VOLUME 20, NUMBER 3 MAY/JUNE 2006

© Copyright 2006 American Chemical Society

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History of the Development of Low Dosage Hydrate Inhibitors
Malcolm A. Kelland*
Department of Mathematics and Natural Sciences, Faculty of Science and Technology,
UniVersity of StaVanger, 4036 StaVanger, Norway
ReceiVed December 21, 2005. ReVised Manuscript ReceiVed March 2, 2006

Low dosage hydrate inhibitors (LDHIs) are a recent and alternative technology to thermodynamic inhibitors
for preventing gas hydrates from plugging oil and gas production wells and pipelines. LDHIs are divided into
two main categories, kinetic inhibitors (KHIs) and anti-agglomerants (AAs), both of which are successfully
being used in field applications. This paper reviews the research and development of LDHIs with emphasis on
the chemical structures that have been designed and tested. The mechanisms of both KHIs and AAs are also
discussed.

Introduction
Gas hydrates are ice-like clathrate solids that are formed from
water and small hydrocarbons at elevated pressures and at lower
temperatures (Figure 1).1 The temperature below which hydrates
can form increases with increasing pressure and can sometimes
be as high as 30 °C. Gas hydrates are a problem to the oil and
gas industry as they can block flow lines, valves, wellheads,
and pipelines, causing loss of production. Low dosage hydrate
inhibitors (LDHIs) have been researched and developed over
the past 15 years as an alternative method to control gas
Figure 1. Two commonest clathrate hydrates, structure I (McMullan
hydrates. They are now established tools for the prevention of and Jeffrey, 1965) (left) and structure II (Mak and McMullan, 1965)
gas hydrate plugging of oil and gas pipelines and gas wells. A (right).
wide range of OPEX savings, possible extended field lifetime
and multi-million dollar CAPEX savings, are economic drivers previously unpublished work from RF-Rogaland Research (RF,
for choosing LDHIs instead of other hydrate prevention now International Research Institute of Stavanger, IRIS). Some
methods.2 qualitative theory regarding the mechanism of LDHIs is also
This paper documents the chemistry and history of the provided.
development of LDHIs. It is written from a somewhat Norwe- Due to the confidential nature of much of the research, very
gian perspective, where the author is based, and includes few research papers on the chemistry of LDHIs have been
published in the public domain. Consequently, this paper has
* Telephone: +47 51 83 18 23. Fax: +47 51831750. E-mail: made extensive use of the patent literature. In particular, patent
malcolm.kelland@uis.no. applications (and not just awarded patents) give a good
(1) Sloan E. D. Clathrate Hydrates of Natural Gases, 2nd ed.; Marcel indication of what each research group was working on at the
Dekker: New York, 1998. time. To give a full flavor of the chemistries investigated, both
(2) Frostman, L. M.; Thieu, V.; Crosby, D. L.; Downs, H. H. In
Proceedings of the SPE International Symposium on Oilfield Chemistry, successful and unsuccessful attempts to commercialize LDHIs
Houston, TX, February 5-8, 2003; SPE 80269. are described.
10.1021/ef050427x CCC: $33.50 © 2006 American Chemical Society
Published on Web 04/01/2006
826 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 2. Pressure-temperature graph for a typical natural gas hydrate.
Before we delve into the history, it will help to explain a
few terms and types of equipment that are used in the research
stages. The term LDHI was coined in the mid 1990s to
differentiate these inhibitors from the more well-known ther-
modynamic inhibitors such as methanol and glycols. LDHIs are
usually dosed at a concentration of ca. 0.1-1.0 wt % (active
component) based on the water phase, whereas thermodynamic
inhibitors are dosed at much higher concentrations of ca. 20-
50 wt %. For commercial applications, LDHIs can be subdivided
into two basic categories:
•kinetic hydrate inhibitors (KHIs or KIs)
•anti-agglomerants (AAs)
KHIs act primarily as gas hydrate anti-nucleators, although
most of them also delay the growth of gas hydrate crystals. KHIs
are generally water-soluble polymers. There are a number of
non-polymeric hydrate crystal growth inhibitors that are poor
anti-nucleators (e.g., tetrapentylammonium bromide, butoxy-
ethanol, certain polyetheramines). These often work as KHI
synergists. KHIs allow you to transport hydrate-forming fluids
for a certain period of time before hydrates start to form. The
time to the formation of the first hydrate crystals is called the
induction time. AAs allow hydrates to form, but they prevent
them from agglomerating and subsequently accumulating into
large masses. An AA enables the hydrates to form as a
transportable nonsticky slurry of hydrate particles dispersed in
the liquid hydrocarbon phase. As will become apparent later,
there are two mechanisms by which the AA effect can be
accomplished. In general, the water-cut for AAs should be below
approximately 50%, otherwise the hydrate slurry gets too viscous
to transport.
The best AAs perform at higher subcoolings than the KHIs.
The subcooling (∆T) is a measure of the driving force for
hydrate formation in a system. Subcooling is the difference
between the hydrate equilibrium temperature and the operating
temperature at a given pressure (Figure 2).
In this paper, the performance of an LDHI is given as the
maximum subcooling for which a produced fluid can be safely
transported without fear of hydrate deposition and plugging.
The subcooling values quoted for a given LDHI are generic. In
practice, the actual performance of a KHI, and to a lesser extent
some AAs, depends on the detailed composition of the liquid
hydrocarbon phase. Other factors such as pressure, salinity, other
additives, and mixing also have an effect.
Several types of equipment have been designed for studying
LDHIs, and very brief descriptions are given here. The simplest,
but a very effective, technique for studying growth inhibition
involves measuring the growth rate of a single THF hydrate
ReViews
crystal.3,4 THF forms structure II hydrate, the same structure
that is usually formed by natural gas hydrates. A second
apparatus is the ball-stop rig or rocker rig. These are small cells
or test tubes that are placed in a cooling bath within which a
metal ball rocks back and forth. When the balls stop moving,
the cell has plugged with hydrates. The time to hydrate
formation (induction time) is determined as the time when the
liquid goes cloudy and/or as the time when gas consumption
due to hydrate formation is observed. Both THF hydrate5,76 and
natural gas hydrate6,76 can be made in such ball-stop cells. The
rocker rig using natural gas hydrate is a simple but excellent
test equipment for AAs. A third commonly used apparatus is
(3) Makogon, T. Y.; Larsen, R.; Knight, C. A.; Sloan, E. D. J. Crystal
Growth 1997, 179, 258-262.
(4) Zeng, H.; Wi, L. D.; Walker, V. K.; Ripmeester, L. A. In Proceedings
of the 4th International Conference on Natural Gas Hydrates, Yokohama,
Japan, May 19-23, 2002.
(5) Jussaume, L.; Canselier, J. P.; Montfort, J. P. In Proceedings of the
AICHE Spring National Meeting, Houston, TX, March 14-18, 1999.
(6) Deaton, W. M.; Frost, E. M. Oil Gas J. 1937, 36 (1), 75.
(7) Arjmandi, M.; Ren, S.-R.; Yang, J.; Tohidi, B. In Proceedings of
the 4th International Conference on Natural Gas Hydrates, Yokohama,
Japan, May 19-23, 2002.
(8) Oskarsson, H.; Lund, A.; Hjarbo, K.; Uneback, I.; Navarrete, R. C.;
Hellsten, M. In Proceedings of the SPE International Symposium on Oilfield
Chemistry, Houston, TX, February 2-4, 2005; SPE 93075.
(9) Lund, A.; Akporiaye, D. E.; Tayebi, D.; Wendelbo, R.; Hjarbo, K.
W.; Karlsson A.; Dahl, I. M. U.S. Patent 6688180, 2004.
(10) Urdahl, O.; Lund, A.; Mork, P.; Nilsen, T. Chem. Eng. Sci. 1995,
50 (5), 863-870.
(11) Lund, A.; Urdahl, O.; Gjertsen, L. H.; Kirkhorn, S.; Fadnes, F. In
Proceedings of the 2nd International Conference on Natural Gas Hydrates,
Toulouse, France, June 2-6, 1996; pp 407-414.
(12) Lippmann, D.; Kessel, D.; Rahminian, I. In Proceedings of the 5th
International Offshore and Polar Engineering Conference, The Hague, The
Netherlands, June 11-16, 1995.
(13) Reed, R. L.; Kelley, L. R.; Neumann, D. L.; Oelfke, R. H.; and
Young, W. D. In Proceedings of the 1st International Conference on Natural
Gas Hydrates, New York, 1993; p 430.
(14) Kuliev, A. M. GazoV. Delo 1972, 10, 17-19.
(15) Matthews, R. R.; Clark, C. R. European Patent Application 309210,
1989.
(16) Sugier, A.; Bourgmayer, P.; Behar, E.; Freund, E. European Patent
Application 323307, 1989.
(17) Sugier, A.; Bourgmayer, P.; Behar, E.; Freund, E. European Patent
Application 323774, 1989.
(18) Sugier, A.; Bourgmayer, P.; Stern, R. European Patent Application
323775, 1989.
(19) Bourgmayer, P.; Sugier, A.; Behar., E. In Proceedings of the 4th
Multiphase Flow Conference, BHR, 1989.
(20) Sloan, E. D. U.S. Patent 5420370, May 30, 1995.
(21) Long, J.; Lederhos, J.; Sum, A.; Christiansen, R. L.; Sloan, E. D.
In Proceedings of the 73rd Annual GPA ConVention, New Orleans, LA,
March 7-9, 1994.
(22) Sloan, E. D. U.S. Patent 5432292, July 11, 1995.
(23) Sloan, E. D.; Christiansen, R. L.; Lederhos, J.; Panchalingam, V.;
Du, Y.; Sum, A. K. W.; Ping, J. U.S. Patent 5639925, June 17, 1997.
(24) Sloan, E. D. U.S. Patent 5880319, March 9, 1999.
(25) Yeh, Y.; Feeney, R. Chem. ReV. 1996, 601, 96 (2) and references
therein.
(26) Edwards, A. R. In Proceedings of the 1st International Conference
on Natural Gas Hydrates, New York, 1993; p 543.
(27) Anselme, M. J.; Reijnhout, M. J.; Klomp, U. C. WO Patent
Application 93/25798, 1993.
(28) Klomp, U. C.; Kruka, V. C.; Reijnhart, R. In Proceedings of
Controlling Hydrates, Waxes and Asphaltenes, IBC Conference, Aberdeen,
October 1997.
(29) Muijs, H. M.; Beers, N. C.; Van Om, N. M.; Kind, C. E.; Anselme,
M. J. Canadian Patent Application 2036084, 1991.
(30) Reijnhout, M. J.; Kind, C. E.; Klomp, U. C. European Patent
Application 0 526 929 A1, 1993.
(31) Klomp, U. C.; Kruka, V. C.; Reijnhart, R. WO Patent Application
95/17579, 1995.
(32) Duncum, S.; Edwards, A. R.; Osborne, C. G. European Patent
Application 0536950 A1, 1993.
(33) Duncum, S.; Edwards, A. R.; Gordon, K. R.; Holt, C. B.; Osborne,
C. G. WO Patent Application 94/25727, 1994.
(34) Duncum, S.; Edwards, A. R.; Lucy, A. R.; Osborne, C. G. WO
Patent Application 94/24413, 1994.
ReViews
the high-pressure stirred cell or autoclave.7 The cell is placed
in a cooling bath, and the pressure, temperature, and sometimes
torque exerted on the stirrer are measured. Some cells have
(35) Duncum, S.; Edwards, A. R.; Lucy, A. R.; Osborne. C. G. WO
Patent Application 95/19408, 1995.
(36) Duncum, S.; Edwards, A. R.; Osborne. C. G. WO Patent Application
96/04462, 1996.
(37) Duncum, S.; Edwards, A. R.; James, K.; Osborne, C. G. WO Patent
Application 96/29501, 1996.
(38) Duncum, S.; Edwards, A. R.; James, K.; Osborne, C. G. WO Patent
Application 96/29502, 1996.
(39) Carver, T. J.; Drew, M. G. B.; Rodger, P. M. J. Chem. Soc., Faraday
Trans. 1995, 91 (19), 3449-3460.
(40) Kelland, M. A.; Svartaas, T. M.; Dybvik, L. A. In Proceedings of
the SPE Offshore European Conference, 1995; SPE 30420.
(41) Kelland, M. A.; Svartaas, T. M.; Lekvam, K.; Dybvik, L. A. In
Proceedings of the 2nd International Conference on Natural Gas Hydrates,
Toulouse, France, June 7-9, 1996.
(42) Kelland, M. A.; Svartaas, T. M.; Dybvik, L. A. In Proceedings of
the SPE 70th Annual Technical Conference and Exhibition, Dallas, TX,
October 1995; SPE 30695.
(43) Kelland, M. A.; Svartaas, T. M.; Dybvik, L. A. In Proceedings of
the SPE 69th Annual Technical Conference and Exhibition, New Orleans,
LA, October 1994; SPE 28506.
(44) Colle, K. S.; Oelfke, R. H.; Kelland, M. A. U.S. Patent 5874660,
February 23, 1999.
(45) Moon, C.; Taylor, P. C.; Rodger, P. M. Can. J. Phys. 2003, 81,
451-457 and references therein.
(46) Kvamme, B. In Proceedings of the 13th Symposium on Thermo-
physical Properties, Boulder, CO, June 22-27, 1997.
(47) Kvamme, B. In Proceedings of the 2nd International Conference
on Natural Gas Hydrates, Toulouse, France, June 2-6, 1999; pp 131-146
and references therein.
(48) Colle, K. S.; Costello, C. A.; Talley, L. D.; Longo, J. M.; Oelfke,
R. H.; Berluche, E. WO Patent Application 96/08672, 1996.
(49) Colle, K. S.; Talley, L. D.; Oelfke, R. H.; Berluche, E. WO Patent
Application 96/41784, 1996.
(50) Colle, K. S.; Costello, C. A.; Talley, L. D.; Oelfke, R. H.; Berluche,
E. WO Patent Application 96/41834, 1996.
(51) Colle, K. S.; Costello, C. A.; Talley, L. D. Canadian Patent
Application 96/2178371, 1996.
(52) Colle, K. S.; Talley, L. D.; Oelfke, R. H.; Berluche, E. WO Patent
Application 96/08673, 1996.
(53) Colle, K. S.; Costello, C. A.; Talley, L. D.; Oelfke, R. H. U.S. Patent
Application 6222083, 1996.
(54) Colle, K. S.; Costello, C. A.; Talley, L. D.; Oelfke, R. H.; Berluche,
E. WO Patent Application 96/41786, 1996.
(55) Talley, L. D.; Oelfke, R. H. WO Patent Application 97/07320, 1997.
(56) Namba, T.; Fujii, Y.; Saeki, T.; Kobayashi, H. WO Patent
Application 96/38492, 1996.
(57) Namba, T.; Fujii, Y.; Saeki, T.; Kobayashi, H. WO Patent
Application 96/37684, 1996.
(58) Lehmann, B.; Moritz, R. WO Patent Application 98/16719, 1998.
(59) Colle, K. S.; Costello, C. A.; Talley, L. D.; Pfeiffer, D. G.; Rabeony,
M.; Wright, P. J. WO Patent Application 96/08636, 1996.
(60) Colle, K. S.; Costello, C. A.; Talley, L. D.; Pfeiffer, D. G.; Rabeony,
M.; Wright, P. J. WO Patent Application 96/08456, 1996.
(61) Sugier, A.; Durand, J. P. U.S. Patent 5244878, 1993.
(62) Sugier, A.; Durand, J. P. European Patent Application 582507.
(63) Sugier, A.; Durand, J. P. European Patent Application 582507, 1994.
(64) Durand, J. P.; Delion, A. S.; Gateau, P.; Velly, M. European Patent
Application 594479, 1995.
(65) Durand, J. P.; Delion, A. S.; Gateau, P.; Velly, M. European Patent
Application 740048, 1995.
(66) Rojey, A. French Patent Application, Fr. 2735210, 1996.
(67) Rojey, A. French Patent Application, Fr. 2735211, 1996.
(68) Pierrot, A.; Doerler, N.; Goodwin, S. In Proceedings of the Offshore
Northern Seas Conference, Stavanger, August 28, 1992.
(69) Behar, E. Gas Hydrate Seminar, Trondheim, Norway, June 1994.
(70) Bloys, B.; Lacey, C. In Proceedings of the 27th Annual Offshore
Technology Conference, Houston, TX, 1995; OTC 7772.
(71) Notz, P. K.; Bumgartner, S. B.; Schaneman, B. D.; Todd, J. L. In
Proceedings of the 27th Annual Offshore Technology Conference, Houston,
TX, 1995; OTC 7777.
(72) Corrigan, A.; Duncan, S.; Edwards, A. R.; Osborne, C. G. In
Proceedings of the SPE 70th Annual Technical Conference, Dallas, TX,
October 1995; SPE 30696.
(73) Philips, N. J. In Proceedings of the 8th International Oilfield
Chemical Symposium, Geilo, Norway, March 1997.
(74) Argo, C. B.; Blaine, R. A.; Osborne, C. G.; Priestly, I. C. In
Proceedings of the SPE International Symposium on Oilfield Chemistry,
Houston, TX, February 1997; SPE 37255.
Energy & Fuels, Vol. 20, No. 3, 2006 827
windows for visual observations or may be entirely made of
sapphire. Recently, mini-autoclaves have been developed for
rapid screening of LDHIs.8,9,221The next apparatus in terms of
(75) Lederhos, J. P.; Long, J. P.; Sum, A.; Christiansen, R. L.; Sloan E.
D. Chem. Eng. Sci. 1996, 51 (8), 1221-1229.
(76) Talley, L. D.; Mitchell, G. F.; Oelfke, R. H. Ann. N.Y. Acad. Sci.
2000, 912, 314-321.
(77) Makogon, T. Ph.D. Dissertation, Colorado School of Mines, 1997.
(78) Larsen, R. Ph.D. Thesis, Norwegian University Of Science and
Technology, Trondheim, Norway, 1997.
(79) Larsen, R.; Knight, C. A.; Sloan, E. D. Fluid Phase Equilib. 1998,
150-151, 353-360.
(80) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J. In Proceedings of the
3rd Natural Gas Hydrate Conference, Salt Lake City, July 1999.
(81) Cohen, J. M.; Wolf, P. F.; Young, W. D.; U.S. Patent Application
5723524, 1998.
(82) Angel, M.; Negele, A. WO Patent Application 99/64717, 1999.
(83) Talley, L. D.; Mitchell, G. F. In Proceedings of the 30th Annual
Offshore Technology Conference, Houston TX, May 3-6, 1998; OTC
11036.
(84) Talley, L. D.; Mitchell, G. F. In Proceedings of the SPE Annual
Technical Conference and Exhibition, September 1999; SPE 56770.
(85) Fu, S. B.; Cenegy, L. M.; Neff, C. In Proceedings of the SPE
International Symposium on Oilfield Chemistry, Houston, TX, February 13-
16, 2001; SPE 65022.
(86) Talley, L. D.; Edwards, M. Pipeline Gas J. 1999, March.
(87) Peiffer, D. G.; Costello, C. A.; Talley, L. D.; Wright, P. J. WO
Patent Application 99/64718, 1999.
(88) Klomp, U. C.; Reijnhart, R. WO Patent Application 96/34177, 1996.
(89) Urdahl, O.; Lund, A. In Proceedings of the IIR Conference on
Waxes, Hydrates and Asphaltenes, Aberdeeen, Scotland, June 17-18, 1998.
(90) Phillips, N. J. Personal communication, 2001.
(91) Palermo, T.; Sinquin, A.; Dhulesia, H.; Fourest, J. M In Proceedings
of Multiphase 1997; BHR Group: 1997; p 133.
(92) Sinquin, A.; Velly, M.; Durand, J. P. European Patent Application
789132, 1998.
(93) Cingotti, B.; Sinquin, A.; Durand, J. P.; Palermo, T. Ann.N.Y. Acad.
Sci. 2000, 912, 766.
(94) Sinquin, A.; Velly, M.; Durand, J. P. European Patent Application
807678.
(95) Pakulski, M. U.S. Patent Application 6331508, 2001.
(96) Pakulski, M. U.S. Patent European Patent Application 5741758,
1998.
(97) Pakulski, M. U.S. Patent European Patent Application 6025302,
2000.
(98) Pakulski, M. In Proceedings of the SPE International Symposium
on Oilfield Chemistry, Houston TX, February 18-21, 1997; SPE 37285.
(99) Pakulski, M.; Prukop, G.; Mitchell, C. In Proceedings of the SPE
Annual Technical Conference, New Orleans, LA, September 27-30, 1998;
SPE 49210.
(100) Lovell, D.; Pakulski, M. In Proceedings of the SPE Gas Technology
Symposium, Alberta, Canada, 2002; SPE 75668.
(101) Budd, D.; Hurd, D.; Pakulski, M.; Schaffer, T. D. In Proceedings
of the SPE Annual Technical Conference and Exhibition, Houston, TX,
September 26-29, 2004; SPE 90422.
(102) Phillips, N. J.; Kelland, M. A. Industrial Applications of Surfactants
IV; Karsa, D. R., ed.; Royal Society of Chemistry: London, 1999; 244-
259.
(103) Kelland, M. A.; Rodger, P. M.; Namba, T. WO Patent Application
98/53007, 1998.
(104) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J. Ann. N.Y. Acad. Sci.
2000, 912, 281-293.
(105) Kelland, M. A.; Klug, P. World Patent Application 98/23843, 1998.
(106) Kelland, M. A.; Klug, P. U.S. Patents 6369004 and 6544932, 2002.
(107) Feustel, M.; Klug, P. U.S. Patent 6566309, 2003.
(108) Klug, P.; Feustel, M.; Frenz, V. World Patent Application WO
98/22557, 1998.
(109) Klug, P.; Holtrup, F. European Patent Application EP 0933415A2,
1999.
(110) Klug, P.; Feustel, M.; Frenz, V. WO Patent Application 98/03615,
1998.
(111) Talley, L. D. ExxonMobil Upstream Research Company, personal
communication, 2005.
(112) Huo, Z.; Freer, E.; Lamar, M.; Sannigrahi, B.; Knauss, D. M.;
Sloan, E. D. Chem. Eng. Sci. 2001, 56, 4979-4991.
(113) Bakeev, K.; Chuang, J.-C.; Drzewinski, M. A.; Graham, D. E. U.S.
Patent 6117929, 2000.
(114) Bakeev, K.; Myers, R.; Chuang, J.-C.; Winkler, T.; Krauss, A.
U.S. Patent 6242518, 2001.
(115) Bakeev, K.; Harris, K.; Argo, C. B.; Drzewinski, M. A.; Graham,
D. E. U.S. Patent 6451892, 2002.
(116) Thieu, V.; Bakeev, K.; Shih, J. S. U.S. Patent 6359047, 2002.
828 Energy & Fuels, Vol. 20, No. 3, 2006
the level of complexity is the vertical placed pipe-wheel or loop-
wheel. The pipe is usually of 1-3 in. i.d. and can have a window
for visual observation. It is pressurized and then rotated in a
cooling chamber. Pressure, temperature, and torque exerted on
the wheel can be measured.10-12 The last apparatus is the
horizontal flow loop. A simple flow loop can be built for tests
(117) Bakeev, K.; Chuang, J.-C.; Winkler, T.; Drzewinski, M. A.;
Graham, D. E. WO Patent Application 01/27055, 2001.
(118) Bakeev, K.; Chuang, J. C.; Winkler, T.; Drzewinski, M. A.;
Graham, D. E. U.S. Patent 6281274, 2001.
(119) Bakeev, K.; Myers, R.; Graham, D. E. U.S. Patent 6180699, 2001.
(120) Cohen, J. M.; Young, W. D. U.S. Patent 6093863, 2000.
(121) Cohen, J. M.; and Young, W. D. U.S. Patent 6096815, 2000.
(122) Phillips, N. J.; Grainger, M. In Proceedings of the Annual Gas
Technology Symposium, Calgary, Alberta, Canada, March 15-18, 1998;
SPE 40030.
(123) Palermo, T.; Argo, C. B.; Goodwin, S. P.; Henderson, A. Ann.
N.Y. Acad. Sci. 2000, 912.
(124) Leporcher, E. M.; Fourest, J. M.; Labes Carrier, C.; Lompre, M.
In Proceedings of the 1998 SPE European Petroleum Conference, The
Hague, The Netherlands, October 20-22, 1998; SPE 50683.
(125) Klomp, U. C. WO Patent Application 99/13197, 1999.
(126) Klomp, U. C. Shell Global Solutions, personal communication,
2005.
(127) Knott, T. Holding hydrates at bay. Offshore Eng. 2001, February.
(128) Shoup, G. BP, personal communication, 1999.
(129) Glenat, P.; Palermo, T. In Proceedings of the 3rd Natural Gas
Hydrate Conference, Salt Lake City, July 1999.
(130) Velly, M.; Gateau, P.; Sinquin., A.; Durand, J. P. European Patent
Application EP 0896123.
(131) Toulhoat, H.; Sinquin, A. U.S. Patent 6028236, 2000.
(132) Velly, M.; Delion, A.-S.; Durand, J. P. European Patent Application
EP 812977.
(133) Velly, M.; Hillion, M.; Sinquin, A.; Durand, J. P. European Patent
Application EP 905350.
(134) Kelland, M. A.; Namba, T.; Tomita, T. Norwegian Patent Ap-
plication 2278, 1999.
(135) Kelland, M. A.; Tomita, T. Norwegian Patent Application, 1999
(withdrawn before publication).
(136) Klomp, U. C. WO Patent Application 01/77270, 2001.
(137) Rivers, G. T.; Crosby, D. L. U.S. Patent Application 2004/0110998,
2004.
(138) Rivers, G. T.; Crosby, D. L. WO Patent Application 2004/22909,
2004.
(139) Klomp, U. C. Shell Global Solutions, personal communication,
2004.
(140) Dzialowski, A.; Patel, A.; Nordbo, K. In Proceedings of the
Offshore Mediterranean Conference, Ravenna, Italy, March 28-30, 2001.
(141) Fu, B.; Neff, S.; Mathur, A.; Bakeev, K. SPE Production and
Facilities, August 2002; SPE 78823. This is the revised version of Fu, B.;
Neff, S.; Mathur, A.; Bakeev, K. In Proceedings of the SPE Annual
Technical Conference and Exhibition, New Orleans, LA, September 30-
October 3, 2001; SPE 71472.
(142) Rasch, A.; Mikalsen, A.; Austvik, T.; Gjertsen, L. H.; Li, X. In
Proceedings of the 4th International Conference on Gas Hydrates,
Yokohama, Japan, May 19-23, 2002.
(143) Rasch, A.; Mikalsen, A.; Gjertsen, L. H.; Fu, B. In Proceedings
of the 10th International Multiphase Conference, Cannes, France, June 13-
15, 2001.
(144) Neubecker, K. BASF, personal communication, 2005.
(145) Angel, M.; Neubecker, K.; Stein, S. World Patent Application WO
2004/042190, 2004.
(146) Dahlmann, U.; Feustel, M.; Kayser, C.; Morschchaeuser, R. U.S.
Patent Application 2004/0030206, 2004.
(147) Thieu, V.; Bakeev, K.; Shih, J. S. U.S. Patent 6451891, 2002.
(148) Toyama, M.; Seye, M. World Patent Application WO 02/10318,
2002.
(149) Colle, K.; Talley, L. D.; Longo, J. M. World Patent Application
WO 2005/005567, 2005.
(150) Talley, L. D. Nucleation Workshop; Ecole Nationale Superior de
Mines: St. Etienne, France, June 2003.
(151) Glenat, P.; Peytavy, J. L.; Jones, N. H.; Grainger, M. In Proceed-
ings of SPE Middle East Conference, Abu Dhabi, U.A.E, 2004; SPE 88751
(152) Fu, S. F. Nalco, personal communication, 2005.
(153) Frostman, L. M.; Crosby, D. In Proceedings of the Deep Offshore
Technology Conference, Marseille, France, November 19-21, 2003.
(154) Mehta, A. P. Shell Global Solutions, personal communication,
2005.
(155) Petrie, M. Clariant, personal communication, 2005.
(156) Swanson, T. A.; Petrie, M.; Sifferman, T. R. Flow Assurance
Forum, Galveston, TX, 2004.
ReViews
using THF hydrates at atmospheric pressure; however, this type
of loop has limited scope of use.98 Most loops used today are
(157) Swanson, T. A.; Petrie, M.; Sifferman, T. R. In Proceedings of
the SPE International Symposium on Oilfield Chemistry, Houston, TX,
February 2-4, 2005; SPE 93158.
(158) Collins, I. R. WO Patent Application 03/021078, 2003.
(159) Frostman, L. M.; Downs, H. In Proceedings of the 2nd Interna-
tional Conference on Petroleum and Gas-Phase BehaViour and Fouling,
Copenhagen, Denmark, August 2000.
(160) Frostman, L. M. In Proceedings of the SPE Annual Technical
Conference and Exhibition, Dallas, TX, October 1-4, 2000; SPE 63122.
(161) Frostman, L. M.; Przybylinski, J. L. In Proceedings of the
International Symposium on Oilfield Chemistry, Houston, TX, February 13-
16, 2001; SPE 65007.
(162) Mehta, A. P.; Herbert, P. B.; Cadena, E. R.; Weatherman, J. P. In
Proceedings of the Offshore Technology Conference, Houston TX, May
6-9, 2002; OTC 14057.
(163) Frostman, L. M.; Crosby, D. In Proceedings of the Deep Offshore
Technology Conference, Marseille, France, November 19-21, 2003.
(164) Frostman, L. M.; Crosby, D. Poster presented at the SPE Forum
on Gas Hydrates, St. Maxime, France, September 1999.
(165) Thieu, V.; Frostman, L. M. In Proceedings of the International
Symposium on Oilfield Chemistry, Houston, TX, February 2-4, 2005; SPE
93450.
(166) Przybylinski, J. L.; Rivers, G. T. U.S. Patent 6596911 B2, 2003.
(167) Klomp, U. C.; Le Clerq, M.; Van Kins, S. In Proceedings of the
2nd Petromin Deepwater Conference, Shangri-La, Kuala Lumpur, Malaysia,
May 18-20, 2004.
(168) Gateau, P.; Sinquin, A.; Beunat, V.; Vilagines, R. U.S. Patent
Application 2004/0162456, 2004.
(169) Palermo, T. IFP, personal communication, 2005.
(170) Fadnes, F. H. Fluid Phase Equilib. 1996, 117, 186-192.
(171) Le Porcher, E. M.; Peytavy, J. L.; Mollier, Y.; Sjoblom, J.; Labes-
Carrier, C. In Proceedings of the SPE Annual Technical Conference and
Exhibition, New Orleans, LA, September 27-30, 1998 and references
therein; SPE 49172.
(172) Camargo, R.; Palermo, T.; Sinquin, A.; Glenat, P. Ann. N.Y. Acad.
Sci. 2000, 912, 906.
(173) Sinquin, A.; Bredzinsky, X.; Beunat, V. In Proceedings of the SPE
Annual Technical Conference and Exhibition, New Orleans, LA, September
30- October 3, 2001; SPE 71543.
(174) Sinquin, A.; Miao, M.; Beunat, V.; Jussaume, L. In Proceedings
of the 4th International Conference on Gas Hydrates, Yokohama, Japan,
May 19-23, 2002.
(175) Fu, S.; et al. Patent pending, filed October 2004.
(176) Milburn, C. R.; Sitz, G. M. U.S. Patent 6444852 B1, 2002.
(177) Dahlmann, U.; Feustel, M. U.S. Patent Application 2004/0163306,
2004.
(178) Dahlmann, U.; Feustel, M. U.S. Patent Application 2004/0163307,
2004.
(179) Dahlmann, U.; Feustel, M. U.S. Patent Application 2004/0164278,
2004.
(180) Dahlmann, U.; Feustel, M. U.S. Patent Application 2004/0167040,
2004.
(181) Dahlmann, U.; Feustel, M. U.S. Patent Application 2004/0159041,
2004.
(182) Cowie, L.; Shero, W.; Singleton, N.; Byrne, N.; Kauffman, L.
Deepwater Technology; Gulf Publishing Co.: 2003; pp 39-41.
(183) Fu, S. F. In Proceedings of the 5th International Conference on
Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p 4040.
(184) Burgazli, C. R. World Patent Application WO 2004/111161, 2004.
(185) Burgazli, C. R.; Navarrete, R. C.; Mead, S. L. Presented at the
Petroleum Society’s Canadian International Petroleum Conference, Calgary,
Alberta, Canada, June 10-12, 2003; Paper 2003-070.
(186) Storr, M. T.; Montfort, J.-P.; Taylor, P. C.; Rodger, P. M. In
Proceedings of the 4th International Conference on Gas Hydrates,
Yokohama, Japan, May 19-23, 2002.
(187) Storr, M. T.; Taylor, P. C.; Montfort, J.-P.; Rodger, P. M. J. Am.
Chem. Soc. 2004, 126, 12569-1576.
(188) Duffy, D. M.; Moon, C.; Irwin, J. L.; Di Salvo, A. F.; Taylor, P.
C.; Arjmandi, M.; Danesh, A.; Ren, S. R.; Todd, A.; Tohidi, B.; Storr, M.
T.; Jussaume, L.; Montfort, J.-P.; Rodger, P. M. Chemistry in the Oil
Industry, Symposium VIII, Manchester, England, 2003.
(189) Dahlmann, U.; Feustel, M.; Holtrup, F.; Jestel, M.; Fuss, R.-W.;
Papenfuhs, B.; Steuer, M. WO Patent Application 02/084072, 2002.
(190) Walker, V.; Ripmeester, J. A.; Zeng, H. WO Patent Application
03/087532, 2003.
(191) Kelland, M. A.; Iversen, J. E. Unpublished results.
(192) Makogon, T.; Sloan, E. D. In Proceedings of the 4th International
Conference on Gas Hydrates, Yokohama, Japan, 2002; pp 498-563.
(193) Frostman, L. M. In Proceedings of the SPE International Sympo-
sium on Oilfield Chemistry, Houston, February 13-16, 2001; SPE 65006.
ReViews
high-pressure loops using natural gas, condensate, or oil and
an aqueous phase. They can range from the mini-loop (e.g.,
1/4 in. i.d.) to the full scale pilot loop of 4 in. i.d. or more.13,76
A disadvantage is that in some cases the pump can crush
hydrates making AA experiments difficult to interpret.
Early History of the Development of LDHIs
The history of LDHIs actually begins in the early 1970s with
a Russian engineer called Kuliev, who was well before his
time.14 He was experiencing gas hydrate problems in his gas
wells. He decided to try adding commercial surfactants to the
top part of the wells and discovered that the hydrate problem
went away. It is unclear from his paper how the surfactants
(194) Crosby, D. Baker Petrolite, personal communication, 2005.
(195) Boyne, K.; Horn, M.; Bertrane, D.; Fournie, F.; Cooper, T.; Quinn,
P.; Coudeville, F.; Buchan, D.; Allan, K.; Arnott, S. In Proceedings of the
Offshore Europe Conference, Aberdeen, UK, September 2-5 2003; SPE
83975.
(196) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent
Application 20050081714, 2005.
(197) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent
Application 20050081432, 2005.
(198) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent
Application 20050085396, 2005.
(199) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent
Application 20050085675, 2005.
(200) Panchalingham, V.; Rudel, M. G.; Bodnar, S. H. U.S. Patent
Application 20050085676, 2005.
(201) Maximilian, A.; Neubecker, K.; Sanner, A. U.S. patent 6867262,
2005.
(202) Dalhlmann, U.; Feustel, M. U.S. Patent Application 20050101495.
(203) Moon, C.; Taylor, P. C.; Rodger, P. M. J. Am. Chem. Soc. 2003,
125, 4706.
(204) Høiland, S.; Askvik, K. M.; Fotland, P.; Alagic, E.; Barth, T.;
Fadnes, F. J. Colloid. Interface Sci. 2005, 287, 217.
(205) Karaaslan, U.; Parlaktuna, M. Energy Fuels 2002, 16, 1387.
(206) Zanota, M. L.; Dicharry, M.; Graciaa, A. Energy Fuels 2005, 19,
584.
(207) Angel, M.; Stein, S.; Neubecker, K. U.S. Patent 6878788, 2005.
(208) Ohtake, M.; Yamamoto, Y.; Kawamura, T.; Wakisaka, A.; de
Souza, W. F.; de Freitas, A. M. V. J. Phys. Chem. 2005, 109, 16879.
(209) Pakulski, M.; Qu. Q.; Pearcy, R. SPE International Symposium
on Oilfield Chemistry, The Woodlands, TX, February 2-4, 2005; SPE
92971.
(210) Szymczak, S.; Sanders, K.; Pakulski, M.; Higgins, T. SPE Annual
Technical Conference and Exhibition, Dallas, October 9-12, 2005; SPE
96418.
(211) Dong Lee, J.; Englezos, P. In 5th International Conference on Gas
Hydrates, Trondheim, Norway, June 13-16, 2005; p 44.
(212) Zeng, H.; Brown, A.; Wathen, B.; Ripmeester, J. A.; Walker, V.
K. In 5th International Conference on Gas Hydrates, Trondheim, Norway,
June 13-16, 2005; p 1.
(213) Hawtin, R. W.; Moon, C.; Rodger, P. M. In 5th International
Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p
118.
(214) Grainger, N.; Hawtin, R.; Moon, C.; Rodger, P. M.; Rogers, S. In
5th International Conference on Gas Hydrates, Trondheim, Norway, June
13-16, 2005; p 317.
(215) Arla, D.; Dicharry, C, Graciaa, A.; Hurtevent, C.; Jussaume, L.;
Peytavy, J. L.; Sinquin, A. In 5th International Conference on Gas Hydrates,
Trondheim, Norway, June 13-16, 2005; p 322.
(216) Vebenstad, A.; Larsen, R.; Straume, E.; Argo, C. B.; Fung, G. In
5th International Conference on Gas Hydrates, Trondheim, Norway, June
13-16, 2005; p 1193.
(217) Camargo, R. M. T.; Concalves, M. A. L.; Montesami, J. R. T.;
Cardoso, C.; Minami, K. Offshore Technology Conference, Houston, 2004;
OTC 16687.
(218) Palermo, T.; Mussomeci, A.; LePorcher, E. Offshore Technology
Conference, Houston, 2004; OTC 16681.
(219) Arjmandi, M.; Ren, S. R.; Tohidi, B. In 5th International
Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p
1178.
(220) Clark, L. W.; Anderson, J. In 5th International Conference on Gas
Hydrates, Trondheim, Norway, June 13-16, 2005; p 1249.
(221) Oskarsson, H.; Uneback, I.; Navarrete, R. C.; Hellsten, M.; Lund,
A.; Hjarbo, K. W. In 5th International Conference on Gas Hydrates,
Trondheim, Norway, June 13-16, 2005; p 1283.
Energy & Fuels, Vol. 20, No. 3, 2006 829
worked, but it is the first recorded example of using a low
dosage of a chemical to prevent hydrate plugging.
We have to go forward to the mid 1980s before any further
work on LDHIs took place. Conoco patented the use of scale
inhibitors as gas hydrate inhibitors.15 They cited an example
using a fairly high concentration of scale inhibitor to prevent
gas hydrate in the gas well. The use of scale inhibitors at these
concentrations is uneconomical for pipeline use, and no further
work was reported.
In 1987, IFP (The French Petroleum Institute) filed a series
of patent applications on using surfactants as LDHIs.16-19 They
listed a wide range of surfactants and basically claimed all
surface-active chemicals as hydrate inhibitors. This last claim
was to cause some concern to oil companies developing or using
LDHIs and not wishing to be dependent on IFP’s patent. It was
not clear from IFP’s patents which surfactants they were
focusing on or the mechanism for their ability to prevent hydrate
agglomeration. Later, it became apparent that the surfactants
were producing a special kind of water-in-oil emulsion. (The
surfactant dosage was ca. 0.8 wt % based on the water phase.)
This emulsion confined hydrates to form within the water
droplets, and the hydrates never agglomerated. The end product
was a slurry of hydrate particles in a hydrocarbon phase. This
we shall call the IFP AA mechanism. IFP calls their AAs
dispersant additives. Examples of surfactants in IFP’s patents
include diethanolamides, dioctylsulfosuccinates, sorbitans, ethox-
ylated polyols, ethoxylated fatty acids, and ethoxylated amines.
They also gave examples of polymeric surfactants based on
polyalkenyl succinic anhydride. The products in the examples
in their patents showed only weak KHI effects.
Also, in the late 1980s the Colorado School of Mines (CSM)
was carrying out research on gas hydrates. CSM noticed that
some materials catalyzed hydrate formation at low dosages and
were encouraged by their consortium members to look for
materials that would have the opposite effect. This initiated a
long program on searching for kinetic hydrate inhibitors. CSM
constructed a THF hydrate ball-stop rig and began screening a
vast range of commercial products.
One other initiative on LDHIs began in the late 1980s in
Norway within the state-funded PROFF research program. The
program included two projects on gas hydrates. The first, carried
out at SINTEF, studied the consistency of hydrates under
flowing conditions. They observed that at low water conversion
the hydrates were sticky and liable to agglomerate and deposit
on the pipe walls. However, at high water conversion the
hydrates were a nonsticky powder that appeared to be transport-
able in the hydrocarbon phase. Thus if a chemical could be
found to prevent the hydrates from agglomerating during the
early stages of water conversion, it should be possible to produce
a transportable slurry of hydrates.
The second gas hydrate project in the PROFF program was
carried out at RF. RF began screening additives in high-pressure
cells to observe any inhibiting effects. The best product from
RF’s studies was a quaternary corrosion inhibitor from Black-
smith, which showed some positive AA effect, but the work
was not taken further. In 1991, at the end of the PROFF
program, Esso Norge (now ExxonMobil Norge) began sponsor-
ing RF on a 3-year program to develop LDHIs. The results were
to be fed into Exxon’s own internal program on LDHIs at Exxon
Production Research (EPR, now ExxonMobil Upstream Re-
search Company) in Houston. Meanwhile, Shell and BP were
also putting together their own programs for developing LDHIs.
Thus, at the beginning of the 1990s, three institutes and three
oil companies were involved in the search for LDHIs.
830 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 3. Structure of poly(vinylpyrrolidone).
Figure 4. Monomer units in the terpolymer Gaffix VC-713.
Figure 5. Structure of polyvinylcaprolactam.
Early 1990s
Discovery of PVP and PVCap at CSM. The first break-
through in KHI technology came at CSM in 1991. In their ball-
stop rig tests they came across a polymer, poly(vinylpyrrolidone)
(PVP), which delayed the formation and the agglomeration of
THF hydrates (Figure 3).20,21
The apparent AA effect of PVP as noted by CSM does not
transfer to real hydrocarbon systems, which plug rapidly once
a certain amount of gas hydrate is formed, but the KHI effect
does. They also found that hydroxyethylcellulose (HEC)
performed moderately in the ball-stop rig, but PVP was better.
PVP is the five-ring member of the series of polyvinyllactams,
which have two main suppliers, ISP and BASF. Nippon
Shokubai also manufactures PVP. CSM kept to this series and
tested a hair-care product from ISP called Gaffix VC-713 a
terpolymer, which contains a high proportion of the seven-ring
monomer, vinylcaprolactam (VCap) as well as vinyl pyrrolidone
(VP) and dimethylaminoethyl methacrylate (DMAEMA) (Figure
4).
This polymer outperformed PVP in the ball-stop test. CSM
then set up a collaboration agreement with ISP to develop better
KHIs. Realizing that VCap was the key monomer in Gaffix
VC-713, CSM tested the homopolymer polyvinylcaprolactan
(PVCap) (Figure 5).
PVCap gave a similar performance to Gaffix VC-713 and
became a standard by which other KHIs would be compared.
This early high molecular weight version of PVCap (or Gaffix
VC-713) gave 24 h hydrate nucleation delays up to a subcooling
of 8-9 °C at a dosage of 0.5 wt %. The results from CSM’s
work were patented22,23 and communicated to their consortium
members, who began to test the polyvinyllactams in their own
laboratories. CSM also discovered that other polymers could
act as synergists increasing the performance of the polyvinyl-
lactams, particularly PVCap.24 In their patent applications in
1994, they claimed polyelectrolytes, polyether block copolymers,
polyvinylamides, polyalkylacrylamides, and polyalkyloxazolines
as synergists for polyvinyllactams. The examples included
polyethylacrylamide, poly(N-methyl-N-vinyl acetamide), and
polyethyloxazoline (Figure 6).
Each of these polymers was shown to be a hydrate growth
inhibition synergist for PVCap. In the patent application, the
amide polymers were claimed to have C1-4 alkyl groups,
although no examples were given with C3-4 alkyl groups.
ReViews
Figure 6. Structures of polyethylacrylamide, polyvinyl-N-methyl
acetamide, and polyethyloxazoline.
Shell’s Research and the Discovery of Quaternary Sur-
factant AAs. In the early 1990s, Shell became aware of certain
fish, such as the winter flounder, which contained anti-freeze
proteins and glycoproteins (AFPs and AFGPs).25,26 These AFPs
and AFGPs prevent ice crystals from forming in the fish by
binding to the surface of ice nuclei. This allows the fish to
survive in sub-zero temperatures. It occurred to Shell that
artificial AFPs and AFGPs might bind to the surface of gas
hydrate nuclei. The AFPs and AFGPs themselves were found
to be expensive and fairly poor KHIs, but a screening of
perceived “protein-like” water-soluble polymeric amides led
Shell to independently (although somewhat later than CSM)
discover PVP. Shell tested PVP and a polymer called Antaron
P-904 or Agrimer P-904 (butylated PVP) in its own laboratories.
They discovered that the butylated PVP performed better than
PVP. They patented the results in 1992 but later reassigned the
rights to CSM.27
After studying AFPs and PVPs, and based on the results of
a field trial in Michigan and in the Groningen field in which
PVP failed to prevent hydrate formation, Shell realized that
kinetic inhibitors would not give them the high subcooling
performance they desired for their oncoming deepwater projects.
They calculated using standard nucleation theory that you could
not stop hydrates nucleating indefinitely at subcoolings above
10 °C.28 Since Shell was mostly interested in deepwater
applications with high subcoolings, they concentrated on
developing AAs. The first useful class of AAs they came across
were the alkylarylsulfonates.29 (Interestingly, these surfactants
were chosen among others by Kuliev back in the early 1970s.)
However, it was found that their performance was mediocre,
so Shell moved on to other products.
The next class of products that was patented by Shell were
alkyl glucosides.30 The multi-hydroxyl headgroup was envisaged
to bond to water molecules on the hydrate surface. However,
after further testing, it appeared that these surfactants gave very
limited AA performance, and Shell moved on to what was to
be a major breakthrough.
Shell reasoned that quaternary ammonium surfactants would
be ideal candidates as AAs as they are known to be good particle
dispersants. Shell was also aware of the work on quateranry
ammonium and phosphonium salt clathrates as reported by
Jeffrey.230 In particular, they noticed that tetrabutylammonium
bromide (TBAB) and tetrapentylammonium bromide (TPAB)
(222) Zeng, H.; Walker, V. K.; Ripmeester, J. A. In 5th International
Conference on Gas Hydrates, Trondheim, Norway, June 13-16, 2005; p
1295.
(223) Pakulski, M.; Hurd, D. In 5th International Conference on Gas
Hydrates, Trondheim, Norway, Norway, June 13-16, 2005; p 1444.
(224) Cowie, L.; Bollavaram, P.; Erdogmus, M.; Johnson, T.; Shero, W.
Offshore Technology Conference, 2005; OTC 17328.
(225) Pakulski, M.; Dawson, J. C. U.S. Patent Application, 2004/
0231848, 2004.
(226) Pakulski, M.; Dawson, J. C. U.S. Patent 6756345, 2004.
(227) Kvamme, B.; Huseby, G.; Førrisdahl, O. K. Mol. Phys. 1997, 90
(6), 979.
(228) Lee, J. D.; Englezos, P. Chem. Eng. Sci. 2005, 60, 5323.
(229) Lee, J. D.; Englezos, P. Chem. Eng. Sci. 2006, 61, 1368.
(230) Jeffrey, J. Inclusion Compounds, Vol. 1; Academic Press: New
York, 1984; pp 159-190.
ReViews
Figure 7. Structure of good quaternary ammonium or phosphonium
hydrate growth inhibitors, where M ) N or P and at least two of the
R groups are n-butyl, n-pentyl, or isopentyl.
Figure 8. Structure of Shell’s quaternary AAs (R1 ) long chain
hydrocarbon tail; R2 ) n-butyl, n-pentyl, or isopentyl; M ) N or P; X
is an optional spacer group).
had clathrate hydrate structures with the 51264 cage, the same
cage found in structure II gas hydrate. They tested a large range
of quaternary salts and found that salts with two or more n-butyl,
n-pentyl, and isopentyl groups were the best at delaying the
growth of THF hydrate crystals (Figure 7).
Shell’s next inspiration was to replace one or two of the small
alkyl groups with a long hydrophobic tail (8-18 carbon atoms).
These materials are not anti-nucleators, so they are poor KHIs.
In fact, some of these small quaternary ammonium and also
phosphonium salts can promote hydrate nucleation by being
templates. Shell called these chemicals “hydrate growth inhibi-
tors” (HGIs). These quaternary surfactants salts with two or three
n-butyl, n-pentyl, and isopentyl groups performed extremely well
as hydrate AAs (Figure 8). Shell patented their results at the
end of 1993.31
The mechanism for Shell’s quaternary AAs is not the same
as that for IFP’s water-in-oil emulsifying AAs. Shell’s AAs are
designed with a hydrate-philic (hydrate seeking) headgroup and
a hydrophobic tail. Being surfactants, the AAs will accumulate
at the water-oil interface, where hydrate formation first occurs.
The hydrate-philic headgroup, which is the quaternary center,
will bind to hydrate particles. The butyl/pentyl groups penetrate
open 51264 cavities on the hydrate surface and can even become
embedded in the surface as the hydrate grows around the alkyl
groups. The long hydrophobic tail prevents the hydrate from
continuing to grow on that surface. The hydrophobic tail also
makes the surface more attractive to the hydrocarbon phase.
Once several AA molecules have attached to the surface, the
particle is easily dispersed in the hydrocarbon phase. The
quaternary AA will also be attracted to the pipe walls (also
indicated by the fact that some of these AAs are very effective
corrosion inhibitors). The hydrophobic tails will then help
prevent hydrate from growing or adhering to the pipe walls.
All in all, the Shell AAs are well-designed molecules for their
task, and it seemed like Shell was on to a winner, perhaps even
the silver bullet. Shell divided up the development work. Shell
Houston was to develop the more water-soluble single-tailed
quaternary AAs, while Shell Amsterdam was to optimize the
more oil-soluble twin-tailed quaternary AAs.
BP’s Research. BP’s own work on LDHIs began with the
study of amino acids. Tyrosines and related chemicals gave
some weak KHI effect, and the results were patented.32 BP also
patented various blends containing vinyl polymers such as PVP
and synergists.33-35 The synergists included corrosion inhibitors,
amino alcohols, amino carbohydrates, lactones, amino acids,
hydroxyacids, and glycol ethers. Some of the patent applications
were later withdrawn in favor of better KHIs. BP was a member
of the CSM consortium and therefore had access to the
Energy & Fuels, Vol. 20, No. 3, 2006 831
polyvinyllactam KHIs. They were also collaborating with Shell
in the mid 1990s and had access to their quaternary AA
technology. They combined a polyvinyllactam with small
quaternaries such as tetrabutylammonium bromide (TBAB) and
found they gave a synergistic KHI effect.36 (Actually, Shell had
included blends of Gaffix VC-713 and tetrapentylammonium
bromide (TPAB) in their AA patent but was not so interested
in the KHI effect.) BP called their blends “threshold hydrate
inhibitors”, but perhaps since the acronym THI could be
confused with thermodynamic hydrate inhibitors, it did not catch
on. BP patented the results along with blends with other
production chemicals.37,38 BP had their sights set on using their
synergistic KHI blends on their Southern North Sea gas fields
where the subcooling was less than 10 °C and ideal for KHIs.
BP was also thinking ahead to a planned field in the ETAP
province where the subcooling was about 6-8 °C. BP licensed
their KHI technology to TR Oil Services (TROS, now Clariant
Oilfield Services), who were used to bring the technology to
the field. TROS built their own pressure cells based on BP’s
design and worked on finding the optimum blends for BP’s
fields.
BP also initiated molecular modeling studies of PVP on gas
hydrate surfaces at the University of Reading, U.K.39 The results
show that the pyrrolidone ring bonded to the structure I hydrate
surface via hydrogen bonding to the amide and van der Waals
interaction between the ring and the hydrate surface. At that
time, no studies were carried out showing interactions with or
penetration of structure II cavities.
It is thought that TPAB (or TBAB) works synergistically with
PVCap because of their different geometries. Thus, TPAB and
PVCap should attach to different sites on the hydrate crystal
surface. So what is happening at the molecular level with TPAB?
Molecular modeling carried out at the University of Reading
for RF in the mid 1990s shows that TPAB penetrates a 51264
cavity on the 1,1,1 structure II hydrate surface. Two of the other
pentyl groups lay in channels on the hydrate surface where new
51264 cages would normally be formed. It therefore seems
possible that these cages could partially form, trapping or
imbedding the pentyl groups in the hydrate surface. Below the
critical nuclear size, growth of the nuclei is energetically
unfavorable (∆G is positive). So, TPAB will not be embedded
in the surface of the nuclei but will more easily detach. Above
the critical nuclear size, TPAB can become embedded in the
hydrate surface as partial hydrate cages form around the pentyl
groups, but further structure II growth is prevented by the
remaining pentyl groups.
The embedding mechanism for the quaternary salts explains
why tetrapropylammonium bromide (TPrAB) and tetrahexyl-
ammonimum bromide (THAB) are poor hydrate growth inhibi-
tors. TPrAB has an even weaker van der Waals interaction with
cavities and channels on the hydrate surface than TBAB. TPrAB
will more easily detach from the surface even if some water
molecules start to build cavities at the ends of the propyl groups
(i.e., it is less quickly embedded in the surface). On the other
hand, THAB has alkyl groups that are too long to give strong
van der Waals interactions with more than one cavity on the
surface and will therefore detach easily. In fact, THAB cannot
easily get embedded in the surface of structure I or II hydrate.
RF-Rogaland Research (RF) Projects for Esso/Exxon (now
ExxonMobil) and Elf (now Total). Back at the beginning of
the 1990s, RF began their research program with Essso Norge
and Exxon Production Research (now ExxonMobil Upstream
Research Company, EMURC). RF carried on from where they
left off in the PROFF project by looking for a better AA than
832 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 9. Structure of poly-L-proline.
the Blacksmith corrosion inhibitor. Tests were carried out on a
condensate with 20% water cut in stirred sapphire cells. The
cell was cooled from 20 to 4 °C over 2 h at a pressure of ca. 90
bar at 700 rpm stirring rate. RF tested a range of surfactants
with varying headgroups, ionicity, and tail-lengths. Some
surfactants with multiple hydroxyl or carboxylic acid headgroups
were prepared in-house hoping to find hydrate-philic surfactants.
Positive results were obtained with some neutral and cationic
surfactants, but only at low subcooling. (An n-butylpolyglycol
from Witco gave a slower growth of hydrates but was not
identified as a synergist for KHI polymers at the time). RF had
the right idea for making AAs, but not the right hydrate-philic
headgroups such as those found by Shell.
In their work on looking for surfactant AAs, RF observed
that products with a high degree of propoxylation gave beneficial
effects. This initiated a study of over 30 polypropoxylated
products. Polypropoxylates are interesting molecules. They are
not as hydrophilic as polyethoxylates, which tend to surround
themselves with water molecules, neither are they like alkyl-
chains, which tend to partition in nonpolar solvents. Because
of this amphiphilic behavior, polypropoxylates often end up at
the interface between the aqueous and nonpolar phase. This
makes them useful as defoamers and demulsifiers.
The best AA was an amine polyalkoxylate having a molecular
weight of approximately 6000. This product gave excellent
dispersion of hydrates in the hydrocarbon phase at subcoolings
below ca. 10-13 °C at 700 rpm stirring. It is interesting to
observe that BJ Unichem patented related polyether/polyamines
as LDHIs in the late 1990s and that Akzo Nobel patented
polyalkoxylated amines in the new millennium.
RF carried out two smaller projects on LDHIs for Elf (now
Total) in the early 1990s.40-42 The first project looked at natural
and biodegradable surfactants as potential AAs. The best product
was Plantaren 600 CPUS, an alkyl glucoside from Henkel. This
product worked well at moderate subcooling at 0.5 wt %. It is
interesting that Shell patented similar surfactants as AAs called
alkyl glycosides. The second project tested various water-in-
oil emulsions made with commercial monomeric surfactants.
No good results were obtained, indicating that compounds that
are effective in creating water-in-oil emulsions do not necessarily
show good AA performance.
Returning to the Exxon/Esso program, RF moved away from
studying AA surfactants and looked more at water-soluble
polymers as potential KHIs. The first class of polymers that
gave results were polyamino acids, which are related to fish-
anti-freeze proteins. The best results were obtained with poly-
L-proline (Figure 9). This polymer gave a subcooling of only a
few degrees Celcius, but its structural relationship to PVP was
the most important feature. Both poly-L-proline and PVP
contained a five-member ring and an amide group in the
repeating unit.
During RF’s work for Exxon/Esso, RF did indeed discover
PVP as a KHI giving about 5 °C subcooling and shortly
thereafter PVCap, which gave about 8-9 °C subcooling.43 These
discoveries were made independently of, but later than those
of CSM and Shell (PVP only). RF showed that PVCap gave a
lower subcooling performance with structure I methane hydrates
as compared to structure II natural gas hydrates.80 A reduced
ReViews
Figure 10. Structure of N-methyl-N-vinylacetamide:vinyl caprolactam
1:1 copolymer (VIMA:VCap) where a ) b.
Figure 11. Structures of polyacryloylpyrrolidine, polydiethylacryla-
mide, and polyisopropylacrylamide.
Figure 12. Structures of polyethylmaleimide, ring-opened polyeth-
yloxazoline, and ring-closed polyethyloxazoline.
performance with structure I hydrates relates to the higher
symmetry of structure I hydrate crystals. On a suggestion from
Exxon to test VCap copolymers, RF synthesized and tested
N-methyl-N-vinylacetamide:VCap 1:1 copolymer (VIMA:VCap
1:1) (Figure 10). This copolymer performed better than PVCap
by 2-3 °C subcooling in a sapphire cell test. Exxon, who had
commissioned the work at RF and owned the results, synthesized
similar copolymers in their own laboratories. Tests in Exxon’s
mini-loop confirmed RF’s findings, subsequently Exxon and a
researcher at RF jointly patented the copolymer as a KHI in
1995.44
RF synthesized and tested other VCap copolymers such as
VCap:vinyl imidazole. This also gave good performance, but
the work was not taken further. The last polymer of note that
RF tested was a ring-opened polyethyloxazoline, which contains
ethylamide groups in the repeating unit. Although the perfor-
mance in the THF hydrate ball-stop rig was only moderate,
interestingly it belonged to a different class of KHIs than the
vinyl lactam polymers.
LDHIs from Exxon Production Research (EPR). Esso
Norge and Exxon Production Research (EPR, now EMURC)
discontinued their support of RF’s work at the end of 1994 and
decided to continue the work on their own. Exxon had deduced
that a key element in many KHI polymers was the presence of
an amide group attached to a hydrophobic group in the repeating
unit. Exxon had their own theory for KHIs which involved
maximizing the hydration volume of the polymer in water. The
hydrophobic group would form hydrate cavities around it while
the carbonyl oxygen atom of the amide group would form
hydrogen bonds with water molecules. Several of these interac-
tions would be needed; hence, a polymer or oligomer was
required. The inhibitor could thus interrupt nucleation of
hydrates in the water phase. Exxon used molecular modeling
to deduce the best inhibitor structures. Their theory is somewhat
related to that of other modelers.45-47,213,214,227
Exxon filed patents on a number of classes of polymer-
containing amide groups. These included polyalkylacrylamides48
(Figure 11), polydialkylacrylamides48 (Figure 11), polyvinyl-
amides,49 polyallylamides,50 polymaleimides51 (Figure 12),
polymers of cycliciminoethers52 such as polyacylalkyleneimines
and polyalkyloxazolines (ring-opened and ring-closed) (Figure
12), and amides or esters of N-acyldehydroalanine.53 The best
ReViews
Figure 13. Polyisobutylacrylamide.
Figure 14. Polyisopropylmethacrylamide.
Figure 15. Structure of polyisopropylmethacrylamide:N-vinyl-N-
methyl acetamide copolymer (VIMA:iPMA).
KHI performance was obtained with the acrylamide polymers,
probably because the optimum size alkyl group was not used
for the other classes of polymer. (For example, it is difficult to
synthesize N-vinyl amides with the wide variety of alkyl groups
that is possible for acrylamides.) The best acrylamide ho-
mopolymer was polyacryloylpyrrolidene (polyAP) followed by
polydiethylacrylamide and then polyisopropylacrylamide (poly-
iPAm).
Polyisobutylacrylamide was not tested because it is insoluble
in water (Figure 13). (In 1996, RF tested some copolymers of
isobutylacrylamide with VIMA and VP with KHI performance
results similar to polyisopropylacrylamide.)
Exxon found that the addition of a methyl group to the
backbone of the acrylamide polymers increased their perfor-
mance. For example, the subcooling performance of polyiso-
propylmethacrylamide (Figure 14) was found to be approxi-
mately 2 °C greater than that of polyisopropylacrylamide.
Exxon patented this idea of adding a small alkyl group to
the backbone of a KHI polymer to increase its performance.54
The only polyvinylamide to be tested by EPR was polyVIMA,
which was found to be a poor KHI. However, copolymers of
VIMA with other alkylamide polymers gave surprisingly high
subcoolings, very much like what RF had seen with the VIMA:
VCap copolymer. For example, compared to polyiPMAM,55 a
1:1 VIMA:iPMA copolymer (Figure 15) gave a 4.2 °C higher
subcooling. For this copolymer, Exxon reported an actual
subcooling of 17.5 °C. However, it should be noted that a
subcooling of 4 °C was obtained by a test with no additives,
and Exxon’s test method is different from that of others.
Other interesting results were obtained with ring-closed
oxazoline polymers. These represent the first class of polymers
that do not contain amide groups and still show substantial KHI
(anti-nucleation) performance.
Exxon also found that a VIMA:vinyl butyrate copolymer gave
a surprisingly high performance both as an anti-nucleator in
the high-pressure mini-loop and as a hydrate crystal growth
inhibitor with THF hydrates. The mini-loop performance was
better than PVCap, polyiPMAM, and polyAP. (At that time none
of the polymers were optimized for molecular weight.) It is clear
Energy & Fuels, Vol. 20, No. 3, 2006 833
that the butyrate groups in the VIMA:vinyl butyrate copolymer
contribute to the inhibition performance since it is known that
polyVIMA is a fairly poor KHI. As a hydrate crystal growth
inhibitor, the propyl part of the butyrate group may be interacting
with open large cavities on the structure II hydrate surface. It
remains unclear whether the ester groups as well as the amide
group in the VIMA units form hydrogen bonds with the hydrate
surface. It is probable that both do, but hydrogen bonding with
the ester group is probably weaker than with the amide. We
can deduce this since polyvinyl esters are not water-soluble (low
hydrophilicity), but polyvinylamides are water-soluble. (For
example, polyvinyl acetate is not water-soluble at room tem-
perature, but polyvinylacetamide is. Again, polyethylacrylate
is not water-soluble but polyethylacrylamide is.) In fact, the
reduced hydrophilicity of VIMA:vinylbutyrate polymer probably
contributes to the increased KHI performance relative to
polyVIMA. This is because, compared to polyVIMA, the
copolymer will favor interactions with the hydrate surface more
than with free water. Several research groups believe that the
hydrophilicity of a polymer (measured as its cloud point) is
related to its performance as a KHI, but no systematic study
has been published. In addition, no group has studied water-
soluble vinyl ester copolymers as KHIs. Exxon did carry out a
study that concluded that cloud point is not a sufficient condition
for increasing KHI performance.111 Cloud point can be adjusted
by total carbon in the monomer or by salinity of the solution.
Exxon found there was no change in rank order of subcooling
for various structures when salinity greater than seawater was
scanned. Increasing carbon in the monomer only resulted in an
insoluble polymer that cannot inhibit hydrates. Exxon concluded
that the exact positioning of carbon in a monomer or polymer
is more important than the cloud point. This is the point of their
methylated backbone patent where a carbon on the backbone
was more effective than another carbon in the pendant amide
group.
Exxon obtained one of the polyalkyloxazolines from Nippon
Shokubai in Japan (NS). After discussions with Exxon, NS
became interested in LDHIs and built their own THF hydrate
ball-stop rig. NS synthesized polyAP and found that it gave a
very good performance in their rig. They patented the results
in Japan in 1994,56 not knowing that Exxon had already done
that a few weeks before. NS and RF remained unaware of this
until 1996. NS also filed a patent application on alkyl acrylate:
VP copolymers.57 They found, for example, that butyl acrylate:
VP gave increased KHI performance as compared to PVP. The
argument for its increased performance is identical to that given
above for VIMA:vinyl butyrate copolymer tested by Exxon (i.e.,
a higher “hydrate-philicity” of the copolymer as compared to
PVP and interaction of the butyl ester group with the hydrate
surface).
Exxon applied for two further patents in 1994 and 1995. The
first patent covered surfactants with a hydrophobic tail of 12
carbons or less as AAs,59 while the second patent covered their
use as synergists with KHI polymers.60 Examples given included
butyl sulfate, sodium valerate, zwitterionics such as butyldi-
methylammonium butylene sulfonate, and N-dodecylpyrroli-
done. On their own, these products gave reasonable performance
in the THF hydrate ball-stop rig. When combined with alkyl-
amide polymer KHIs, they gave good synergistic results. This
can be explained by their function as hydrate growth inhibitors.
The butyl group or pyrrolidone group can interact with open
51264 cavities on the hydrate surface. RF confirmed that butyl
sulfate is indeed a hydrate growth inhibitor, although weaker
than TBAB, in the single-crystal THF hydrate growth test.
834 Energy & Fuels, Vol. 20, No. 3, 2006
Exxon conducted two mini-loop AA tests on butyl sulfate. At
0.25 wt % no effect was observed, but at 0.5 wt % the blocking
temperature of the loop was over 13 °C below the equilibrium
temperature. RF tested butyl sulfate as an AA in their sapphire
cells but obtained very poor results. It seems that these small
surfactants are best used as synergists for KHI polymers.
IFP and Emulsion AAs. The last institute to be mentioned
in the early 1990s is IFP. IFP continued to patent classes of
AAs in the early 1990s.61-67 It was difficult to tell what
chemistry they were focusing on, but IFP had begun to narrow
their choice of dispersants to just a few products by 1994. It
seemed from their patent application that they were concentrat-
ing on polymeric emulsifiers such as polyglycol derivatives of
polyalkenylsuccinic anhydride. Early conference talks in Sta-
vanger, Norway, in 1992 described the use of 0.5-2.0 wt %
dispersant additives.68 IFP later gave a talk at a seminar in
Trondheim, Norway, in 1994 where they showed successful
results of an AA at 0.8 wt %.69 In addition, Norsk Hydro tested
IFP’s products in autoclaves and got promising results using a
dosage of 2.0 wt %.
Mid 1990s
At the beginning of the 1990s, LDHI technology was just a
good research idea with a lot of potential. By the mid 1990s,
many of the classes of LDHIs used today had been discovered,
although there was plenty more chemistry yet to come. The
service companies and several chemical companies began to
get actively involved in designing and formulating LDHIs
hoping to get a slice of the market that was opening up. By
1995 Shell, BP, and Exxon had decided on their strategies for
developing their LDHIs. Shell had their quaternary surfactant
AAs (“quat AAs”), which gave high subcoolings, BP had settled
for KHI blends that gave moderate subcooling, and Exxon had
a range of KHIs that could give a fairly high subcooling in their
mini-loop.
First KHI Field Trials. The polyvinyllactams discovered by
CSM were beginning to reach the market via the chemical
suppliers, ISP and BASF, and the service companies. One
service company even advertised PVP under a new brand name
as an effective KHI at 50 ppm at the exhibition hall of the SPE
Technical Conference in 1994. It remained to be seen who
would be first to try out these new LDHIs in the field. Who
would dare risk using these new products with no track record?
The first pioneers to report their field trials were Arco,70
Texaco,71 and BP.72 Arco was the first to go offshore in 1995
with a KHI when they tested Gaffix VC-713 on a Southern
North Sea gas field. The trials showed that 0.5 wt % of polymer
could handle 8-9 °C of subcooling. Texaco tested PVP in
Wyoming and Texas showing it is useful at limited subcooling
only. BP carried out six field trials on another Southern North
Sea gas field (Ravensburn-Cleeton) in 1995-1996 using their
KHI blends formulated by TR Oil Services (now Clariant). The
KHI blends were based on mixtures of TBAB and VCap
polymers. (Besides being a synergist, TBAB has the additional
beneficial effect of increasing the cloud point of the VCap
polymer). In addition, TBAB is roughly half the price of PVCap.
The field trials were successful up to the maximum subcooling
of 10 °C. This success led BP to switch from glycol to KHI on
their West Sole/Hyde, 69 km wet gas pipeline in 1996 where
the subcooling was a maximum of 8 °C.73,74 This became the
first offshore field application of a KHI and, in fact, any LDHI.
CSM’s Consortium. CSM continued to screen potential
LDHIs up until the mid 1990s, but they did not make any further
KHI discoveries besides that of the polyvinyl lactams and their
ReViews
synergy with some other polymer classes. CSM carried out a
range of studies on PVCap, PVP, and VP:VCap copolymers
supplied by ISP and BASF.75 They showed for example that
laboratory autoclave experiments could be correlated with
experiments in a pilot loop, in this case EPR’s loop.76,239 They
also showed that the performance of PVCap was negatively
impacted by methanol and a low concentration of salt.77,238
Higher salt concentrations (> 5.5 wt %) were actually beneficial
to the performance of PVCap. In addition, CSM carried out
studies on the dependence of the performance of PVCap on
molecular weight.78 CSM found that the highest subcooling
performance was obtained with a PVCap having a molecular
weight of 900. Samples of PVCap were made at the University
of Akron in Ohio. The University only measured the number
average molecular weight, not the weight average molecular
weight, which is the more common figure to quote. It is therefore
difficult to say how many monomer units are in CSM’s low
molecular weight PVCap polymers. Even so, at these low
molecular weights, it is probably best to use the term oligomer
rather than polymer.
CSM also carried out extensive studies on THF hydrates
giving structure II and ethylene oxide hydrate giving structure
I.79 They confirmed RF’s findings80 with gas hydrates that
PVCap gave a lower subcooling performance on structure I
hydrate as compared to structure II hydrate at the same dosage.
In addition, work carried out at CSM on the growth of single
THF hydrate crystals showed that stirred solutions needed a
lower dosage of KHI to totally inhibit crystal growth as
compared to static solutions. This has implications in pipelines
during shut-in situations. The dosage necessary to inhibit
hydrates will be higher in a shut-in than under flowing
conditions. This is because polymer diffusion to the hydrate
surface is slower under static conditions. This also implies that
a low molecular weight polymer with high mobility will perform
better than a larger polymer.
ISP and BASF. CSM’s agreement with ISP was not
satisfactory for ISP, who wanted better control of the market
for their KHI polymers. Consequently, ISP ended their col-
laboration with CSM and built their own autoclave equipment.
In this way, ISP could test any new polymers synthesized in
their laboratories and patent any new LDHI inventions. The first
patent that ISP filed concerned the use of small alcohols and
glycol ethers with a tail of 3-5 carbon atoms as synergists for
vinyl caprolactam polymers.81 The main synergist example was
butyl glycol ether (BGE). BGE was not only a good synergist
for polymers such a PVCap, it could also be used as the solvent.
This patent application was a problem to ISP’s competitor
BASF. At the time BASF had been using small alcohols and
glycol ethers in the manufacture of VCap polymers. Now BASF
was forced to find other solvents. In the end, BASF ended up
(231) Crosby, D. L.; Rivers, G. T.; Frostman, L. M. U.S. Patent
Application 2005/0261529, 2005.
(232) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J.; Tomita, T.; Mizuta,
K. Chem. Eng. Sci. Submitted for publication.
(233) Kelland, M. A.; Svartaas, T. M.; Øvsthus, J.; Tomita, T.; Chosa,
J. Chem. Eng. Sci. Submitted for publication.
(234) Arjmandi, M.; Tohidi, B.; Danesh, A.; Todd, A. C. Chem. Eng.
Sci. 2005, 60, 1313.
(235) Koh, C. A.; Westacott, R. E.; Zhang, W.; Hirachand, K.; Creek,
J. L.; Soper A. K. Fluid Phase Equilib. 2002, 192, 4, 143.
(236) Koh, C. A.; Wisbey, R. P.; Wu, X. P.; Westacott, R. E.; Soper A.
K. J. Chem. Phys. 2000, 113, 6390.
(237) Kvamme, B.; Kuznetsova, T.; Aasoldsen, K. J. Mol. Graphics
Modell. 2005, 23, 524.
(238) Sloan, E. D.; Subramanian, S.; Matthews, P. N.; Lederhos, J. P.;
Khokhar, A. A. Ind. Eng. Chem. Res. 1998, 37, 3124.
(239) Lederhos, J. P.; Sloan, E. D. In SPE Annual Technical Conference
and Exhibition, October 5-9, 1996, Denver; SPE 36588.
ReViews
using ethylene glycol and water as solvents for their products.
ISP applied for several further patent applications in the late
1990s, which will be discussed later.
In contrast to ISP, their competitor in vinyl lactam polymers,
BASF, took a less active stance in trying to capture the market
for their KHI polymers. During the mid 1990s they did not test
their own polymers as LDHIs, nor did they file patent applica-
tions for any of their own products. (BASF did patent vinyl
formamide copolymers with more hydrophobic monomers, but
the performance of them appears to be poor.82) Instead, BASF
relied on synthesising polymers at the request of any customer
using their extensive experience in polymer chemistry, which
went beyond the polyvinyllactams. Later BASF began to be
more active in testing and patenting their own discoveries.
ExxonMobil Research. Exxon (now ExxonMobil) ap-
proached BASF because they wanted to commercialize the
VIMA:VCap copolymer that had been patented in 1995. BASF
made samples of VIMA:VCap, which ExxonMobil tested in
their loops. When ExxonMobil was convinced of the improved
performance of VIMA:VCap copolymer, they signed a license
agreement with Nalco Exxon Energy Chemicals (now Nalco)
to commercialize the technology. ExxonMobil began using KHIs
in the field from 1996.83,84 ExxonMobil and Nalco reported
several field applications in 1999-2001 including the first
deepwater application of an LDHI.85,86 Royalties from the use
of VIMA:VCap copolymer were paid by Nalco to ExxonMobil
and CSM because the copolymer contained VCap monomer.
Sales of the copolymer were low until a North Sea application
greatly increased the volume. Today however, VIMA:VCap is
no longer commercially available due to the difficulty in
obtaining the VIMA monomer and its high price. In the mid
1990s Clariant was the only manufacturer of VIMA monomer,
which was used for making cheese wrap. Nalco bought a
quantity of this monomer from Clariant to make VIMA:VCap
copolymer, but they have not bought anymore since then. BASF
and ISP have both been approached by Nalco to make further
quantities of VIMA:VCap copolymer, but it seems that neither
company has delivered this product.
The other class of polymer that ExxonMobil wanted to
commercialize was based on alkylacrylamides. They had used
a proprietary theory to deduce that isopropylmethacrylamide
(IPMA) polymer was the most potent KHI of the alkylacryl-
amides. Since it performed better than isopropylacrylamide
polymer, ExxonMobil deduced that adding a methyl group to
the backbone was beneficial. The same benefit was found for
other polymer classes such as polyvinyloxazolines. ExxonMobil
patented the idea of adding a methyl group to the backbone to
increase polymer performance.54
ExxonMobil’s theory, that led them to the conclusion that
the IPMA polymer is the most effective alkylacrylamide
polymer, is proprietary. The theory has to do with maximizing
the hydration volume of the polymer in order to perturb the
nucleation of hydrates. Clearly IPMA and VCap polymers must
be perturbing water molecules around the side chain functional
groups at some distance so that they are unavailable for forming
hydrate clusters, thereby preventing hydrate nucleation. They
exploited this idea in a new patent application on modified
AMPS (acrylamidopropylsulfonic acid) polymers. (Figure 16).87
PolyAMPS is a poor KHI, but ExxonMobil found that the
addition of a hydrophobic tail between the amide and the
sulfonic acid group increased the performance of the polymer.
The optimum size of the tail was 5 carbon atoms long. A
homopolymer of this monomer gave a performance in Exxon-
Mobil’s mini-loop, similar to PVCap. Moreover, copolymers
Energy & Fuels, Vol. 20, No. 3, 2006 835
Figure 16. Structure of modified AMPS polymers where R1 is an alkyl
tail of 1-6 carbon atoms and R2 is H or Me.
of this modified AMPS monomer with VCap gave even better
performance. However, it does not appear that ExxonMobil has
sought to commercialize this technology.
Shell’s Quaternary AAs. While the first KHI field trials were
taking place, Shell was preparing the first generation of the
quaternary AAs. The Shell U.S. team was responsible for the
development of the single-tail quaternary AA. The preferred
molecules in their patents contained a hydrophobic tail of 10-
14 carbon atoms, a tributylammonium or tripentylammonium
headgroup, and a counterion. (A tripentylammonium headgroup
would give a better hydrate growth inhibitor, but the precursor
tripentylamine is roughly twice the price of tributylamine.) This
quaternary AA performed extremely well coping with subcool-
ings of 20+ °C in systems containing saline (> 1.5 wt % salt)
water. However, the AA did not perform so well in freshwater.
This may be due to the strength of the ion pairing in an aqueous
phase of low ionicity. Second, the concentration needed for
optimum performance was fairly high at 0.6-1.0 wt % actives.
Baker Petrolite was given a worldwide license to commercialize
the technology. They spent the mid and late 1990s building their
own LDHI test equipment and getting up to speed on testing
procedures.
Shell and Baker Petrolite’s biggest hurdle in getting the single-
tail water-soluble quaternary AA to the field was its environ-
mental impact. Quaternary surfactants are known to be toxic,
and the quaternary AA was no exception. Added to that, the
majority of the quaternary AA partitioned into the aqueous phase
and would therefore be discharged into the sea (although the
single-tail quaternary AA is seen to phase separate in a warm
oil-water separator containing high salinity produced water.
Therefore in such cases very little of it may be discharged in
the overboard water). Second, being a tetraalkyl quaternary AA,
it had low biodegradability. This meant that the toxic molecule
would survive in the sea for a considerable time and could
possibly bioaccumulate. The environmental impact of the
quaternary AA made Baker Petrolite initially unsure about its
commercial viability. Being a new molecule, it had to go through
pre-market notification, and Baker Petrolite was unsure whether
this was worth the trouble. But eventually the green light was
given to go ahead with its manufacture and commercialization.
However, no field trials were reported in the 1990s, indicating
that field implementation was a fairly long process.
The development of the twin-tailed quaternary AA was the
responsibility of the Dutch Shell team. They enlisted the help
of a neighboring chemical company, Akzo Nobel, to make their
AAs. The first prototype molecules were based on tetraalkyl-
ammonium salts with two tails such as dicocoyldibutylammo-
nium bromide.88 This quaternary AA performed well up to a
subcooling of ca. 14 °C in Shell’s flow loop in several
hydrocarbon fluids at 0.25 wt %. In contrast to the single-tail
quaternary AAs, it also worked in freshwater systems. The
biggest drawback with the tetraalkylammonium salts was their
environmental impact. These quaternary AAs gave almost zero
biodegradation in standard OECD (Organization for Economic
Cooperation and Development) tests. Added to that they were
836 Energy & Fuels, Vol. 20, No. 3, 2006
toxic and even more bioaccumulative than the single-tail
quaternary AAs. Akzo Nobel went back to the laboratory and
synthesized diester quaternary AAs instead. These were diesters
of dibutyldiethanolammonium halides and 2 mol of a long-chain
alkyl carboxylic acid. These products biodegraded ca. 50% in
28 days. The ester groups degrade within 5 days, leaving a small,
less surface active, and less toxic quaternary ammonium salt.
The optimum chain length for the carboxylic acid appeared to
be coconut fatty acids with 12-14 carbon atoms. This cocoyl
diester quaternary AA performed well up to subcooling of 15
°C in the tests described by Shell in their patent. The product
performed equally well in freshwater as in saline water. The
concentration necessary was only 0.25 wt % based on the
aqueous phase. In addition, this diester quaternary AA parti-
tioned ca. 95% into the liquid hydrocarbon phase. This meant
that the active concentration in the bulk water phase was only
approximately 125 ppm. This seems surprisingly low for such
a powerful product. However, the concentration of the AA at
the liquid hydrocarbon/water interface, where hydrate formation
first takes place, is undoubtedly a lot higher. Akzo Nobel
formulated the cocoyl diester quaternary AA as a 33% solution
in a hydrocarbon solvent. This was made available to the service
companies for commercialization.
One oil company interested in Shell’s quaternary AAs was
Statoil. Statoil had been collaborating with the Dutch Shell team
in the mid 1990s testing Shell’s/Akzo Nobel’s twin-tail qua-
ternary AAs in their wheel-loops. Statoil was impressed by their
performance and went ahead with a field trial on their Tom-
meliten field in 1995. Only a few details have been published
on the field trial, the results of which do not appear to have
dampened Statoil’s enthusiasm for using the quaternary AAs.89
In fact, Statoil wanted to use the twin-tail quaternary AA on a
new field development called Kvitebjørn. The most economical
solution was a tie-back using multiphase transportation. The
subcooling for hydrate formation was calculated to be under
15 °C and ideal for the twin-tail quaternary AA. Statoil asked
TROS (now Clariant Oilfield Services) to make an application
to the Norwegian environmental authorities (SFT) to use the
diester quaternary AA on the Kvitebjørn field.90 Unfortunately,
the SFT turned down TROS and Statoil’s application. It seems
that the reason given was that the diester quaternary AA was
insufficiently biodegradable. The SFT did not like the fact that
the degraded product, dibutyldiethanolammonium bromide, did
not degrade any further in a 28 day OECD test even though
this degraded product was far less toxic. TROS submitted further
data to show that the degraded quaternary does degrade
eventually in a 70 day test, but it was to no avail, the SFT stood
by their decision. This meant that Statoil had to cancel their
plans for developing the Kvitebjørn field since no alternative
economical solution could be found. The field still remains
undeveloped to this day. But the failure to get the twin-tail
quaternary AA accepted for use on the Kvitebjørn field had
wider repercussion. It meant that no quaternary AAs, single-
or twin-tail would ever be allowed in Norwegian waters. Statoil
then began to look elsewhere for alternative LDHI technology.
They joined the CSM consortium as a late participant hoping
to find a high-performing KHI. They also joined a new industry
project (JIP), which started at RF in April 1995. They also
carried out a field trial on BP’s PVCap/TBAB KHI technology
commercialized by TROS (now Clariant).89 The field trial lasted
only 3 h as the subcooling at 9 °C was just outside the
performance limit of the KHI at 0.5 wt %. Meanwhile, the Dutch
Shell team had to look elsewhere for field trials of their diester
quaternary AA.
ReViews
Figure 17. Example of a polyetherdiamine.
IFP and Project EUCHARIS. Another JIP that started in
the mid 1990s centered on the technology and facilities at IFP.
The project was called EUCHARIS and was supported by six
oil companies and the HSE Department of the U.K. The main
aim of the project was to be a springboard for IFPs emulsion
AA technology. After almost a decade of laboratory research,
IFP had narrowed down the choice of AA candidates to just a
few products, largely polymeric surfactants. One of them called
Emulfip 102b made by FINA (now Total) was the preferred
product. Emulfip 102b is a 50% solution of polymerized fatty
acids and amides in rapeseed oil. Although no environmental
data was published, this product was expected to be considerably
greener than Shells quaternary AAs. To test Emulfip 102b
further, IFP used their newly completed pilot-scale flow-loop.
The product was tested at two concentrations and a range of
conditions.91 At 0.4 wt % the results were poor, but at 0.8 wt
% the tests were much more successful. Fine slurries of
transportable hydrates were formed up to the maximum sub-
cooling of 13 °C. There were, however, a couple of drawbacks
to the emulsion AA technology. First, the water phase had to
be thoroughly emulsified before entering hydrate-forming
conditions, otherwise hydrate agglomeration and deposition is
likely. Could this be guaranteed in the field? Second, hydrates
formed from condensed water on the upper walls of the pipe
during laminar flow or during shut down. Nevertheless the JIP
committee recommended IFP to go ahead with field trials, which
took place in the late 1990s.
IFP also carried out studies on KHIs for the first time. They
tested a BP KHI blend commercialized by TROS (now Clariant
Oilfield Services) in their pilot loop. They also filed two patent
applications on new KHIs.92,94 The first patent application
claimed polymers with at least one sulfonate group. The best
examples were acrylamide:AMPS copolymers.93 But these gave
only moderate performance, no better than PVP. The second
patent application claimed polymers with at least one nitrogen
containing monomer such as the dimethylaminomethylacrylate
monomer. These gave a similar fairly weak performance as the
sulfonated copolymers.
BJ Unichem and Gas Well AAs. The only service company
to be actively involved in inventing LDHIs in the 1990s was
BJ Unichem Chemical Services. A one-man effort has seen new
products taken through from laboratory research all the way to
several field applications. The laboratory test rig used was a 1
mm i.d., 64 m long flowline. The liquid phase was THF in 3.6%
brine, and the flow rate was slow at less than 1 mm/s. BJ
Unichem found that polyetherpolyamines and polyetherdiamines
(particularly of the oxypropylene type) lowered the blocking
temperature or gave a longer time to blocking than a test with
no additives.95,96 Examples were taken from the Jeffamine range
by Huntsman Corporation (Figure 17) and Ethoduomeen by
Akzo Nobel.
BJ Unichem also patented quaternized polyetherpolyamines
by reaction of polyamines with a long-chain alkyl bromide.97
These products performed better in the THF hydrate flowline
than PVCap, TBAB, and several Shell-type quaternary AAs.
At least four field applications have been reported in gas wells
both offshore and one onshore.98-101 One report included details
of an autoclave test in which the polyetherpolyamine was a good
synergist for PVCap. The same product dispersed gas hydrates
in the remaining unconverted water. Use of the polyetheramines
in completion and fracturing fluids has also been patented.226
ReViews Energy & Fuels, Vol. 20, No. 3, 2006 837

It is difficult to know how to categorize BJ’s products or

indeed understand the mechanism for their action. (See also
results in the early 1990s by RF on propylene glycols.) They
are clearly not KHIs, as BJ’s autoclave tests on polyether-
polyamines gave zero induction time. (However, a later paper
does show significant anti-nucleation effect for some poly- Figure 18. Structure of polyallyl isopentanamide.
etheramines, as well as good synergy with a polymeric KHI223.)
Neither are they true AAs because they have not been proven
to work at full water conversion with a liquid hydrocarbon
phase. In both the laboratory studies and the field applications,
gas hydrates that form are being dispersed in unconVerted water
(or water plus a minor % of hydrocarbon phase). Therefore,
when used alone it is probably best to call these products gas
well AAs (GWAAs) in order to distinguish them from true AAs, Figure 19. Structures of VP:isobutylacrylamide and VIMA:isobuty-
which work in pipelines with a hydrocarbon phase at full water lacrylamide copolymers.
conversion. They are also synergists for KHI polymers such as
PVCap.225 Regarding their mechanism as synergists, the poly-
etherpolyamine may be interacting with cavities on the hydrate
surface via the amine headgroups. The polyether chain may
interact weakly with the hydrate surface or just act as a barrier
to prevent the hydrate nuclei from growing. Many small amines Figure 20. Structure of VP:butyl acrylate copolymer.
are known to form clathrate hydrates. This includes ethylamine,
which is the same size as the ethyleneamine groups on the ends
of the polyetherpolyamines.
RF JIP: KI Studies. When Exxon dropped out of supporting
RF’s studies at the end of 1994, this left RF briefly without
any LDHI work. However, by April 1995, RF had launched its
own JIP. The JIP was supported by seven oil companies, TR
Oilfield Services (now Clariant Oilfield Services), Hoechst (now Figure 21. Structures of polypyrrolidinyl aspartate (polyAS) and
Clariant), and the Norwegian Research Council (NFR). The aim polyglyoxylpyrrolidine (polyGP).
of the project was to design better LDHIs (both KHI and AA)
alkylamide a greater degree of rotational freedom as compared
than were previously available. RF’s approach was to use
to polyvinyl amides. This means polyallylamides will lose this
molecular modeling and a good deal of intuition to design
rotational freedom (entropy) on binding two hydrate surfaces
improved products. The modeling work was carried out at the
making the process less favorable than with polyvinylamides.
University of Reading. The goal was to find functional groups
The next class of polymers with alkylamide groups that RF
that would interact strongly with structure II hydrate surfaces.102
investigated were polyalkylacrylamides. Polyisopropylacryla-
These functional groups could then be placed into water-soluble
mides (polyiPA), synthesized in house, performed better than
polymers to make KHIs and into surfactants to make AAs.
polyethylacrylamides but a little worse than Gaffix VC-713.
Functional groups investigated by modeling included alkyla-
Polyisobutylacrylamide (polyiBA) was also synthesized but
mides, lactams and many other heterocyclic groups, amine
found to be water-insoluble. Therefore, 1:1 copolymers of iBA
oxides, quaternary ammonium salts, and betaines. The alkyl
with VIMA and VP were prepared with cloud points of 30 °C
amides with the strongest structure II hydrate interactions were
(Figure 19). Both these copolymers performed somewhat better
found to contain alkyl groups with 3-4 carbon atoms. Moreover,
than polyiPA and similar to Gaffix VC-713. No further
the interaction was strongest when the alkyl group was branched
polyalkylacrylamides were synthesized in house as RF began
(i.e., isopropyl and isobutyl).
to be supplied with this class of polymer by Nippon Shokubai
To confirm the modeling results, RF sought to make KHI Company Ltd. of Japan (NS).
polymers containing optimum alkylamide groups. They em- NS had independently discovered polyacryloylpyrrolidine
ployed the University of Oslo to make vinyl alkyl amide (polyAP) as a KHI and had patented the result in 1995.56 RF
polymers. The University succeeded in making N-vinyl-N-propyl later became a co-owner of the patent along with a second patent
propanamide, but this monomer refused to polymerize, even on VP:alkyl acrylates, which performed better than PVP, (e.g.,
with comonomers such as VP. Clariant also tried to make VP:butyl acrylate copolymer) (Figure 20).57
polyvinylalkylamides. They synthesized N-vinyl-N-isobutyl ac- Besides polyAP, the first patent also included other polymers
etamide, but this also refused to polymerize. with carbonyl pyrrolidine groups in the side chains (e.g..
Stumped by the lack of access to polyvinylamides, RF looked polypyrrolidinyl aspartate (polyAS) and polyglyoxyl pyrrolidine
for other polymers containing alkylamide groups. Polyallyla- (polyGP)) (Figure 21). Bayer later patented polyaspartate and
mides with pendant alkyl groups of 1-5 carbon atoms were related polymers with succinyl units.58
made available to RF by Nitto Boseki of Japan. The most RF tested NS’s polyAP and found it to be an excellent KHI,
effective KHI in this class was polyallyl isopentanamide, with superior to Gaffix VC-713. (PolyGP performed equally as well
a pendant isobutyl on the amide (Figure 18). This result was in as polyAP and polyAS a little less so.) Extensive work was
agreement with the modeling studies. The performance was carried out optimizing polyAP. The optimum molecular weight
significantly less than Gaffix VC-713 for two reasons. First, (Mw) for best performance was found to be 1000-3000. This
the degree of amidation of the original polyallylamine was only represents only eight monomers in the chain of the shortest
40%. Second, the alkylamide groups are separated from the polymers (oligomers). Only one copolymer, AP:VCap copoly-
polyvinyl backbone by methylene spacer groups. This gives the mer, was found that performed better than polyAP. The best of
838 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 22. Structure of the active monomer unit in amidated maleic
anhydride copolymers. R+ is H+, a metal ion or a quaternary ammonium
ion. The isobutyl group can be exchanged with isopropyl.
the other AP copolymers was 1:1 AP:acrylamide copolymer.
AP:VIMA copolymers were not investigated, although Exxon-
Mobil’s results with methacryloylpyrrolidine:VIMA (MAP:
VIMA) copolymers suggest they could outperform polyAP.
Molecular modeling of AP monomer indicated that it
interacted strongly with the deep holes on the (1,1,1) structure
II hydrate surface. VCap did not interact well with the surface,
and VP interacted in a different way to AP. This suggested to
RF that PVCap and PVP might be synergists for polyAP. This
was confirmed through laboratory experiments. The best
synergistic blend that was formulated was a 4:1:1 triple blend
of polyAP (Mw ) 5000):PVCap (Mw ) 19000):Antaron P904
(Mw ) 16000). A 6000 ppm solution of this triple blend
prevented hydrates from forming for at least 17 h at 16 °C
subcooling in autoclave and wheel tests. The conditions were
90 bar and 2 °C while the fluids were 3.6% synthetic seawater,
Exxol D60, and a natural gas blend (C1-C4, CO2, and N2).
By this time, RF and NS were aware that ExxonMobil had
beaten them to the patent office for polyAP and other poly-
alkylacrylamides. Therefore, RF and NS took out a joint patent
on their synergistic blend technology hoping that ExxonMobil
would give them a license to commercialize them.103 Two
hurdles got in the way of commercializing polyAP and
synergistic blends. First, ExxonMobil would not give RF and
NS a license before having tested the technology themselves.
Second, it was discovered that pyrrolidine, the starting material
for making polyAP, was prohibitively expensive (ca. 12 euro/
kg). Therefore, NS and RF decided to switch strategies and
concentrate on polyiPA, which was expected to be cheaper to
manufacture than PVCap. PVCap was found to be a synergist
for polyiPA but not to the same degree as for polyAP. The best
synergistic blend was found to be a 2:1 blend of 90/10 iPA/
AMPS:PVCap. A 6000 ppm solution of this blend delayed
hydrates for over 1 day, including a 6 h shut-in at 12 °C
subcooling in autoclave and wheel tests.104 A sample of this
blend was sent to ExxonMobil for testing. A similar subcooling
was obtained in loop tests as RF had found in the autoclave
and wheel tests. ExxonMobil’s prior licensing agreements
precluded a license to NS and RF. Not being able to com-
mercialize AP or iPA polymers, NS decided to synthesize new
classes of surfactant AAs that RF would test. This chapter in
the history of LDHIs is discussed later in the section entitled
“The Late 1990s”.
In mid-1996, RF discovered a new class of KHIs based on
amidation of maleic anhydride copolymers. Maleic anhydride
does not easily polymerize by itself but does so with a variety
of vinylic comonomers giving regular ABAB copolymers.
Reaction of these copolymers with alkylamines (cyclic imines)
opens the anhydride ring to give two different neighboring side
chains: first, an alkylamide group and, second, a carboxylic
acid or carboxylate group (Figure 22).
RF made a series of amidated copolymers using various
amines. They found that isobutylamine gave a copolymer with
marginally better performance than a copolymer made using
isopropylamine. Copolymers made from n-propylamine, n-
butylamine, and tetrahydrofurfurylamine gave poorer perfor-
ReViews
Figure 23. Structure of one of Clariant’s synergists for maleic
anhydride copolymers.
mance. RF patented the results in 1997. Unknown to RF at the
time, Clariant, who had heard RFs initial results at a JIP meeting,
had patented a modification of RF’s technology. Clariant had
noted that RF’s maleic copolymers had low cloud points, a
feature, which at the time was thought to be a disadvantage.
Clariant’s idea was to substitute some of the alkylamine for a
diamine in the amidation process. For example, reaction of a
80:20 blend of isobutylamine:dimethylaminopropylamine with
a maleic anhydride:vinyl acetate copolymer gave a useful KHI
with a high cloud point. The pendant dimethylamino groups
help solubilize the copolymer in water to higher temperatures.
The performance of the copolymer is a little less than a polymer
amidated with isobutylamine alone but is still useful to a
subcooling of approximately 8 °C at 5000 ppm (this is without
added synergists). RF and Clariant decided to combine their
two patents at a later stage.105,106 Clariant continued to carry
out studies on amidated maleic anhydride copolymers with the
German Petroleum Institute at Clausthal. Clariant also developed
synergists for these polymers, which have been patented
separately.107 These consist of small, surfactant-like molecules
with alkylamide headgroups (Figure 23). The technology has
been successfully field trialled and is now commercially
available through Clariant Oilfield Services.
Clariant. Clariant filed three further patent applications
during their time in the RF JIP. The first application claimed
the use of amphiphilic polymers as KHIs.108 The polymers
contained equal amounts of cationic and ionic monomers. Initial
results were obtained through the JIP and used in the patent
application. RF later tested Clariants polymers as KHIs but
obtained poor performance. Sometime later Clariant withdrew
its patent application.
The second patent application claimed the use of isobutyl
glycol ether (iBGE) as a synergist solvent for KHI polymers.109
Clariant noted that ISP had already patented small alcohols and
glycol ethers as synergists for their VCap polymers. ISP’s
preferred synergist was n-butyl glycol ether (BGE), a com-
mercial product. Clariant found that iBGE was a better synergist
for the amidated maleic copolymers than BGE. Presumably, the
isobutyl group interacts better with hydrate cavities than the
n-butyl, which fits with RF’s observations on alkylamides.
However, iBGE did not become a commercial product, and the
patent application lapsed. It seems that the marginal performance
improvement of iBGE over BGE was outweighed by the cost
of commercializing a new solvent in limited quantities.
The third patent application from Clariant appeared to hold
a lot of promise.110 At that time, 1996, Clariant was selling
PVCap/TBAB blends to BP through their daughter company
TROS (now also called Clariant Oilfield Services). Neither
PVCap or TBAB were manufactured by Clariant, who were
keen to sell their own chemicals. In talks between RF and
Clariant the idea arose of using amine oxides as a substitute
for TBAB. TBAB, TPAB, and tributyl phosphine oxide were
all known to form clathrate hydrates, so it was assumed that
tributylamine oxide (TBAO) and tripentylamine oxides (TPAO)
would do the same. Clariant synthesized these amine oxides
by simple oxidation of the corresponding trialkylamines.
RF found that TBAO performed at least as well as TBAB in
inhibiting the growth of single crystals of THF hydrates. TPAO
performed even better but was not studied further since the cost
ReViews
of tripentylamine was rather high and would make the price of
TPAO uneconomic. TBAO proved to be an excellent synergist
for VCap polymers. Optimized blends produced some of the
most powerful KHIs tested at RF in the 1990s, superseded only
by the best polyAP triple blends. However, TBAO did not
become a commercial product, and the patent application on
amine oxides was withdrawn. The problem was its poor
biodegradability. At less than 20% in a 28 day OECD test,
TBAO was no better than TBAB and therefore offered no
advantage to the best available technology at the time.
Due to the high performance of TBAO, RF was convinced
that there was more mileage in amine oxide products. In
particular, they thought surfactants amine oxides would make
good AAs. These are discussed in the next section under “RF
JIP: AA Studies”.
Late 1990s
In the late 1990s a few research groups were still actively
pursuing KHI technology, but it was becoming increasingly clear
that this was not going to be an economic solution for high
subcooling conditions. Improvements in KHI technology were
few and incremental, and no big breakthroughs occurred. Thus,
as far as LDHIs are concerned, deepwater applications were
the domain of AAs only. Perhaps the only company that might
justifiably argue with this conclusion is ExxonMobil. They had
produced experimental data from their mini-loop to suggest that
KHIs could be used at 15+ °C subcooling. At 1 wt % their
best inhibitor VIMA:IPMA 1:1 low molecular weight copolymer
(oligomer) failed at a subcooling of 22-23 °C.111 The experi-
mental method is to slowly cool the mini-loop 1 °C at a time
until the line is blocked. With no additives, the line was blocked
at a subcooling of 4 °C. It should also be added that ExxonMobil
has not used any synergists or synergist solvents in these
experiments. It is difficult to say how long the induction time
is at any one subcooling at this high concentration as this
information is not available; but the data obtained is still
impressive.
ExxonMobil spent 3 years from 1998 to 2001 looking for
manufacturers of their alkylacrylamide polymers. IPMA mono-
mer was not commercial then and still is not today. ExxonMobil
first looked for a manufacturer of VIMA:IPMA copolymer
rather than VIMA:IPMA oligomer and then finally IPMA
homopolymer. Their sources told them that IPMA monomer
would cost 2-3 times the price of VCap monomer. Even at
this high price ExxonMobil still believes they have an applica-
tion for an IPMA polymer, and they wish to explore this avenue
further. ExxonMobil finished their research program in 1998,
and one or two patent applications are still to be released.
CSM also carried out studies on KHIs into the late 1990s. In
particular, they showed that PVCap oligomer performed better
than higher molecular weight PVCap.3 Samples were obtained
from BASF and the University of Akron, Ohio. BASF’s PVCap
oligomer became a commercial product through the service
company Nalco. Nalco now uses polymers supplied by ISP.
CSM Studies on AAs. CSM’s consortium members could
see that PVCap oligomer was not going to be good enough for
deepwater applications at higher subcooling. They therefore
encouraged CSM to study AAs as the only LDHI alternative.
CSM responded by setting up equipment and test procedures
for studying AAs. They then tested a range of commercial
surfactants with different headgroups and HLB (hydrophilic
lipophilic balance) values as well as about 70 new surfactant
AAs synthesized at the University of Akron, Ohio.112 None of
the commercial surfactants performed particularly well, the best
Energy & Fuels, Vol. 20, No. 3, 2006 839
Figure 24. Structure of dodecyl-2-(2-caprolactamyl) ethanamide.
of them being a Span sorbitan surfactant that prevented
agglomeration at 2 wt % concentration at up to 11.5 °C
subcooling. The synthetic surfactants were designed to contain
headgroups found in KHIs. The caprolactam ring was an obvious
choice, as it was known from CMS’s studies to attach to hydrate
crystal surfaces. The best AAs were mono-tail surfactants
containing the caprolactam headgroup as well as polymeric
surfactants based on vinyl caprolactam oligomer or N,N-
dialkylacrylamides with alkyl thioether end groups. The single
best product was dodecyl-2-(2-caprolactamyl) ethanamide (Fig-
ure 24) At 0.75 wt % this AA prevented hydrate agglomeration
at 11.5 °C subcooling including a 3-day shut-in/start-up test.
ISP KHI Patents. ISP filed a number of patent applications
on KHIs in the late 1990s. They were all based on VCap
polymer technology. Three of the patent applications claimed
very low molecular weight PVCap (i.e., PVCap oligomer).113-115
The lowest molecular weight PVCap oligomer that gave the
best performance had a molecular weight (Mw) of 1500. This
represents about 11 monomer units in the oligomer. Some of
the experimental work was carried out in collaboration with
BP. The fourth and fifth patent applications claimed copolymers
of VCap with small amounts of dimethylaminoethylacrylate or
N-(3-dimethylaminopropyl)methacrylamide.116 The function of
this comonomer in aiding KHI performance is not given, but it
may be related to the comonomers’ ability to open out polymer
chains that might otherwise curl up on themselves in aqueous
solution. The sixth and seventh patent applications claimed the
use of VCap:vinyl pyridine copolymers.117,118 The function of
the second monomer in one patent application was to give the
copolymer KHI and corrosion inhibition properties. An eighth
patent application claimed the use of polyoxyalkylenediamines
as synergists for VCap polymers.119 This synergy was originally
discovered by BJ Unichem a couple of years earlier. Two further
patents claimed a KHI synergist effect between VCap polymers
and an alcohol containing 3-5 carbon atoms and one hydroxy
group.120,121
KHIs for the Eastern Trough Area Project (ETAP). The
last report on KHIs in the late 1990s concerns their use on the
BP-operated Eastern Trough Area Project (ETAP) in the British
sector of the North Sea.122,123 ETAP consists of several fields
tied back to a central processing unit. Plans for ETAP began in
the early 1990s, and production began in 1998. Fluids from two
of the fields were expected to be operating 6-8 °C into the
hydrate region. Both fields were therefore ideal for using BP’s
KHI technology, which was being field-trialed in the Southern
North Sea Gas Basin. (Shell, who is a partner in ETAP, hoped
to use their AA technology in one of the fields, but this never
materialized.) The use of KHI gave BP and their partners a
CAPEX saving of 40 million U.S. dollars as compared to using
methanol. The main cost saving was due to eliminating a
methanol regeneration plant and the platform space it required.
TROS (now Clariant) who had the license for BP’s KHI were
asked to formulate KHI products for ETAP. They had to
overcome compatibility issues such as the combined use of
corrosion and scale inhibitors. Injection of KHI began in 1998
and the field has been operating smoothly since. The originally
KHIs were based on BP’s PVCap/TBAB synergists blend
technology (A similar product was used by Elf, now Total, to
840 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 25. Early version of the twin-tail diester quaternary AA (A),
improved version of the AA where R ) Me or Et (B), and a worse
version of the AA with propylene spacer groups (C).
replace methanol in an onshore multiphase transport line124).
The PVCap was supplied by BASF and amounted to ap-
proximately 100-120 ton per year. This made ETAP the biggest
KHI application anywhere in the world. (The later RasGas KHI
application in Qatar in the Middle East is of similar magnitude.)
In 2001 Clariant lost the contract to Nalco for topside chemical
injection on ETAP. Nalco also used PVCap technology for their
KHIs, but they chose to source the polymer from BASF’s
competitor ISP. This cut BASF’s sales of PVCap in half.
(Clariant’s current biggest sale of KHI is for seasonal use of
ca. 70 ton/year for a Middle East application.155) Thus we can
estimate that at the beginning of the new millennium sales of
PVCap-based polymers for KHI applications were ca. 300-
500 ton per year.
Oil-Soluble Twin-Tail Quaternary AA. Compared to KIs,
progress in getting AAs into full field applications was slow.
One of the main reasons was that all the AAs were new
chemicals and had to go through manufacturing regulations
beginning with Pre-Market Notification (PMN). The twin-tail
quaternary AA also had to undergo a small but important
modification. The first version of the AA was made from
N-butyl diethanolamine and had ethylene spacer groups between
the ester groups and the quaternary nitrogen atom (Figure 25,
molecule A). Shell found that addition of a small alkyl branch
(methyl or ethyl) to the spacer group improved the performance
of the AA (Figure 25, molecule B).125 Specifically, the
performance of shut-in/start-up loop test with preformed hy-
drates slurries were improved. A longer spacer group such as
propylene (molecule C) gave a worse performance. The twin-
tail quaternary AA also contained a certain amount of unquat-
ernized amine in the finished product from Akzo-Nobel. The
amine actually improves the performance of the AA as well as
helping break emulsions.
Field trials on the oil-soluble twin-tail quaternary AA were
carried out in Holland, Great Britain, and New Zealand from
the mid to late 1990s.126 A first field application was planned
on a British North Sea gas/condensate field in the Sole Pit
area.127 However, the produced water became so saline that a
hydrate inhibitor was not required anymore. Shell had to wait
a few more years for the first field application of the oil-soluble
twin-tail quaternary AA.
Water-Soluble Single-Tail Quaternary AA. No data were
published in the open literature in the late 1990s by either Shell
or Baker Petrolite concerning progress with the water-soluble
single-tail quaternary AA. The supplier Baker Petrolite was
undoubtedly going through the motions of getting the product
ready for field trials, which began in 1999. It seemed that Baker
ReViews
Petrolite had overcome any environmental hurdles for the Gulf
of Mexico (GoM) at least. Here the environmental law is not
so restrictive as it is for example in the North Sea. In the GoM,
it is the toxicity of the discharged water and its dilution that
are the critical factors. In the North Sea it is the toxicity,
biodegradability, and bioaccumulation of the injected chemicals
that are evaluated. On top of this, the British sector demands
20% biodegradability for new chemicals, something the single-
tail quaternary AA does not have but the twin-tail quaternary
AA does. The Norwegian sector normally demands 60+%
biodegradability on new chemicals, which rules out all LDHIs
commercialized to date.
Some news about the single-tail quaternary AA did filter
through on the grapevine. For example, Amoco (now BP) had
been testing it in their high-pressure autoclave and found it gave
excellent results, especially in saline water.128 The single-tail
quaternary AA was also tested as part of the Deep Star program
alongside other LDHIs. Deep Star was a series of deepwater
technology projects funded by most of the major oil companies
and managed by Texaco (now Chevron Texaco). Westport
Technology (now Intertek Westport Technology Centre) un-
dertook the test program using a high-pressure autoclave. The
single-tail quaternary AA outperformed all the other LDHIs
giving transportable hydrate slurries at 16+ °C subcooling. It
was clearly a product the oil companies wanted to see used in
the field.
DeepStar also began funding the reconstruction of an on-
land pipeline in Wyoming for LDHI testing. Unfortunately, the
budget got out of control and the project was never finished.
IFP Patents and Field Trials on Emulfip 102b. As part of
the EUCHARIS project, IFP carried out two field trials on their
emulsion AA, Emulfip 102b, in 1998-1999.129 The site was a
3 in., 2.5 km onshore pipeline as part of Total’s Canadon field
in southern Argentina. The pipe pressure was 40 bar, water cut
20%, and the salinity 10 g/L. The subcooling in the first field
trial was a maximum of 10-12 °C. The AA was pumped in
pulses rather than using continuous injection. IFP deemed the
first field trials as a success. A downstream emulsion was
formed in the separator caused by Emulfip 102b, but this
problem was not addressed by IFP.
A second field trial was carried out in June-July 1999 at
Total’s Canadon field. The subcooling varied from 10 to 20 °C
depending on the time of the day. The product worked for a
short time but then failed, resulting in the plugging of the line.
Two plugging mechanisms were proposed. First, accumulation
of hydrate particles in the line, not necessarily at low points.
Second, deposition of hydrate at the upper pipe walls from
condensed water. NB: The flow is stratified flow and Emulfip
102b is not in the gas phase. This effect was seen in IFP’s loop
test, but being a loop the deposits did not build up.
Thus, it appears that Emulfip 102b was able to disperse the
hydrates formed. The condensed water problem and slurry
transportation difficulties may be overcome when the flow is
not stratified (higher liquid volumes and flow rates).
IFP filed several patent applications in the late 1990s on both
KHIs and AAs.130-133 The first patent application claimed water-
soluble polyoxyalkylene macromers and/or polymacromers
alone or in combination with known KHIs such as Gaffix VC-
713 as KHIs. A second patent application claimed water-soluble
KHI polymers characterized by a specific number of rotational
degrees of freedom and degree of polymerization. Examples
are polymers of propylene glycol alginate, poly(ethylene glycol)
monomethacrylate, and AMPs. A third patent application
claimed AAs based on mixtures of copolymers of polyisobu-
ReViews
Figure 26. Structure of amine oxide surfactant AAs.
tylene succinate/poly(ethylene glycol) and alkyl (meth)acrylate:
VP copolymers. A fourth patent application claimed amphiphilic
nonionic polymeric surfactants as AAs formed by reacting a
polymerized unsaturated oil and an amino alcohol (e.g., flax
oil and diethanolamine).
RF JIP: AA Studies. The RF JIP began searching for new
AAs as early as 1995. However, it was not until the late 1990s
that they concentrated their efforts on this class of LDHI. They
set a goal of finding an AA that at 0.5 wt % in 3.6% brine
would perform as well as Shell/Akzo Nobel’s oil-soluble
quaternary AA but was more environmentally friendly. This
meant lower toxicity or higher biodegradability or both.
Almost all the potential AAs were new surfactants synthesized
by various chemical companies under collaboration agreements.
A range of polymeric surfactants with pendant alkyl- and
dialkylamide groups were tested, but they gave poor results.
Better performance was obtained with monomeric surfactants.
The first noteworthy AA was a triester quaternary ammonium
salt with one long tail made by Stepan Europe. It performed
well up to 10 °C subcooling and had >60% biodegradability.
However, the performance of this class could not be improved
so RF looked elsewhere.
The next class of surfactants that gave positive AA results
were the cationic caprolactams. They contained a caprolactam
head and a quaternary nitrogen spacer group. They worked well
up to 10-11 °C subcooling but were toxic and were not
investigated further.
Tributylamine oxide had been shown by RF to be an excellent
THF hydrate growth inhibitor on a par with TBAB. It was
therefore of great interest to investigate amine oxide surfactants
as AAs. Commerical surfactants from Clariant with dimethyl-
amine oxide headgroups gave poor results. Better results were
obtained with two surfactants synthesized by Clariant although
neither had an optimum structure. The first surfactant was
dodecylbutylmethylamine oxide (DDBMAO) (Figure 26). By
having only one butyl group rather than two at the head, it was
not ideal. As expected it gave moderate results in the cell and
wheel. The second surfactant is also shown in Figure 26 and
has a diethylamine oxide headgroup. However, it also gave only
moderate results in the cell and wheel. The surfactant also turned
out to be very toxic to skeletonema. For these reasons Clariant
decided not to synthesize further amine oxide surfactants, and
the patent application on amine oxide was dropped. More
recently, Stavanger University has synthesized the more desir-
able surfactants with dibutylamine oxide headgroups.
In 1998-1999 RF and Nippon Shokubai prepared and tested
monomeric surfactants with alkylamide or dialkylamide groups
in the head.232 This led to a patent application in 1999.134 The
groups were mostly carbonylpyrrolidine and isopropylamide
groups that had been shown to perform well in KHI polymers.
Several classes of these surfactants performed fairly well in cell
tests, but two classes stood out for also having low environ-
mental impact. These are shown in Figure 27. Both surfactant
classes have a branching carboxylic acid group which gives them
high biodegradability. Further, the higher the HLB (the shorter
the tail) the lower the toxicity of the surfactants. Both classes
performed very well in cell and wheel tests at 13 °C subcooling.
Statoil also tested the isopropylamide surfactant in their wheel
and obtained similar results. However, both classes failed at 15
°C subcooling. As there seemed no performance advantage over
Energy & Fuels, Vol. 20, No. 3, 2006 841
Figure 27. Structures of carbonylpyrrolidine and isopropylamide
carboxylic acid surfactants tested by RF. R ) C8-14.
Figure 28. Structure of betaines tested by RF. R is a long alkyl chain
with various spacer groups.
the Shell quaternary AAs, further work on the alkylamide
surfactants was dropped and the patent application withdrawn.
The last AA idea RF investigated in their JIP was to take the
single-tail quaternary AA and place the anion in the molecule
thereby making it zwitteronic.135,233 Nippon Shokubai made a
range of these betaine surfactants, which RF tested (Figure 28).
The results were fairly promising in cell and wheel tests, but
the subcooling limit at 0.5 wt % was approximately 13 °C.
Clearly, the anion was best separated from the quaternary
nitrogen atom. RF concluded that Shell’s original idea of using
quaternary surfactant AAs with two or three butyl or pentyl
groups in the head was still the best class of AAs discovered
yet.
Following this conclusion, RF did get a chemical company
to make a new class of quaternary AA. They were only briefly
tested with good results in RF cells before RF turned to other
studies in the new millenium. Stavanger University is now
testing this promising class.
Into the New Millenium
Polyesteramide LDHIs. By the end of the millennium, all
three LDHI JIPs were coming to a close. CSM and RF had
seen new KHIs brought to commercialization whereas IFP had
still to see their AAs and KHIs reach full application. Exxon
had shut down its R&D program and were no longer investigat-
ing new chemistry. So one may be excused for thinking that
after all this effort the best chemistry had been discovered.
However, Shell was still open for new LDHI ideas when they
came across a new class of polymer marketed by the Dutch
company, DSM, under the tradename Hybranes. Hybranes are
hyper-branched polyesteramides. Shell found that certain poly-
esteramides performed well as KHIs while others showed AA
behavior. They patented the results in 2002.136 The basic
polyesteramides are fairly cheap to manufacture, cheaper than
PVCap according to Shell. They are made by condensing a
cyclic acid anhydride with a dialkanolamine in a ratio of n:n +
1 where n is an integer. (By varying n one can vary the
molecular weight of the polymer.) This gives a polymer with
hydroxyl groups at the tips. The hyper-branching is caused by
the dialkanolamine, which has three reactive groups. By adding
a third molecule to the reaction mixture, such as a secondary
amine, the tips of the polymer can be modified to become more
or less hydrophilic. In their patent application, Shell used
polymers made from di-2-propanolamine as the dialkanolamine.
The best choice for the cyclic acid anhydride appears to be
hexahydrophthalic anhydride. This combination gives polymers
with the structural units shown in Figure 29.
The resemblance of the polyesteramide with earlier KHIs such
as PVCap and polyIPMA is now apparent. All three KHI
842 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 29. Repeat unit in a polyesteramide made from di-2-
propanolamine and hexahydrophthalic anhydride.
polymers have a hydrophobic group attached to an amide group.
The hydrophobic group forms a van der Waals interaction with
hydrate surfaces (and/or perturbation of free water), while the
amide hydrogen bonds to water molecules in the hydrate surface.
This disrupts further growth of the hydrate particles. In the case
of the polyesteramide shown in Figure 29, the hydrophobic
group is the cyclohexyl ring, although the methyl group of the
di-2-propanolamine may make a contribution. The ester groups
may also take part in hydrogen bonding. The feature that singles
out the polyesteramides from all other KHI polymers is their
hyper-branching. All other KHI polymers are linear snake-like
molecules with a polyvinyl backbone. To use an analogy for
KHI bonding to hydrate surfaces, the polyesteramides are like
a hand clutching a hydrate ball, whereas other KHIs are like a
single long finger attached to the ball. The molecular weight of
the polymer does not need to be very high either. Shell found
that polymers with molecular weights of 1500 gave good KHI
performance. This is roughly the same figure found for
polyvinyl-based KHIs such as PVCap.
In Shell’s patents on polyesteramides, they found that some
hydrophobically modified polymers gave moderate AA perfor-
mance. Shell has spent considerable effort exploring polyes-
teramides as AAs, but in May 2004 they discontinued research
concluding that the performance was not good enough to make
a commercial AA product.139
Baker Petrolite and Polyesteramide KHIs. Polyesteramide
KHIs are commercially available through Baker Petrolite. They
will give PVCap some competition on the KHI market. Baker
Petrolite has also patented new KHIs137 and synergists138 for
polymers including polyesteramide dendrimers. In one example
given in the synergist patent application, polyethyleneimine is
reacted with formaldehyde and caprolactam. This gives polymers
with pendant caprolactam rings just as one finds in PVCap.
Although PVCap is also a synergist for the polyesteramides, it
seems that Baker Petrolite is avoiding the use of PVCap in their
KHI products. This gives them PVCap-free KHI technology,
which is only rivalled by Clariant’s amidated maleic anhydride
copolymers with ether carboxamide surfactant synergists.
Another KHI synergist from Baker Petrolite is made by reacting
N-methyl butylamine with formaldehyde and polyacrylamide.
Other synergists mentioned are nonpolymeric surfactants with
caprolactam or alkylamide headgroups. A small amount of a
quaternary AA can also be formulated with the KHI blend to
improve the performance. In their patent application, Baker
Petrolite also mentions a typical polyesteramide as being made
from di-2-propanolamine, hexahydrophthalic anhydride and bis-
(dimethylaminopropyl)imine. The latter molecule gives the
polymer pendant dimethylamino groups, which help to make
the polymer more water-soluble. Baker Petrolite has carried out
two field trials on the polyesteramides in 2004, and several field
applications have already begun. In addition, Baker Petrolite
has found that their polyesteramide-based KHIs have better
performance on structure I hydrates than other KHI chemistries
such as PVCap.194 Some fields have such a high percentage of
methane that structure I hydrate is formed rather than structure
II. Baker Petrolite is already looking at structure I field
applications for their polyesteramides.
ReViews
KHIs for Drilling and Completion Fluids. Gas hydrate
formation can be a hazard in deep water drilling if gas
breakthrough occurs. To avoid hydrates from forming the
drilling fluid can be formulated with salts and glycols, which
act as thermodynamic inhibitors. However, there are some
situations in which the drilling fluid will be under-inhibited.
For example, the density of the fluid required, so that the fracture
gradient is not exceeded, might limit the amount of salt that
can be added. Second, in ultra-deep water drilling, it may be
impossible to avoid hydrate formation with some types of water-
based drilling fluids. Westport Technology Center International,
RF, MI, and Norsk Hydro140 have all carried out projects to
investigate the use of KHIs in under-inhibited drilling fluids.
PVCap and other KHI polymers with low cloud points cannot
be used, as they will not be compatible with highly saline drilling
muds at the maximum circulation temperature of the mud (often
40-50 °C). Hence it has been necessary to design the KHI with
a higher cloud point in saline solutions. Westport carried out a
matrix of tests on KHIs for drilling fluids for a consortium of
oil companies and mud companies. They determined that the
KHIs lost performance probably by adsorption onto clay (mud)
particles in the drilling fluid. RF carried out several projects
for oil companies and MI Swaco. They also noted the effect of
clay particles on some KHI polymers. However, they did
identify two polymers that were useful KHIs for drilling fluids
giving an extra 8-10 °C subcooling protection with a 24 h
nucleation delay at 0.6 wt %. MI Swaco found a KHI polymer
that gave 8 °C added subcooling protection with a 10 h
nucleation delay at a concentration of 1 wt %.140 However, no
clay was used in these tests. BJ Chemical Services has used a
proprietary blend of thermodynamic inhibitor, KHI and GW
AA in a packer fluid for a Gulf of Mexico application.209
KHIs Based on PVCap. Low molecular weight PVCap-
based products with added synergists are probably the best KHIs
for structure II hydrate inhibition on the market today. ISP and
Nalco reported that such a KHI blend gave at least 48 h hydrate
inhibition at a subcooling of 13 °C.141 This represents an
improvement of about 5-6 °C subcooling since the VCap-based
terpolymer Gaffix VC-713 was first discovered. ISP and Nalco
had their low molecular weight PVCap-based KHI tested in the
wheel loop by Statoil. The results were some of the best
recorded for any KHI.142,143 The KHI was tested using two shut-
in/start-ups. For one condensate the KHI passed the test at 17-
19 °C subcooling, whereas for another condensate the maximum
subcooling was only 8-12 °C. The maximum subcooling in a
crude was 13-16 °C whereas in a gas/water system the
maximum subcooling was 11-12 °C. This underlines the
dependency of the KHI on the liquid hydrocarbon phase and
the need to test a KHI in the actual fluids from the field. It
would be interesting to determine what a condensate or crude
contains that has such a beneficial effect on a KHI and then
build this into improved KHIs.
Nalco also showed that KHI polymer cloud point is not such
a critical issue for field implementation.141 Earlier it was thought
that the polymer had to be soluble up to the maximum
temperature in the well stream, which is usually at the injection
site. Otherwise it might precipitate out in the pipeline. This made
it difficult to use PVCap, which has a cloud point of ap-
proximately 30-42 °C in freshwater. Nalco ran tests to show
that PVCap polymer will remain within solvent droplets in the
hydrocarbon phase until the temperature of the aqueous phase
drops below the cloud point of the polymer. At this point the
polymer will dissolve in the aqueous phase.
ReViews
Even with the good KHI results mentioned above Statoil
could not use PVCap technology in their Norwegian fields. The
reason is that the Norwegian Pollution Authority (SFT) demands
that all new chemicals offshore have 60+ % biodegradability.
Nalco’s PVCap-based KHI has very poor biodegradability,
although it is low in toxicity like all water-soluble polymers.
Since quaternary AAs were already banned from use in Norway,
and now KHIs could not be used either, this led Statoil to shut
down their LDHI research program in 2001. ExxonMobil Norge
has a potential KHI application on their Ringhorn field where
the subcooling was fairly low. However, the SFT would not
allow the use of poorly biodegradable polymers, so the plan
was dropped.
The British environmental authorities demand only 20+ %
biodegradability for new offshore chemicals. However, even
this is higher than the biodegradation of normal PVCap. This
has led BASF, Clariant and ISP to search for more biodegradable
polymers. So far, BASF has reported that they have managed
to synthesize a low molecular weight lactam-based polymer with
approximately 20% biodegradability, which performs as well
as earlier KHI VCap-based products.144
Recently, BASF took out a patent application on water-soluble
vinyl lactam copolymers.145 A preferred polymer was 80:20 VP:
butyl acrylate which performed better than a PVCap sample in
the THF hydrate ball-stop rig. The copolymer is very similar
to copolymers patented earlier by Nippon Shokubai and RF. A
second patent application by BASF concerns the use of ethylene
glycol as a high flash point solvent for VCap polymers.207
Although not a manufacturer of the VCap monomer, Clariant
has also filed a patent application on copolymers where the bulk
of the examples concern VCap:alkyl(meth)acrylate ester co-
polymers.146 With short-chain alkyl methacrylates, such as
methyl methacrylate, the VCap copolymer gave improved KHI
effect over PVCap samples. With long chain alkyl methacrylates,
such as oleyl methacrylate the VCap copolymer gave some AA
effect.
A new synergist for PVCap has been identified as high
molecular weight poly(ethylene oxide) (PEO).211,228 However,
it does not perform as well as butoxyethanol.51 A small amount
of PEO added to a PVCap solution also dramatically reduced
the hydrate memory effect.229
KHIs Based on Isopropylmethacrylamide (IPMA). The
high performance of polyIPMA, discovered by ExxonMobil,
and its possible competition with PVCap has been recognized
by Mitsubishi and ISP as they have both filed patent applications
on polyIPMA. ISP claimed that polyIPMA synthesized in butyl
glycol gave a far better performance than polyIPMA synthesized
in 2-propanol.147 Mitsubishi patented polyIPMA with hydroxyl
end groups, claiming it to be a better KHI polymer than normal
polyIPMA.148
In 2003, ExxonMobil (EMURC) filed a patent application
claiming KHIs that are polymers with a bimodal molecular
weight distribution.149 The bimodal distribution can be made
from a single polymerization or by mixing two polymers with
unequal molecular weight distributions. The preferred polymer
is polyIPMA although PVCap and other polymers are also
claimed. The increase in performance over a polymer with a
monomodal molecular weight distribution is most striking for
polyIPMA. For example, a hold time of 20 h was possible at
43.5 °F (24.1 °C) subcooling using 0.5 wt % of a poly IPMA
with a bimodal molecular weight distribution. The bulk of the
polymer has a molecular weight average of ca. 1000-3000.
This result is the highest subcooling recorded to date for a KHI
product. The mechanism for the increased performance is not
Energy & Fuels, Vol. 20, No. 3, 2006 843
discussed in the patent application. RF had the same idea in
the late 1990s carrying out studies on mixtures of high and low
molecular weight polyAP. They observed some increase in
performance relative to a low molecular weight sample only.
RF postulated that the increase in KHI performance is related
to the size and mobility of the different molecular weight
samples. The low molecular weight sample, like a motorbike,
moves quickly in solution to the site of hydrate nuclei growth.
It will adsorb onto the surface of the hydrate but only weakly.
The high molecular weight sample, like a lorry, moves slowly
but can then replace the low molecular weight sample on the
surface adsorbing more strongly and preventing hydrate nuclei
growth for longer periods. The motorbike-lorry analogy can
also be used for the synergistic blend of TBAB (motorbike)
and PVCap (lorry) discussed earlier. In fact, RF has showed
that TBAB is a better KHI synergist with high molecular weight
PVCap than with low molecular weight PVCap.
ExxonMobil also presented a paper in 2003 at a nucleation
workshop on the results of mini-loop experiments of KHI hold
time versus subcooling at fixed KHI concentrations in a gas
condensate system.150 The hold time, which is repeatable, is
the time from when the loop fluids reach the constant cooldown
temperature until hydrates are first detected. The data fitted an
exponential function in subcooling at all KHI concentrations
of the form y ) mx + b where y ) ln(1/hold time), x )
subcooling, m was a constant at all KHI concentrations making
the curves of hold time versus subcooling have the same shape,
differing only in intercept, and b was dependent in a nonlinear
fashion on KHI concentration. The function b versus KHI
concentration was similar to the function maximum subcooling
versus KHI concentration that approaches an asymptote above
0.5 wt % active polymer.
KHI Applications Continue to Increase. By 2005, it is
estimated that there are about 40-50 KHI applications world-
widespread between a handful of service companies. Recently,
the first application in the Middle East was reported by Clariant
and Total for a field called West Pars. Injection of KHI was
successful throughout a 10-month period.151 Nalco has also
reported that they have a KHI application for RasGas in the
Middle East.152
A new field called Otter in the British sector of the North
Sea and operated by Total will become only the second field,
following ETAP, where a KHI application is planned during
the field development. Otter is an oil field tied back in a 10 in.
line to existing infrastructure. Production began in 2003.153,195
KHI is injected during planned shutdowns or short-term low
flow.
Another hurdle the service companies have had to overcome
is combining KHIs with other production chemicals in a single
injection line. On ETAP and a southern North Sea Gas field,
KHIs have been successfully combined with corrosion and scale
inhibitors by Clariant.155 Clariant also recently reported the
successful use of KHI combined with paraffin inhibitor,156,157
while Baker Petrolite has reported studies on KHI/corrosion
inhibitor blends.220
Another application area for KHIs is their combination with
thermodynamic inhibitors. For example, late in field life the
water cut may be too high (> 50%) to use AAs. The subcooling
may also be too high for commercial KHIs alone. Boosting the
subcooling performance by combining the KHI with methanol
or glycol is a possibility. A West African field that is due to
start up soon, and for which Shell is the operator, has been
planned in this way. Baker Petrolite plans the early life of the
field with application of a quaternary AA.154 BJ Chemical
844 Energy & Fuels, Vol. 20, No. 3, 2006
Services has published a paper on the use of KHI combined
with methanol for a subsea production line in the Gulf of
Mexico.210
Novel LDHIs. In 2003 BP filed a novel patent application
for a method of delaying hydrate formation.158 The method
comprises mixing a polymeric emulsifier and optionally a
nonionic nonpolymeric co-emulsifier with the hydrocarbon and
aqueous fluids so as to generate a water-in-oil emulsion. The
emulsifiers form a substantially gas impermeable interfacial
layer, which prevents hydrate from forming in the encapsulated,
aqueous droplets. Nucleation delays of over 16 h were obtained
at 12 °C subcooling. The concentration of the emulsifiers used
was 2 wt %. BP recommends recovering and reusing the
emulsifiers in order to make the process economically viable.
However, no suggestions are made as to how this should be
done.
RF investigated two novel LDHI ideas in 2000. The first idea
was to use super water-adsorbent polymers to take out all the
water before hydrate formation occurred. The experiments failed
because a suspension of water-adsorbed polymer particles could
not be maintained. Coagulation may have been avoided with
polymer particles with membranes but this is too expensive.
However, the second idea gave some success. The idea was to
use an ion pair blend of ionic KHI polymer and surfactant with
the opposite charge to give an AA effect. The KHI would control
hydrate growth and the surfactant would drag the hydrate KHI-
coated particles to the hydrocarbon phase by electrostatic forces.
An anionic IPA:AMPS copolymer with a cationic surfactant
worked well at 14 °C and 90 bar but failed at higher subcoolings.
No further work was carried out after the project finished at
the end of 2000.
First Field Trials and Field Applications of the Quater-
nary AAs. In the year 2000, Baker Petrolite presented a paper
discussing the first field trials with the water-soluble quaternary
AA.159 The first trial actually took place in the Gulf of Mexico
(GoM) in 1999 and was a success. Later AAs have been used
in the GoM to mitigate against hydrate plugging during shut-
in/start-up situations in black oil systems. The first field
application with continuous injection of AA was in 2002, again
in the GoM on a Shell field called Popeye.160 Since then the
number of AA applications particularly in the GoM has
increased rapidly.161-163 For example, ExxonMobil ran the Diana
field oil flowlines with a Baker Petrolite AA from 2002 to 2003;
oil production ended on high watercut.111 A field application
in West Africa is also planned.153
Baker Petrolite claimed at an SPE Forum that 1 wt % actives
of the water-soluble quaternary could treat any subcooling.164
It seems like this product is the proverbial silver bullet. So far
it has been lab tested successfully up to 7000 psi (500 bar) and
22 °C (40 °F) subcooling, and used successfully in the field at
ca. 14 °C (25 °F) subcooling. Along with KHIs they have also
been found to work in highly sour systems where the H2S has
been thought to affect the hydrate equilibrium properties.165
Finally, compatibility with materials193 and other production
chemicals such as corrosion and wax inhibitors appears to have
been overcome for both KHIs and AAs.
Baker Petrolite has also patented a method to increase the
performance of the water-soluble quaternary AA.166 The water-
soluble quaternary AA (onium compound) is formulated with
an amine salt and optionally a solvent. The amine salt will
increase the ionic strength of the water phase, which may make
the AA perform better in freshwater. The amine salt contained
preferably alkyl or hydroxyalkyl groups with 1-3 carbon atoms
or an ammonium salt could be used.
ReViews
Two methods to reduce the environmental impact of quater-
nary surfactant AAs have been patented. Shell has patented a
method to phase separate a quaternary AA by adding sufficient
inorganic salt to the produced water to render the AA insoluble.
Baker Petrolite has patented methods to detoxify quaternary AA
surfactants by the addition of anionic polymers or anionic
surfactants.240-242
Very recently a new patent application from Baker Petrolite
(Baker Hughes Incorporated) was laid open.231 They found that
the effective concentration of a quaternary surfactant AA could
be reduced by the addition of a minor amount of an anionic,
nonionic, or amphoteric compound. The mixture, called an ion
pair, allows lower concentrations of the quaternary surfactant
to be used in practice, which reduces the treatment cost as well
as the environmental impact. For example, the effective
concentration of quaternary ammonium surfactant AA was
reduced from 0.75 wt % to 0.15 wt % by the addition of 0.12
wt % alcohol ether sulfate (AES) for AA tests with a GoM
condensate. In another example with a GoM condensate, the
effective concentration of the quaternary AA could be reduced
from 0.59 wt % to 0.30 wt % by the addition of 0.04 wt %
sodium dodecyl sulfate (SDS). Both AES and SDS are known
to have little or no AA hydrate inhibiting ability.
In another version of the invention, Baker Petrolite found
that mixing dodecylbenzenesulfonic acid (DDBSA) with a small
quaternary ammonium compound with appendages containing
less than 6 carbon atoms, to give an ion pair, also gave a product
that performed as an AA. Neither the ammonium compound or
DDBSA showed any appreciable AA activity individually. An
example of a small quaternary compound could be TPAB,
known to be a hydrate crystal growth inihibitor. Baker Petrolite’s
idea is similar to RF’s idea of using an ion pair AA made from
an anionic KHI with a cationic surfactant discussed earlier.
Baker Petrolite has reversed the charges using a cationic hydrate
growth inhibitor with an anionic surfactant.
The first application for which the field was specifically
designed to use an AA was Shell’s K7-FB field in the Dutch
sector of the North Sea in 2003.167 The oil-soluble quaternary
AA from Akzo Nobel is presently supplied through Clariant
Oilfield Services. The field produces gas condensate and
freshwater and the subcooling is a maximum of 8-9 °C. One
of the drawbacks of the oil-soluble quaternary AA is that it has
a shelf life at ca. 20 °C of about 1 year. One of the tails of the
surfactant gradually degrades off leaving a mono-tail quaternary
surfactant, which has much poorer AA performance. Conse-
quently, the operator has to make sure that the turnover of the
quaternary AA, especially in a hot climate, is kept to under a
year.
LDHIs from IFP. By 2005, IFP had still not managed to
find a field application for their emulsion AA, Emulfip 102b,
following mixed results from the field trials in Argentina. The
tendency for the hydrates to drop out during shut-in was an
issue that they addressed in a new patent application.168 This
claimed the use of hydrophobic oil-soluble block copolymers
that when used together with an emulsion AA would prevent
the settling out of hydrates during shut-in. A typical block
copolymer mentioned is made from styrene/ethylene/propylene.
A typical emulsion AA is made by reacting a polyalkenylsuc-
cinic anhydride with a monoether of poly(ethylene glycol).
(240) Blytas, G. C.; Kruka, V. R. International Patent Application WO
01/38695.
(241) Rivers, G. T.; Downs, H. H. U.S. Patent Application 20040144732,
2004.
(242) Rivers, G. T.; Frostman, L. M.; Pryzbyliski, J. L.; McMahon, J.
A. U.S. Patent Application 20030146173, 2003.
ReViews
Figure 30. Structure of alkyl ether tributylammonium bromide AAs.
R has 12-14 carbon atoms.
IFP has since put Emulfip 102b back on the shelf and instead
are trying to promote another polymeric surfactant emulsion
AA called IPE 202b, which they hope to commercialize through
the service company Shrieve in the GoM.169 IFP’s KHIs such
as AMPS:acrylamide are also in a stand-by situation and which
they hope to be commercialized through a new partner.
Natural LDHIs. It has been known since the mid 1990s that
natural surfactants in crude oils affect hydrate plugging tenden-
cies. Attempts to isolate these natural AAs have been carried
out by chromatography but have led to very complicated
mixtures.170 For crudes it seems the maltene fraction (which
are surfactants) and possibly asphaltenes are responsible for the
AA effect. Later work seems to show that there are two types
of crude oil, only one of which has hydrate-plugging tenden-
cies.171-173,215-218
New Quaternary AAs. By the new millennium it was
becoming clear to the chemical manufacturers and service
companies that the only surfactants that gave high AA perfor-
mance were quaternary surfactants with 2 or 3 butyl or pentyl
groups, first discovered by Shell. The research work of CSM,
RF, and others had not provided any better AAs. Since the turn
of the millenium Nalco,175 Goldschmidt,176 Clariant,177-181,202
and Champion Technologies196-200 have all filed patent ap-
plications on new quaternary surfactant AAs. Both Nalco and
Clariant already have commercially available quaternary AAs
that will compete with the Shell quaternary AAs available
through Baker Petrolite and Akzo Nobel.
Nalco appears to have found a way around the original Shell
patents allowing them to use the desired surfactants with a
quaternary center with butyl or pentyl groups. After 2 years of
testing at Nalco and Westport Technology Centre, the new AA
is already being used in a field application on BP’s Horn
Mountain in the GoM.182 Injection is continuous and began in
2003. Other applications have recently been reported.183
Goldschmidt’s patent application176 claims the use of qua-
ternary ammonium salt surfactants as AAs with an ether spacer
group between the quaternary nitrogen atom and the long alkyl
tail (Figure 30). The AAs are claimed to have improved water
dispersibility over tetraalkylammonium salts such as hexade-
cyltributylammonium bromide. There appears to be no public
information as to whether Goldschmidt’s AAs have been
commercialized.
Clariant now has its own quaternary AA, which has been
successfully field-trialled and is commercially available. Clariant
has filed several patent applications on surfactant AAs, some
products of which can also be used as synergists for KHI
polymers such as PVCap. For example, alkylaminoalkyl mono-
and diesters are claimed in one patent application and shown
to work as AAs as well as synergists for KHI polymers such as
PVCap. The products also exhibited good corrosion inhibition
properties. In a second patent application N,N′-dialkylaminoalkyl
ether carboxylates are claimed as corrosion and gas hydrate
inhibitors with improved water solubility and biodegradability.
Examples are shown to work as AAs as well as synergists for
KHI polymers such as PVCap. A third patent application with
Energy & Fuels, Vol. 20, No. 3, 2006 845
Figure 31. Structure of a preferred polyalkoxylated amine where a +
b + c ) 14.9.
Figure 32. Structure of tributylammoniumpropylsulfonate (TBAPS).
similar claims covers alkylaminoalkyl/alkoxy monoesters. A
fourth patent application with similar claims covers alkoxylated
amine ether carboxylic acids and their quaternized products.
These surfactants could in theory contain dibutylammonium
headgroups, as originally claimed by Shell for AAs, although
no examples are given. Their synergy with PVCap is also
claimed. A fifth patent application covers alkenylsuccinimi-
doalkylamines as KHI synergists and corrosion inhibitors with
improved water solubility and biodegradability.
Besides various quaternary ammonium surfactants Champion
Technologies’ patent applications196-200 also cover amine oxides
and betaine surfactants, a subject first researched by RF in the
late 1990s.
There was a reluctance by operators to use the early
quaternary AAs since their unit price per barrel of water treated
was about the same as methanol. However, the later quaternary
AAs are now much more competitive and can be dosed at lower
concentrations.224,231
New KHIs. In 2003, Akzo Nobel filed a patent application
on a new class of LDHI called polyalkoxylated amines.184,185
The alkoxylation is preferably done with propylene oxide (PO).
A preferred amine for making KHIs is triethanolamine but
ammonia and other alkanolamines can be used. The amine can
also be quaternized. The best example given in the patent
application is triethanol with a total of 14.9 PO units (Figure
31). At 1.0 wt % this reduced the hydrate onset temperature
from ca. 42 °F (5.6 °C) in a blank test to 32.9 °F (0.5 °C). AAs
are covered in the patent application by adding a long
hydrophobic tail to the polyalkoxylated amine, but no examples
are given.
Molecular modeling work carried out at the Universities of
Warwick and Reading, England, and hydrate testing at ENSI-
ACET & LGC, Toulouse, France, and Heriot-Watt University,
Edinburgh, Scotland, has led to a class of zwitterionic KHI
synergists.186,187(They also have potential as AAs.219) The only
chemical mentioned in detail is tributylammoniumpropylsul-
fonate (TBAPS), which performed only slightly better than PVP
in the THF hydrate ball-stop rig (Figure 32). Instead of binding
inside potholes on the hydrate surface, TBAPS and related
compounds lie along the surface and actually cap the pothole.
The modeling was carried out in a vacuum and does not take
into account free water-LDHI interactions. A later paper
mentions a product called J3 designed using molecular model-
ing, which performed significantly better than a commercial
PVCap blend, giving an induction time of over 4000 min with
structure II hydrates.188 It will be interesting to see how this
class of KHI develops.
846 Energy & Fuels, Vol. 20, No. 3, 2006
Figure 33. Structure of poly(vinyl alcohol) based KHIs where R1 has
1-6 carbon atoms, R2 or R3 is H, COOH, C1-10 alkyl or C6-C12
aryl, and R4 is H or CH3.
Kuraray Specialties Europe filed a patent application in 2001
on a new class of polymer KHI.189 The polymers are based on
derivatives of poly(vinyl alcohol) by reaction with aldehydes.
The structure of a typical product is shown in Figure 33. It
contains vinyl ester acetal functionalities besides some unreacted
vinyl alcohol monomer units. A preferred aldehyde is butyral-
dehyde, giving pendant propyl groups. Some of the polymers
are also claimed to work as AAs.
Since the early 1990s, it has been known that anti-freeze
proteins not only inhibit ice growth but also inhibit hydrate
formation.26,28 Queen’s University, Kingston, Canada, has sought
to commercialize the idea by claiming anti-freeze proteins, active
fragments of these anti-freeze proteins, and mimetics thereof,
as KHIs. The anti-freeze proteins or active fragments are derived
from insects, plants, fungi, protests, or bacteria presumably in
a process that allows for large-scale manufacture since isolation
of large quantities of anti-freeze proteins from these sources is
prohibitively expensive.190,212
In 2001 BASF patented the use of grafted polymers as
KHIs.201 The backbone is preferably a polyalkylene glycol, a
polyalkyleneimine, a polyether, or a polyurethane, and the active
functional side groups are made by grafting VP or VCap to the
backbone using radical initiators. The heteroatoms in the
backbone should help to increase the biodegradability of the
polymer.
Although quaternary ammonium salts with 2 or 3 butyl or
pentyl groups had been known for over a decade from Shell’s
work to work as hydrate growth inhibitors and as AAs, no one
it seems had tried to make polymer KHIs with quaternary
ammonium groups. In 2004 RF and Stavanger University
rectified this situation by testing polyquaternaries with pendant
tributylammonium groups.191 Perhaps not unexpectedly they also
turned out to be excellent synergists for VCap polymers such
as Gaffix VC-713 performing better than TBAB as synergist.
So far the work, which is still ongoing, has not been taken
beyond the laboratory stage.
Future LDHI Research
LDHI R&D appears to have come near to the top of the
S-curve. As of late 2005, there is relatively little activity by oil
companies, institutes, and the academic community in designing
higher performing products. It now seems to be primarily the
job of the service companies and chemical manufacturers in
fine-tuning existing chemistries. However, a number of new
academic research groups have taken up the batton and are
beginning to explore LDHIs, some in collaboration with service
companies. This may also lead to new or greener versions of
known LDHI classes. Further, fundamental studies on the
mechanisms of nucleation and agglomeration of hydrates are
also being carried out, either as molecular modeling203,213,214,237
or as experimental work.204-208,222,235,236 These studies will surely
help our understanding of the mechanisms of LDHIs but are
unlikely to result in fundamentally new commercial LDHIs.
Better experimental procedures that match the true field condi-
tions (not just a single subcooling limit) are also needed for
ReViews
LDHI testing. The effect of pressure, and not just the subcooling,
on the performance of LDHIs also needs further investiga-
tion.80,234
Conclusion
Low dosage inhibitors for mitigating other oilfield problems
are well-known and include wax, scale, corrosion, and asphalt-
ene inhibitors. Low dosage inhibitors for the prevention of
plugging by gas hydrates are the latest tools to have been
developed. This paper has reviewed the development of LDHIs
with focus on the various chemistries that have been investi-
gated. Both commercial and unsuccessful attempts have been
included for completeness. Since the start of LDHI research in
the late 1980s over 240 documents have been published. The
fact that nearly 100 of these are patent applications gives some
idea of the interest in this subject. However, there have been
far fewer patent applications in the last 2-3 years.
The use of LDHIs is now rapidly becoming an accepted
method for preventing hydrate plugging in gas wells and oil
and gas pipelines. Already LDHIs are a million dollar business
for some of the oilfield service companies. By the end of 2005,
there are and have been ca. 50-70 field applications of LDHIs,
the majority of them related to KHIs although the number of
AA applications are now increasing almost as rapidly. Most
LDHI applications to date have been retrofits (i.e., methanol or
glycol use has been exchanged with the more economical use
of an LDHI). However, as the technology becomes more well-
known, more fields will be planned with the use of LDHIs since
the CAPEX savings can be very significant.224
KHIs will continue to dominate the market for applications
where the hydrate subcooling is below 10 °C. Some commercial
KHIs when dosed at >5000 ppm have been used in the field at
subcoolings up to approximately 15 °C.155 Other KHIs have
been shown to work at much higher subcoolings, but they are
not commercially available. The best example is ExxonMobil’s
VIMA:IPMA oligomer. Blends of thermodynamic inhibitors and
KHIs are also being used in the field.210 AAs can of course
also be used at low subcoolings where the water cut is under
50%, and in some cases they may be more economical than
KHIs.
The mechanism for kinetic hydrate inhibition (nucleation
inhibition) by water-soluble polymers is still not fully under-
stood, at least in the public domain, although models have been
presented. Usually these relate to adsorption of the polymer onto
hydrate embryos or crystal structures,192 although some work
now suggests that water pertubation is also critical.188,213,214
More work is needed on molecular modeling of hydrate-
water-polymer interactions in an aqueous environment not just
hydrate-polymer interactions in vacuo. In addition, ExxonMo-
bil’s proprietary theory related to maximizing the hydration
volume of the KHI polymer in water needs investigating further.
After all, their polymers (e.g., VIMA:IPMA oligomer) appear
to have the highest performance of KHIs reported to date.
Finally, the mechanism of the effect of the hydrocarbon phase
on the performance of a KHI needs investigating.
For high subcooling applications, AAs seem the only com-
mercial LDHI alternative. Applications of AAs are expected to
move to higher subcoolings as operators and service companies
become experienced with their use. Single-tailed quaternary AAs
appear to be the only LDHIs that can consistently perform at
15+ °C subcooling. So far they have only been field proven in
flow lines to 14 °C subcooling, although laboratory experiments
suggest that 20+ °C subcoolings can be obtained (BP’s Holstein
field did use an AA at start-up where the subcooling could have
ReViews Energy & Fuels, Vol. 20, No. 3, 2006 847

been as high as 25 °C224). Emulsion-based AAs have yet to like to thank my wife, Evy, who patiently typed a large part of the
reach field applications. There is still a need for greener AAs manuscript while I was recovering from a long-term illness.
for use in environmentally sensitive waters such as offshore
Norway. GWAAs are different from pipeline AAs and have so Nomenclature
far only been shown to work at low water-to-hydrate conversion AA ) anti-agglomerant
in gas wells. They are however good synergists for PVCap- AFP ) anti-freeze protein
based KHI polymers. AFGP ) anti-freeze glycoprotein
AMPS ) acrylamidopropylsulfonic acid
CSM ) Colorado School of Mines
Acknowledgment. I would like to thank my fellow LDHI EMURC ) ExxonMobil Upstream Research Company
researchers at RF-Rogaland Research: Thor Martin Svartaas, Knut IFP ) Institut Francais du Petrole
Lekvam, Svante Nilsson, Lindy Dybvik, Jorunn Øvsthus, and Jan IPA ) isopropylacrylamide
Erik Iversen during the years 1991-2001. I would also like to thank IPMA ) isopropylmethacrylamide
the participants in LDHI projects carried out at RF-Rogaland KHI ) kinetic hydrate inhibitor
Research. They include Larry Talley (ExxonMobil Upstream LDHI ) low dosage hydrate inhibitor
Research Company), Nick Wolf and Stan Swearingen (Conoco- NS ) Nippon Shokubai Company Ltd.
Phillips), George Shoup (BP), Emil LePorcher and Jean-Louis OECD ) Organization for Economic Cooperation and Development
Peytavy (Total), Keijo Kinnari and Anita Rasch (Statoil), Finn PolyAP ) polyacryloylpyrrolidine
Fadnes (Norsk Hydro), Agostino Mazzoni and Carla Consoloni PVP ) poly(vinylpyrrolidone)
(ENI), Nick Phillips (Clariant Oilfield Services, now Baker Petro- PVCap ) polyvinylcaprolactam
lite), and Peter Klug (Clariant). Yuji Sugiura, Takashi Tomita, RF ) RF-Rogaland Research
Takashi Namba, Yoshihiro Arita, Jun-ichi Chosa, and Keiichiro THF ) tetrahydrofuran
Mizuta at Nippon Shokubai Company Ltd, are also acknowledged TROS ) TR Oil Services (now Clariant)
for their collaboration and excellent synthetic skills. I thank Larry TPAB ) tetrapentylammonium bromide
Talley and Ulfert Klomp (Shell Global Solutions) for reading the TBAB ) tetrabutylammonium bromide
manuscript and making helpful comments. I am also grateful for VIMA ) N-vinyl-N-methyl acetamide
the help of Piers Crocker who read to me many LDHI articles and
reports while I was unable to do so. Finally, but not least, I would EF050427X