This Handout....

Chemicals are one of the tools that can be used at an oil production or treating installation to solve a problem, increase the production, give better water quality or give a better quality of the oil or gas. Chemicals are being used in many process systems, among them:

Water Injection Oil & gas production Gas separating & dehydrating Utilities etc..

There is almost always a large stock of various chemicals on the installations, each dedicated to a particular purpose. Therefore specialized products are necessary to ensure that they
are optimally effective are being used in a safe way are being used in an economical way

This handout describes chemical treatment of all types and gives a short description of typical properties for each chemical.

Why Are Chemicals Needed?

Production of oil, gas and water:
The oil can contain wax, asphaltenes and other solids. Water can cause corrosion in process equipment and pipe lines, precipitation of salts, and give emulsion with oil. Gas can cause foaming, and corrosion due to CO2 or H2S. These problems are solved with correct design or USE OF CHEMICALS.

Process of Oil and Produced Water

This group of chemicals are used when the process equipment is not functioning properly, or there are problems such as scale, corrosion, foaming or emulsions.
Again, these chemicals are divided into water soluble and oil soluble, depending upon in which phase they are to be used. All chemicals that are supplied and used shall have approved safety data sheets, and complete environ- mental documentation.

Typically, topside process chemicals may include:

Anti foam Emulsion Breaker Scale Inhibitor Corrosion Inhibitor Wax / Asphaltene inhibitor Flocculant Microbiocides

Where do problems occur in oil production ?

Water injection:
Scale, Corrosion, Bacteria growth

Topside Process:
Emulsions Foam Scale Corrosion

Utility:
Scale Corrosion

Export:
Wax Water Hydrates

Perforating zone/ Production tubing:

Scale Wax Asphaltenes

Water to sea/ Produced water:

Scale Corrosion Oil content

Well and flow line

Scale dissolver:
In production tubing / flow line, acids are normally used to remove calcium carbonate. For barium sulphate, sequestrants (Scale Dissolvers) must be used. Acids: Depending of the steel quality the acid and inhibitor that effectively removes the carbonate scale, but at the same time shows acceptable corrosivity against the steel quality must be defined and blended. Examples of acids are: hydrochloric acid, phosphoric acid, nitric acid or citric acid. Process specific corrosion inhibitors are required. Sequestrants: Are normally used to remove/dissolve sulphate scale. The chemicals are often based on EDTA or its homologs. They do not release gas or give a noticeable exothermic reaction. These are more generic.

Well and flow line

Hydrate Inhibition:
Normally methanol is used to avoid hydrates in pipeline, or when starting or closing a well. Methanol is toxic and flammable and must be handled with care. To overcome the HSE issues of methanol new easily handled chemicals are applied. These chemicals are specific for each type of process and distribution system

Oil Processing
Crude oil is a geographically unique and complex substance, that is formed under high pressure and temperature. An infinite mixture of organic chemical components exist in light, paraffinic, or heavy oils. These include, waxes up to C60, esters, organic acids, asphaltenes and napthalenes. Depending on the make up of the above components, the crude oil has its own specific characteristics such as, specific gravity, wax content, pour point, colour, etc. The crude oil can cause a series of problems such as: Wax deposition Emulsion problems Residual Oil in Water problems

North Sea oil

Texas oil

Utah oil

Process of Oil and Produced Water

Wax Inhibitors
Mode of operation Change the crystal structure in such a way That further growth is not possible. Some of the wax inhibitors are defined as disperssant type chemicals that keep the wax crystals in Solution and prevent them from depositing.

Typical injection point

For well and production tubing: Downhole injection For topside process: Production manifold For export lines: upstream of the oil coolers
Depending on the wax content of the oil, but normally 20 - 200 ppm Flash point Viscosity: Health: <63 deg C (depends on the solvent) 20 - 100 cP Irritating, depending of the solvent (see MSDS sheet)

Typical Dosage rates Typically physical properties

Compatibility

Depends upon the solvent in the product, but in general; Not compatible with water or other water soluble chemicals. Use white spirit or naphtha for dilution Compatible with most steel types

Process of Oil and Produced Water

Wax
Wax is present in most crude oils at normally < 5%. In the Pacific Rim wax content ranges from 10 to 60%. Wax is detected by industry specific analytical methods (IP) and normally represents that fraction of the oil with carbon number C-18 to C-60. Wax crystals are formed when the oil is cooled, in connection with production from the wells. . Subsea pipelines No of Carbon Melting point, Heat exchange
Atoms Celsius

The wax crystals form at specific temperatures (wax appearance point).

Methods to avoid wax precipitation

16 17 18 19 20 23 25

18 22 28 35 37 50

Heat Solvents (e.g. xylene) Wax inhibitors Mechanical equipment

Pipeline and Process

Wax inhibitors
Wax inhibitors modifies the structure on the growing crystal, either by co - crystallization or by absorption to the surface of the wax crystal Further growth will then be stopped
Depositions

H3C-(CH2)N-CH3 Higher alkanes (n,iso,cyklo-) Deposit and forms tick, firm layer of wax at specific conditions

Modifying of wax crystals Wax crystal

treatment with wax inhibitors

Inhibit further 3D growth

treatment with disperssents or surfactants

Wax particles

Keeps the wax particles dispersed in the oil phase

Process of Oil and Produced Water

Asphaltenes
Asphaltenes are present in most oil, and is mainly responsible for the black colour of the oil. Chemically asphaltenes can be described as very complex hydrocarbons with a ring structure. They are charged molecules, and therefore they can agglomerate due to electrochemical binding mechanisms. Asphaltenes are defined as the hydrocarbons that are not soluble in pentane - C5.

Asphaltenes deposit during production after the following process changes: Physical effects as pressure drop Cooling Mixing of oil from several wells/formations.

Typical molecule structure of an asphaltene molecule

Process of Oil and Produced Water

Emulsions
Emulsions are defined as one phase dispersed in another Emulsions are dynamic, they change with operating conditions. There are two types of emulsions Water in oil emulsions (WIO) Oil in water emulsions (OIW), or reverse emulsions Oil will easily emulsify with water, when the following conditions are present: Energy - normally pressure loss over the choke or valve and mixing in a high shear pump Emulsifier - normally a chemical component in the oil or other substances such as wax, solids etc. Separators are designed for separation of oil, gas, and water, but if an emulsion is formed. To help the separation process, we use; Heat Chemicals (emulsion breaker) Chemicals (flocculants)

Typical example of the breaking of an emulsion

Process of Oil and Produced Water

Emulsion Breaker
Mode of operation Reduces the surface tension on the micro water droplets. These will then coagulate to form larger water droplets and fall out of the oil. They separate the water from the oil and give a sharp clear interface Normally they are injected as early in the system as possible. If that's not possible, increased dosage rate may compensate for this. Normal dosage rate for emulsion breakers is in the area 5 - 25 ppm based on total flow Rate (oil + water). Some heavy crudes require much higher doses Flash point Viscosity: > 63 0C 20 - 100 cP depending of the temperature and solvent

Typical injection point(s)

Typical dosage rate

Typical physical data

Process Oil and Produced Water

Emulsion breakers are used when the natural separation of oil / water is not satisfactory.

Demulsifie r Treatment

Water - in oil emulsion

Surface active polymer

Separation of oil and water

Emulsion breakers are formulated for each process. Because the process of oil changes with time (caused by new wells, increased water cut, etc.) the system specific emulsion breakers must be optimised from time to time. Emulsion breakers are made up of three to four active components in a solvent system. The active components normally consist of polymers, of esters, polyols, block polymers and other surface active polymers. Total active content of an emulsion breaker is usually 30 - 40 %, but dosage rates are calculated as ppm of product.

Process of Oil and Produced Water

Flocculants / Polyelectrolytes
Flocculant chemistry works by reducing/eliminating the charge on the oil droplet. The oil droplet will be bound together into larger droplets, and will be separated from the water due to higher specific gravity. Today anionic flocculants are being used more and more due to low toxicity against marine environment
-

Treatment +
+ +

+ + + +

+
-

+
-

+ + + +
-

Oil drops are normally negative charged

Positive charged polymer (cationic)

Flocculation

+ +

+ + + + + ++

+ +

+ + + + +

Treatment
- -

+ +

Negative + + charged polymer Positive charged ion (anionic) (e.q. calcium) can change the charge on the oil drop

+ +

+ + +

++

-++ + +

-+
+ +

+ + + +

Flocculation

Process of Oil and Produced Water

Gas Hydrates
Hydrates start forming even at moderate pressure and temperature below 10 0C. Hydrates are snow-like crystals that are build up of methane and water. This hydrocarbon ice can plug pipelines and destroy process equipment. 1m3 of hydrate contains 150 m3 of methane. Hydrates can be avoided by injection of methanol or glycol, and the same chemicals can be used to dissolve ice plugs Methanol is very toxic and very flammable. Safe handling procedures must be impressed upon the customer. Be careful!

Generally
Methanol is very flammable. Flash point -16 0C. Neutralizing amines and alkanolamines are often irritating

To skin and have a sharp smell Most corrosion inhibitors are toxic to marine life