MADMACKENZIE SOLUTIONS

Performance as PrescribedTechnical Product Presentation: GreenZyme

Everyone wants to get the most from their oil wells

But who is actually doing something about it?We Are.MADMACKENZIE

SOLUTIONS

MadMackenzie Solutions

A Texas born company located in Houston, the MadMackenzie team is a small and

effective group of experienced oil and gas professionals. Our team is comprised of

backgrounds in the fields of reservoir engineering, geoscience engineering,

project management and business management.

We believe when good people come together to provide a good solution, great

things happen! We treat our clients like they were

neighbors and we follow through with what we say we can do.

~ Performance as Prescribed

MadMackenzie Solutions is a proud provider and

authorized Agent of GreenZyme®

GreenZyme®

GreenZyme was invented by Dr. Philip Lau. Dr. Lau obtained his PhD in Chemical Engineering from Texas A&M University. Dr. Lau’s first job was with Dow Chemical where he invented 6 products during his eight years as Research Group Leader. In 1986 Apollo Engineering

Company was formed in Houston, Texas by Dr. Lau. The company later changed its name to

Apollo Separation Technologies USA.Originally used to clean-up oily-sludge tanks and toxic sites, GreenZyme later found its

way into major oilfields in 1990 as an effective EEOR (enzyme enhanced oil

recovery) method.Today, the EEOR process is a worldwide

practice where the GreenZyme product is leading the way as the premiere enzyme EOR solution. As a biological solution that is 100% biodegradable, GreenZyme has been injected

into over one thousand wells for various clients including major operators all over the world for successful enhanced oil recovery.

GreenZyme is an environmentally friendly EOR solution. Product is proudly manufactured in USA.

To meet rising demand for crude oil consumption in the coming decades, most major energy companies are putting their research efforts in newer and better technologies in all kinds of enhanced oil recovery projects.There are three main branches of EOR technologies, solutions based on chemistry, physics and biology. All three branches are coming to a new age of development, with various degrees of success in oilfield applications.DNA based bio-enzymes, acting as a pure catalyst in E-EOR (Enzyme Enhanced Oil Recovery) has had a great deal of historical success. GreenZyme®, being the first bio-enzyme extensively applied to major oilfields since 1990s, is the clear outlier having significant enhancement achievements.E-EOR with GreenZyme is approached from theoretical basis, an analytical basis, and from an applications perspective to find strong candidates for EOR success with MadMackenzie Solutions. The following slides show how GreenZyme is manufactured as a biological solution for oil field enhanced recovery, and how this solution becomes such a catalytic success in reservoirs during the EOR process.

For more information please contact MadMackenzie Solutions at: info@madmackenzie.com

Abstract

EOR will be key to satisfy demand for world oil consumption.

The future of World Oil

Chemistry

• ASP, polymers• Hot oils• Acid and caustic• Fracturing

Biology• Microbes – Living• Enzymes – Non-

living

Physics

• Water-flooding• Steam -injection• Microwave• Radio Frequency

EOR

COMING TOGETHER IS A BEGINNING; KEEPING TOGETHER

IS PROGRESS; WORKING TOGETHER IS UCCESS.

Dr. Partha Pratim

Methods Biology Non-Living Biology Living Chemistry Physics

Process Used Enzyme Microbe

Acid, alkaline, hot oils, organic,

inorganic, polymers,

surfactants…

Steam injection, waterflooding, hi-

temp, CO₂, N₂, ultra sound, and microwave

Real Catalyst Yes Yes No No

Real DNA Molecules Yes Yes No No

Environmentally Friendly Yes Mostly Yes No Mostly Yes

Use of Simple Pumping Yes No No No

Duration EOR Lasts 18-36+ months 3-4 months 3-6 months 3-6 months

Volume of Oil Increase High Small Average Average

How to choose the best available EOR technologies?

OIL OIL OIL OIL OIL OIL

H2O

FIRE CLEAN

Common Methods for Oil Well Stimulation

WaterFlooding

Chemical Injection

Live Microbes

Fracturing(Hi Pressure)

Combustion(Hi Temperature)

Apollo GreenZyme®

Produced water. Polymers; Acids; Caustics; Chemical

Surfactants; Injectionof: Steam, CO2, N2,Ch4, etc. --- GASP.

Live Microbes. Fracturing Chemicals. Mixtures of :Oxygen, fuels,

Ignition dynamicsfor combustion.

Biological Enzymes.

ESSAY

Cheap.

Simple process.

Very popular.

Most oilfield uses it.

Gaining Popularity.

Life livingenvironment

required.

Very high temperatures.

Also known as:Clean-burn-white-

-sand process.

Simple, safeProcess; high 90+%

Success rate.

Significant increaseIn oil production.

EnvironmentallyFriendly.

PRO

Little effect &capability to “release oil”.

Corrosive; need Effective-radius;Weakens itself

instantly; short lifespan & effect.

High failure rate.Works slowly.

Low oil productionImprovement.

High cost; complextechnology needed.

High risk, permanentformation damage.

Complex process.Very high cost.Hard to operate.

May damageformation.

Proprietaryprocess.

CON

Popular in EOR.

If success, canproduce quite

significant increasein oil production.

G ࢤ ሺܔܖ

Gሻ

Effectiveness comparison of EOR technologies

Darcy’s Law:Where = Oil volume rate of flow; = Permeability of porous medium.

= Length of cylindrical shell section; = Viscosity of oil.

= Radius of a point inside pay zone; r = Tubing radius of oil well;

ࢤ = Pressure difference between R and perforation.

EOR Methods Parameters improved Effectiveness

Water-flooding drive Increase ࢤ Very limited

Chemical drive – surfactants Decrease Very modest

Chemical drive – polymers Decrease , increase and Modest

Chemical drive – CO , CH , N etc. Decrease Modest

Chemical drive - fracturing Increase and Good

Steam-huff-and-puff cycle Decrease Modest

Combustion – high temperature drive Increase ࢤ decrease , Good

Biological – live microbes Decrease Very modest

Biological – Apollo GreenZyme® Increase ࢤ , , (restored) The Best

How is GreenZyme made Biologically?

Requires 2-step process

Protein Donor

Protein Acceptor

Site “A”

P DNAC

AT

TCGT

AG

TAC

Amino Acid Groups:

A: AdenineT: ThymineG: Guanin

C: Cytosine

Step 1: Create water-soluble protein

Living Protein with DNA

Site “B” CA

TTCGT

AG

TAC

Amino Acid Groups:

A: AdenineT: ThymineG: Guanin

C: Cytosine

M DNA

Step 2: Identify natural oil-eating microbes,

create DNA transfer

B

OH-

H+

A

Non-Living Livin

g

(i.e. P DNA M DNA)

Site “A” DNA becomesSite “B” DNA and

Vice Versa

DNA transfer between man-made proteins and

natural oil-eating microbes takes place

GreenZyme (Non-

Living)

Inert Protein (Living)

This is Active Site!

Note: Only GreenZyme molecules

are involved in EEORFinal Products

Oil releasing process with GreenZyme catalyst

Solid Solid

Crude Oil

H+

OH-From a solid covered in crude, to catalytic oil released surface, to finally a protected GreenZyme-

wetted surface.

Solid

FEATURES REMARKSAppearance Clear amber color liquid, 100% water soluble.

Odor Fermentation odor.pH 3.5-5.0 concentrate; diluted form: 6.5-7.0.

Composition: Microbes GreenZyme®

Living, inert; about 500,000 counts /ml.Non-living, active; about 1.73 g/L.

Tolerance: Formation pH Not affected, pH 1-14, see Petrobras report.

Tolerance: Temperature Tested @270 C; good >425 C steam-huff-and-puff cycles, see CNPC report.

Tolerance: Salinity Total Wax

Any.> 50% paraffin, asphaltene, wax, H2S etc.

Tolerance: All Metallic Ions Not affected in any concentration.

Tolerance: NORM Not affected.Environmental Studies Non-toxic; pass EU tests; see OECD reports.

GreenZyme Features

Why & How GreenZyme is so successful in oil fields

Core Unclogging

Tests

Contact Angle

Oil Releasing Tests

Interfacial Tension

(IFT)

GreenZyme

Concentration %

Interfacial Tension

(IFT) (mN / m)

0% 19.36

2% 2.39

4% 1.49

5% 0.01

6% 0.1

8% 0.11

10% 3.95

Effect of GreenZyme on interfacial tension of crude

oil in reservoir

Composition of Sample Oil

Density: 0.93Viscosity: 1130 – 4350 mPa.sWax: 1.5 – 2%Asphalt: < 2%Resin: 36-38%Freezing: 15-21°C

Oil-releasing capability tests & results using GreenZyme

Time (Hours) 0.3 0.5 1.0 3 5 10 24 48 72

% Oil Recovered by

salt water0.3% 0.7% 0.9% 1.5% 1.8% 2.3% 2.8% 3.0 5.1%

% Oil Recovery by

10% GreenZyme

8.5%

12.4%

16.6%

23.5%

28.6%

33.5%

46.8%

48.6%

49.1%

Procedure:

1.) Place 1.5Kg quartz sand in baking oven for 2 hours at 120°C, then put sand sample in desiccator chamber for later use at ambient temperature.

2.) Take 1Kg of the quartz sand, and mix well with 125g of crude oil. Bake in oven at 85°C for 24 hours. Then cool sample.

3.) Oil releasing capability tests: Take 5g of the baked sample and place inside the WAOR Instrument. Then add the required % GreenZyme mixed solution.

4.) Place everything inside a constant room-temperature box for observation.

5.) Take timely-measured readings of oil being released from the baked sample.

OIL OIL OIL

Contact Angle (i.e. θ) of Oil Droplet on Sandy Surface in Water Phase

Sandy surface Sandy surface Sandy surface Sandy surface

۶ O – Phase Equilibrium

θ

Contact angle = Contact angle < �ૢ Contact angle = �ૢ Contact angle > �ૢ Perfectly water-wetted Highly water-wetted Neutrally wetted Highly oil-wettedFrom Young’s equation of capillarity:

ܚܗ�ૢ ܚܟ�ૢ = ܗܟ�ૢ + cos θ eq. (1)

Work of adhesion or de-adhesion: W

ܟ܅ ܚܗ�ૢ = ܗܟ�ૢ + - Gܚܟ eq. (2)

ܟ܅ ܗܟ�ૢ = ( 1 + cos θ ) eq. (3)

For oil-phase, contact angle = ૡ - θ

ܗ܅ ܗܟ�ૢ = ( 1 + cos (ૡ െ�θ ))

ܗ܅ ܗܟ�ૢ = ( 1 – cos θ ) eq. (5)

Where ૢ� G = IFT between oil & water (mN/ m)r = radius of capillary tube (m).θ = contact angle (degree). o = oil phase; w = water phase.

۽����܅ ܟ܅ & = work of adhesion (Ɋ ܕ )

GreenZyme® in formation changes:

a) Weakly oil-wetted surface to strongly GZ-water-wettedsurface in a short period of time, with surface protection.

b) Weakly water-wetted surface instantly to stronglyGZ-water-wetted surface, with surface protection.

c) Increase relative permeability of oil-phase for faster flow.

d) Decrease relative permeability of water-phase.

e) For water-wetted formation, GreenZyme® can increase thedriving force, i.e. ΔP From Darcy’s law - Inhibition Process.

f) For oil-wetted formation, GreenZyme® can improve theresistance force of oil movement - Drainage Process.

Contact angle of oil droplet on solid surface

Time( Minutes ) 0 3 5 7 10

Salt water( Degree )

10% GreenZyme® ( Degree )

GreenZyme®

( % ) 0% 5% 10% 20% 30%

Contact angle

( Degree )125% 56% 42% 35% 32%Effect of different % GreenZyme on contact angle changes recorded in 10

minutes.

Effect of 10% GreenZyme on contact angle changes at sandy surfaces.

Type of coreCore

diameter(CM)

Initial water penetration

rate

Initial water pumping pressure

(MPa)

Initial oil penetration rate

Pumping pressure after 10%

GreenZyme®(MPa)

Oil penetration rate after

10% GreenZyme

®Natural sand

Low permeability 7.85 8.6 2.86 2.1 1.12 6.052

Quartz sandHigh

permeability 13.55 85.04 2.35 18 1.45 55.6

Core unclogging experiments & results using GreenZyme

Raw material: Natural sand (NS) with low permeability. Quartz sand (QS) with high permeability. Crude oil: Gudong oil, Shengli Oilfield, ~18 API. Oil-contaminated water (OCW), i.e. water + 10% oil.

Procedures:1.) Core sample go through complete vacuum, then let saturated with water soak. Measure water penetration rate, and pumping pressure required to pump through core sample.

2.) Force pumping OCW through the core: NS core: 0.3 ml/min pumping rate to create uniform primary cross-sectional clogging. QS core: same with 1.0 ml/min rate for primary clogging, also allow free migration of solids to create secondary clogging.

3.) Pump 1 core-volume of 10% GreenZyme® into core sample for all tests.

4.) Rest all tested materials at constant room temperature for 48-hours.

5) Pump salt water at 0.3 ml/min rate through core, and record pressure changes needed for pumping.

Simulation experiments to show how GreenZyme® is effective to remove formation blockage problems in an oilfield (to be continued)

Goal: To lower temperature to accelerate deposition of resin and asphaltene in a core to simulate formation-blockage.

Procedure:

1) Use Darcy’s law, Q = �ૢ ሺઢܐ۹ ሻ۾��ஜܔܖ ሺ

܀ܚ ሻ

Measure ۹ , the steady state core permeability to brine-water.

2) Using lower temperature method to block the core with resin and asphaltene.

3) Measure ۹ , the core permeability to brine-waterbefore plug removal.

4) Use GreenZyme® between 2% to 14%, each time inject 2-core volumes of GreenZyme® to coresample, and let it soaked for 24-hours time.

5) Measure ۹ , the core permeability to brine-waterafter plug removal.

Calculations: from the core

a) Extent of Blockaded Permeability (i.e. BP)

BP = ۹ ۹ î 100%

b) Formation Damage (i.e. FD)

FD = ۹ ି� ۹

۹ î 100%

c) Extent of Unclogged Permeability (i.e. UP)

UP = ۹ ۹ î 100%

d) Efficiency of GreenZyme® in plug removal ( i.e. ۳۵ ܈ ሻ

۳۵ ܈ = ۹ ି� ۹

۹ î 100%

۳۵ ܈ = UP – BP

DataPoint

GZ

%

BP

%

FD

%

UP

%1 0.360 0.0697 0.0382 10% 19.36% 80.64% 10.61% -8.75%2 0.474 0.0656 0.0398 10% 13.84% 86.16% 8.40% -5.44%3 0.907 0.0034 0.0134 10% 0.37% 99.63% 1.47% 1.10%4 1.370 0.0138 0.355 10% 1.01% 98.99% 25.91% 24.90%5 1.635 0.0312 0.194 10% 1.91% 98.09% 11.87% 9.96%6 2.307 0.950 1.701 8% 41.18% 58.82% 73.73% 32.55%7 2.503 0.860 1.388 2% 34.36% 65.64% 55.45% 21.09%8 2.872 0.921 1.714 10% 32.07% 67.93% 59.68% 27.61%9 2.912 0.930 1.657 13% 31.93% 68.06% 56.93% 25.00%10 2.958 1.394 2.234 6% 47.13% 52.87% 75.52% 28.39%11 3.100 1.101 1.786 14% 35.51% 64.48% 57.63% 22.12%12 3.224 1.608 2.380 4% 49.88% 50.12% 73.82% 23.94%

Results of simulation below shows how GreenZyme is effective to remove formation blockage problems

Heavy oil in GreenZyme

Heavy oil in brine water

Crude oil with suspended solids in high wax, paraffin, &

asphaltene sample

GreenZyme molecules working inside pores of oil

reservoir

How GreenZyme E-EOR works to release crude oil in formation

1) Oil-wetted sandy surface to GreenZyme®-water-wetted surface, with surface protection.2) Water-wetted surface to GreenZyme®-water-wetted surface, with surface protection.3) GreenZyme® releases oil from sandy surface catalytically.4) GreenZyme® unclog any formation-blockages.5) GreenZyme® increases permeability, restore formation pressure due to blockages.

1 2 3 4 5

Oil released by GreenZyme

E-EOR with GreenZyme® Chemicals

1) Non-consumable. No need to calculate Consumable. Need to calculate effective radius; a real catalyst. effective radius; not a catalyst at all.

2) EOR lasts longer, mostly anywhere from EOR lasts shorter, mostly anywhere 18 months to over 3 years. From 3 months to 6 months.

3) Molecule with DNA. No chemical reaction No DNA. Strong chemical reactions with crude oil. with crude oil.

4) Produced biologically. Produced chemically.

5) 100% water diffusible. May or may not.

6) High EOR success rate. Average 90+%. Average EOR success rate is 50%. Total volume of crude oil increase is huge. Total volume of crude oil increase is low.

7) More friendly to environment. Relatively speaking, more toxic.

GreenZyme E-EOR versus Chemicals

Enzyme (Apollo GreenZyme®) Microbes

1) EOR lasts longer, mostly anywhere from EOR lasts shorter, mostly anywhere from 18 months to over 3 years. 3 months to 6 months. 2) Non-living protein molecules with DNA. Living protein molecules with DNA. 3) A catalyst, no need for core sample tests. Not a catalyst, need core sample test.

4) Formation temperature >270° C applications. Formation temperature < 80° C only.

5) Easier to mass produce with human controls. Not easily controlled by human factors.

6) 100% water diffusible. Mostly not. 7) Higher EOR success rate. Average 90+%. Lower EOR success rate. Average 50%. Volume of crude oil increase is huge. Volume of crude oil increase is modest.

8) Environmentally friendly. Relatively speaking more toxic.

GreenZyme E-EOR versus Microbes

GreenZyme is immune?

You do not need to worry about the following conditions: pH of fluid in sand formation. Salinity of fluid in sand formation. Temperature in sand formation. In laboratory tests, GreenZyme® does

not degrade under pressure up to 270 degrees C. Presence of any metallic ions in sand formation; since GreenZyme® is

a biological agent, not a chemical agent, GreenZyme® does not react with most natural chemicals present inside typical sand formations.

Presence of paraffins, naphthalene, asphaltenes or sulfur at any percentage content.

Any radio-active isotopes (i.e. NORM) in the crude oil.

Target oilfield applications for GreenZyme

Both vertical and horizontal wellsSingle well booster applicationMultiple wells flooding applicationsSandstone formation: GreenZyme®

onlyCarbonate formation: GreenZyme®

plus acidOil wells treated by polymers,

fracturing chemicals, cycling steamOffshore oil wells: sameNewly drilled oil wellsNewly repaired oil wells

Required equipment for GreenZyme applications

Oil field service pumping truck able up to 5000 psigHigh pressure piston pump, orHigh pressure plunger pump, orHigh pressure triplex pump

Onsite mixing tanks.

Pump GreenZyme® down casing-side or central tubing to formations.

Shut-in time after GreenZyme applications

Shut-in Time Oil Well Conditions

3 days Oil density < 0.85; porosity >20%, little wax

4 - 5 daysOil density < 0.95; porosity >20%, little wax

6 - 7 daysOil density < 1.0; porosity >15%, little wax

7 – 8 daysOil density < 1.0; porosity >10%, some wax

9 days Every condition is BAD! Heavy wax problem

Quantity of GreenZyme used in an oil well

Vertical oil well

< 10 meter 4 – 5 drums

10 – 20 meter 6 – 8 drums

20 – 30 meter 8 – 10 drums

> 30 meter 4 – 5 drums

Horizontal oil well

< 500 meters 8 – 10 drums

> 500 meters 10 – 12 drums

Offshore oil well

< 1,000 meters 14 – 16 drums

> 1,000 meters 18 – 20 drums

Note: For water-flooding drive oil wells, use your regular quantity of produced water with 250 – 750 ppm strength GreenZyme® as slug-application.

Problem oil wells? GreenZyme can help

Water-cut > 90+% Use water-blocking chemicals, then GreenZyme®.

Sand leaking problems. Use sand control screen & chemicals, then GreenZyme®.

Limestone formation, low porosity. Use 1-2% HCl before or after GreenZyme®.

Fracturing job. Use GreenZyme® before fracturing chemicals job.

Repeated chemical-polymer wells. Use GreenZyme® alone for EOR & formation detoxification.

Repeated acid or caustic jobs. Use GreenZyme® alone for EOR & formation detoxification.

Heavy oil, steam huff-and-puff job. Use GreenZyme® before steam application process.

Extensive water-flooding wells. Use GreenZyme® in water-flooding EOR, reduce energy use.

Can GreenZyme help your well?Contact MadMackenzie Solutions to find out!

info@madmackenzie.com

Thank you for your time.