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Article
Comparison of Kinetic Hydrate Inhibitor Performance on Structure I and
Structure II Hydrate-Forming Gases for a Range of Polymer Classes
Eirin Abrahamsen, and Malcolm A. Kelland
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b03318 • Publication Date (Web): 18 Dec 2017
Downloaded from http://pubs.acs.org on December 23, 2017

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Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street
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Page 1 of 29 Energy & Fuels

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3 Comparison of Kinetic Hydrate Inhibitor Performance on Structure I and
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Structure II Hydrate-Forming Gases for a Range of Polymer Classes
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11 Eirin Abrahamsen* and Malcolm A. Kelland
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Department of Mathematics and Natural Sciences, Faculty of Science and Technology,
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16 University of Stavanger, N-4036 Stavanger, Norway.
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Corresponding author: eirin.abrahamsen@uis.no
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24 ABSTRACT
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27 A series of water-soluble polymers has been investigated for comparison of their potential as
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kinetic hydrate inhibitors (KHIs) for both Structure I (SI)- and Structure II (SII)-forming gas
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mixtures. A slow constant cooling test method and steel rocking cells have been used for
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34 these experiments. The average hydrate onset temperatures (To) have been used to rank the
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36 polymers according to their KHI ability, the lower To values gives a higher rank. The object of
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38 the study was a comparison of the KHI performance for SI versus SII inhibition for a range of
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40 polymers, not a study to find the optimal polymer for each hydrate structure.
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43 The most interesting comparative results were the large deviations of the ethyl derivative of
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45 poly(N-alkylglycine) for the two hydrate systems, where this polymer performed very well
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47 with the SI-forming gas, but had significantly less effect on the SII-forming gas. Also poly(2-
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ethyl-2-oxazoline) (PEtOx) and poly(iso-propenyloxazoline)-01 (PiPOx-01) ranked better
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52 with SI hydrates in comparison with the SII hydrate system. In general the polymers that work
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54 well on the SI-forming gas, works well on SII-forming gas as well. KHI mechanistic insights
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56 from this study was discussed.
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3 Although other KHIs outside this study may be available with better performance, we found
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5 that the best KHIs for SII hydrates were two N-vinyl caprolactam polymers in the synergistic
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7 solvent 2-butoxyethanol and the best KHIs for SI hydrates were an N-iso-propylacrylamide
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9 homopolymer and the same two N-vinyl caprolactam polymers.
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16 INTRODUCTION
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19 Production of oil and gas under certain temperature and pressure conditions can lead to gas
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21 hydrate formation, which can cause severe blockage of the pipelines. 1-3
Gas hydrates form
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when there is free water together with gas at elevated pressures and low temperatures, which
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26 are typical conditions for fields in cold climate areas and for subsea pipelines. Common
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28 components of the produced natural gas mixtures that can promote the formation of gas
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30 hydrates include small hydrocarbons such as methane, ethane, propane, (iso-)butane as well as
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32 carbon dioxide and hydrogen sulfide. 2, 4, 5
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35 To prevent plugging of the pipelines by gas hydrates, thermodynamic chemical inhibition has
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37 been commonly used for many decades. Low dosage hydrate inhibitors (LDHIs) such as
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39 kinetic hydrate inhibitors (KHIs) are becoming more widespread since they can be used at
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very low dosages (less than 5 wt. % of the aqueous phase). 6 This compares to conventional
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44 thermodynamic hydrate inhibitors (THIs) that often need to be dosed in very large amounts
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46 (up to 50 wt.% or more of the produced water). 2, 7, 8 The KHIs have also in many cases been
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48 used together with THIs in order to decrease the large amounts of chemicals needed to get
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50 sufficient inhibition. 9, 10
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53 The majority of oil and gas fields produce natural gas mixtures that lead to Structure II (SII)
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55 gas hydrate as the most thermodynamically stable phase. 3 That is why studies on developing
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3 kinetic hydrate inhibitors have concentrated on using a SII-forming gas mixture. However,
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5 fields that are very rich in methane gas can give Structure I (SI) hydrate as the most stable
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7 phase. 3 In addition, SI hydrate can also form as a stable phase using SII-forming gas mixtures
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9 when the phase boundary for SI formation is past when cooling. The fluids will cool beyond
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both the SII and SI equilibrium curve in slow constant cooling experiments. An example is
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14 shown in Figure 1 with a graph of the SI- and SII equilibrium curves and the change in
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16 pressure/temperature (PT) profile during a slow constant cooling test. In this example two PT
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18 profiles are shown where the green curve starts at 110 bar and the red curve starts at 76 bar. In
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20 a closed system the pressure will decrease as the temperature decreases. The equilibrium
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22 temperature (Teq) for the SI-forming gas, at 110 bar, is approximately 15-16 °C and at 76 bar
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the Teq is approximately 12.5-13.5 °C. For the SII-forming gas, at 110 bar the Teq is
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27 approximately 21.5-22.5 °C and at 76 bar the Teq is approximately 20-20.5 °C. The range of
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29 the Teq values is based on various software such as PVTSim from Calsep and Mutiflash from
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31 KBC. 11
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26 Figure 1. Equilibrium temperature curves for SI (dotted red) and SII (dotted green). Pressure
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vs. temperature profile for the constant cooling experiments (SI red, SII green).
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34 The potential for formation of SI hydrate may be the main reason for the subcooling limit for
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36 use of KHIs in SII-forming systems. Therefore, it is important to understand which KHIs are
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38 best suited for inhibiting SI hydrate-forming systems.
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41 Among the first commercial KHIs and probably of the most common classes to be used in
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43 KHI formulas are homo- and copolymers of N-vinyl lactams such as VP and VCap. These
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polymers were also found to give increased KHI performance with solvents such as BGE and
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47 12-14
48 MEG. Similar polymers and copolymers with different ring sizes have also been
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50 investigated as KHIs, where increasing the lactam ring size was found to give increasing KHI
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52 performance.15, 16
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3 Other polymers that have been investigated often contain amide groups, such as the lactam
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5 polymers. The amide group seems to help with good inhibition effects.17-19 For example
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7 polyaspartamides in which have been investigated mainly because of the potential of an all-
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9 around green KHI.20, 21
Other well-known KHI polymer classes are based on N-
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alkyl(meth)acrylamides and hyperbranched polyesteramides.3, 22, 23
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14 A more recent focus have been to find environmentally friendly KHIs, specifically with high
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biodegradation rates in seawater. One of the early ideas of hydrate inhibition came from
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19 natural anti-freeze proteins that can be found in certain species of fish, insects, plants and
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21 bacteria.18, 24
Since then, several proteins and peptides have been investigated as KHIs,
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23 because they are expected to be readily biodegradable. Amino acid and derivatives thereof
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25 have also been investigated as KHIs, but the KHI performance on natural gas or CO2 hydrate
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27 is poor.26-28
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30 Over the past 25 years, and particularly the last 10 years, a wide range of polymer classes
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32 have been tested for their KHI performance on a SII hydrate-forming gas mixture. This gives
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34 us a unique position to be able to test the KHI performance of the same polymers on SI
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methane hydrate for comparison.
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39 We report here our KHI performance results on a wide range of water-soluble polymers using
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the slow constant cooling test method in steel rocking cells. Both pure methane gas (giving SI
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44 hydrates) and a synthetic natural gas mixture (giving preferably SII hydrates) were used. We
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46 underline that this study is not designed to find the optimal polymers to inhibit either hydrate
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48 structure as more optimal polymers in the classes being studied could probably be found.
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3 EXPERIMENTAL METHODS: KINETIC HYDRATE INHIBITOR PERFORMANCE
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5 TESTS
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8 Materials
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11 Solvents and commercial products were used as received from supplier, without any further
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13 purifications. Polyacrylamide (PAM), 50 wt.% in H2O) Mw = 1500 and polyethylene glycol
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15 (PEG), Mw = 400 was supplied by Sigma Aldrich.
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18 Products supplied by Nippon Shokubai are poly(N-iso-propylacrylamide) (PNIPAM) as FX-
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20 AAM IP1000-11 (Mw = 2.1k, Mn = 1.1k) and iso-propylacrylamide /
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22 (acrylamide)propanesulfonic acid (NIPAM/AMPS) copolymer (10 wt.% AMPS) as IP 1010
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ASN. Products supplied by Ashland (ISP) are N-vinyl caprolactam (VCap / VOH) copolymer
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27 36 wt.% in 2-butoxyethanol (or butyl glycol ether, BGE) as Inhibex BIO-800, poly(N-vinyl
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29 caprolactam) (PVCap) 50 wt.% in BGE, Mw = 2k as Inhibex 101, poly(N-vinyl pyrrolidone)
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31 (PVP) as PVP K-15 and butylated PVP (Bu-PVP) as Antaron P904. Products supplied by
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33 BASF are VCap / N-vinyl pyrrolidone (VCap/VP) (1:1) copolymer (53.8 wt.% in H2O) as
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35 Luvicap55 W, PVCap 41.1 wt.% in monoethylene glycol (MEG) low and high molecular
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(HM) weight as Luvicap EG and Luvicap EG HM. A hyperbranched polyesteramide-based
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40 KHI 30 wt.% in unknown solvent was supplied by Baker Hughes as HI-M-PACT 83701.
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42 Pectin Citrus was supplied by Alfa Aesar (purchased via VWR). Hydroxyethyl cellulose
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44 (HEC), Mw = 100k supplied by Schlumberger.
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47 The following polymers have been synthesized in our laboratories and/or have previously
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49 been tested in our group (see the references for further information): poly(N-vinyl piperidone)
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51 (PVPip) , Mw = 25k, poly(N-vinyl caprolactam) UiS (PVCap UiS), Mw = 4000 , poly(N-
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53 vinyl azacyclooctanone) (PVACO), 35.6 wt.% in iso-propanol (iPA) Mw = 4000-5000 15
,
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55 poly(N-methylglycine) (PNMG) Mn = 1200 26
, poly(N-ethylglycine) (PNEG) Mn = 1900 26
,
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3 poly(N-propylglycine) (PNPG) Mn = 1700 26, poly(N-iso-propylglycine) (PNiPG) Mn = 3000
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5 , poly(N-iso-propylmethacrylamide) (PNIPMAM) , poly(N-ethylmethacrylamide)
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7 (PNEMAM), poly(N,N-dimethylhydrazidomethacrylamide) III (P(DMHMAM) III) 29
,
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9 polyaspartamide (iso-butyl / methyl) (80/20) (PAsp iBu/Me) 44.6 wt.% in dimethyl sulfoxide
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(DMSO) 20, poly(dimethylamineoxide) ethylacrylate (PDMAOEA) 21.4 wt.% in H2O, poly(2-
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14 ethyl-2-oxazoline) (PEtOx) 30, poly(iso-propenyloxazoline)-01 (PiPOx-01) Mn = 2000, PDI =
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16 1.26 , KHI 530 is a natural polymer, 40 wt.% in aqueous medium ,
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18 tetraethylenepentaminebutylated amine oxide (TEPA-Bu-AO), 35.1 wt.% in H2O. The
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20 structures of the different polymers synthesized and/or previously tested in our lab are shown
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3 a) O R b) c)
4 R1 R1
N
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N H
6 H
n n
7 n
8 O NH O NH
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10 R N
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O e) f)
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N H
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H n
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18 O NH N O O R

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HN R
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R
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N N O O O
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Bu Bu
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N
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34 n n n n O
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O
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45 Figure 2. Molecular structures of the different polymers synthesized and/or previously tested
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47 in our lab. a) Poly(N-alkylglycine)s, b) poly(N-alkyl(meth)acrylamides, c) P(DMH(M)AM),
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49 d) polyaspartamides, e) PiPOx, f) poly(2-alkyl-2-oxazoline), g) TEPA-Bu-AO, h)
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51 PDMAOEA, i) PVP, j) PVPip, k) PVCap, l) PVACO. R = alkyl group and R1 = H or CH3.
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3 High-Pressure Rocking Cell Tests with Pure Methane Gas and Synthetic Natural Gas
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5 The procedure for the KHI performance tests were carries out by the same procedure as done
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7 previously in our group, for better comparison of the results.11, 34 The test equipment used was
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9 supplied by PSL Systemtechnik, Germany, a rocker rig that can hold up to five high-pressure
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steel rocking cells. Each cell can hold up to 40 ml where 20 ml was filled with an aqueous test
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14 solution. To simulate turbulent flow, a steel ball was placed in each cell so the liquid is
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16 properly agitated. The system was then pressurized using either a SI- or SII-forming gas. Pure
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18 methane gas was used as the SI-forming gas hydrates. Correspondingly, a synthetic natural
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20 gas mixture (SNG) containing the components listed in Table 1 was used as the SII-forming
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22 gas.
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28 Table 1. Synthetic natural gas (SNG) mixture used in the KHI performance tests.
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31 Component mol %
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N2 0.10
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34 CO2 1.84
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36 methane 80.67
37 ethane 10.20
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39 n-propane 4.90
40 iso-butane 1.53
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42 n-butane 0.76
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3 The procedure for loading the cells and setup of the standard constant cooling test for the KHI
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5 performance tests are as follows:11, 34
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8 1. The polymer was diluted to desired concentration in deionized water at least one day
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10 before testing it. 20 ml sample was loaded in each cell at room temperature and
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12 placed in the water bath at 20.5 °C to equilibrate.
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14 2. Before purging the cells with 3-5 bar of the hydrate-forming gas, vacuum was applied
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in order to remove air in the system. After depressurizing the system, vacuum was
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19 applied again.
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21 3. The system was pressurized to the desired test pressure, the cells were rocking at a
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23 rate of 20 rocks/min or 10 cycles/min through an angle of ± 40°.
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25 4. The starting temperature was set to 20.5 °C and with a cooling rate of approximately
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27 1 °C/hour, the minimum temperature was set to 2 °C.
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29 5. Each cell is equipped with temperature- and pressure sensors. In addition, there is a
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sensor on the cooling bath. All the data is logged on a local computer.
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37 For the SII-forming gas, a pressure of approximately 76 bar is used as in previous work in our
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39 group, where 20.5 °C is the Teq found from calculations done in Calsep’s PVTSim software.
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For the SI-forming gas, we had to increase the pressure to 110 bar in order to be able to
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44 observe the pressure drop for the best performing KHIs reported in this paper. The SI
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46 envelope lies within the SII envelope at higher pressures and lower temperatures (as shown in
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48 Figure 1). Absolute pressure does affect KHI performance as several studies have shown, but
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50 results so far indicate that it does not appear to affect the ranking. 36-39
In these KHI
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hydrates, is not analyzed. Thus, the exact composition of the clathrate structures involved are
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3 Because the system is closed, the pressure will decrease correspondingly as the temperature
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5 decreases at a constant rate. In addition, the pressure will decrease a few bars at the start of
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7 the test as the gas dissolves in the aqueous phase.
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10 The pressure and temperature data are plotted against the time to give a pressure and
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12 temperature graph where we can find the onset temperature (To) and the temperature for rapid
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14 hydrate formation (Ta) (Figure 3 and Figure 4). To is the value of most interest because this is
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the temperature at which the first macroscopic hydrate formation is observed. The nucleation
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19 process is not detectable in these graphs and may have taken place earlier than the given time
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21 of To. From Figures 4, the data for each cell can be analyzed.
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3 Figure 3 shows a summary of the graph from all five cells and from this, the graphs for each
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5 cell can be generated for analysis. The To value is found by the first deviation from the linear
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7 slope as shown in Figure 4. The Ta value is found by the point of the largest pressure drop in
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9 the slope after To. P1 is the pressure graph for cell 1, T1 is the temperature for cell 1. From the
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figure, the To was found at 12.1 °C after approximately 544 minutes and Ta was found at 11.1
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3 In total, 8-10 individual experiments were carried out for each polymer in these tests, using
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5 the slow constant cooling test method. Exceptions are for the polymers of limited amounts or
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7 if the polymer had poor performance in addition to causing problems such as foaming.
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9 There were no observations of any systematic error in any of the cells, i.e. none of the cells
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gave consistently better or worse results than the others for each experiment.
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16 RESULTS AND DISCUSSION
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19 The results will be divided into the following categories for the main discussion; N-vinyl
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21 lactam-based polymers, poly(N-alkylglycine)s, miscellaneous polymers and PVP blends with
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23 other water-soluble polymers. This has been done to give the reader a better overview. In
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25 addition, we will summarize the most important results regarding KHIs that gave significant
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differences in ranking between the SI and SII gases. The complete list of tested polymers is
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30 summarized in Table 2 with the overall rank based on the average To values. For
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32 simplification, we illustrated only the To values in the figures.
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35 We underline that this is a comparative study to understand how structural differences may
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37 affect rankings between SI and SII. Comparisons of KHI rankings within one hydrate
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39 structure can be misleading since the optimum polymers within the polymer classes tested
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41 may not be represented, particularly those that are not commercial KHIs.
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3 Table 2 Average To values and ranking of the tested polymers at 2500 ppm by weight.
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6 To-av To-av
7 KHI 2500ppm Methane Rank SNG KHI 2500ppm
8 [°C] [°C]
9 DIW 12.2 17.5 DIW
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PNIPAM 4.4 1 2.6 VCap/VOH 36 wt.% in BGE
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12 VCap/VOH 36 wt.% in BGE 4.6 2 5.2 PVCap 50 wt.% in BGE
13 PVCap 50 wt.% in BGE 4.8 3 6.0 PNPG
14 PNEG 5.5 4 6.0 Hyperbranched polyesteramide
15 VCap/VP 53.8 wt.% in water 5.8 5 6.2 PNIPAM
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17 PNiPG 6.0 6 6.5 VCap/VP 53.8 wt.% in water
18 VCap 41.1 wt.% in MEG 6.4 7 8.0 PNiPG
19 PNPG 6.7 8 8.2 TEPA-Bu-AO 35.1 wt.% H2O
20 PiPOx-01 6.8 9 8.3 VCap 41.1 wt.% in MEG
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VCap HM 41.1 wt.% in MEG 7.0 10 8.3 VCap HM 41.1 wt.% in MEG
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23 Hyperbranched polyesteramide 7.2 11 8.7 PAsp iBu/Me 44.6 wt.% in DMSO
24 PNIPMAM 7.5 12 9.5 PNIPMAM
25 TEPA-Bu-AO 35.1 wt.% H2O 7.8 13 9.7 PVACO 35.6 wt.% in iPA
26 PVACO 35.6 wt.% in iPA 8.0 14 10.0 KHI 530 (40 wt.% in aq. medium)
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28 PVCap UiS 8.1 15 10.1 PVCap UiS
29 PVPip 8.1 16 10.3 NIPAM/AMPS (10% AMPS)
30 NIPAM/AMPS (10% AMPS) 8.1 17 10.5 PVPip
31 PNEMAM 8.3 18 10.5 Bu-PVP
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Bu-PVP 8.3 19 10.9 PNEMAM
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34 PVP 9.3 20 11.1 PVP
35 KHI 530 (40 wt.% in aq. medium) 9.5 21 11.1 PiPOx-01
36 PVP/PAM/HEC a)
9.5 22 12.6 PNEG
37 PVP/PAM/PEG 9.7 23 13.6 P(DMHMAM) III
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39 PVP/PEG 9.7 24 13.6 PVP/PAM/PEG b)
40 PEtOx 9.8 25 13.6 PVP/PAM b)
41 PVP/HEC a) 9.8 26 13.7 PVP/HEC b)
42 PVP/PAM 10.0 27 13.9 PVP/PAM/HEC b)
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PAsp iBu/Me 44.6 wt.% in DMSO 10.5 28 13.9 PVP/PEG b)
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45 P(DMHMAM) III 11.9 29 16.6 PNMG
46 Pectin Citrus 12.0 30 16.7 Pectin Citrus
47 HEC 12.1 31 16.8 PDMAOEA 21.4 wt.% in H2O
48 PAM 50 wt.% in H2O 12.1 32 17.0 PEG
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50 PNMG 12.1 33 17.0 PEtOx
51 PEG 12.2 34 17.1 HEC
52 PDMAOEA 21.4 wt.% in H2O 12.2 35 17.4 PAM 50 wt.% in H2O
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5 experiments on SI-forming gas, 5 experiments on SII-forming gas (4 experiments for
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3 Main results of N-vinyl lactam-based KHIs
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5 The results for the N-vinyl lactam-based polymers are summarized in Figure 5. The KHI
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7 performance trend for this category, the lactam polymers, is similar for both SI and SII
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9 hydrates.
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Figure 5. Average To for the N-vinyl lactam-based polymers.
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41 Two of the best performing KHIs for both SI and SII hydrates, giving the second and third
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43 lowest To values of all the polymers tested (SI ranking) were two commercial KHI polymers,
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45
both are VCap-based and supplied in BGE solvent which is known to act as a good synergist.
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48 Compared to the SII ranking, the same two polymers ranked as the two best of all the
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50 polymers tested.
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53
Another low molecular weight PVCap supplied in MEG and a VCap/VP copolymer supplied
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55 in water, also performed well and ranked similarly for both SI and SII hydrates. The ranking
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3 of the homopolymers with different sizes of lactam rings (5-8-rings i.e. PVP, PVCap, PVPip
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5 and PVACO) of similar molecular weights and without organic solvents, had similar
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7 performance ranking for SI and SII hydrates. For the SII system, it is known that increasing
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9 the lactam ring size of the homopolymers will increase the KHI performance. This trend is
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11
similar for the SI system, however the To values are very close and not significantly different
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14 (except for PVP). This was checked with statistical t-tests, finding the p-value to be less than
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16 0.05. 40
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19 It is well known that 5- and 6-rings such as cyclopentane, tetrahydrofuran, 1,4 dioxane or
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21 tetrahydropyran are the largest rings that can be accommodated in the large SII (51264) cages,
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23 sometimes with a help gas such as methane. 1, 41 - 44 PVCap with synergists (particularly BGE)
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25 have a significantly better KHI performance than PVCaps with non-synergistic solvents or no
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27 solvent at all. Since most of the lactam ring sizes are too large to be accommodated in any 512,
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29 51262 or 51264 cavity.41 The ranking results suggest that these polymers find some way to
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31
32
inhibit both the SI or SII hydrates. This shows that the polymer interaction is not structure
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34 specific to either of the hydrate surfaces (7-rings lactams cannot penetrate any of the 512, 51262
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36 or 51264 cavities), but can still find a way to inhibit both hydrates. A more distance interaction
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38 to the surface, or perturbation of the bulk water structure are suggested as mechanisms that
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40 are more probable.
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43
44
45
46 Main results of poly(N-alkylglycine)s
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48 A series of poly(N-alkylglycine)s were tested on SII hydrates by Reyes et al.26 The chosen
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50 polymers tested on the SI-forming gas had pendant alkyl groups varying in size from 1-4
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52 carbon atoms. The results for the poly(N-alkylglycine)s are summarized in Figure 6.
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26 Figure 6. Average To for the poly(N-alkylglycine)s category.
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32 As seen previously for SII hydrates, often the polymers containing propyl and iso-propyl
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34 pendant groups are more effective as KHIs, whereas ethyl and methyl groups often show
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36 weaker KHI performance. 26, 45, 46
This trend might be related to the ability of the pendant
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38 alkyl groups to penetrate 51264 cavities, whether on the hydrate surface or free cavities
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40
forming in solution.
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43 The graph in Figure 6 shows that PNPG and PNiPG have very good KHI performance for
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45
both SI and SII hydrates. The methyl derivative showed worst KHI performance on both
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47
48 hydrate structures. Interestingly, the ethyl derivative shows intermediate KHI performance on
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50 SII hydrate, however it gave very good performance on SI hydrates (slightly inferior to the
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52 best VCap-based polymers is BGE). PNEG also ranked better than PNiPG and PNPG for the
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54 SI system, showing To values that are close, however significantly different. This suggests
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56 that the ethyl group gives a weaker interaction with the SII hydrates (not the optimal size for
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3 51264 cavities), but is small enough to interact properly with the SI cavities. Ethane can better
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5 penetrate and stabilize 51262 cages. 1, 2
This may be why PNEG with pendant ethyl groups
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7 performs well with the SI-forming gas.
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9
10
11
12
13 Main results of miscellaneous polymers
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15 Several different polymer classes have been investigated as KHIs where the following results
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17 are categorized as miscellaneous polymers. The results have been summarized in Figure 7,
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19 which shows the average To values for both the SI and SII system.
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Figure 7. Average To values for the miscellaneous series.
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3 The polymers that showed little or no significant KHI effect have small or negligible
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5 hydrophobic character in the side chains. The necessity of hydrophobic groups in water-
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7 soluble polymers is a well-known feature of KHI polymers. 18, 47
8
9
10 Surprisingly, PNIPAM ranked higher than PNIPMAM for both SI and SII hydrates. In fact,
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12 PNIPAM was ranked number one for the SI-forming gas, but with an average To value quite
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14 close to the best VCap-based polymers in BGE. However, neither the PNIPAM nor
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16
PNIPMAM were structurally optimized for inhibiting either hydrate structure. Studies by
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18
19 Exxon Mobil suggest that PNIPMAM when optimized will perform better than PNIPAM. 48
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21 PEtOx has some effect as a KHI on the SI hydrates, however significantly weaker effect on
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23
24
SII hydrates. The KHI ability of the ethyl group on SI hydrate inhibition lines up with the
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26 result of the ethyl derivative of poly(N-alkylglycine), i.e. is more optimal in size for
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28 interaction with the large SI cages (51262) but not the large SII cages (51264). In addition,
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30 PEtOx has an amide group where the nitrogen atom, which could hydrogen-bond to water
31
32 molecules, is more hidden in the polymer backbone than when the whole amide group is in
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34 the side chain. This may also explain the weaker KHI performance on SI hydrate compared to
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36
PNEG.
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39 The hyperbranched polyesteramide, Pasp iBu/Me and P(DMHMAM)III are higher up on the
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41
ranking in Table 2 for SII hydrates than SI hydrates, indicating that they are possibly better
42
43
44 performing KHIs for SII hydrates. The hyperbranched polyesteramide also has a good KHI
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46 effect for SI hydrates, PAsp iBu/Me has a mediocre KHI effect and P(DMHMAM)III has
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48 little to no effect on SI hydrates. The large deviation of PAsp iBu/Me in the two systems (rank
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50 28 for SI and rank 11 for SII) can indicate that the iso-butyl pendant group is not structurally
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52 compatible with the SI hydrate surface, as iso-butyl is too big to interact strongly with open SI
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cavities.
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3 PiPOx-01 ranked surprisingly much better for SI hydrates than for SII hydrates (rank 9 versus
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5 rank 21). However the To value was still relatively good for both systems. For the SII
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7 hydrates, the performance is similar to PVP. For the SI hydrates, the performance is even
8
9 better than some of the VCap-based polymers without solvent synergists.
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11
12 PiPOx-01 has a 5-ring pendant oxazoline group, roughly the same size as pyrrolidone, but it is
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14 not a polyamide like most of the polymers in this study. The superior performance on SI for
15
16
PiPOx-01 could be due to a better direct interaction with the SI hydrate surface causing good
17
18
19 crystal growth inhibition. This polymer has been shown to have very poor THF hydrate
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21 crystal growth inhibition, backing up its weaker performance on SII gas hydrates. 31 Although
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23 PVP is a crystal growth inhibitor, PVP has also been shown from computer modelling studies
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25 to work as an anti-nucleator, destabilizing SI hydrate clusters from a distance without sitting
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27 directly on the hydrate surface. 16, 49
If PiPOx-01 is assumed to be primarily a gas hydrate
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29 anti-nucleator it would not explain the difference in performance between SI and SII gas
30
31
32
hydrates, since the actual hydrate structure does not appear to be important when destabilizing
33
34 these clusters from a distance.
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36
37
38
39 Main results of PVP blends of PAM, PEG and HEC
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41
A study of PVP blended with other water-soluble polymers has been reported to give
42
43
44 increased induction times on methane hydrate. 50 We investigated with similar polymer blends
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46 and concentrations using the slow constant cooling method with the rocking cells and with
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48 both SI- and SII-forming gas. The average To values are plotted in Figure 8.
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26 Figure 8. Results from test series of PVP with synergists.
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32 From our results, PAM, PEG and HEC were tested by themselves, and showed little or no
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34 inhibition effect with both types of gases. PVP improved the KHI effect of PAM, PEG and
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36 HEC when mixed. However, PVP by itself was the best performing KHI considering the SII
37
38 system, with significantly lower To value compared to the PVP blends. For the SI system,
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40
there was little or no significant difference in the results with PVP by itself or PVP mixed
41
42
43 with the other polymers.
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3 CONCLUSION
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6 A range of polymers have been tested and ranked for their KHI performance on both SI- and
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8 SII-forming gas, using the slow constant cooling test method and steel rocking cells. The rank
9
10 was based on the average To values, where a lower To give the higher rank. The ranked results
11
12 were compared for the polymers potential as a KHI.
13
14
15 For SII system, a higher subcooling can be achieved before hydrate formation occurs
16
17 compared to the SI system, i.e. hydrate formation happens faster within the SI envelope. In
18
19 this case, for the SI system, we used a higher pressure in order to be able to observe the
20
21 pressure drop for the best KHIs. However, this should not affect the ranking of the polymers.
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23
24 The polymers that had a good KHI performance on the SI hydrates, generally had a good
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26 performance on SII hydrates as well.
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28
29 A series of N-vinyl lactam-based polymers such as PVP, PVPip, PVCap, PVACO and
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31 copolymers thereof, with varying molecular weights were tested. The best performing lactams
32
33
for both gas types are VCap/VOH copolymer and VCap homopolymers both with BGE as a
34
35
36 synergist, in addition to a VCap/VP copolymer. All these rank among top ten of all the
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38 polymers tested in this paper. The lactam homopolymers show a similar inhibition trend for
39
40 both types of gases, which suggests a probable inhibition mechanism that is not specific to
41
42 either of the hydrate surface structures.
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44
45 A series of poly(N-alkylglycine)s from previous work done on SII-forming gas was retested
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47 on methane gas for comparison. For SI hydrates these polymers showed great potential as
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49 KHIs, with only the methyl derivative giving poor performance. One of the more interesting
50
51 results in this study was the large deviation in KHI ranking of the poly(N-ethylglycine)
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(PNEG) between the two different gas systems. PNEG performed very well with the SI-
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3 forming gas, but only had a mediocre performance with the SII-forming gas. These results
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5 suggest that PNEG has a better structural compatibility with the SI hydrates.
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7
8 Other miscellaneous polymers were also tested on the SI-forming methane gas for
9
10 comparison, including (meth)acrylamide polymers, ring-closed/open polyoxazolines,
11
12 polyaspartamides, hyperbranched polyesteramides and others. Amongst these polymers, some
13
14 of the better performing KHIs were poly(N-iso-propylacrylamide) (PNIPAM), poly(iso-
15
16
propenyloxazoline) (PiPOx-01) and a commercial formulation based on hyperbranched
17
18
19 polyesteramide, all with low molecular weights. (PiPOx-01) ranked surprisingly better with
20
21 the SI-forming gas in comparison with the SII-forming gas. The PNIPAM performed better
22
23 than the methacrylamide derivative, PNIPMAM, for both systems. However, these two
24
25 polymers were made by different polymerization methods and were not optimized for these
26
27 experiments.
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29
30 The ranked comparisons of PNEG and PiPOx-01 indicates that the inhibition mechanism is
31
32 more structure specific i.e. the interaction with the SI hydrate surface is better than for the SII
33
34 surface. Similarly for PAsp iBu/Me which is more structure specific to the SII surface than for
35
36
the SI surface.
37
38
39 The best SI KHIs may be useful to blend with the best SII KHIs to extend the subcooling limit
40
41
for SII-forming gases further within the SI-forming envelope. This investigation is currently
42
43
44 ongoing and will be reported on subsequently.
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46
47
48
49 ACKNOWLEDGEMENTS
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51
52 Many thanks to my fellow co-workers in the group who have synthesized and previously
53
54 tested some of the KHIs listed in this work.
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5
6
7 REFERENCES
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60 ACS Paragon Plus Environment