Environmentally Friendlier
Drilling Mud Base Fluids
M. Fefer
Petro-Canada Lubricants
This paper is to be presented at the Petroleum Societys Canadian International Petroleum Conference 2001, Calgary, Alberta,
Canada, June 12 14, 2001. Discussion of this paper is invited and may be presented at the meeting if filed in writing with the
technical program chairman prior to the conclusion of the meeting. This paper and any discussion filed will be considered for
publication in Petroleum Society journals. Publication rights are reserved. This is a pre-print and subject to correction.
1
of the PureDrill HT-40 is manufactured through a other low flash oils, none is needed with PureDrill HT-
process known as hydroisomerization and deep 40.
hydrogenation.
PureDrill HT-40 is colourless, while diesel is a strong
The resulting PureDrill HT-40 and PureDrill IA-35 yellow colour which is a function of the high aromatic
fluids are highly enriched in paraffins. In the case of and polynuclear aromatic content of diesel as shown in
PureDrill HT-40 polynuclear aromatic levels are <100 Table 2.
ppm. Furthermore, PureDrill HT-40 has an inherent low
To accommodate the frigid conditions of the
pour point of < -33C, which is important for drilling in
Canadian winter, PureDrill HT-40 is manufactured with
cold weather conditions. The typical physical and
an inherent pour point of > -30C.
compositional properties of the two drilling fluids are
shown in Table 1. PureDrill HT-40 is composed of 98+ % of cyclic and
branched paraffins with a average carbon number of
C16. While the aromatic level of PureDrill HT-40 is <
PUREDRILL HT-40 VERSUS DIESEL
2.2wt%, the level of polynuclear aromatics is less than
PureDrill HT-40 is compositionally distinct from 0.01 wt%. As a consequence muds formulated with
diesel; it has significantly lower aromatics content than PureDrill HT-40 meet the requirements for maximum
the oils that were traditionally used for drilling in BTEX (benzene, toluene, ethyl benzene, xylenes) and
Western Canada. The preference for diesel-like drilling polynuclear aromatics values, as set out in the Alberta
fluids stemmed from the low product cost of diesel and Tier 1 Criteria for Contaminated Soil Assessment and
the preconception that diesel offers the ultimate in Remediation. Nitrogen and oxygen containing molecules
drilling performance. It was assumed that other types of are reduced to below detectable levels. This results in
drilling fluids could not achieve the penetration rates enhanced storage stability since some of these
observed with diesel. We have developed data which heteroatom containing molecules can initiate rapid
very convincingly shows that this is not the case. degradation of the oil and its properties.
As far as the economics are concerned, it is true that Although the composition of PureDrill HT-40 is
the unit price of diesel is less expensive than a product dramatically different from diesel oil, it has been
as compositionally pure as PureDrill HT-40. At the same repeatedly shown that outstanding performing drill muds
time a holistic analysis reveals that PureDrill HT-40 is can be formulated using exactly the same additives as
indeed cost effective and rivals the total costs incurred those used to formulate diesel based muds. Thus, there is
through the use of diesel based mud systems. Although no need to formulate PureDrill HT-40 muds with exotic
more will be said about these two issues below let us additives that are typically used with synthetics such as
begin by comparing the compositions, manufacturing internal olefins.
process and eco-toxicological characteristics of Diesel
and PureDrill HT-40.
MANUFACTURING PROCESS
COMPOSITIONAL DIFFERENCES As mentioned above, PureDrill HT-40 is
PureDrill HT-40 is a product with a much narrower manufactured by combining of a severely hydrocracked
distillation range than diesel. In addition, it does not low tox mineral oil and a synthetic hydroisomerized
possess the very light ends which contribute to the low isoparaffinic fluid. The severely hydrocracked portion of
flash and the irritating odour of diesel. Accordingly, PureDrill HT-40 is manufactured using Petro-Canadas
PureDrill is not classified as a fire hazard as per patented 2 stage severe Hydrocracking process in its
Canadas WHIMIS regulations whereas, diesel is Mississauga Ontario manufacturing facility (s e e
classified as a fire hazard which necessitates added Figure 1 Severe Two-Stage Hydrocracking Process).
handling precautions. For example, whereas grounding
precautions have to be used when handling diesel or
2
Much has been written about the mechanisms tested included fresh water fish, worms, shrimp
transpiring across the catalytic hydrocracking step and it plankton, algae and 3 different plant species. The worm,
is not the intent to give a detailed description of the and plant tests were carried with soil samples that were
reaction mechanisms. However, severe hydrocracking spiked with either 2 or 5 wt% of PureDrill HT-40 or
(carried out at ca. 2500 psig hydrogen pressure, 380C) Diesel. The tests clearly revealed that PureDrill HT-40 is
leads to severe molecular weight reduction through a innocuous to higher organisms such as fish. The LC50
complex series of ring opening and saturation reactions. result obtained in the standard Rainbow Trout test was
>400,000 ppm. In other words we were able to replace
The synthetic portion of PureDrill HT-40 is made
40% of the water with the PureDrill HT-40 without a
using a process known as hydroisomerization which
single trout mortality. This is in marked contrast to
involves cascading a purified paraffin rich stream over a
results reported in the literature for diesel where 96h
solid catalyst at elevated temperatures and hydrogen
LC50 value of ca. 1500 ppm are typical for fish (1). In
partial pressures. There is very little molecular weight
addition the results obtained with the mysids, algae and
reduction that takes place across hydroisomerization.
plankton was above the levels typically assumed to be
Instead linear hydrocarbons are rearranged to form
toxicologically acceptable.
branched paraffins otherwise known as isoparaffins or
isoalkanes (see Figure 2 Hydroisomerization) While the worms were able to tolerate the presence of
5 wt% PureDrill HT-40 in soil, all of the worms died at a
COMPOSITION AND TOXICITY diesel dose level of 2 wt%. In the plant tests there was a
marked decrease in root elongation as a result of having
Most multi-cellular living organisms are
2 wt% diesel while PureDrill HT-40 only had a minor
toxicologically susceptible to aromatics and / or low
impact on root elongation. In the Microtox test which is
molecular weight hydrocarbons. The latter being more
carried out with the use of photo-luminescent bacteria,
mobile and invasive which ultimately leads to a
PureDrill HT-40 yielded a PASS while diesel failed.
disruption in the life processes. Aromatic molecules can
penetrate living cells because of their enhanced solvency
properties thus providing a pathway for the penetration BIOREMEDIATION TESTS
of hydrocarbons which leads to cellular damage in both Field trials on the bioremediation of drill mud cuttings
plants and animals. contaminated with PureDrill HT-40 and diesel were
carried out using a technique known as land farming.
Some recent work carried out by the University of
The cuttings which originated from drilling operations in
WS in Australia with various plant species showed that
the Alberta foothills contained PureDrill HT-40 and
oxidized hydrocarbons are particularly toxic. In this
diesel drill mud residues. The drill mud cuttings were
respect the aromatic molecules are know to be one of the
plowed into virgin soil with a resulting hydrocarbon
most oxidatively unstable molecular types. Aromatics
concentration of ca. 3.2% for the PureDrill HT-40
readily oxidize to form hydroperoxides which are known
cuttings, and in the case of the diesel cuttings the
to be aggressive towards living cells. Furthermore, the
hydrocarbon concentration in the virgin soil was spiked
most toxic subset of the aromatics is the polynuclear
up to 1.3 wt%.
variety, ie the conjugated or condensed aromatic types,
with benzopyrene being a typical example. The In the case of land farming diesel based muds, it is
following table compares 14 classes of polynuclear common practice not to exceed a hydrocarbon
aromatics along benzene in Diesel and PureDrill HT-40 concentration of 2 wt% because of concerns of toxicity.
in relation to the Alberta Tier 1 criteria - (see Table 3). Following the incorporation of the cutting, both sites
were seeded with oats. The oats served as an indicator of
A number of tests were carried out comparing the
plot decontamination. Following a 2 month period, the
toxic reaction of various organisms to PureDrill HT-40
health of the two plots was evaluated by comparing plant
and Diesel (see Table 4 - Toxicity). The organisms
3
height, and root elongation. As it can be seen from the observed with the Diesel cuttings (see Figure 3
Table below, the plot containing the PureDrill HT-40 Land Farming Results (Hydrocarbon Concentration).
mud cuttings was visibly healthier as judged from the
plant height and root elongation measurements (see VISUAL POLLUTION
Table 5 Land Farming)
In the presence of sunlight on wet surfaces Diesel-like
The Microtox test served to confirm the non toxic oils are prone to exhibiting an iridescence or rainbow
nature of the PureDrill HT-40 plot while the diesel effect. This phenomenon is a visual marker for presence
containing soil failed after a 2 month weathering period. of pollution and can become apparent as a result of
Even after weathering for a about 1 year the diesel water run-off at the disposal site or where pools of water
containing soil failed to pass the Microtox test (see are formed.
Table 6 Microtox Results).
The appearance of sheen is related to the presence of
aromatics and polynuclear aromatics. The fact that
BIODEGRADATION PureDrill HT-40 is virtually free of polynuclear
The biodegradability potential of PureDrill HT-40 aromatics is the reason why it does not contribute to
was evaluated through the use of the standard CEC-L33- sheen formation.
A-82 test, whereas the biodegradability of the
hydrocarbon portion of the drill mud cuttings containing HUMAN HEALTH AND SAFETY
PureDrill HT-40 and diesel cutting was evaluated
through laboratory soil degradation studies and through Animal Testing
the use of land farming. A significant amount of work was carried out to
clarify the impact of PureDrill HT-40 on human health.
On its own, PureDrill HT-40 quickly as evidenced by
Standard toxicity tests, carried out on higher animal
the following data. Although we did not evaluate diesel
organisms did not reveal any significant toxic reaction
in this test the literature suggests that the
(see Table 9 Human Health & Safety)
biodegradability of similar oils is in the order of 15 to
40% - (see Table 7 Biodegradation). Although we did not run tests with diesel, it is well
know that some workers can develop a strong allergic
Soil degradation studies carried out in the laboratory
reaction to diesel especially with regards to dermatitis.
with cuttings also revealed a similar trend (see Table 8
Over the course of 4+ years of use of PureDrill HT-40,
Soil Degradation)
not a single a toxic or allergic reaction was ever
In a separate land farming experiment, the levels of reported.
residual hydrocarbons were monitored over the course of
In addition diesel is known to contain significant
52 weeks. Land farming was carried out with cuttings
quantities of polynuclear aromatics and benzene, some
which originated from drilling operations in the Alberta
of which are powerful human carcinogens (see Table
foothills which contained residues of PureDrill HT-40
10 Aromatic Composition)
and diesel muds. The drill mud cuttings were plowed
into virgin soil to a hydrocarbon concentration of ca. Odour and Volatility
5.0% for the PureDrill HT-40 cuttings, and in the case of Anyone who has worked around diesel based muds or
the diesel cuttings the hydrocarbon concentration in the
diesel based drill cuttings is well aware of how offensive
virgin soil was spiked up to 2.1 wt%.
and aggressive the diesel fumes can be. This is due to
The degradation results were quite dramatically the fact that diesel has both significant amounts of light
different; the hydrocarbons associated with the PureDrill C 8 to C10 hydrocarbons as well as high levels of low
HT-40 cuttings degraded at a much higher rate than that molecular weight aromatics. This can become an
important issue for workers who are routinely exposed
4
to drilling fluids through the manifestation of respiratory diesel are the light aromatic components which can act
and dermal issues. as a solvent leading to elastomer swelling and
degradation of properties. The following example
PureDrill HT-40 on the other hand, does not have an
illustrates what the impact is of diesel and PureDrill HT-
unpleasant irritable odour; its odour can be characterized
40 is on the properties of a commonly used elastomer
as having a slight non-aggressive hydrocarbon like
Buna N rubber (see Table 12 Elastomer
smell. And being virtually odourless makes PureDrill
Compatibility).
HT-40 much more comfortable for the rig hands to work
with the product. The volatility of PureDrill HT-40 was Clearly the structural integrity is distorted to a much
evaluated through the use of the standard ASTM 2887 greater extent in the case of diesel.
methodology. At a temperature of 100C we were not
able to detect any volatiles (see Table 11 Volatility) Drilling Performance Data
It is well known that drilling muds based on diesel
Fire Potential maximize the rate-of-penetration. Consequently, there
Also due to the absence of the very light was some healthy skepticism that similar drilling rates
hydrocarbons, PureDrill HT-40 exhibits a much higher could be achieved using other fluids, which are
flash point than diesel and consequently is less prone to compositionally very different from diesel. Generating
flash fires. good back-to-back drilling rate data is not a trivial
matter and is subject to the particular geology of the
Recommended Industry Practices formation, the mud age and fines levels as well as
A recent development in the oilfield industry is the hydrocarbon composition. Although we had generated
formation of an industry committee directed by the field data that indicated that PureDrill HT-40 performs
Drilling and Completions Committee (DACC) to at par with Diesel based muds the above mentioned
develop a new Industry recommended practices uncertainties prompted us carry out a controlled
(IRP#14) that covers the safe use and handling of non- experiment at TerraTek laboratories. The TerraTek
aqueous based drilling fluids. The main issues involved experiments were carried out with the use of freshly
are the health and safety concerns resulting from prepared PureDrill HT-40 and Diesel muds using six
exposure due to drilling operations that use oil based different rock types including a variety of shale,
fluids. limestone and sandstone rock types. In these
experiments the performance of diesel and PureDrill
During 2000, an in-depth analysis was carried out on
HT-40 were similar regardless of the rock types.
a variety of available fluids including PureDrill HT-40,
diesel and many others. The fluid characteristics
evaluated included: flash, aniline point, aromatic REFERENCES
content. The study (still in print) concluded that 1. Hinds et al., Diesel Bases And Low Toxicity Oil
PureDrill HT-40 was one of the best fluids. Mud Systems, SPE1189/1, p 169-177, 1998.
5
TABLE 1: TYPICAL PHYSICAL AND COMPOSITIONAL PROPERTIES
OF PUREDRILL HT-40 AND PUREDRILL IA-35
6
TABLE 3: ALBERTA TIER 1 CRITERIA
TABLE 4: TOXICITY
% Hydrocarbon in Soil 5 2
7
TABLE 5: LAND FARMING RESULTS
Oat Height, cm 15 8
Root Elongation, cm 16 1
TABLE 7: BIODEGRADATION
DIESEL 6.4
8
TABLE 9: HUMAN HEALTH & SAFEY TESTS
PureDrill HT-40
Volatility@100C, % (ASTMD2887) 0
9
FIGURE 1: Severe Two-Stage Hydrocracking Process
ATMOSPHERIC
DISTILLATION SOLVENT
DEWAXING
HYDROGEN HYDROGEN
FIGURE 2: Hydroisomerization
ATMOSPHERIC
DISTILLATION
HYDROGEN HYDROGEN
Purified
Isoalkane
Paraffin
Feedstock Higher Viscosity
Fluids
HYDROISOMERIZATION HYDROGENATION
VACUUM
DISTILLATION
10
FIGURE 3: LAND FARMING RESULTS
HYDROCARBON CONCENTRATION
6
HYDROCARBON, %
PureDrill HT-40
4
Diesel
0
0 20 40 60
WEEKS
11