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PAPER 2001-069

PETROLEUM SOCIETY
CANADIAN INSTITUTE OF MINING, METALLURGY & PETROLEUM

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.

PureDrill HT-40 is essentially free of carcinogenic


polynuclear aromatics.

ABSTRACT
Two drilling mud base fluids are reviewed - the semisynthetic PureDrill HT-40 and the fully synthetic fluid
PureDrill IA-35. The former is targeted for on-shore
applications whereas the latter is used in the more
environmentally sensitive offshore and on-shore areas.

PHYSICAL CHARACTERISTICS AND


COMPOSITION
Petro Canada manufactures two drilling mud base
fluids - PureDrill HT-40 is a semi-synthetic fluid and is
designed for on-shore use while the synthetic PureDrill
IA-35 is targeted for offshore drilling applications. The
latter fluid is more compositionally pure so as to
accommodate the more stringent offshore regulatory
requirements.

PureDrill HT-40 is an environmentally superior


alternative to diesel; it is non toxic to animals and plants
and degrades at a much faster rate than diesel using
standard land farming practices. At the same time,
despite the radical difference in composition, it is
possible to formulate drilling muds for on-shore
applications using the same additives as those used to
formulate diesel based muds. Additionally, it has been
shown that it is possible to drill just as fast with muds
based PureDrill HT-40 as it is with diesel mud.

PureDrill HT-40 is composed of a blend of severely


hydrocracked low tox mineral oil and a synthesized
isoparaffin fluid while PureDrill IA-35 is exclusively
composed of the synthesized isoparaffins. Severe
hydrocracking serves to eliminate the aromatic
molecules along with other undesirables such as sulphur
and nitrogen containing molecules. The synthetic portion

Because PureDrill HT-40 has extremely low levels of


aromatics and does not possess the very light C7 C10
hydrocarbons it is far superior to diesel in term of
human health and safety. In further contrast to diesel,

other low flash oils, none is needed with PureDrill HT40.

of the PureDrill HT-40 is manufactured through a


process known as hydroisomerization and deep
hydrogenation.

PureDrill HT-40 is colourless, while diesel is a strong


yellow colour which is a function of the high aromatic
and polynuclear aromatic content of diesel as shown in
Table 2.

The resulting PureDrill HT-40 and PureDrill IA-35


fluids are highly enriched in paraffins. In the case of
PureDrill HT-40 polynuclear aromatic levels are <100
ppm. Furthermore, PureDrill HT-40 has an inherent low
pour point of < -33C, which is important for drilling in

To accommodate the frigid conditions of the


Canadian winter, PureDrill HT-40 is manufactured with
an inherent pour point of > -30C.

cold weather conditions. The typical physical and


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 <
2.2wt%, the level of polynuclear aromatics is less than
0.01 wt%. As a consequence muds formulated with
PureDrill HT-40 meet the requirements for maximum
BTEX (benzene, toluene, ethyl benzene, xylenes) and
polynuclear aromatics values, as set out in the Alberta
Tier 1 Criteria for Contaminated Soil Assessment and
Remediation. Nitrogen and oxygen containing molecules
are reduced to below detectable levels. This results in
enhanced storage stability since some of these
heteroatom containing molecules can initiate rapid
degradation of the oil and its properties.

PUREDRILL HT-40 VERSUS DIESEL


PureDrill HT-40 is compositionally distinct from
diesel; it has significantly lower aromatics content than
the oils that were traditionally used for drilling in
Western Canada. The preference for diesel-like drilling
fluids stemmed from the low product cost of diesel and
the preconception that diesel offers the ultimate in
drilling performance. It was assumed that other types of
drilling fluids could not achieve the penetration rates
observed with diesel. We have developed data which
very convincingly shows that this is not the case.
As far as the economics are concerned, it is true that
the unit price of diesel is less expensive than a product
as compositionally pure as PureDrill HT-40. At the same
time a holistic analysis reveals that PureDrill HT-40 is
indeed cost effective and rivals the total costs incurred
through the use of diesel based mud systems. Although
more will be said about these two issues below let us
begin by comparing the compositions, manufacturing
process and eco-toxicological characteristics of Diesel
and PureDrill HT-40.

Although the composition of PureDrill HT-40 is


dramatically different from diesel oil, it has been
repeatedly shown that outstanding performing drill muds
can be formulated using exactly the same additives as
those used to formulate diesel based muds. Thus, there is
no need to formulate PureDrill HT-40 muds with exotic
additives that are typically used with synthetics such as
internal olefins.

COMPOSITIONAL DIFFERENCES
PureDrill HT-40 is a product with a much narrower
distillation range than diesel. In addition, it does not
possess the very light ends which contribute to the low
flash and the irritating odour of diesel. Accordingly,
PureDrill is not classified as a fire hazard as per
Canadas WHIMIS regulations whereas, diesel is
classified as a fire hazard which necessitates added
handling precautions. For example, whereas grounding
precautions have to be used when handling diesel or

As mentioned above, PureDrill HT-40 is


manufactured by combining of a severely hydrocracked
low tox mineral oil and a synthetic hydroisomerized
isoparaffinic fluid. The severely hydrocracked portion of
PureDrill HT-40 is manufactured using Petro-Canadas
patented 2 stage severe Hydrocracking process in its
Mississauga Ontario manufacturing facility (s e e
Figure 1 Severe Two-Stage Hydrocracking Process).

MANUFACTURING PROCESS

tested included fresh water fish, worms, shrimp


plankton, algae and 3 different plant species. The worm,
and plant tests were carried with soil samples that were
spiked with either 2 or 5 wt% of PureDrill HT-40 or
Diesel. The tests clearly revealed that PureDrill HT-40 is
innocuous to higher organisms such as fish. The LC50
result obtained in the standard Rainbow Trout test was
>400,000 ppm. In other words we were able to replace
40% of the water with the PureDrill HT-40 without a
single trout mortality. This is in marked contrast to
results reported in the literature for diesel where 96h
LC50 value of ca. 1500 ppm are typical for fish (1). In
addition the results obtained with the mysids, algae and
plankton was above the levels typically assumed to be
toxicologically acceptable.

Much has been written about the mechanisms


transpiring across the catalytic hydrocracking step and it
is not the intent to give a detailed description of the
reaction mechanisms. However, severe hydrocracking
(carried out at ca. 2500 psig hydrogen pressure, 380C)
leads to severe molecular weight reduction through a
complex series of ring opening and saturation reactions.
The synthetic portion of PureDrill HT-40 is made
using a process known as hydroisomerization which
involves cascading a purified paraffin rich stream over a
solid catalyst at elevated temperatures and hydrogen
partial pressures. There is very little molecular weight
reduction that takes place across hydroisomerization.
Instead linear hydrocarbons are rearranged to form
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
diesel dose level of 2 wt%. In the plant tests there was a
marked decrease in root elongation as a result of having
2 wt% diesel while PureDrill HT-40 only had a minor
impact on root elongation. In the Microtox test which is
carried out with the use of photo-luminescent bacteria,
PureDrill HT-40 yielded a PASS while diesel failed.

COMPOSITION AND TOXICITY


Most multi-cellular living organisms are
toxicologically susceptible to aromatics and / or low
molecular weight hydrocarbons. The latter being more
mobile and invasive which ultimately leads to a
disruption in the life processes. Aromatic molecules can
penetrate living cells because of their enhanced solvency
properties thus providing a pathway for the penetration
of hydrocarbons which leads to cellular damage in both
plants and animals.

BIOREMEDIATION TESTS
Field trials on the bioremediation of drill mud cuttings
contaminated with PureDrill HT-40 and diesel were
carried out using a technique known as land farming.
The cuttings which originated from drilling operations in
the Alberta foothills contained PureDrill HT-40 and
diesel drill mud residues. The drill mud cuttings were
plowed into virgin soil with a resulting hydrocarbon
concentration of ca. 3.2% for the PureDrill HT-40
cuttings, and in the case of the diesel cuttings the
hydrocarbon concentration in the virgin soil was spiked
up to 1.3 wt%.

Some recent work carried out by the University of


WS in Australia with various plant species showed that
oxidized hydrocarbons are particularly toxic. In this
respect the aromatic molecules are know to be one of the
most oxidatively unstable molecular types. Aromatics
readily oxidize to form hydroperoxides which are known
to be aggressive towards living cells. Furthermore, the
most toxic subset of the aromatics is the polynuclear
variety, ie the conjugated or condensed aromatic types,
with benzopyrene being a typical example. The
following table compares 14 classes of polynuclear
aromatics along benzene in Diesel and PureDrill HT-40
in relation to the Alberta Tier 1 criteria - (see Table 3).

In the case of land farming diesel based muds, it is


common practice not to exceed a hydrocarbon
concentration of 2 wt% because of concerns of toxicity.
Following the incorporation of the cutting, both sites
were seeded with oats. The oats served as an indicator of
plot decontamination. Following a 2 month period, the
health of the two plots was evaluated by comparing plant

A number of tests were carried out comparing the


toxic reaction of various organisms to PureDrill HT-40
and Diesel (see Table 4 - Toxicity). The organisms

observed with the Diesel cuttings (see Figure 3


Land Farming Results (Hydrocarbon Concentration).

height, and root elongation. As it can be seen from the


Table below, the plot containing the PureDrill HT-40
mud cuttings was visibly healthier as judged from the
plant height and root elongation measurements (see
Table 5 Land Farming)

VISUAL POLLUTION
In the presence of sunlight on wet surfaces Diesel-like
oils are prone to exhibiting an iridescence or rainbow
effect. This phenomenon is a visual marker for presence
of pollution and can become apparent as a result of
water run-off at the disposal site or where pools of water
are formed.

The Microtox test served to confirm the non toxic


nature of the PureDrill HT-40 plot while the diesel
containing soil failed after a 2 month weathering period.
Even after weathering for a about 1 year the diesel
containing soil failed to pass the Microtox test (see
Table 6 Microtox Results).

The appearance of sheen is related to the presence of


aromatics and polynuclear aromatics. The fact that
PureDrill HT-40 is virtually free of polynuclear
aromatics is the reason why it does not contribute to
sheen formation.

BIODEGRADATION
The biodegradability potential of PureDrill HT-40
was evaluated through the use of the standard CEC-L33A-82 test, whereas the biodegradability of the
hydrocarbon portion of the drill mud cuttings containing
PureDrill HT-40 and diesel cutting was evaluated
through laboratory soil degradation studies and through
the use of land farming.

HUMAN HEALTH AND SAFETY


Animal Testing
A significant amount of work was carried out to
clarify the impact of PureDrill HT-40 on human health.
Standard toxicity tests, carried out on higher animal
organisms did not reveal any significant toxic reaction
(see Table 9 Human Health & Safety)

On its own, PureDrill HT-40 quickly as evidenced by


the following data. Although we did not evaluate diesel
in this test the literature suggests that the
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
reaction to diesel especially with regards to dermatitis.
Over the course of 4+ years of use of PureDrill HT-40,
not a single a toxic or allergic reaction was ever
reported.

Soil degradation studies carried out in the laboratory


with cuttings also revealed a similar trend (see Table 8
Soil Degradation)
In a separate land farming experiment, the levels of
residual hydrocarbons were monitored over the course of
52 weeks. Land farming was carried out with cuttings
which originated from drilling operations in the Alberta
foothills which contained residues of PureDrill HT-40
and diesel muds. The drill mud cuttings were plowed
into virgin soil to a hydrocarbon concentration of ca.
5.0% for the PureDrill HT-40 cuttings, and in the case of
the diesel cuttings the hydrocarbon concentration in the
virgin soil was spiked up to 2.1 wt%.

In addition diesel is known to contain significant


quantities of polynuclear aromatics and benzene, some
of which are powerful human carcinogens (see Table
10 Aromatic Composition)
Odour and Volatility
Anyone who has worked around diesel based muds or
diesel based drill cuttings is well aware of how offensive
and aggressive the diesel fumes can be. This is due to
the fact that diesel has both significant amounts of light
C 8 to C10 hydrocarbons as well as high levels of low
molecular weight aromatics. This can become an
important issue for workers who are routinely exposed

The degradation results were quite dramatically


different; the hydrocarbons associated with the PureDrill
HT-40 cuttings degraded at a much higher rate than that

diesel are the light aromatic components which can act


as a solvent leading to elastomer swelling and
degradation of properties. The following example
illustrates what the impact is of diesel and PureDrill HT40 is on the properties of a commonly used elastomer
Buna N rubber (see Table 12 Elastomer
Compatibility).

to drilling fluids through the manifestation of respiratory


and dermal issues.
PureDrill HT-40 on the other hand, does not have an
unpleasant irritable odour; its odour can be characterized
as having a slight non-aggressive hydrocarbon like
smell. And being virtually odourless makes PureDrill
HT-40 much more comfortable for the rig hands to work
with the product. The volatility of PureDrill HT-40 was
evaluated through the use of the standard ASTM 2887
methodology. At a temperature of 100C we were not

Clearly the structural integrity is distorted to a much


greater extent in the case of diesel.
Drilling Performance Data
It is well known that drilling muds based on diesel
maximize the rate-of-penetration. Consequently, there
was some healthy skepticism that similar drilling rates
could be achieved using other fluids, which are
compositionally very different from diesel. Generating
good back-to-back drilling rate data is not a trivial
matter and is subject to the particular geology of the
formation, the mud age and fines levels as well as
hydrocarbon composition. Although we had generated
field data that indicated that PureDrill HT-40 performs
at par with Diesel based muds the above mentioned
uncertainties prompted us carry out a controlled
experiment at TerraTek laboratories. The TerraTek
experiments were carried out with the use of freshly
prepared PureDrill HT-40 and Diesel muds using six
different rock types including a variety of shale,
limestone and sandstone rock types. In these
experiments the performance of diesel and PureDrill
HT-40 were similar regardless of the rock types.

able to detect any volatiles (see Table 11 Volatility)


Fire Potential
Also due to the absence of the very light
hydrocarbons, PureDrill HT-40 exhibits a much higher
flash point than diesel and consequently is less prone to
flash fires.
Recommended Industry Practices
A recent development in the oilfield industry is the
formation of an industry committee directed by the
Drilling and Completions Committee (DACC) to
develop a new Industry recommended practices
(IRP#14) that covers the safe use and handling of nonaqueous based drilling fluids. The main issues involved
are the health and safety concerns resulting from
exposure due to drilling operations that use oil based
fluids.
During 2000, an in-depth analysis was carried out on
a variety of available fluids including PureDrill HT-40,
diesel and many others. The fluid characteristics
evaluated included: flash, aniline point, aromatic
content. The study (still in print) concluded that
PureDrill HT-40 was one of the best fluids.

REFERENCES
1. Hinds et al., Diesel Bases And Low Toxicity Oil
Mud Systems, SPE1189/1, p 169-177, 1998.
2. M. Voltz et al., Biodegradability of Lubricant Base
Stocks and Fully Formulated Products, Synthetic
Lubricants, p 215, 1999.

Elastomer Compatibility
Failure of elastomer containing components such as
those found in the stator motors can be the cause of
costly delays and downtime. The cause of these failures
can sometimes be traced back to incompatibility with the
drilling fluid. Therefore to keep failures to a minimum it
is preferable to use higher quality elastomer components
and / or to use a less aggressive drilling fluid. From a
molecular perspective the aggressive components in

TABLE 1:

TYPICAL PHYSICAL AND COMPOSITIONAL PROPERTIES


OF PUREDRILL HT-40 AND PUREDRILL IA-35
PureDrill HT-40

PureDrill IA-35

Water White

Water White

None

None

Viscosity, cSt @ 40C

3.4

3.5

Density, kg/L @ 15C

0.84

0.83

Flash point, (PM) C

126

120

Pour Point, C

-30

-57

<2.2

<0.01

<0.01

<0.001

222 345

222-234

Appearance
Odor

Total Aromatic Content %


Polynuclear Aromatics (PAH), %
Distillation, Range, C

TABLE 2:

TYPICAL PROPERTIES OF PUREDRILL HT-40 AND DIESEL


PureDrill HT-40
C11-C21

Petro-Canada Winter
Diesel
C7-C23

Water White

Yellow

None

Strong

Viscosity, cSt @ 40C

3.4

1.6-2.4

Density, kg/L @ 15C

0.83

0.8434

Flash point, (PM) C

126

63

Pour Point, C

-30

-33

Aromatics Content %

<2.2

32.2

Polynuclear Aromatics (PAH), %

<0.01

12.5

222 - 345

110 379

<5

>5000

Carbon Distribution
Appearance
Odor

Distillation, Range, C
Sulphur + Nitrogen content, ppm

TABLE 3:

ALBERTA TIER 1 CRITERIA

PureDrill HT-40
BENZENE

DIESEL

ALBERTA TIER 1 CRITERIA

<0.01 159

0.05

<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5

1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0

POLYNUCLEAR AROMATIC TYPES, PPM


NAPHTHALENE
ACENAPHTHALENE
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
PYRENE
BENZO(a)ANTHRACENE
CHRYSENE
BENZO-FLUORANTHENES
BENZO(a)PYRENE
INDENO(1,2,3-c,d)PYRENE
DIBENZO-ANTHRACENE
BENZO(g,h,i)PERYLENE

449
8
83.3
224
317
9.3
120
359
0.5
5
<0.5
<0.5
<0.5
<0.5

TABLE 4: TOXICITY

PureDrill HT-40

Diesel

Pass
> 400,000
>1,000,000
>2000
>1000

Fail

98
98
95
98

0
78
48
27

Toxicity Tests
Microtox
Rainbow Trout, ppm, LC50, 96h
Mysid Shrimp, ppm, LC50@96h
Acartia Tonsa, ppm, EC50@48h
Skeletonema Costatum, ppm, EC50@72h
% Hydrocarbon in Soil
Worm Survival %, 24 hours
Lettuce, % Root Elongation
Canola, % Root Elongation
Barley, % Root Elongation

TABLE 5:

LAND FARMING RESULTS


PureDrill HT-40 Plot

Diesel Plot

Oat Height, cm

15

Root Elongation, cm

16

TABLE 6:

MICROTOX RESULTS
PureDrill HT-40 Plot

Diesel Plot

Pass

Fail

Microtox

TABLE 7: BIODEGRADATION

Biodegradability, % CEC-L33-A-82
* Literature values (2)

Diesel *
15-40

PureDrill HT-40
87.5

TABLE 8: SOIL DEGRADATION STIDIES


TOTAL HYDROCARBON LOSSES (IN PERCENT) DUE TO MICROBIAL
DEGRADATION AFTER 45 DAYS:
HYDROCARBON CONTENT IN SOIL

2%

6%

PureDrill HT-40

10.2

10.4

DIESEL

6.4

TABLE 9:

HUMAN HEALTH & SAFEY TESTS

ACUTE ORAL TOXICITY


TSCA 40 CFR 178.1175

PRACTICALLY NON-TOXIC
LD50: >5,000 MG/KG

ACUTE DERMAL TOXICITY


TSCA 40 CFR 178.1100

LD50: >2,000 MG/KG

ACUTE EYE IRRITATION/CORROSION


TSCA 40 CFR 178.4500

SLIGHT EYE IRRITANT

ACUTE INHALATION TOXICITY


TSCA 40 CFR 178.1150

LC50: >2,300 MG/M_

TABLE 10:

AROMATIC CONTENT
PureDrill HT-40

Benzene, ppm
Polynuclear aromatics, wt%

DIESEL

<0.01
<0.01

TABLE 11:

159
11.2

VOLATILITY
PureDrill HT-40

Volatility@100C, % (ASTMD2887)

TABLE 12:

ELASTOMER COMPATIBILITY

BUNA N RUBBER
SWELL, %@80C/22Hr

Diesel
11

DUROMETER POINTS @80C/22Hr

PureDrill HT-40
-0.15
0

FIGURE 1: Severe Two-Stage Hydrocracking Process

ATMOSPHERIC
DISTILLATION

SOLVENT
DEWAXING

HYDROGEN

HYDROGEN

Gas Oil

ULTRA PURE
OILS

HYDROCRACKER

WAX

HYDROGENATION

VACUUM
DISTILLATION

FIGURE 2: Hydroisomerization
ATMOSPHERIC
DISTILLATION
HYDROGEN

HYDROGEN

Purified
Paraffin
Feedstock

Isoalkane
Higher Viscosity
Fluids
HYDROISOMERIZATION

HYDROGENATION
VACUUM
DISTILLATION

10

FIGURE 3:

LAND FARMING RESULTS

HYDROCARBON, %

HYDROCARBON CONCENTRATION

6
PureDrill HT-40

4
Diesel

2
0
0

20

40
WEEKS

11

60

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