates were each.
obtained and recrystallized from water and ethanol to give 3. A repeated test is automatically conducted for the previous
methylenephosphonates SI-2, SI-3, and SI-4 in good yields. The concentration of SI that led to scale formation.
route for the synthesis of all new SIs is summarized in Figure 4. In 4. Second blank test with no scale inhibitor.
addition, Table 1 shows the structures and spectral data of all new
aromatic phosphonates SIs. The scale rig is connected to a computer with software that
2.4. High-Pressure Dynamic Tube-Blocking Test Methods. automatically controls the minimum inhibition concentration of the
The high-pressure dynamic tube-blocking test is a standard laboratory SIs. For example, the concentrations of SI are set to 100, 50, 20, 10, 5, 2,
and 1 ppm for 1 h each or until scale is formed in the coil. The lower
limit for the SI concentration, the fail inhibitor concentration (FIC), is
set to the SI concentration where the differential pressure increases
more than 0.5 bar (7 psi). (FIC must not be confused with MIC, which
is the minimum inhibitor concentration that prevents scale formation.)
Between each concentration added, the coil is cleaned with ethyl-
enediaminetetraacetic acid (EDTA) (pH = 12−13) for 10 min at 9.99
mL/min flow rate, and for the next 10 min the coil is flushed with
distilled water at the same flow rate, 9.99 mL/min. Then, the coil is
ready for the next test concentration.
In this work, we chose to use model fluids based on production from
the Heidrun oilfield, Norway. Table 2 shows the composition of
aqueous produced fluids from this field. We used 50:50 volume mixture
Figure 4. Synthesis of aminomethylenephosphonate-based aromatic of formation water and synthetic seawater to produce barium sulfate
derivatives. scaling. The brines in Table 2 are mixed and stirred until the salts are

230 DOI: 10.1021/acs.energyfuels.8b03531

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Table 1. Structures and Spectral Data of New Methylenephosphonate-Based Aromatic Derivatives

Figure 5. Equipment used for high-pressure tube-blocking testing of SIs (from the left: pump 1, pump 2, and pump 3).

completely dissolved. Then, the brines were degassed for 15 min using a ppm. After 9 min at 2 ppm, the scale builds up rapidly again. The fourth
vacuum pump to remove dissolved gas. Bubbles in the water might stage is the repeated blank test.
cause a pump to stop as they prevent brines from flowing through the 2.5. Compatibility Tests. Mixing of scale inhibitors and brine can
line. The same procedure was used for preparing EDTA solution. cause issues when they react with each other. The reaction can cause a
After a test of a SI in the dynamic tube-blocking rig is conducted, the change in the physical and chemical structures of the scale inhibitor.
results are exported to Excel file. Excel is used to plot the results. A Compatibility tests are needed to check that the inhibitor does not
typical graph is illustrated in Figure 6. The graph shows the four stages precipitate when mixing with formation brines causing formation
in one single run: from the left, a blank test with no inhibitor, a test to damage.4 Chemicals that affect the pH of the produced water will affect
determine the FIC, a repeat for FIC, and ends with a repeated blank the carbonate scaling potentials.32,33 The use of some amino-
test. In Figure 6, SI was injected at 20, 10, 5, 2, and 1 ppm for 1 h each. methylenephosphonate SI derivatives in the presence of high calcium
At 2 ppm, the scale builds up rapidly after 14 min. After cleaning with ion concentrations can lead to precipitation. Too much calcium ions
EDTA and water, the repeated SI test is run, but starting from MIC, 5 lead to incompatibility with the SI. This leads to precipitation and

231 DOI: 10.1021/acs.energyfuels.8b03531

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Table 2. Composition of Heidrun Oilfield, Formation Water, tion, carbon dioxide production, and the condition of inorganic carbon
Seawater, and a 50:50 Mixture intermediates.36
To predict the biodegradation behavior of a SI in natural
Heidrun formation water seawater 50:50 mixed brine environments, the test should simulate such an environment as closely
ion (ppm) (ppm) (ppm) as possible. This is the reason for having several standardized amounts
Na+ 19 510 10 890 15 200 of test methods so the best test is chosen for the specific purpose. In this
Ca2+ 1020 428 724 project, a method based on OECD 306 guidelines is used to determine
Mg2+ 265 1368 816.5 the marine biodegradability of the SIs. For each SI, the biological
K+ 545 460 502.5 oxygen demand (BOD) was measured using the OxiTop Control
manometric system (WTW, Germany) over a 28 day period. By
Ba2+ 285 0 142.5
comparing the measured BOD and the calculated theoretical oxygen
Sr2+ 145 0 72.5
demand (ThOD) values, the percentage of biodegradability can be
SO42− 0 2960 1480 calculated. Seawater was used as the test medium, without added
HCO3− 880 120 500 inoculum. To ensure nonlimiting conditions for microbial activity and
growth, nutrients were added.
To accomplish this test, test flasks containing seawater, nutrients,
and the test chemical (SI) are needed. Three different types of control
flasks are used: (1) one blank with nutrient-amended seawater only, to
indicate contamination during the experiment; (2) negative controls
with autoclaved seawater, nutrients, and the test compounds at 69 mg/
L final concentration; and (3) positive controls with nutrient-amended
seawater and an easily biodegradable substrate, sodium benzoate, at 100
mg/L final concentration. The positive and negative controls are used
to minimize the influence of false positives and negatives.21
The seawater used in the test (20 L) was collected at the
International Research Institute of Stavanger (IRIS) in Mekjarvik
(Stavanger, Norway). On the sampling day, the seawater had a
temperature of 12 °C. The collected seawater was stored in a dark room
Figure 6. Graph showing the four stages of an SI test in the scale rig at 20 °C overnight. The next day, seawater (297 mL) was distributed
(pressure−time). into 510 mL-volume amber bottles and the nutrient solution was added.
The OxiTop control setup was prepared according to recommenda-
tions of the manufacturer, and bottles with measuring heads were
deposition, not of inorganic scale but a calcium−SI complex. This can incubated for 3 h at 20 °C prior to the start of the experiment. After the
cause poor placement of the SI and formation damage.4,34 3 h of incubation, 1.8 mL of a 1.0% (w/w) solution (in distilled water)
The compatibility test follows a procedure. Solutions with different of each test compound was added to the test and negative control flasks,
calcium contents were mixed with various inhibitor concentrations to whereas 1.0 mL of a 30 g/L sodium benzoate solution was added to the
evaluate if precipitation occurs. Scale inhibitors of 100, 1000, 10 000, positive control flask. The bottles were capped with measuring heads
and 50 000 ppm were dissolved in 2 mL of deionized water in 50 mL and placed on magnetic stirrers in the incubator cabinet, and the
glass bottles. Then, 30 000 ppm sodium chloride (3.0 wt %) and measuring heads were started immediately.
calcium dihydrate in doses from 10 to 10 000 ppm were added. The Oxygen consumption data were recorded over a 28 day period, while
bottles were shaken until everything was dissolved and the solution all flasks were incubated in the dark at 20 °C. After 28 days, data were
looked clear. The bottles were placed in the oven at 80 °C; the test time recorded and results were collected. ThOD of each scale inhibitor was
was generally 24 h. The turbidity and/or precipitation of SIs with calculated as described in the OECD 306 guidelines, taking into
calcium ion in a synthetic brine solution were checked after 30 min, 1 h, account complete nitrification. Blank oxygen consumption values
4 h, and 24 h. (BOD values representing background respiration in seawater) were
2.6. Thermal Stability Test. For high-temperature reservoir deducted from the BOD of each test compound prior to determining
applications, thermal aging tests need to be carried out. This is to percent biodegradability according to the OECD 306 guidelines.
make sure that the SIs are stable at the respective temperatures for the
expected squeeze lifetime.4 To accomplish this test, a 20 wt % additive 3. RESULTS AND DISCUSSION
solution in deionized water is nitrogen-sparged for 1 h and placed in a
pressure tube. It is then sparged again with nitrogen to minimize 3.1. Chemistry. The Moedritzer−Irani reaction has been
headspace of oxygen in the tube before heating at 100−170 °C for 1 used for synthesizing all aromatic scale inhibitors. The
week. The resultant solution is then checked for high-pressure tube- Moedritzer−Irani reaction has the advantage of affording the
blocking testing to compare the SI inhibition performance before and phosphonates directly without a hydrolysis step using water as a
after thermal aging. green solvent.37 Aminomethylenephosphonate-based phenolic
2.7. Seawater Biodegradability Test. Biodegradability test is a
laboratory test method, which is used to determine the biodegradability
moiety SI-1 was prepared in a good yield by refluxing phenolic
of SIs. This is an important parameter for the evaluation of the α-amino acid derivative with phosphorous acid and form-
ecological behavior of the substances. Degradable substances will not be aldehyde in the presence of hydrochloric acid as a catalyst
a long-term risk for the environment. There are internationally (Figure 3). The 31P NMR spectroscopy is the most efficient
standardized methods (ISO, OECD) for the biodegradability test. method for elucidating the structure of the organophosphorus
The authorities have established quality criteria (GLP, EN 45000, ISO compounds. The phosphonate moiety (−PO3H2) of SI-1 in the
9000), which are used to quantify the degree of biodegradation. These 31
P NMR spectrum displayed a singlet signal at δ 17.00 ppm. To
are used in this study to quantify the degree of biodegradation.35 explore novel aromatic phosphonate SIs, three new phospho-
The biodegradability testing measures the biochemical process that
develops when microorganisms consume a given type of material. The
nate-based aromatic cores were synthesized using the
test gives an indication of the product’s ability to biodegrade, which Moedritzer−Irani reaction. For example, PABA has been
depends on the amount of carbon available for microbial consumption. phosphonated via the Moedritzer−Irani reaction affording SI-
The regulations require that the biodegradability test be based on 3 in a good yield. The 31P NMR spectra of SI-3 showed a distinct
aerobic biodegradation, which normally measures oxygen consump- singlet signal at δ 18.00 ppm for the phosphonate group.
232 DOI: 10.1021/acs.energyfuels.8b03531
Energy Fuels 2019, 33, 228−237
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3.2. High-Pressure Dynamic Tube-Blocking Test. High- significant scale inhibition performance. One reason for this
pressure dynamic tube-blocking test on sulfate and carbonate inhibition may be the optimum distance between the
scales was used to evaluate the performance of all novel SIs and methylenephosphonates for DTPMP and ATMP as explained
find the fail inhibitor concentration (FIC) for each SI. The previously in our published articles.21
results from the test apparatus at 100 °C and 80 bar are In addition, L-phenylalanine-based methylenephosphonates
consistent for the first and second tests for all tested SIs. In our PADMP was prepared and tested for sulfate scale.24 PADMP
study, inhibitors were flushed at concentrations of 100, 50, 20, gave a poor scale inhibition performance. The FIC of PADMP
10, 5, and 1 ppm for 1 h at each concentration until scale formed. was 100 ppm after 16−18 min. This is the poor result we are
Two blank experiments with no inhibitor were also tested in trying to improve on. Under our test conditions with reasonable
each run. At FIC, it is hard to evaluate the scaling rate as the time sulfate scale tendency, PADMP gives a poor performance, which
it takes for the apparatus to detect the scale varies between the gave us the motivation to investigate other aromatics to get
first and second tests for many of the samples. Consequently, the better performance. The fact that the literature indicates minor
apparatus can be used to detect FIC but not the scaling rate. The decomposition of PADMP (4.3% for PADMP) at 140 °C led us
pH of the injected SI solution in this study was kept in the range to try related products with more phosphonate groups for
4−9. Very low pH solutions were not used in order to avoid improved performance while maintaining good thermal
significant protonation of the SI, which would be detrimental to stability.24
the scale inhibition performance.38 For the novel synthesized aromatic SIs, the new phospho-
We have evaluated scale inhibition performances for all nated aromatic with hydroxyl group SI-2 showed a weak
synthesized aromatic phosphonate SIs as well as two commercial inhibition performance at 100 ppm for the sulfate scale. The FIC
phosphonate products DTPMP and ATMP for sulfate and of SI-2 gave rapid scaling after 12 min for the first experiment
carbonate scales. and 13 min for the second experiment at 100 ppm as presented
For the sulfate scale experiments, the FICs of the two in Figure 7. In contrast, the phosphonated benzoic acid
commercial products DTPMP and ATMP were 5 and 10 ppm, derivatives revealed good to moderate antiscaling activities.
respectively, as presented in Table 3. DTPMP and ATMP gave a The phosphonated para-aminobenzoic acid SI-3 gave a
moderate inhibition performance. The FIC of SI-3 was 50
Table 3. FIC Values for Commercial and New Aromatic Scale ppm after 40−45 min for both runs separately. Interestingly, the
Inhibitors (SIs) for Sulfate Scale phosphonated benzoic acid with attached two amino groups SI-
4 gave fairly higher scale inhibition than SI-2 and SI-3. For SI-4,
first second
blank first scale test second scale test blank high-pressure dynamic tube-blocking results indicate that the
first and second tests gave FIC at 20 ppm after 10 min.
time concn time concn time time
inhibitor (min) (ppm) (min) (ppm) (min) (min) For the new phosphonated phenolic α-amino acid, SI-1
DTPMP 5 5 9 5 11 7
showed very good barite scale inhibition, with an FIC of 10 ppm
ATMP 4 10 13 10 16 6
after 10 min for both runs, which was significantly better than
SI-1 7 10 20 10 20 10
other aromatic phosphonates for both runs. The graphical
SI-2 10 100 12 100 13 11
results of FIC and time for this test are shown in Figure 8.
SI-3 7 50 40 50 45 11
Our explanation for the significant inhibition performances of
SI-4 8 20 10 20 10 10
SI-1 and SI-4 for sulfate scale may be related to extra
PADMP 11 100 18 100 16 12 diphosphonate groups on the SIs backbone, in which increasing
SI-1a 5 20 4 20 5 11 the active sites of the surface for the diphosphonate binding and
inhibition of barium sulfate, as explained by the graphical
a
SI-1 was tested for sulfate scale after thermal aging at 130 °C for 7
days.
molecular modeling package Chem-X7.39 Moreover, the number
of methylene linkages between the aminomethylenephospho-
nate moieties in their backbone structures will affect the
adsorption of the SI on the scale crystal surface.40

Figure 7. Determination of FIC and time values for high-pressure dynamic tube-blocking experiments of SI-2 for sulfate scale.

233 DOI: 10.1021/acs.energyfuels.8b03531

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Figure 8. Determination of FIC and time values for high-pressure dynamic tube-blocking experiments of SI-1 for sulfate scale.

Figure 9. Determination of FIC and time values for high-pressure dynamic tube-blocking experiments of SI-1 for carbonate scale.

For carbonate scale experiments, two commercial SIs, ATMP SI-1 (10) > SI-4 (20) > SI-3 (50) > SI-2 (100)
and DTPMP, showed moderate performances, with FIC values For carbonate scale inhibition:
of 20 and 10 ppm, respectively. The main reason for the SI-1 (2) > SI-4 (20) > SI-3 (50) > SI-2 (100)
moderate inhibition performances of these SIs is related to the For squeeze applications, we run a long-term thermal stability
compatibility of the ATMP and DTPMP with group II metal test for the best SI compounds in harsh conditions such as high
ions such as calcium ions, as explained previously.21 These SIs temperature and high pressure. A mixture of 5 wt % solution of
form precipitates with calcium ions, making the SI unavailable SI-1 was heated in a pressure tube at 130 °C for 1 week under the
for calcite inhibition. In addition, PADMP shows very poor protection of nitrogen. Tables 3 and 4 show the results for the
carbonate scale inhibition, with an FIC of 100 ppm after 15 min thermal aging test. For sulfate scale, the FIC was 20 ppm after 4−
for both experiments. This is in line with the sulfate results 5 min after each run. For the carbonate scale test, the FIC went
presented above that this product is not as good an SI as with test from 2 to 10 ppm for both experiments (Figure 10). This shows
conditions reported previously.23,24 Moreover, some of the new that the SI is not thermally stable, but it still has some good
phosphonated aromatic compounds revealed poor to moderate inhibition effect.
antiscaling activities. For example, FIC values for SI-2 and SI-3 3.3. Calcium Compatibility. The monitoring of calcium
were 100 and 50 ppm, respectively. In addition, SI-4 gave a good compatibility for the SIs is well known in oilfield applications.
scale inhibition, with an FIC of 20 ppm after 46−51 min for both The SIs interact with Ca2+ ions affording a calcium−SI complex,
tests. It was investigated that SI-1 gave a significant carbonate which causes many problems in the oil production. The high-
scale inhibition compared to all new synthesized aromatic SIs. pressure dynamic tube test results give an indication of calcium
The FIC of SI-1 was 2 ppm after 30−35 min for both runs. compatibility for the SIs. The gradual increase in pressure slope
Figure 9 shows the graphical data for this test. The ranking and gives an indication of Ca2+ ion tolerance toward SIs. Dynamic
FIC (parts per million) of the scale inhibition performance for tube-blocking tests for SI-1 showed a significant scale inhibition
all new synthesized aromatic compound-based phosphonates performance for sulfate and carbonate scales as shown in Figures
for carbonate and sulfate scales were as follows. 9 and 10, respectively. Therefore, we decided to study the
For sulfate scale inhibition: calcium compatibility of SI-1 at different concentrations of SI
234 DOI: 10.1021/acs.energyfuels.8b03531
Energy Fuels 2019, 33, 228−237
Energy & Fuels Article

Table 4. FIC Values for Commercial and New Aromatic Scale Table 5. Compatibility Tests in 10 ppm of Ca2+ and 30 000
Inhibitors (SIs) for Carbonate Scale ppm (3.0 wt %) NaCl for SI-1
first second appearance
blank first scale test second scale test blank
SI dose (ppm) at mixing 30 min 1h 4h 24 h
time concn time concn time time
inhibitor (min) (ppm) (min) (ppm) (min) (min) SI-1 100 clear clear clear clear clear
SI-1 1000 clear clear clear clear clear
DTPMP 7 10 20 10 20 9
SI-1 10 000 clear clear clear clear clear
ATMP 7 20 26 20 44 9
SI-1 50 000 clear clear clear clear clear
SI-1 7 2 30 2 35 14
SI-2 8 100 24 100 12 10
SI-3 7 50 40 50 42 11
Table 6. Compatibility Tests in 100 ppm of Ca2+ and 30 000
SI-4 6 20 46 20 51 8
ppm (3.0 wt %) NaCl for SI-1
PADMP 11 100 15 100 15 12 appearance
SI-1a 8 10 18 10 15 7
SI dose (ppm) at mixing 30 min 1h 4h 24 h
a
SI-1 was tested for carbonate scale after thermal aging at 130 °C for SI-1 100 clear clear clear clear clear
7 days.
SI-1 1000 clear clear clear clear clear
SI-1 10 000 clear clear clear clear clear
and calcium ions. The SI concentrations were changed from 100 SI-1 50 000 clear clear clear clear clear
to 50 000 ppm, whereas the Ca2+ concentration was varied from
10 to 10 000 ppm. The compatibility tests were carried out at 80 Table 7. Compatibility Tests in 1000 ppm of Ca2+ and 30 000
°C using a brine concentration of 30 000 ppm NaCl to give some ppm (3.0 wt %) NaCl for SI-1
representation of a typical salinity of Heidrun oilfield formation
appearance
water. The calcium compatibility results are given in Tables 5, 6,
7, and 8. SI dose (ppm) at mixing 30 min 1h 4h 24 h
It was found that SI-1 showed good calcium compatibility at SI-1 100 haze haze haze haze haze
all inhibitor concentrations for 10 and 100 ppm of calcium ions SI-1 1000 haze haze haze haze haze
as shown in Tables 5 and 6. In addition, SI-1 afforded a hazy SI-1 10 000 haze haze haze haze haze
solution with 1000 ppm of Ca2+ ions at all inhibitor SI-1 50 000 haze haze haze haze haze
concentrations over the test period (Table 7). These calcium
compatibility results agree with the graphical slope data of the
high-pressure dynamic tube test for SI-1 (Figure 10). Moreover, products (DTPMP and ATMP), as well as sodium benzoate as
the compatibility was worse with 10 000 ppm of Ca2+ ions at all the biodegradable reference.
SI concentrations because a precipitate formed of the calcium− For the reference substance sodium benzoate, the lag time
SI complex (Table 8). before the onset of degradation was short and the time to reach
3.4. Biodegradation Tests. All biodegradation experi- 50% degradation was about 5 days. The degradation after 28
ments were conducted in accordance with the OECD 306 test days was 83% relative to the theoretical oxygen demand. This
procedure: Biodegradability in Seawater, Closed Bottle Method. indicates that the bacterial activity in the test system (seawater)
The results from the evaluation of biodegradation effects are was normal.
summarized in Table 9. All aromatic SIs (SI-1, SI-2, SI-3, SI-4, For the commercial phosphonate SIs, the results showed a
and PADMP) were compared with commercial phosphonate poor degradation rate of 15% in 28 days for DTPMP and a

Figure 10. Determination of FIC and time values for high-pressure dynamic tube-blocking experiments of SI-1 after thermal aging at 130 °C for
carbonate scale.

235 DOI: 10.1021/acs.energyfuels.8b03531

Energy Fuels 2019, 33, 228−237
Energy & Fuels Article

Table 8. Calcium Compatibility Experiments in 10 000 ppm of Ca2+ and 30 000 ppm (3.0 wt %) NaCl for SI-1
appearance
SI dose (ppm) at mixing 30 min 1h 4h 24 h
SI-1 100 precipitated precipitated precipitated precipitated precipitated
SI-1 1000 precipitated precipitated precipitated precipitated precipitated
SI-1 10 000 precipitated precipitated precipitated precipitated precipitated
SI-1 50 000 precipitated precipitated precipitated precipitated precipitated

Table 9. Biodegradability Activity Measured by the OECD inhibition performance for both sulfate and carbonate scaling.
306 Procedure over 28 Days The FIC of SI-1 was 10 ppm after 20 min for sulfate scaling and 2
ppm after 30−35 min for carbonate scaling. Other new SIs
inhibitor % BOD by OECD 306
showed moderate scale inhibition performance for sulfate and
seawater 0 carbonate scales. In addition, SI-1 showed good thermal stability
sodium benzoate 83 activity for sulfate scaling, affording only a small loss of scale
DTPMP 15 inhibition performance when aged for 1 week at 130 °C under
ATMP 34 anaerobic conditions. FIC went from 10 to 20 ppm. FIC of SI-1
SI-1 9 went from 2 to 10 ppm for carbonate scaling after thermal aging
SI-2 11 at the same test conditions. SI-1 also showed good calcium
SI-3 30 compatibility at all inhibitor concentrations for 10 and 100 ppm
SI-4 0 of calcium ions. However, SI-1 showed poor seawater
PADMP 63 biodegradation. In contrast, SI-3 showed reasonable biode-
gradation of 30% in 28 days and superior performance to
moderate biodegradation rate of 34% for ATMP. For the PADMP on both barite and calcite scaling.
aromatic SIs, PADMP gave the highest biodegradation property Overall, the results indicate that, although useful for the scale
of 63% over 28 days in the OECD 306 test. This makes this SI a inhibition performance, too much aromatic ring-substitution
very green product, but the performance as an SI for sulfate or leads to lower biodegradation activity. In addition, biodegrada-
carbonate scale was not very good (Tables 3 and 4). The new tion may be higher when the bacteria can recognize a natural
aromatic SIs showed poor to moderate biodegradation activity. compound that is known to be biodegradable, such as the amino
For example, SI-4, SI-1, and SI-2 gave low 28 day acid phenylalanine. We are continuing to explore other aromatic
biodegradation amounts of 0, 9, and 11%, respectively. SI-3 derivatives to lend further support to these conclusions.
showed a moderate biodegradation activity of 30% seawater
biodegradation over 28 days in the OECD 306 test. This gives
SI-3 the best inhibitor profile among the new aromatics. Its
■ AUTHOR INFORMATION
Corresponding Author
inhibition performance is superior to PADMP on both barite
*E-mail: [email protected].
and calcite scales, and it has a biodegradation in the 20−60%
bracket, which together with expected low bioaccumulation and ORCID
toxicity would make it environmentally acceptable in many Mohamed F. Mady: 0000-0002-4636-0066
regions such as the U.K.17,19 Malcolm A. Kelland: 0000-0003-2295-5804
The biodegradation results indicate that multiple aromatic Notes
ring substitutions may be detrimental to the ability of aromatic
The authors declare no competing financial interest.

■
SIs to biodegrade rapidly. The fact that benzoic acid and
PADMP have high biodegradation rates suggests this, although
the bacteria may also have greater recognition of natural ACKNOWLEDGMENTS
compounds such as the amino acid phenylalanine. We gratefully acknowledge Total E&P Norge AS for financial
support.

■
4. CONCLUSIONS
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237 DOI: 10.1021/acs.energyfuels.8b03531

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