Performance of PNIPAM-based Kinetic Hydrate Inhibitors For Nucleation and Growth of Natural Gas Hydrates

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Article
Performance of PNIPAM-based Kinetic Hydrate Inhibitors
for Nucleation and Growth of Natural Gas Hydrates
Juwoon Park, Kelly Cristine da Silveira, Qi Sheng, Colin D. Wood, and Yutaek Seo
Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 20 Feb 2017
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Page 1 of 32 Energy & Fuels
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1 Performance of PNIPAM-based Kinetic Hydrate
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11 2 Inhibitors for Nucleation and Growth of Natural Gas
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15 3 Hydrates
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20 4 Juwoon Park,1 Kelly Cristine da Silveira,2,3 Qi Sheng,4 Colin D. Wood,4* Yutaek Seo,1*
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5 Department of Naval Architecture and Ocean Engineering, Research Institute of Marine
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26 6 Systems Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826,
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28 7 Republic of Korea
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8 Federal University of Rio de Janeiro, Institute of Macromolecules, Rio de Janeiro, Brazil
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35 9 Polytechnic Institute, State University of Rio de Janeiro, Nova Friburgo, Brazil
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38 10 CSIRO Australian Resources Research Centre, Kensington, WA 6152, Australia
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45 12 CORRESPONDING AUTHORS: Yutaek Seo and Colin D. Wood
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49 13 AUTHOR EMAIL ADRESSES: yutaek.seo@snu.ac.kr and colin.wood@csiro.au
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53 14 TELEPHONE: YS +82-2-880-7329; CDW +61 8 6436 8701
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57 15 FAX: YS +82-2-888-9298; CDW +618-6436-8555
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16 ABSTRACT
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7 17 Hydrate prevention strategies for offshore flowlines are now moving toward hydrate risk
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10 18 management by delaying its nucleation and growth using water-soluble polymers, known as
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12 19 kinetic hydrate inhibitor (KHI). This study investigates the natural gas hydrate inhibition
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20 performance of three poly(N-isopropylacrylamide) (PNIPAM) based KHIs (PNIPAM-co-AA
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17 21 (poly(N-isopropylacrylamide-co-acrylic acid), PNIPAM-co-Cp (poly(N-isopropylacrylamide-co-
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19 22 cyclopentylamine), and PNIPAM-co-C4t (poly(N-isopropylacrylamide-co-tert-butylamine)) by
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23 determining the hydrate onset time, growth rate and resistance-to-flow using a high pressure
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24 24 autoclave. These data are compared to three control groups (water, Luvicap solution and PVP)
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26 25 under various cooling rates (0.25, 0.033, and 0.017 K/min). The results show that the nucleation
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29 26 of hydrate crystals was delayed in the presence of the KHI candidates as assessed using from the
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31 27 onset time at different cooling rates. The effect of the KHI candidate on the hydrate growth
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33 28 characteristics was also studied by determining the initial growth rate and torque changes with
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36 29 increasing hydrate fraction in the liquid phase. The obtained results confirmed the synthesized
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38 30 PNIPAM-based KHIs showed a high subcooling temperature, which is comparable to those of
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31 commercial KHIs. The modification of the base polymer (PNIPAM-co-AA), improves the
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43 32 kinetic inhibition performance for PNIPAM-co-Cp (13.9 K, 12.5 K, and 7.8K for 0.25, 0.033,
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45 33 and 0.017 K/min cooling rate, respectively) however results in decreased performance for the
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48 34 PNIPAM-co-C4t (9.6 K. 9.9K, 7.6 K for 0.25, 0.033, and 0.017 K/min cooling rate, respectively).
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50 35 After the hydrate onset, PNIPAM-co-C4t showed slow growth rate and stable torque during the
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52 36 hydrate formation than PNIPAM-co-Cp, suggesting its potential role as a crystal growth
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55 37 inhibitor. These results suggest that the performance of PNIPAM-based KHIs can be evaluated
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57 38 with the holistic investigation on nucleation and growth of hydrate crystals.
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6 40 KEYWORDS Gas hydrate, flow assurance, kinetic hydrate inhibition, PNIPAM, nucleation
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8 41 delay, crystal growth inhibition
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44 1. Introduction
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7 45 Gas hydrates are nonstoichiometric crystalline compounds consisting of host water and guest
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9 46 hydrocarbon molecules such as methane, ethane, and propane1. They are formed through
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11 47 hydrogen bonding between water molecules that enclathrate guest molecules at high pressures
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14 48 and low temperatures. These conditions are found in subsea oil and gas flowlines, as the
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16 49 production of offshore oil and gas fields have been moving into deeper and remote regions1-3.
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50 Industry practice has relied on the injection of vast quantities of alcohol- or glycol-based
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21 51 thermodynamic hydrate inhibitors (THIs) to completely prevent hydrate formation in subsea
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23 52 flowlines;4,5 however, handling large amounts of THI in remote offshore fields significantly
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26 53 increases the capital and operational expenditures, thereby adversely affecting the economics of
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28 54 field development. Consequently, hydrate prevention strategies are now moving toward hydrate
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30 55 risk management, through delaying nucleation of hydrate crystals, or the prevention of the
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33 56 agglomeration of the hydrate particles.
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35 57 Alternative strategies exist such as kinetic hydrate inhibitors (KHIs) low dosage hydrate
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37 58 inhibitors which are water soluble polymers that consist of a hydrophobic backbone with pendant
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40 59 groups such as amide or imide groups which can hydrogen bond with the hydrate. KHIs can
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42 60 delay hydrate formation by increasing the energy barrier to form hydrate nuclei, or by adsorbing
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61 to the surface of the hydrate crystals6,7. These include the homo- and co-polymers of N-vinyl
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47 62 carprolactam (VCap) and N-isopropyl acrylamide (NIPAM). Unlike THIs these inhibitors are
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49 63 effective at lower concentrations in the aqueous phase lowering the concentration from 30 wt%
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52 64 to 60 wt% down to 0.5 wt% to 3 wt% thereby lowering the cost of injection for storage space and
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54 65 simplifying the logistics of inhibition. However, the performance of KHIs is affected by factors
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56 66 such as the subcooling, gas and oil composition, gas-oil ratio, and salinity. Among these factors,
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67 the subcooling is the most important one regarding the screening the performance of KHIs8-10.
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6 68 The subcooling indicates the temperature difference between the hydrate equilibrium
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8 69 temperature and the fluid temperature, i.e., the thermal driving force for hydrate formation11.
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70 High driving force induces a large number of the hydrate nuclei that are created in the aqueous
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13 71 phase, and this creates a large surface area for the KHIs to act on, requiring an increased
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15 72 concentration or modified polymer structures.
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18 73 The performance test for KHIs has generally been carried out with a cooling of the KHI
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20 74 candidate solution at a constant rate, and a measurement of the hydrate onset time that indicates
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22 75 how long the hydrate formation is delayed in the presence of the KHI candidate. The cooling of
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25 76 the hydrocarbon mixture in a subsea flowline will be affected by the seawater temperature and
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27 77 the insulation materials for the subsea flowline; however, most of the performance tests for KHIs
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78 have been carried out with a fixed cooling rate or under isothermal conditions12-14. It is still
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32 79 challenging to transfer the laboratory test result into conditions relevant to the field operation, so
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34 80 there have been many attempts to develop advanced test protocols to screen the KHI candidates;
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37 81 however, there is scarce literature studying the effect of varying cooling rate on the performance
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39 82 of KHI.
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42 83 Moreover, recent works by Anderson et al.15 suggested that KHIs disturb the gas capture into
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45 84 hydrate cages by their adsorption into the growing hydrate crystals, and this directly affects the
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47 85 growth of the hydrate as well as its nucleation. Along with the measurement of the hydrate onset
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86 temperature, a catastrophic growth temperature was measured to indicate the way that the KHIs
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52 87 effectively suppressed the growth of the hydrate crystals ; however, the growth of hydrate
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54 88 crystals involves a more complex processes of hydrate particle growth and their agglomeration,
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89 which ultimately form the solid hydrate plug. In the proposed mechanism for hydrate particle
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90 agglomeration, a hydrate shell forms on the water droplets, and then the cohesive interaction
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6 91 between the hydrate shell-covered particles results in the formation of multi-particle aggregates
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92 . It seems that the agglomeration of hydrate particles can be prevented by avoiding multi-
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93 particle aggregation; however, controlling the growth rate of hydrate is challenging, as the mass
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13 94 transfer for hydrate formation is too fast to avoid the sintering and cohesion of the hydrate shell-
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15 95 covered water droplets. Joshi et al.16 suggested that hydrate particles will aggregate faster when
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18 96 the hydrate fraction in the liquid phase is larger than 10 ~ 20 vol%, which is supported by high
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20 97 pressure autoclave studies by Akhfash et al.17,18. These results indicate that the performance of a
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22 98 KHI must be investigated with the amount of hydrate and the resulting resistance-to-flow to
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25 99 evaluate its performance as a potential crystal growth inhibitor.
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28 100 Our previous work using high throughput test for KHI candidates19 suggested the modification of
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101 PNIPAM-co-AA by attaching cyclopentylamine (PNIPAM-co-Cp) or tert-butylamine
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33 102 (PNIPAM-co-C4t) results in the increased hydrate onset time than pure water. However, the
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35 103 stochastic nature of hydrate nucleation induces scattering of the experimental results, demanding
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38 104 more investigation in larger scale. In this work, the performance of the KHI candidates was
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40 105 investigated with the holistic investigation on both nucleation and growth of hydrates as follows:
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42 106 1) Measuring the hydrate onset time with a varying cooling rate in the nucleation stage, then 2)
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45 107 measuring the torque changes of the fluids as a function of the hydrate fraction in the growth
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47 108 stage. By employing a holistic investigation, a more effective characterization of the PNIPAM-
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109 based KHIs was possible.
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111 2. Materials and method
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7 112 2.1. Materials
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10 113 All reagents were used without purification. The following materials were purchased from Sigma
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12 114 Aldrich: N-(3-dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride (EDC, commercial
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15 115 grade); N-hydroxysuccinimide (NHS, 98%); cyclopentylamine (Cp, 99%); tert-butylamine (C4t,
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17 116 99.5%). Poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-co-AA) was synthesized in-
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19 117 house19. Luvicap and PVP were used as commercial inhibitors. Luvicap® EG HM was supported
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22 118 by BASF and polyvinylpyrrolidone (PVP K15, Mw = 9000 Da) was obtained from Ashland
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24 119 Chemical Co. An artificial natural gas (90.0 mol % CH4, 6.0 mol % C2H6, 3.0 mol % C3H8, and
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120 1.0 mol % n-C4H10) was supplied by Special Gas (Korea). Deionized water (purity: 99.99 mol%)
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123 2.2. Synthesis of PNIPAM-derivative polymers
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37 124 In order to produce KHI candidates through post-synthetic modification, the base polymer
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39 125 poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-co-AA) was synthesized by free radical
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126 polymerization19,20. The produced copolymer has 20 mol% of acrylic acid (AA), 80 mol% of N-
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44 127 isopropylacrylamide (NIPAM) and, as measured by gel permeation chromatography (GPC),
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46 128 ഥ௡ ) of 11.5 kDa and polydispersity
PNIPAM-co-AA has a number average molecular weight (‫ܯ‬
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49 129 index of 1.79. Through post-synthetic modification of the base polymer, similar molecular
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51 130 weight polymers were synthesized, which allows the direct comparison of the different
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53 131 functional groups in this study. After full activation of the acrylic acid content (20 mol%) via
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56 132 carbodiimide mediated coupling (EDC/NHS), additional KHI candidates, PNIPAM-co-Cp and
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133 PNIPAM-co-C4t, were generated by adding cyclopentylamine (Cp) and tert-butylamine (C4t),
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6 134 respectively. Synthesis protocol and characterization details can be found in our previous work17.
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136 2.3. Hydrate formation kinetics experiments
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16 137 All the experiments were conducted using a high-pressure autoclave equipped with a
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18 138 magnetically coupled stirrer with an anchor-type impeller. The reactor was constructed out of
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20 139 316 SUS. 80 mL of liquid was loaded into the reactor which has a total volume of 360mL, the
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23 140 total liquid consisted of a 60:40 volume ratio of water and hydrocarbon (in this work, decane).
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25 141 After the liquid was loaded, the cell was flushed three times using natural gas to remove any
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142 residual air. Then, the autoclave was placed in the circulating bath (RW 2040G; Jeio Tech). For
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30 143 the continuous stirring of the liquid in the cell, the anchor-type impeller was placed on a shaft
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32 144 and connected to a motor (BLDC 90). The cell was pressurized to 120 bar with a syringe pump
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35 145 at 24o C and the contents were stirred at 600 rpm to ensure the liquid was saturated with the
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37 146 natural gas. The fluids at the 600 rpm speed are in a turbulent regime with an approximate
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39 147 Reynolds number of 32,000. Once the pressure and temperature became stable, the cell was
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42 148 cooled down to the target temperature of 4 oC with various cooling rates (0.25 K/min, 0.033
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44 149 K/min, and 0.017 K/min) using a constant cooling method under isochoric conditions. The
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46 150 temperature was maintained at 4 oC for 10 hours followed by ramping up to 28o C where the
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49 151 temperature was retained for three hours to dissociate the hydrate and eliminate any residual
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51 152 hydrate structures. It is worth noting that the dissociation temperature is below the measured
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153 cloud point for the polymers so they remain soluble under these conditions. The temperature,
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56 154 pressure, and torque were measured using a PT 100 Ω (± 0.15o C), a transducer (0 bar to 200 bar,
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155 ± 0.1 bar) and a torque sensor (TRD-50KC) (± 0.3 %), respectively. The temperature, pressure,
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6 156 and torque were logged using a data acquisition system. Five experiments were repeated for each
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8 157 PNIPAM-based KHIs (total 15) to average the hydrate onset time, subcooling temperature, and
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158 hydrate volume fraction. The other 15 experiments for the three control systems, pure water +
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13 159 decane mixture, 0.5 wt% PVP solution + decane mixture, and 0.5 wt% Luvicap solution +
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15 160 decane mixture, were carried out for a direct comparison with the 15 experiments for the
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18 161 PNIPAM-based KHI systems (0.5 wt% PNIPAM-co-AA solution + decane mixture, 0.5 wt%
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20 162 PNIPAM-co-Cp solution + decane mixture, and 0.5 wt% PNIPAM-co-C4t solution + decane
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22 163 mixture).
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165 3. Results and Discussion
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7 166 3.1. Hydrate onset characteristics at different cooling rate
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10 167 Once the fluid temperature becomes lower than the hydrate equilibrium temperature, hydrate
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12 168 nuclei would be formed instantly from the thermodynamic point of view; however, there needs
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15 169 to be a driving force to initiate the nucleation. The primary function of kinetic hydrate inhibitors
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17 170 is to delay the nucleation of hydrate crystals under the given subcooling condition. Therefore, the
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19 171 hydrate onset characteristics were analyzed according to the hydrate onset time and subcooling
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22 172 temperature. In the constant cooling experiments, the hydrate nucleation point was determined
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24 173 by the rapid gas decrease from the hydrate formation. Table 1 presents the mean value and
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174 standard deviation over five repeat trials for the subcooling temperature (∆Tsub) and the hydrate
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29 175 onset time (tonset) at different cooling rate.
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32 176 The subcooling temperature is a significant factor presenting the required thermal driving force
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35 177 for the nucleation of hydrate crystals; thus, it can be a criterion for the estimation of the kinetic
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37 178 inhibition performance of the potential KHI candidate. The concentration of KHI candidate was
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39 179 0.5 wt% in aqueous phase, as in the control groups. The increase of the cooling rate indicates
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42 180 high thermal energy was applied over a certain period, resulting in a different hydrate nucleation
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44 181 point. For pure water, the subcooling temperature changes from 3.3 to 4.7 K with increasing
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46 182 cooling rate, while the onset time decreases 200.8 to 20.4 min. The addition of Luvicap and PVP
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49 183 increases the subcooling temperature as well as the onset time, clearly indicating the polymer
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51 184 structure acts on the hydrate nucleation process. The synthesized PNIPAM-base KHIs also
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185 increased the subcooling temprature and onset time compared to pure water.
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187 Table 1. Hydrate onset conditions for 0.5 wt% PNIPAM-based KHIs and control systems.
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7 Cooling rate Subcooling temperature Onset time
8 PNIPAM derivatives
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11 0.25 14.1 (0.1) 80.4 (2.0)
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14 PNIPAM-co-AA 0.033 7.6 (0.1) 241.6 (0.9)
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16 0.017 7.1 (0.3) 436.2 (21.0)
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19 0.25 13.9 (0.9) 71.0 (8.6)
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21 PNIPAM-co-Cp 0.033 12.5 (0.1) 389.4 (2.4)
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24 0.017 7.8 (0.8) 481.6 (47.8)
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26 0.25 9.6 (0.6) 54.5 (5.4)
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29 PNIPAM-co-C4t 0.033 9.9 (1.0) 311.4 (1.1)
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31 0.017 7.6 (1.1) 468.8 (65.6)
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34 0.25 4.7 (0.6) 20.4 (2.1)
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36 Pure water 0.033 3.3 (0.1) 104.4 (3.9)
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39 0.017 3.3 (0.1) 200.8 (4.7)
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41 0.25 11.6 (0.2) 83.8 (5.2)
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44 Luvicap 0.033 11.4 (0.9) 353.2 (26.3)
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46 0.017 7.9 (0.9) 484.8 (56.2)
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49 0.25 12.5 (1.2) 73.9(10.3)
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51 PVP 0.033 10.2 (0.5) 323.0 (11.9)
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54 0.017 8.5 (0.1) 548.5 (2.6)
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56 188 The standard deviation of subcooling temperature and onset time is shown in parenthesis.
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190 Figure 1 and Figure 2 showed the comparison of the hydrate onset time and subcooling
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6 191 temperature between the PNIPAM-based KHIs and the control group. The PNIPAM-co-AA
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8 192 solution showed subcooling temperatures of 14.1 K, 7.6 K, and 7.1 K with the cooling rates of
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193 0.25 K/min, 0.033 K/min, and 0.017 K/min, respectively; furthurmore, the onset times were 80.4
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13 194 min, 241.6 min, and 436.2 min. For the PNIPAM-co-Cp system the subcooling temperatures of
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15 195 13.9 K, 12.5 K, and 7.8 K with the cooling rates of 0.25 K/min, 0.033 K/min, and 0.017 K/min,
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18 196 respectively; moreover, the onset times are 71.0 min, 389.4 min, and 481.6 min. The
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20 197 modification of the base polymer structure, PNIPAM-co-AA, with cyclopentylamine enhanced
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22 198 the kinetic inhibition performance at the cooling rate of 0.033 K/min. For the PNIPAM-co-C4t,
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25 199 the subcooling temperatures were 9.6 K, 9.9 K, and 7.6 K and the onset times were 54.5 min
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27 200 311.4 min, and 468.8 min, respectively. We also included a PNIPAM-co-AA modified with tert-
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201 butylamine PNIPAM-co-C4t which adversely affected the performance of PNIPAM-based KHI,
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32 202 where the subcooling was higher than in pure water but lower than in PNIPAM-co-AA solution.
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35 203 Compared to the performance of PNIPAM-based KHIs, the commercial KHIs, both Luvicap and
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38 204 PVP, showed high subcooling temperature and long onset time. For fast cooling rate of 0.25
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40 205 K/min, the subcooling temperature of PVP solution was 12.5 K and slightly less than that of
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42 206 PNIPAM-co-AA and PNIPAM-co-Cp. When reducing the cooling rate to 0.033 K/min, Luvicap
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45 207 solution showed the subcooling temperature of 11.4K, however the value was still less than that
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47 208 of PNIPAM-co-Cp. For slow cooling rate of 0.017 K/min, the subcooling temperatures for KHI
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209 candidates were obtained at around 8.0 K, except PNIPAM-co-AA solution. As seen in Figure 1
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52 210 and Figure 3, the variation of subcooling temperature was less than 50% at the studied cooling
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54 211 rate ranges, however the onset time increased almost seven times with decreasing the cooling
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212 rate. Thus the subcooling temperature might need to be evaluated along with the onset time.
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28 215 Figure 1. Hydrate onset time comparison between the PNIPAM-based KHIs, commercial KHIs
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52 217
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55 218 Figure 2. Hydrate subcooling temperature comparison between the PNIPAM-based KHIs,
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220 standard deviation.
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221 Figure 3 shows the hydrate onset time as a function of subcooling temperature with various
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6 222 cooling rates. The leading KHI would result in a high subcooling temperature and long hydrate
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8 223 onset time. For the application of KHI for offshore fields, the maximum value for the subcooling
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224 temperature is the maximum difference between sea water temperature and hydrate equilibrium
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13 225 temperature of hydrocarbon fluid, while the maximum value for the onset time is the longest
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15 226 duration of hydrocarbon fluid inside the subsea flowlines. In this work, the maximum subcooling
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18 227 temperature came from the target cooling temperature, 277.15K and the hydrate equilibrium
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20 228 temperature, 293.15K. The maximum onset time was 600 min from the duration of experiment.
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23 229 For the cooling rate of 0.25 K/min, the obtained onset time showed linear increase with
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26 230 increasing the subcooling temperature depending on the added KHIs. Pure water showed the
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28 231 shortest onset time 20.4 min and the lowest subcooling temperature 4.7 K while PNIPAM-co-
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232 AA showed the longest onset time 80.4 min at the highest subcooling temperature 14.1 K. The
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33 233 performance of PNIPAM-co-Cp was close to the base polymer and Luvicap was next. When
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35 234 reducing the cooling rate to 0.033 K/min, the linear relationship shifted to a lower hydrate risk
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38 235 area due to increased onset time. The performance of PNIPAM-co-Cp was the best in this
39
40 236 cooling rate and Luvicap followed. For the cooling rate of 0.017 K/min, commercial KHIs,
41
42 237 Luvicap and PVP, performed better than PNIPAM-based KHIs with slight difference. As seen in
43
44
45 238 Figure 3, the performance of KHIs can not be simply judged from the measured subcooling
46
47 239 temperature and would be better evaluated from the relationship between the subcooling
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240 temperature vs. the onset time. Moreover, the cooling rate also affects the relationship. Figure 3
50
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52 241 suggests that the cooling rate of 0.033 K/min maintains high subcooling temperature and long
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54 242 onset time, thus the performance of KHIs placed in the low risk plane. Fast cooling rate 0.25
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243 K/min induces short onset time whereas slow cooling rate 0.017 K/min results in low subcooling
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244 temperature. These results suggest that the insulation design for offshore flowlines may affect the
4
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6 245 performance of the deployed KHI which must be considered in pipeline design.
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9 246 Our previous work adopting High Throughput hydate test showed stochastic hydrate formation
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12 247 for PNIPAM-co-AA, however confirmed an indicative inhibition peformance. Modification of
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14 248 the polymers contributed to the inhibition performance by increasing the hydrophobic content in
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16 249 the polymer structure. In this work, we again confirmed the perfomance of the PNIPAM-based
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19 250 KHIs with quatitative analysis of hydrate onset time and subcooling temperature. The PNIPAM-
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21 251 based KHIs and the commercial KHI have different functional groups and the structure and
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23 252 percentage of each group varies the adsorbing behaviors on the hydrate cage, thereby inducing a
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26 253 delayed hydrate nucleation. These phenomena would come from different functional groups in
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28 254 each PNIPAM-based KHI. It is well known that commercial KHIs such as PVCap and PVP have
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255 a polyethylene backbone that is linked to the pendant groups of one branch (five- or seven-
32
33 256 membered ring), including the amide group, and that the pendant groups enter the hydrate cage
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35 257 when the KHI absorbs on the hydrate crystal with the polymer backbone stretches along the
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38 258 hydrate-crystal surface. By modifying the structure of PNIPAM-co-AA the surface area of the
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40 259 pendant group would change which can result in steric hinderance in terms of hydrate formation.
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42 260 The change in polymer structure also affects the cloud point of the polymer as shown in our
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45 261 previous work so using this synthetic method the performance of the KHIs can be modulated in
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47 262 terms of hydrate peroformance and cloud point.
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32 263
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35 264 Figure 3. Hydrate onset time as a function of subcooling temperature of PNIPAM-based KHIs
36 265 with various cooling rates: 0.25 K/min (yellow region), 0.033 K/min (green region), and 0.017
37 266 K/min (blue region).
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43 268
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269 3.2. Hydrate growth characteristics at different cooling rate
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7 270 After the hydrate onset, hydrate particles quickly consumed dissolved gas molecules in liquid
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9 271 phase and grow further with mass transfer of gas molecules from vapor to liquid phase. The
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11 272 hydrate plug formation would occur when the hydrate fraction in liquid phase was large enough
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14 273 to accompany the agglomeration and bedding of the hydrate particles. Our previous work and
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16 274 literature indicated that the resistance-to-flow due to the agglomeration and bedding of hydrate
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275 particles became evident with hydrate fraction in liquid phase more than 0.10. KHI molecules
20
21 276 may inhibit the hydrate growth by attaching on the surface, thus reducing the growth rate in early
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23 277 stage of hydrate formation process.
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25
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27 278 In this work the performance of crystal growth inhibition for the PNIPAM-based KHIs
28
29 279 (PNIPAM-co-AA, PNIPAM-co-Cp, and PNIPAM-co-C4t was investigated at different cooling
30
31 280 rates and compared to the control groups (pure water, Luvicap solution, and PVP solution). The
32
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34 281 hydrate volume fraction was estimated from the gas consumption during the formation process,
35
36 282 and the amount of gas consumed for hydrate formation was calculated from the pressure
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283 difference between the experimental and calculated pressures with the postulation that no hydrate
39
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41 284 is formed 21,22. This procedure has been suggested as a method for the hydrate formation studies
42
43 285 in a flow wheel23 and in autoclave systems24-27. The hydration number was assumed 6.5 22. The
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45
46
286 growth rate was estimated from the consumed amount of gas while the formation proceeds
47
48 287 linearly in early stage. The hydrate fraction in the liquid phase at 100 min after the hydrate onset
49
50 288 and the value at the end of each cycle are calculated to present the hydrate fraction in early and
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53 289 last stage of the experiment. Table 2 presents the average values and the standard deviation of
54
55 290 the growth rate, hydrate fraction at 100 min, hydrate fraction at 600 min, and water conversion to
56
57 291 hydrate at 600 min.
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292 Table 2. Hydrate formation kinetics characteristics under 0.5 wt% PNIPAM-based KHIs.
4
5
6 Cooling rate Growth rate Hydrate Hydrate Water
7 (vol. frac. / volume fraction volume fraction conversion
8 (K/min) min) at 100 min at 600 min (%)
9
10
11 0.25 1.2×10-3 0.11 (0.02) 0.32 (0.03) 45.8 (3.9)
12
PNIPAM-co-
13 0.033 0.3×10-3 0.02 (0.00) 0.18 (0.02) 25.6 (2.4)
14 AA
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16 0.017 0.2×10-3 0.02 (0.01) 0.18 (0.01) 25.7 (1.5)
17
18 0.25 6.0×10-3 0.25 (0.01) 0.39 (0.03) 56.9 (4.1)
19
20 PNIPAM-co-
21 0.033 3.8×10-3 0.20 (0.01) 0.33 (0.03) 47.2 (5.3)
Cp
22
23 0.017 0.2×10-3 0.02 (0.01) 0.28 (0.02) 40.2 (3.1)
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25
26 0.25 7.7×10-3 0.24 (0.02) 0.42 (0.02) 62.3 (3.9)
27
PNIPAM-co-
28 0.033 2.4×10-3 0.24 (0.05) 0.54 (0.08) 81.3 (13.5)
29 C4 t
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31 0.017 3.6×10-3 0.14 (0.15) 0.47 (0.06) 69.2 (10.2)
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33 0.25 8.9×10-3 0.43 (0.02) 0.50 (0.02) 74.0 (3.9)
34
35
36 Pure water 0.033 14.7×10-3 0.38 (0.03) 0.49 (0.02) 72.5 (3.7)
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38 0.017 6.5×10-3 0.35 (0.01) 0.45 (0.02) 66.5 (2.8)
39
40
41 0.25 4.9×10-3 0.20 (0.06) 0.40 (0.06) 58.9 (9.8)
42
43 Luvicap 0.033 3.8×10-3 0.13 (0.01) 0.38 (0.03) 55.8 (4.2)
44
45
46 0.017 0.2×10-3 0.03 (0.02) 0.38 (0.04) 55.2 (6.5)
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48 0.25 6.4×10-3 0.29 (0.03) 0.38 (0.02) 55.7 (3.8)
49
50
51 PVP 0.033 7.8×10-3 0.32 (0.02) 0.44 (0.02) 64.9 (2.6)
52
53 0.017 10.1×10-3 0.31 (0.01) 0.43 (0.04) 63.3 (6.5)
54
55
293 The standard deviation of the hydrate volume fraction at 100 min and 600 min, and water
56
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58 294 conversion is shown in parenthesis.
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60
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295 Figure 4 shows the growth of hydrate for 100 min after the onset at each cooling rate. For every
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6 296 cooling rate, pure water showed fast hydrate growth than other KHI-added systems. The hydrate
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8 297 fraction reached 0.43 at 100 min with initial growth rate of 0.0089 vol. frac./min and increased
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298 slightly more to 0.50 at 600 min at fast cooling 0.25 K/min. The addition of PVP reduces the
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13 299 initial growth rate 0.0064 vol. frac./min and the hydrate fraction at 100 min was 0.29. Luvicap
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15 300 performed better with the initial growth rate 0.0049 vol. frac./min and the hydrate fraction 0.13
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18 301 at 100 min. The base polymer PNIPAM-co-AA out-performed Luvicap showing the initial
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20 302 growth rate 0.0012 vol. frac./min and the hydrate fraction 0.11 at 100 min. However, by
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22 303 modifying the structure into PNIPAM-co-Cp and PNIPAM-do-C4t showed a growth rate 0.0060
23
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25 304 and 0.0077 vol. frac./min, and the resulting hydrate fraction was 0.24 and 0.25, respectively. As
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27 305 seen in Figure 3 (a), the growth curve for PNIPAM-co-Cp and PNIPAM-co-C4t solutions placed
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306 between PVP and Luvicap. PNIPAM-co-C4t showed very slow growth period during the first 15
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32 307 min, however fast growth was followed soon after. It can be concluded that the base polymer
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34 308 PNIPAM-co-AA outperformed commercial KHIs in terms of crystal growth inhibition, however,
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37 309 further modification adversely affect its performance. This is important because it highlights
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39 310 which functional groups can improve KHIs performance. The trends are more accurate than
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41 311 using other synthetic routes (eg., free-radical co-polymerization) because this approach generates
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44 312 all polymers with similar Mw, same composition and end groups.
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46 313 Similar results were obtained for cooling rate of 0.033 K/min and 0.017 K/min. For the initial
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48 314 growth after the onset, PVP has the fastest growth rate at slow cooling 0.017 K/min, and is even
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51 315 faster than the pure water until the volume fraction of 0.3. The hydrate growth rate of the other
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53 316 systems is slower than that of the pure water. The modified polymers, PNIPAM-co-Cp and
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317 PNIPAM-co-C4t, performed better than PVP and close to Luvicap. The base polymer PNIPAM-
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318 co-AA was the best. The initial growth rate was 0.003 and 0.002 vol. frac./min at cooling rate
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6 319 0.033 and 0.017 K/min, respectively. The hydrate fraction was 0.02 at 100 min and reached 0.18
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8 320 at 600 min, which was about half of the fraction obtained in Luvicap solution. The modification
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321 of the base polymer increased the cloud point and enhanced the nucleation inhibition
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13 322 performance, however it was not straightforward to the performance for the crystal growth
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15 323 inhibition.
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18 324 Figure 4 suggested the cooling rate also affected the performance of KHIs significantly during
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20 325 the formation process. The rapid cooling down of the system would induce relatively higher
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22 326 subcooling temperatures, leading to an excess energy supply for the hydrate formation; therefore,
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25 327 the larger temperature difference of the solution under faster cooling rates was more favorable to
26
27 328 the fast hydrate growth than under slower cooling rates. Insulation of subsea flowlines would
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329 decrease the cooling rate and would help to reduce the hydrate growth as seen in Figure 4 (c).
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32 330 This was true for PNIPAM-based KHIs and Luvicap, however, PVP showed the increase of
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34 331 initial growth rate from 0.0064 to 0.0101 vol.frac./min when reducing the cooling rate from 0.25
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37 332 K/min to 0.017 K/min. As showed in previous section, PVP performed well to inhibit the hydrate
38
39 333 onset, however once the hydrate crystals started to growth, its performance as a crystal growth
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41 334 inhibitor was not as effective as others. More investigation must be carried out to understand the
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44 335 role of functional groups in KHIs during the formation process.
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46 336
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48 337
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339 Figure 4. Comparison of hydrate growth for PNIPAM-based KHIs, commercial KHIs (Luvicap
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5 340 and PVP) 0.5 wt % solutions, and pure water under cooling rate, (a) 0.25 K/min, (b) 0.033 K/min,
6 341 (c) 0.017 K/min
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342 To investigate the relation between the hydrate volume fraction and the resistance-to-flow, the
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6 343 torque with the hydrate growth was measured. Figure 5 (a) – (c) showed the measured torque
7
8 344 changes during the hydrate formation for PNIPAM-based KHIs and control groups at different
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345 cooling rates. The resistance-to-flow is a qualitative parameter to estimate the flowability of
12
13 346 hydrocarbon fluid to keep transporting the hydrate particles without forming the hydrate plug. As
14
15 347 the sintering and bedding of hydrate particles occurs, lower flowability of the hydrocarbon fluid
16
17
18 348 would results in the torque increases. As seen for the pure water in Figure 5 (a) – (c), torque
19
20 349 started to increase when hydrate fraction increased more than 0.10 in liquid phase, suggesting the
21
22 350 agglomeration of hydrate particles would occur for larger hydrate fraction in liquid phase than
23
24
25 351 0.10. The growth rate of the pure water became faster with an increased torque after the 0.15
26
27 352 hydrate fraction, as seen in Figure 5 (a) and (b), which means that the hydrate that had formed in
28
29
353 the system changed from homogeneous to heterogeneous.
30
31
32
33 354 The hydrate growth and torque changes for PNIPAM-based KHIs showed different patterns than
34
35 355 commercial KHIs. PNIPAM-co-Cp and PNIPAM-co-C4t indicated torque increases once the
36
37
38 356 hydrate volume fraction increased more than 0.10. When the cooling rate was 0.017 K/min, the
39
40 357 PNIPAM-co-AA system represented the smallest growth rate and torque value with the least
41
42 358 hydrate volume fraction, followed by the PNIPAM-co-Cp system, as presented in Figure 5 (c).
43
44
45 359 The PNIPAM-co-C4t system showed a plateau, but a sudden increase during the hydrate fraction
46
47 360 reached the moment of 0.10. Overall, the base polymer PNIPAM-co-AA was the best to suppress
48
49
361 the torque increase during the hydrate formation, but its modification into PNIPAM-co-CP and
50
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52 362 PNIPAM-co-C4t did not help to control the increase of resistance-to-flow. More investigation
53
54 363 will be carried out near future to understand the role of KHI during the agglomeration and
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364 bedding of hydrate particles during the formation process.
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43 366
44 367
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46 368 Figure 5. Relation between hydrate fraction and torque in representative cycle for PNIPAM-
47 369 based KHIs, commercial KHIs (Luvicap and PVP) 0.5 wt % solutions, and pure water under the
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370 cooling rate, (a) 0.25 K/min, (b) 0.033 K/min, (c) 0.017 K/min.
50 371
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372 4. Conclusions
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7 373 This study investigates the hydrate inhibition performance of three PNIPAM-based KHIs
8
9 374 (PNIPAM-co-AA, PNIPAM-co-Cp, and PNIPAM-co-C4t) by determining the hydrate onset
10
11
12 375 time, its growth rate, and resistance-to-flow using a high pressure autoclave. Comparison to three
13
14 376 control groups (water, Luvicap solution, and PVP solution) is also performed at various cooling
15
16
377 rates (0.25, 0.033, and 0.017 K/min). The modification of the base polymer structure, PNIPAM-
17
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19 378 co-AA, with cyclopentylamine enhanced the kinetic inhibition performance at the cooling rate of
20
21 379 0.033 K/min. For the PNIPAM-co-C4t, the subcooling temperatures were 9.6 K, 9.9 K, and 7.6 K
22
23
24 380 and the onset times were 54.5 min 311.4 min, and 468.8 min, respectively. The modification
25
26 381 with tert-butylamine adversely affected the performance of PNIPAM-based KHI, where the
27
28 382 subcooling was higher than in pure water but lower than in PNIPAM-co-AA solution. The
29
30
31 383 obtained results confirmed the synthesized PNIPAM-based KHIs presented high subcooling
32
33 384 temperature, which is comparable to those of commercial KHIs. The obtained subcooling
34
35 385 temperature was plotted with the hydrate onset time, which suggested the cooling rate of 0.033
36
37
38 386 K/min maintains high subcooling temperature and long onset time, thus the performance of KHIs
39
40 387 placed in the low risk plane. Using the cooling rate to determine the performance of KHI
41
42
43
388 candidates is a new approach. After the hydrate onset, PNIPAM-co-C4t showed slow growth
44
45 389 rate, but stable torque during the hydrate formation was achieved with PNIPAM-co-Cp,
46
47 390 suggesting the base polymer PNIPAM-co-AA showed best performance as a crystal growth
48
49
50 391 inhibitor. These results suggested that the performance of PNIPAM-based KHIs were able to be
51
52 392 evaluated with the holistic investigation on nucleation and growth of hydrate crystals.
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393
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394 AUTHOR INFORMATION
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6 395 Corresponding authors: Yutaek Seo and Colin D. Wood
7
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9 396 Notes
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11 397 The authors declare no competing financial interests.
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15 398
16
17 399 ACKNOWLEDGMENT
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400 This work was supported by the Technology Innovation Program (10060099) funded by the
20
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22 401 Ministry of Trade, Industry & Energy (MI, Korea) and also supported by the Global Leading
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24 402 Technology Program of the Office of Strategic R&D Planning (OSP) funded by the Ministry of
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403 Trade, Industry & Energy (10042424).
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406 REFERENCES
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Performance of PNIPAM-based Kinetic Hydrate Inhibitors For Nucleation and Growth of Natural Gas Hydrates

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Performance of PNIPAM-based Kinetic Hydrate Inhibitors For Nucleation and Growth of Natural Gas Hydrates

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