Journal of the Japan Petroleum Institute, 56, (4), 221-229 (2013) 221

[Regular Paper]

Safe Disposal Technology of Waste Oil-based Drilling Fluids

Bing HOU＊, Mian CHEN, Ming LIU, and Qiquan XIONG

State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum (Beijing), Beijing 102249, P. R. CHINA

(Received August 30, 2012)

Waste oil-based drilling fluids are hazardous wastes containing oil, heavy-metal and organic pollutants.
However, the common treatment methods at home and abroad these methods not only waste many useful resources
(because the oil is discarded rather than recovered) but also increase the pro-environment cost of oil companies.
This paper develops useful recycling and safe disposal technology of waste oil-based drilling fluids from the per-
spective of utility, efficiency and economy, which not only recycle useful oil but also reuse and dispose of the rest
of mud and waste drilling fluids. The rate of recovery is greater than 90 %, and the quality of the recycled oil is
very good and meets the requirement of −10 # diesel of cars in GB/T 19147-2003. The concentrations of oil,
COD (chemical oxygen demand) and heavy metals in liquid of the processed mud are lower than the secondary
standard number in GB8978-1996. The treated wastewater meets the requirements of sewage comprehensive
emission.

Keywords
Oil-based drilling fluids, Resource recovery, Muddy-ground handling, Wastewater reuse, Harmless treatment,
Recycled oil

1. Introduction cultural sludge is strictly regulated at less than 300 mg/

Oil-based drilling fluids are composed of oil, water,
clay, emulsifier, stabilizer and fluid-loss and other addi-
tives. Their lubricity, inhibition and thermal stability
are very desirable and they protect the hydrocarbon res-
ervoir well; therefore, they are used exclusively over
other drilling fluids in complex geological wells, highly
deviated wells and horizontal wells. Usually, the oil-
based drilling fluids are recycled after drilling because
of their high cost.
However, a large amount of waste oil-based drilling
fluids is created during the drilling operation.
Moreover, the property of the oil-based drilling fluids
deteriorates after repeated use, creating waste oil-based
drilling fluids. Because the waste oil-based drilling
fluids contain a great deal of mineral oil and are classi-
fied as hazardous wastes, their direct discharge would
inevitably cause serious environmental pollution1)∼3).
There are strict requirements about the volume of oil in
cuttings. Europe has required the content of oil in
solid waste material to be less than 1 % since 1993 and
achieved zero emissions after November 2000.
Although China does not explicitly have drilling-waste
mineral-oil-content standards, mineral oil has been clas-
sified as hazardous waste, and the content of oil in agri-
＊
To whom correspondence should be addressed.
＊
E-mail: houbing9802@163.com
kg dry soil. Generally, the methods of disposing of
waste oil-based drilling fluids are the use of a landfill or
re-injection4)∼17), but these methods cannot resolve the
pollution of waste oil-based drilling fluids and waste a
large amount of diesel resources. Various kinds of
waste oil-based drilling fluids treating technologies are
compared in Table 1.
Thus, it is very important to find a cost-effective way
to deal with and recover waste oil-based drilling fluids
from the perspective of environmental protection and
economic efficiency18)∼22) .
2. Experimental Sections
2. 1. Experimental Reagents and Instruments
2. 1. 1. Experimental Reagents
In this experiment, the compound demulsifier is a
mixture containing two industrial demulsifiers. The
demulsifiers are mainly consist of polyoxyethylene poly-
oxypropylene ethyleredi-amines demulsifier (AE) and
polyoxypropylene polyoxyethylene polyoxypropylene-
five ethylenes six amines demulsifier (AP). The coag-
ulants and flocculants are industrial reagents that are
components in oil recovery. The harmless treatment
agent includes adsorbent B (saponin biosurfactant) and
coagulant C (aluminum sulfate), which are also indus-
trial reagents, breaker A (home made, polyaluminium-
iron salt) and petroleum ether (analytical-grade purity,

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Table 1 Comparison between the Treating Technology Presented in the Paper and Commonly Used Technologies
Area Treating technologies
Foreign Formation reinjection
Thermal distillation
Solvent extraction
Detergent demulsification
Domestic Decentralized treatment
Direct solidification
Recycling
Burning
Safety treatment technology of the deserted
oil-based drilling fluid
distillation range is 90-120 ℃).
2. 1. 2. Experimental Instruments
The instruments in the experiment are as follows:
AFS-830A atomic fluorescence chromatograph;
ZEEnit-60 atomic absorption spectrometer; 2100 X-ray
fluorescence spectrometer; Oil460 infrared oil-content
analyzer; DR200-type COD digestion apparatus;
DR2800 Portable Spectrophotometer; and other glass
apparatus.
2. 2. Experimental Methods
2. 2. 1. Waste Oil-based Drilling Fluid Composition
Analysis
This portion of the work mainly analyzes the con-
tents of oil, water and solid in the waste oil-based drill-
ing fluids. The dedicated device is used to determine
the content of water, extract the water from waste fluids
with petroleum ether (90-120 ℃), obtain the water after
condensation, determine the volume of water that was
extracted and compute the content of water in the waste
fluids. The mixture of oil, solid phase and petroleum
ether is collected and dried, and the weight of the mix-
ture is determined to calculate the oil content using the
difference method.
2. 2. 2. Main Pollutants of Waste Oil-based Drilling
Fluids
This portion will primarily analyze the heavy metals
and petroleum of the waste fluids. The experimental
methods are in accordance with the appropriate national
standards or standard methods of lines. The heavy
metals are detected according to GB 5084.3-2007
Identification standard for leaching toxicity of hazard-
ous waste identification23), and the method of petroleum
detection is in accordance with section 1.
2. 2. 3. Main Pollutants of Sludge Leachate and
Wastewater
In this portion, the heavy metal, oil, COD, chrome
and pH value in the lixivium and wastewater are ana-
lyzed. The methods are in accordance with the appro-
priate national standards or standard methods of lines.
The heavy metals are analyzed according to GB 5084.3-
J. Jpn. Petrol. Inst., Vol. 56,
Main results from comparison
High cost; high requirement on the condition of formation
High energy consumption, high requirement on apparatus
High cost; high requirement on treatment environment
Relatively high cost; high solid oil content after separation
Unsuitable for offshore platform
Only able to deal with the drilling waste containing oil content
lower than 8 %
Pretreatment for drilling fluid such as eliminating low-quality
solid phase etc.
High energy consumption, high requirement on equipments
Systematic, integrated, resource recycled, standardized discharge
and reuse
2007 Identification standard for hazardous waste leach-
ing toxicity of identification and GB 7475-87 Quality
copper, zinc, lead and cadmium by atomic absorption
spectrometry24). The detection of oil is in accordance
with GB/T 16488-1996 Quality oil and the determina-
tion of animal and vegetable oils25). COD is tested by
according to HJ/T 399-2007 Determination of chemical
oxygen demand rapid digestion spectrophotometry26).
C h r o m e i s d e t e c t e d a c c o r d i n g t o G B 11903-89
Determination of color quality27), and the pH value is
tested according to GB/T 6920-86 Determination of
water pH, glass electrode28).
3. Results and Discussion
3. 1. Composition Analysis of Waste Oil-based
Drilling Fluid
In this study, we investigate waste oil-based drilling
fluids in Daqing Oilfield, Shengli Oilfield and several
large oil fields in Tarim oilfield and determine the com-
position and major pollutants of waste oil-based drilling
fluids. The measurement results are shown in Tables
2 and 3.
The results show that the oil rate is between 28.0-
40.0 % in the waste oil-based drilling fluids, the mois-
ture content is 47.0-66.0 %, and the solid content is 6.0-
18.0 %. The main pollutant is oil. The direct burial
of waste in a landfill will cause serious environmental
pollution and wastes many useful resources.
3. 2. Oil Recovery from Waste Oil-based Drilling
Fluids
This section explores and develops oil recovering
agent, which minimally contains a demulsifier and a
strongly hydrophilic surface-active agent. The demul-
sifier reduces the demulsifier adsorption on the oil-
water interface, and the strongly hydrophilic surfactant
enhances the solution of the hydrophilic solid particles
into the water phase, leaving the oil-water interface
after the oil recovering agent is added into the waste
oil-based drilling fluid. Moreover, the highly salt-
No. 4, 2013
 223

Table 2 Components of Waste Oil-based Drilling Fluids

Sample source Oil content [%] Moisture content [%] Solid content [%]
The waste slurry pool of DQ-6 well in
31.0 54.0 15.0
Daqing Oil field
The waste slurry pool of Chengbei
28.0 66.0 6.0
NP1 well in Shengli Oil field
Replacement of plasma of Chengbei
40.0 49.0 11.0
NP1 well in Shengli Oil field
The mud pit slurry of HD4-46 well in
30.0 53.0 17.0
Tarim Oil field
Replacement of plasma of HD4-46
35.0 47.0 18.0
well in Tarim Oil field

Table 3 Main Pollutants of Waste Oil-based Drilling Fluids [mg/kg]

Sample source Cr Pb As Hg Cd Oil

The waste slurry pool of DQ-6 well in Daqing Oil field 24.20 14.56 14.60 1.438 0.21 310000
The waste slurry pool of Chengbei NP1 well in Shengli Oil field 13.50 21.20 23.65 0.812 0.49 280000
Replacement of plasma of Chengbei NP1 well in Shengli Oil field 23.71 12.18 16.34 1.309 0.13 400000
The mud pit slurry of HD4-46 well in Tarim Oil field 19.45 32.59 19.72 0.841 0.40 300000
Replacement of plasma of HD4-46 well in Tarim Oil field 10.43 18.32 13.10 0.905 0.53 350000
Control standards for pollutants in sludges from agricultural, GB4284-84 ≤ 1000 ≤ 1000 ≤ 75 ≤ 15 ≤ 20 ≤ 3000

Table 4 Effects of Oil-recovering Treatment on Different Waste Oil-based Drilling Fluids

Sample source The amount of oil revenue [%] Oil recovery [%]
The waste slurry pool of DQ-6 well in Daqing Oil field 40 95.2
The waste slurry pool of Chengbei NP1 well in Shengli Oil field 40 94.6
Replacement of plasma of Chengbei NP1 well in Shengli Oil field 40 93.9
The mud pit slurry of HD4-46 well in Tarim Oil field 40 93.1
Replacement of plasma of HD4-46 well in Tarim Oil field 40 94.7

enhanced emulsion-breaking cation is added to the
fluids. The above factors greatly reduce the emulsion
stability of waste oil-based drilling fluids and lead to
the final emulsion breaking to obtain oil.
3. 2. 1. Preparation of Oil Recovering Agent
The composition formula of oil recovering agent is
as follows: 30 % of demulsifier compound SDPR-6
(15 % demulsifier AE136＋15 % demulsifier AP113),
1.5 % of coagulant (high charged salts, such as CaCl2,
AlCl3), and 2 % of flocculant PAM (concentration is
0.1 %).
First, the compound demulsifier SDPR-6 is added
with stirring. The stirring is maintained for some time
after the addition, and then coagulant and flocculant
PAM are added.
3. 2. 2. Adaptability of Oil Recovering Agent to
Different Waste Oil-based Drilling Fluids
In the study, different waste oil-based drilling fluids
selected from different oil fields were tested to examine
the adaptability of oil recovering agent to different
waste oil drilling fluids. The results are shown in
Table 4.
The results show that oil recovering agent SDPR-6
can handle the waste oil content in different waste oil-
based mud, that the purpose of recovered oil is
achieved, and that the oil recovering agent showed good
adaptability.
3. 2. 3. Quality of the Recovered Oil
According to GB 252-2000 Light Diesel Oil and GB/
T 19147-2003 Automotive Diesel requirements, a pro-
fessional testing organization was commissioned to
analyze the quality of the recovered oil by the selection
of some commonly used oil indexes in this study. The
results are shown in Table 5.
From these results, several measured indicators reach
the requirements of GB252-2000 −10 # light diesel oil
and GB/T 19147-2003 −10 # diesel oil, except for
mechanical impurities and ash indicators. The exces-
sive ash is caused by higher mechanical impurities; if
the recovered oil is filtered through a fine filtration, the
recovered oil will reach the technical requirements of
−10 # diesel oil in GB/T 19147-2003.
3. 3. Analysis of the Major Pollutants in Remaining
Sludge and Wastewater
This portion of this work mainly analyzes sludge and
wastewater using an on-site test because the treatment
of waste oil-based drilling fluids will produce some
wastewater and sludge. The results are shown in

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Table 5 Quality of the Recovered Oil

Item GB252-2000 GB/T 19147-2003 Experimental results

Density [25 ℃, g/cm ] 3
measured - 0.7986
Viscosity [mm2/s] 3.0-8.0a) 3.0-8.0a) 5.23
Flash point [℃] 55a) 55a) 50
Freezing point [℃] −10a) −10a) −11
Sulfur content [%] 0.2 0.05 0.031
Ash [%] 0.01 0.01 0.10
Moisture [%] sign sign ＜0.1
Acidity [mgKOH/100 mL] 7 - 0.22
Toluene insoluble [%] - - 0.15
Mechanical impurities [%] none none 0.017
a) Technical requirements of −10 # diesel oil.

Table 6 Pollutants of Wastewater

a)
The first class of Allowable concentration Experimental results The second category of Allowable concentrationa) Experimental results
pollutants [mg/L] [mg/L] pollutants [mg/L] [mg/L]
Hg 0.05 0.022 pH (dimensionless) 6-9 6.6
Cd 0.10 0.0021 Oil 10 11500
Cr 1.50 0.0011 Suspended solids (SS) 150 322
As 0.50 not detected Chemical oxygen 150 65000
demand (COD)
Pb 1.0 0.0015 Biochemical oxygen 30 28500
demand (BOD5)
Chroma (times) 80 2000
a) Adapted from“Comprehensive discharge standard”(GB 8978-1996).

Table 7 Composition and Main Pollutants of Sludge

Item Oil Water Solid Cr Cd Pb Hg As

Measured value 7.4 % 81.0 % 11.6 % 13.4 mg/kg 0.39 mg/kg 29.87 mg/kg 0.820 mg/kg 17.63 mg/kg
Standard value 3000 - - 1000 20 1000 15 75
From“Control standards for pollutants in sludges from agricultural”(GB4284-84).

Tables 6 and 7.
The heavy-metal pollutants and pH values of waste-
water are within the limits of the standards after the
waste oil-based drilling fluids are washed from the
results of Table 5 in the supporting information.
However, the suspended solids (SS), oil, COD, BOD5 (5
days biological oxygen demand) and chroma indicators
all exceed the standard values. Therefore, the waste
fluids should be further treated before the efflux. The
experimental results of Table 7 in the supporting infor-
mation are similar to the results of pollutants in the
waste oil-based drilling fluids. The oil content has
been greatly reduced by recovering most of oil, but the
sludge content is still higher than the GB4284-84
Control standards for pollutants in sludges from agri-
cultural29), indicating the need for further treatment.
3. 4. Harmless Treatment of Sludge
3. 4. 1. Formulation Analysis of the Harmless
Treatment
The clay-particle surface negative charge will be re-
duced under the physical and chemical effects of the
addition of the harmless treatment agent into the re-
maining sludge. This process will reduce the zeta
potential and the repulsion between particles, diminish-
ing or eliminating the stability of the sludge. At the
same time, the harmful components in the sludge will
be effectively controlled by adding coagulant and
adsorbent agents. Moreover, the treated sludge can be
used for the cofferdam of the well site and the forma-
tion of the ground material. The location of waste oil-
based drilling fluids that was previously occupied by
the well field has also been reused.
3. 4. 2. Determination of the Amount of Breaker A
The sludge system has the basic colloidal character-
istics, containing stable pollutants and moderately
water-soluble organic matter. If it is solidified directly,
the molecular form of the organic matter will not
change, and the organic matter will transfer from the
solid phase to water after the solid is immersed in water,
polluting the water. The breaker will reduce the water
solubility of the organic matter so that the organic mat-
ter will not easily transfer from the solid phase into the
water. The performance of breaker is good; the
amount of organic matter that transfers from the solid to

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Table 8 Effect of Breaker A Dosage on Sludge

Dosage [%] 1.0 1.5 2.0 2.5 3.0 3.5 4.0 5.0
The color of the
leaching agent of Darker Darker Lighter Very light Almost colorless Colorless Colorless Colorless
treated sludge

Table 9 Effect of Adsorbent B Dosage on Pollutant Adsorption

Dosage [%] pH COD [mg/L] Cr [mg/L] Pb [mg/L] As [mg/L] Hg [mg/L] Petroleum [mg/L]
0.5 9-10 186 0.93 0.08 not detected not detected 12.0
1.0 8-9 143 0.65 0.08 not detected not detected 7.0
1.5 8-9 88 0.39 0.03 not detected not detected 4.0
2.0 8-9 59 0.16 0.01 not detected not detected 2.4
Sewage discharge (II) 6-9 150 0.50 1.0 0.50 0.05 10
standard GB8978-1996
Environmental protection 6-9 100 500 500 10 10 30000
standard of Venezuela
DECREE 2635

Table 10 Hardness Classification Table

Curing effect level Physical characterization

0 Should not be frozen after being treated, liquid form
I Very soft surface after being treated, cannot freely move
II Relatively soft surface after being treated, finger can press
III Hard surface, relatively strong, but can be crushed by fingers
IV Hard surface, greater strength intensity, cannot be crushed by fingers

water will be reduced. The color of the sludge con-
taining organic matter is generally brown, so the effect
of the breaker can be determined by observing the color
of the treated sludge. The project team selected breaker
A based on laboratory tests in which it demonstrated
good results for breaking plastic into the sludge.
The experimental selection method of the breaker is
first to add the breaker into the fluids. The sludge is
set on a piece of filter paper with a glass rod after the
completion of the gel breaking. The color observes
the color of soaked part is then observed, and the results
are shown in Table 8.
Based on these experimental data, the color of the
leaching agent is very light or colorless when the con-
centration of breaker A is above 3.0 % for the offshore
polymer drilling fluids, which indicate that it has been
broken. Therefore, the ideal amount of breaker A is
above 3.0 %.
3. 4. 3. Determination of the Amount of Adsorbent
B Using concentrations of breaker A and adsorbent B
The adsorbent strongly adsorbs the harmful pollutants
in the sludge, greatly reducing the amount of pollutants
diffusing into the soil and the surrounding environment.
Thus, the synergistic effect of adsorbent B was studied,
focusing on testing contaminants in sludge adsorption.
In the experiment, the dosage of breaker A is 3.0 %.
The pollutant indexes of treated sludge leaching agent
were determined, and the experimental results are
shown in Table 9.
From the experimental data shown in Table 9, the
addition of adsorbent B in the sludge has a desirable
effect on the adsorption of contaminants. When the
amount of adsorbent B is 1.5 %, the leaching-solution
pollutants of the treated sludge comply with the national
wastewater-discharge standards.
3. 4. 4. Determination of the Amount of Coagulant
C
The addition of coagulant C allows the treated sludge
to have a certain thickness, and also can strengthen the
sealing effect of pollutants. The tightness of the solid-
ified sludge was qualitatively classified to determine the
initial effect of the curing process. The final results
were determined using the optimized method and related
experimental study. After the addition of coagulant C,
the treated sludge’s hardness was tested by the pressure
of hand after 24 h. The hardness classification is
shown in Table 10.
of 3.0 % and 1.5 %, respectively, the effects of different
dosages of coagulant C on the hardness of the treated
sludge are shown in Table 11.
From the results of Table 11 in the supporting in-
formation, for the treated waste oil-based drilling-fluid
sludge with a coagulant-C dosage of 9 % C and a cur-
ing time of 7 days, the sludge has a degree of hardness
that meets the curing requirements.

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The treated drilling fluid extract, hardness of the dilute waste oil-based drilling fluid instead of water
cured solid, processing costs and on-site operational while the other conditions are held constant. The test
and other factors that determine the sludge-treatment results are shown in Table 13.
processing formula of the waste oil-based drilling fluids The water that is produced by washing the oil of the
were determined using indoor studies and comprehen- waste oil-based drilling fluids can be reused many
sive technical indicators after the resumption of oil that times, judging from the results of Table 13, and the re-
is 3.0 % breaker A, 1.5 % adsorbent B, and 9 % coagu- used water will promote the effect of washing oil as
lant C. The curing solid and leaching solution are well. This enhancement may be because the reused
shown in Fig. 1. water also contains a certain amount of oil cleaner, the
3. 4. 5. Contaminant Analysis of the Cured Sludge’s concentration of which is higher than in fresh water.
Leaching Agent Moreover, the oil of the reused water may also be re-
The remaining products of the harmless-treatment cycled back for reuse.
sludge samples were put into a beaker containing dis- 3. 5. 2. Discharge Treatment of Wastewater
tilled water (sample : distilled water＝1 : 10 wt%) for 7 There will be a large amount of oily wastewater after
days, during the color of the leachate, oil, suspended washing the oil of the waste oil-based drilling fluids.
solids, heavy metal, oil, COD and pH were observed to Some of the wastewater can be reused, while the rest
determine whether the sample had broken into syrup. still requires efflux. The testing results of the waste-
The concentration of pollutants in the leachate was then
analyzed; the results are shown in Table 12. COD,
pH, Pb and other major pollutants in monitoring project
after curing are below the GB8978-1996 National
Wastewater Discharge Standard30) Grade II limits.
3. 5. R e u s e a n d D i s c h a rg e Tre a t m e n t o f t h e
Wastewater
3. 5. 1. Reuse of Wastewater
Large amounts of wastewater will be produced after
waste oil-based drilling fluids are washed with oil.
The wastewater contains oil, suspended solids and other
pollutants. The method of direct emissions will pol-
lute the environment and waste valuable water resources.
Reusing the wastewater will reduce water consumption
and the production of wastewater, which is a feasible
option. The reuse of generated water is tested by a
laboratory experiment. The wastewater is used to Fig. 1 Leaching Solution and Curing Agent

Table 11 Effect of the Amount of Coagulant C on the Hardness of Treated Sludge

Dosage [%]
Time
3 5 7 9 11 13 15
5h 0 0 0 I I I I
10 h 0 0 0 II II III III
15 h 0 0 I II III III III
24 h 0 0 I II III IV IV
3 days 0 0 II III IV IV IV
5 days 0 I II III IV IV IV
7 days I II II III IV IV IV

Table 12 Properties and Components of the Cured Sludge’s Leachate

Leaching agent of
Cu [mg/L] Pb [mg/L] As [mg/L] Hg [mg/L] Cd [mg/L] Petroleum [mg/L] COD [mg/L] pH
treated sludge
No. 1 0.45 0.20 0.03 0.0007 not detected 2.945 84.2 8.92
No. 2 0.41 0.15 0.05 0.0004 not detected 3.490 87.7 8.88
No. 1 0.43 0.13 0.06 0.0004 not detected 3.563 91.2 8.80
Sewage discharge 0.5 1.0 0.5 0.05 0.1 10 150 6-9
(II) standard
GB8978-1996

J. Jpn. Petrol. Inst., Vol. 56, No. 4, 2013


water requiring efflux show that petroleum, suspended
solids and other pollutants cannot reach the standards,
so the wastewater needs to be further processed. The
wastewater that is generated by washing oil was pro-
cessed by the “coagulation ＋ filtration” method in lab-
oratory. The treated-water-quality analysis results are
shown in Table 14. The wastewater can reach com-
prehensive wastewater-discharge standards after coagu-
lation and filtration, based on the results of Table 14.
4. Mechanism of the Treatment Agent
4. 1. Mechanism of the Oil Recovering Agent of
Waste Oil-based Drilling Fluids
The waste oil-based drilling fluids can be divided
into “water in oil” and “oil in water” types of oil-based
drilling fluids. “oil in water” is main type of drilling
fluids on-site. When used in the field, some organic
and inorganic stabilizers, such as the oxidation of
asphalt, sulfonated asphalt, clay and other substances, are
added into the “oil in water” oil-based drilling fluids to
improve stability, filtration and other properties of the
system. Some drilling cuttings and formation clay are
mixed with drilling fluids system in the drilling process.
Therefore, the waste oil-based drilling fluid system is a
complex emulsion system. Thus, the oil collection
system of the waste oil-based drilling fluids must weaken
the stability factor; reduce the emulsifier, stabilizer, and
solid particles in the oil_water interfacial adsorption;
compress the interfacial double layer; and weaken the
interfacial film strength. When the system emulsion
ultimately breaks, the dispersed oil droplets will form
large oil beads to separate.
The components of oil recovery system contain one
type of compound demulsifier (containing two types of
demulsifiers and a strongly hydrophilic surface-active
agent component), one type of high-salt electrolyte cat-
ion and one type of polymer. The surfactants will
Table 13 Effects of Reusing Wastewater after Washing Oil
The number of The volume of The rate of
reusing wastewater recovered oil [mL] recovered oil [%]
1 3.1 93.9
2 3.1 93.9
3 3.2 97.0
Table 14 Quality of the Treated Water after Recovering Oil
Pollutants Emission standard [mg/L]a)
pH
Petroleum
Suspended material
COD
BOD5
Chromaticity
a) Adapted from“Comprehensive discharge standard”(GB 8978-1996).
J. Jpn. Petrol. Inst., Vol. 56,
227
react with emulsifiers (cationic surfactant) to form an
unstable adsorbed film (with a branching structure of
the anionic surfactant), offset (oil-soluble surface active
agent) and other mechanisms to demulsify. The elec-
trolyte will mainly compress the double layer, reducing
the surface negative charge of the oil droplet and chang-
ing the hydrophilic-lyophilic balance of the emulsifier.
The polymer mechanism is mainly to promote coales-
cent droplet collisions by a bridge mechanism to de-
mulsify.
After adding the oil-collection system into the waste
oil-based drilling fluids, the demulsifier composition re-
duces the adsorption of emulsifier in the oil_water inter-
face. The hydrophilic surfactant can encourage the
hydrophilic solid particles to leave the oil_water inter-
face for the aqueous phase. The highly charged salts
can strengthen demulsification and promote droplet col-
lision to coalesce. The synergy of several factors un-
dermines the waste oil-based drilling fluids’ emulsion
stability, causing it to demulsify eventually to conden-
sate oil.
4. 2. M e c h a n i s m o f t h e S l u d g e ’ s H a r m l e s s -
treatment Agent
First, the gel breaker will break the stable suspended-
state system to create conditions for adsorbent to adsorb
the heavy metals in the sludge. The coagulant will fix
or seal the harmful substances in the sludge, such as oil
and organic compounds, into an inert solid substrate,
accomplishing stabilization and solidification processes.
The stabilization process refers to inserting the harmful
ingredients in sludge into the lattice by chemical changes
or other methods. The solidification process is the
binding of the harmful ingredients of sludge. The mi-
croscopic structure of waste oil-based drilling fluids is
analyzed before and after treatment using an environ-
mental scanning electron microscope, and the results
are shown in Figs. 2 and 3.
As shown in the Figs. 2 and 3, free water is present
before the treatment of residual sludge, and the oil is
mixed with solid particles in the sludge that do not form
a packaged structure. If the pollutants are immersed
by rain, they will overflow and pollute the surrounding
environment. The sludge particles form a large inclu-
sion matrix after adding the harmless treatment agent;
the particles are tight, and free water and oil are absent,
showing that the treatment agent has sealed the pollut-
Measured value [mg/L]
6-9 6.5
10 7.2
150 104.7
150 127.3
30 20.4
80 60
No. 4, 2013
 228
Fig. 2 Remaining Sludge before the Harmless Treatment
Fig. 3 Remaining Sludge after the Harmless Treatment
ants in the sludge.
5. Field Applications
To date, this technique has been used for more than
30 wells. The application results lead to the following
conclusions:
(1) The effect of oil recovery technology is excellent.
The average rate of oil recovery is 86.1 %, the moisture
content and sand content are both less than 0.1 %, and
the main physical and chemical indicators of recovered
oil meet diesel-fuel standards.
(2) The SDPR-6 oil recovery system and oil recycling
apparatus of waste oil-based drilling fluids are easy to
use and effective.
(3) The sludge generated from the oil washing is harm-
less. The contents of petroleum, heavy metals, COD
and other contaminants of the leaching liquid are below
J. Jpn. Petrol. Inst., Vol. 56,
Fig. 4 Well-site Conditions before Treatment
Fig. 5 Well-site Conditions after Treatment
the GB8978-1996 National Wastewater Discharge
Standard Grade II limits.
(4) The residual sludge has been used to construct the
well-site cofferdam and the roads of well site after treat-
ment because of their strength, which will save 240 mil-
lion cofferdams annually. Meanwhile, the original
land for the storage of waste oil-based drilling fluids
can also be reused, which is a good solution to the in-
situ environmental disposal problem of the waste oil-
based drilling fluids.
The conditions of the well site for waste oil-based
drilling fluids before and after the treatment in a well
are shown in Figs. 4 and 5, respectively.
6. Conclusions
(1) A novel formula of oil recovering agent was devel-
oped. The composition formula of oil recovering
agent is as follows: 30 % of demulsifier compound
SDPR-6 (15 % demulsifier AE136 ＋ 15 % demulsifier
AP113), 1.5 % of coagulant (high charged salts, such as
CaCl2, AlCl3), and 2 % of flocculant PAM (concentra-
tion is 0.1 %).
(2) The sludge-treatment processing formula of the
No. 4, 2013

waste oil-based drilling fluids were determined using
indoor studies and comprehensive technical indicators
after the resumption of oil that is 3.0 % breaker A,
1.5 % adsorbent B, and 9 % coagulant C.
(3) The rate of recovery is greater than 90 %, and the
quality of the recycled oil is very good and meets the
requirement of −10 # diesel of cars in GB/T 19147-
2003. The concentrations of oil, COD and heavy
metals in liquid of the processed mud are lower than the
secondary standard number in GB8978-1996.
Acknowledgment
The authors are grateful for the Project Support by
NNSF of China (No. 51204195, No. 51234006).
References
1) Kirkeby, J. T., Birgisdottir, H., Hansen, T. L., Christensen, T.,
Bhander, G. S., Hauschild, M., Waste Manage. Res., 24, 3
(2006).
2) Meng, M., Yan, G. X., Guo, S. H., Drilling Flu. Compl. Flu., 1,
57 (2008).
3) Melchor, A. E., Costa, A. D., SPE Drilling & Completion, 17,
164 (2002).
4) Albert, D. V., Makram, T. S., Brian, A. W., Kevin, L., Environ.
Sci. Technol., 30, 1764 (1996).
5) Bleckmann, C. A., Oxley, M. E., Wilson E. J., Hayes, K. W.,
Hercyk, N. L., Waste Manage. Res., 15, 223 (1997).
6) Claude, H. C., Jean, L. M., Jean, O., Sci. Technol., 6, 1615
(1995).
7) Egodaha, G. W., Benedict, Sohei, S., Tomoto, I., Waste
Manage. Res., 27, 456 (2009).
8) Haggerty, G. M., Robert, S. B., Environ. Sci. Technol., 3, 452
(1994).
J. Jpn. Petrol. Inst., Vol. 56,
229
9) Irene, M. C., Keith, C. K., Chen, G. H., Environ. Sci. Technol.,
23, 4691 (2001).
10) McQuaid-Cook, J., Simons, C. S., Waste Manage. Res., 7, 219
(1989).
11) Minton, R., Meader, A., Wilson, S. M., World Oil, 10, 47
(1992).
12) Hou, B., Xie, S. X., Chen, M., Liang, C., Deng, H., Wang, R. S.,
Liu, G. Q., J. Residuals Sci. & Tech., 9, 95 (2012).
13) Faur-Brasquet, L. C., Cloirec, P. L., Environ. Sci. Technol., 11,
4249 (2005).
14) Hou, B., Xie, S. X., Deng, H., Chen, M., Wang, R. S., J.
Residuals Sci. & Tech., 9, 143 (2012).
15) Xu, G. R., Zou, J. L., Li, G. B., Environ. Sci. Technol., 19, 417
(2008).
16) Hou, B., Xie, S. X., Chen, M., Jin, Y., Deng, H., Wang, R. S.,
Petrol. Sci. and Tech., 31, 458 (2013).
17) Tuncan, A., Tuncan, M., Koyuncu, H., Waste Manage. Res.,
18, 489 (2000).
18) Adams, J. E., Masias, H., Huang, S. Y., US Pat. 7338608, B2
(2008).
19) Browne, N., Ivan, C., Markanovic, Z., PCT International Pat.
068968, A3 (2006).
20) Farinato, R. S., Kemira, H. M., Garcia, D., Bingham, R., Antle,
G., SPE paper, No.13238, (2009).
21) Ivan, C., Browne, N., US Pat. application 225925, A1 (2006).
22) Pena, J. E., Masias, H., Huang, S. Y, US Pat. 7381332, B2
(2008).
23) GB/T5084.3-2007, China Environmental Science Press,
(2007).
24) GB/T7475-1987, China Standards Press, (1987).
25) GB/T 16488-1996, China Standards Press, (1987).
26) HJ/T399-2007, China Environmental Science Press, (2007).
27) GB11903-1989, China Standards Press, (1989).
28) GB/T 6920-86, China Standards Press, (1986).
29) GB 4284-1984, China Standards Press, (1984).
30) GB8978-1996, China Environmental Science Press, (1996).
No. 4, 2013