This Review presents a comprehensive
literature review of an important
class of kinetic hydrate inhibitors (KHIs) that is based on cyclic
amides (lactams). The major aspects of the KHIs, such as their synthesis,
inhibition mechanism, toxicity, biodegradability, performance, and
cloud point, are thoroughly discussed. Data for 70 KHIs made of homo/co/terpolymers
from 330 experiments are collected and evaluated for performance.
The effects of the inhibitor concentration, molecular weight, monomer
ratio of the co/terpolymers, and 35 different synergist chemicals
on various KHIs are also studied. In conclusion, the top 10 KHIs with
the highest performances that had a cloud point above 70 °C are
presented. The copolymer (1:1) N-vinylpyrrolidone/N-vinyl-caprolactam (VP/VCap) is found to have the highest
induction time (IT) of 13 to 14 h at 0.25 wt % and at a cooling rate
of 1 °C/h. Some KHIs like Inhibex BIO-800 and poly(N-vinyl azacyclooctanone) (PVACO) also have a very high ITs (17 and
13.5 h, respectively) at 0.25 wt % and at a cooling rate of 1 °C/h,
but they have low cloud points (<25 °C). Guanidinium salts
(n-Bu6GuanCl/n-Bu6GuanBr) and a phosphonium salt, (n-Pe)4PBr, are found to be the best synergists for the cyclic-amide-based
KHIs. When used at 0.15 to 0.30 wt % along with the KHIs, they further
increase the IT by 3–5 h.
Three
plant-based polysaccharides, pectin, k-carrageenan, and guar
gum, are investigated as synergists with four kinetic hydrate inhibitors
(KHIs), polyvinylpyrrolidone, polyvinylcaprolactam, Luvicap55w, and
HIOP. The enhancement in the hydrate inhibition performance is characterized
by measuring the increase in the delay/induction time (IT) taken for
hydrate nucleation and the reduction in hydrate growth after nucleation.
Standardized constant cooling rate hydrate formation tests are performed.
Experimental results provided by 0.5 wt % aqueous solutions of reference
KHIs are compared with the results of aqueous solutions made with
combining 0.25 wt % reference KHI with 0.25 wt % polysaccharide synergist.
K-carrageenan showed exceptional inhibition synergy with all KHIs
with ITs enhanced around 20–35% with different reference KHIs
and reduced hydrate growth rates up to 90%. Guar Gum did not increase
the IT provided by reference KHIs. However, it decreased hydrate growth
rates by 77–90% of all KHIs. Pectin showed exceptional hydrate
inhibition synergy with HIOP (commercial KHI), boosting its IT by
45%.
A uniformly dense dispersion of few layer BP (FLBP) nanosheets in PDMS (polydimethylsiloxane) matrix is shown to exhibit a remarkably strong mechanical energy harvesting effect with highest peak-to-peak voltage output of about 350 V.
Hydrate formation experiments are carried out to evaluate
the synergy
between three natural proteins (whey protein, casein peptone, and
bovine serum albumin (BSA)) and four standard references kinetic hydrate
inhibitors (KHIs) (poly(vinylpyrrolidone) (PVP), poly(vinylcaprolactam)
(PVCap), Luvicap 55w, and HIOP-1800) that are used commercially as
well as in research. Hydrate inhibiting efficiency is appraised by
comparing the induction times (delay in hydrate nucleation) provided
by the reference KHIs and by the blends of KHIs with the proteins.
The induction times (ITs) were measured at 0.5 wt% of the reference
KHIs to compare against the blended concentrations with 0.25 wt% of
the reference KHIs and 0.25 wt% of the protein synergists (keeping
the total concentration equal to 0.5 wt.%). Results showed that all
the three proteins have hydrate inhibition synergy with the KHIs.
Amongst the three proteins, BSA showed the most consistent synergy
with the four KHIs and had the largest increase in the ITs. It significantly
enhanced PVP’s and PVCap’s ITs by 32% and 19%, respectively.
It showed exceptional synergy with HIOP-1800 and enhanced its IT by
65%. When blended with Luvicap 55w, BSA provided almost the same IT
as when Luvicap 55w was used alone. Peptone from casein showed its
highest synergy with PVCap, and resulted in its IT increase by 15%.
The third protein, whey, showed its best synergy with HIOP-1800 and
elevated its IT by 15%. Apart from the benefit of enhanced hydrate
inhibition (increase in the ITs of most KHIs), these three natural
proteins when blended with KHIs at the same total concentration of
the inhibitor product make them cost-effective, partially biodegradable,
and more sustainable.
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