2012 Cairn India Limited

IMPORTANCE OF CHEMICAL TREATMENT

-- Mayur Dhole 23 Feb., 2013

Why chemical treatment is important?

Sustain, Maintain & Increase Production (10-3-4: $$$) Asset Integrity Maintain Crude & Water quality Reduce Equipment downtime and Maintenance OPEX & CAPEX HSE & Logistics

Treatment Cost
Expected chemical treatment cost: $ 40 Million/year Actual chemical treatment Cost: $ 6 Million/year Operating cost of oil: $ 3 per BBL Operating cost of oil with Chemicals: 10 cent/bbl Which is 3.3%of the total operating cost of oil

The most common types of problems in Oil & Gas Production with chemical used to solve
Problem
Forward emulsions Reverse emulsions Scaling Corrosion Bacterial Growth Foaming Filter-Aid Dissolved oxygen

Chemical Treatment
Demulsifier Reverse emulsion breakers Scale Inhibitor Corrosion Inhibitor Biocide Anti-foam Coagulants, Flocculants Oxygen scavenger

Reverse emulsions Forward emulsions

Continuous phase being the water

continuous phase being the oil Dispersed phase being the water

Oil droplets are suspended

Causes: 1. Heavy polar material in the crude oil (asphaltenes, resins, waxes, etc), 2. Solids (clays, scales, corrosion products, etc), 3. pH, oil and brine composition. 4. The pressure gradient or velocity gradient 5. Mixing or agitation

Several methods are used to break these emulsions: 1. Time 2. Heat- reduces viscosity 3. Chemical- Changes the surface tension at interface, allowing water to break free 4. Electric current in congestion with Heat & chemical-Disrupts the polarity of emulsifying agent causing them to rearrange & break the wall of film

Demulsifier
Used to Dehydrate & desalt the oil Demulsifier has hydrophobic & hydrophilic properties which unable to penetrate the oil & water film. Works
Dispersed phase being the water

Water Droplets

Continuous phase being the oil

Reverse demulsifier
Used to Clear & clean the water Works
Continuous phase being the water Coagulation Oil Globe

Flocculation

Coalescence

suspended phase being the oil

Difference: Demulsifier: Forms water droplet & settle out Reverse demulsifier: forms oil globe & rise to from layer on the top Product Selection: Demulsifier: Bottle-test is typically used. Reverse demulsifier: Bottle-test & wemco test is typically used.

Scale & Corrosion

Causes: Primary factors 1. Incompatible water 2. Alkalinity 3. Hardness 4. pH Other factors 1. Oxidizing agents 2. Carbon dioxide 3. Dissolved solids

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Scale Inhibitor
Scale deposits in surface equipment can increase operating pressures and reduce efficiency Type of scales: calcium carbonate, calcium phosphate, and magnesium silicate - precipitates out at higher temperature & low pressure. calcium sulfate (gypsum), strontium sulfate, and barium sulfate - precipitates out at lower temperatures & high pressure. Type of chemical compounds (SI) used: Phosphate esters, phosphonates, and acid polymers Treatment: Either in squeeze treatments into the producing formation or by continuous injection.

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Brine Chemistry Used for Scale Predictions

THUMBLI WATER SAMPLE ANALYSIS Measured Value Parameter Units 6.6 Total Suspended Solids Total Dissolved Solids Specific Gravity at 15 C pH at 20 C Components Cations Sodium Potassium Calcium Magnesium Barium Strontium Total Iron Dissolved Iron Anions Chloride Sulphate Bicarbonate Carbonate Carbon dioxide( aq) mg/l mg/l mg/l mg/l mg/l 2377.4 415 114.9 23.18 <0.1 mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l 1460 9.09 275 125 0.12 5.38 0.53 0.1 Anions Chloride Sulphate Bicarbonate Carbonate Carbon dioxide( aq) mg/l mg/l mg/l mg/l mg/l 5830.6 4 534.8 <2 95.9 7.76 mg/l mg/l 8480 1.00 Specific Gravity at 15 C pH at 20 C Components Cations Sodium Potassium Calcium Magnesium Barium Strontium Total Iron Dissolved Iron mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l 2494 151.05 514 136 78.35 7.33 11.93 0.3 6.8 Total Suspended Solids Total Dissolved Solids mg/l mg/l 12085 0.995 FORMATION WATER SAMPLE ANALYSIS Measured Value Parameter Units 169

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Calcium carbonate scale forming mechanism

Carbon dioxide reacts with water to produce carbonic acid CO2 (g) + H2O(l ) H2CO3 (aq) (carbonic acid ) Carbonic acid will continue to dissociate hydrogen, creating new deprotonated species of carbonic acid H2CO3 (aq) + H2O(l) H3O+ (aq) + HCO3 (aq) HCO3 (aq) + H2O(l) H3O+ (aq) + CO2 3 (aq)

In the water mixture there will be a mixture of the species H2CO3, HCO3 and CO2 3 . CO2 3 (aq) + Ca2+ (aq) CaCO3 (s)

CaCO3 (s)

E-415 A (Water injection heaters)

Cross section of scaled tube

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CaCO3 Mass on Mixing of Waters

Calcium carbonate maximum mass for mixing Mangala and Thumbli waters 700

600

Current Ratio of Mangala & Thumbli Waters

65C, 1500psi 70C, 1800psi 85C, 1800psi 70C, 5bar 85C, 5bar

500

Scaling Tendency

400

Mg /l of CaCO3

300

90C, 1bar 90C, 5bar 120C, 5bar

200

100

0 100% Mangala 90% Mangala 80% Mangala 60% Mangala 50% Mangala 40% Mangala 20% Mangala 0% Mangala

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BaSO4 Mass on Mixing of Waters

Barium sulphate maximum mass for mixing Mangala and Thumbli waters 40

35

30

Current Ratio of Mangala & Thumbli Waters

65C, 1500psi 70C, 1800psi 85C, 1800psi 70C, 5bar 85C, 5bar

Maximum Mass (mg/l)

25

20

15

10

0 100% Mangala 90% Mangala 80% Mangala 60% Mangala 50% Mangala 40% Mangala 20% Mangala 0% Mangala

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Corrosion Inhibitor
Most commonly associated with the presence of hydrogen sulfide, carbon dioxide, or oxygen. Corrosion inhibitors work by adsorbing onto exposed metal surfaces Four generic groups: amine imidazolines, amines and amine salts, quaternary ammonium salts, and nitrogen heterocyclic. Corrosion caused by oxygen is controlled by chemical reaction rather than adsorption. Treatment: Continuous treatment, displacement treatment and squeeze treatment.

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Biocide
SRB are the most common biological problem in O&G industry Sulfate reducing bacteria (SRB) reduce the sulfate ion to hydrogen sulfide, which causes chemical corrosion, steel embrittlement, and fouling of equipment by formation of iron sulfide Biocide is surface acting chemical, which kill the planktonic & sessile bacteria and form film on the pipe walls. Types: Chlorine / Hypochlorite, very corrosive, will need a holding tank and neutralizer. Aldehydes: Formaline, probably one of the more cost effective not everywhere allowed. Gluteraldehyde, probably most common used.(so is THPS) Acrolein, can soften/removed deposits, not everywhere allowed, difficult to apply. THPS, cost effective, stops FeS formation through chelating Iron. Quaternary type amines, surface active, less cost effective in time kill tests. Calcium Nitrate, to prevent reservoir souring, probably not a good idea in combination with EOR. Treatment: Slug treatments, batch treatment & continues treatment

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Corrosion mechanism of iron by SRB

The resultant accelerated corrosion mechanism of iron by the sulphate reducing bacteria is illustrated in equations = S-2 + 4 H2O (cathodic depolarization by SRB) 1. SO4-2 + 8 H 2. 8 H2O = 8 OH-1 + 8 H+1 (dissociation of water) 3. 2 H+1 + S-2 = H2S (reversible reaction) 4. Fe+2 + S-2 = FeS (anode corrosion product) 5. 3 Fe+2 + 6 (OH)-1 = 3 Fe(OH)2 (anode corrosion product)
Benefits of Biocide: 1. Control system fouling from iron sulfide 2. Protect formations sour oil and gas production 3. Reduce biomass

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System fouling from iron sulfide

Pump suction strainer chocked

Produced water pump suction line flushing

Back wash pit after startup

Back wash pit at present

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Anti-foam
Antifoam bind to the nucleation sites of the contaminants and reduce their ability to generate foam. They do this by promoting small bubbles to coalesce into larger ones until they destabilize and collapse, causing gas separation and displacing the surface active component on the bubble and making it instable while promoting the fluid component of the foam to drain away. 1. 2. 3. 4. 5. 6. Benefits Reduce oil or condensate in gas flow Improve separator efficiency Reduce produced water foaming Improve pump capacity and efficiency Improve produced fluid flow Reduce pump noise and vibration

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Coagulants & Flocculants

Flocculation, is a process wherein colloids come out of suspension in the form of flock or flakes by the addition of a clarifying agent. The action differs from precipitation in that, prior to flocculation, colloids are merely suspended in a liquid and not actually dissolved in a solution. In the flocculated system, there is no formation of a cake, since all the flocks are in the suspension. Coagulants neutralize the repulsive electrical charges (typically negative) surrounding particles allowing them to "stick together" creating clumps or flocks. Flocculants facilitate the agglomeration or aggregation of the coagulated particles to form larger floccules and thereby hasten gravitational settling. Some coagulants serve a dual purpose of both coagulation and flocculation in that they create large flocks that readily settle

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Oxygen scavengers
Oxygen scavengers chemically react with oxygen present in your source water, removing integrity risks it poses and eliminating its potential to react with other ions present in your system Most commonly chemicals:1) Carbohydrazide 2) Diethyl hydroxylamine (DEHA) 3) Hydroquinone 4) Methyl Ethyl Ketoxime 5) Sodium Sulfite 6) Catalyzed Sodium Sulfite 7) Ammonium Bisulfite. Stoichiometric requirements

As a rule-of-thumb dose 20 mg/L (ppm) of scavenger in excess to the stoichiometric requirement.

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What do we need for better treatment

Suitable chemical with optimized dosage Better infrastructure Identify appropriate & effective injection points

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Questions?

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Thank You..