the$developmentof$green$ chemistry$in$the$oil$and$gas ... · the$developmentof$green$...
TRANSCRIPT
Outline
• What is ‘green chemistry’?
• The oilfield chemical market
• UK North Sea • Regulatory and economic drivers
• Examples of “greening”
• Challenges remaining
• A new approach?
Green Chemistry Defini:ons "Design of chemical products and processes that reduce or eliminate the use or genera:on of substances hazardous to humans, animals, plants, and the environment.” (IUPAC)
The 12 principles of green chemistry – Warner and Anastas:
– 8. Use safer solvents and reac:on condi:ons: Avoid using solvents, separa:on agents, or other auxiliary chemicals. If these chemicals are necessary, use innocuous chemicals.
– 10. Design chemicals and products to degrade a[er use: Design chemical products to break down to innocuous substances a[er use so that they do not accumulate in the environment.
Green Chemistry in the Oilfield
• Focus is on biodegradable, less environmentally harmful materials.
• Li^le is on sustainability or the life-‐cycle of producing these materials.
• An end of pipe vision not an holis:c approach. • This is really only applied in certain geographic loca:ons.
Oilfield Speciality Chemical Market • Expected to reach $6.5 Billion by 2016
Specialty Oilfield Chemicals Market by Types, Applica9ons, Trends & Global Forecasts (2011 – 2016)
• Dominated by interna:onal service companies. – Large amount of addi:onal service is required in applica:on. – In the main products are formulated for applica:on.
• Chemical manufacturers do not supply directly.
• UK North Sea – less oil, more water.
Making Chemistry Green In general, two complementary approaches have been adopted:
– Deriva:on of the exis:ng chemical type to provide a more biodegradable and less harmful structure.
– Examina:on of other chemical structures which are know or presumed to be less harmful to the environment e.g. use of natural product type chemistry.
Corrosion Inhibitors • Produc:on fluids contain corrosive gases:
– CO2 and H2S.
• Retarda:on of corrosion on metal surfaces:
– Corrosion inhibitors. – Film forming surfactants.
• Four main types:
– Fa^y amines and their adducts.
– Quaternary ammonium salts of a variety of amines and amides.
– Imidazolines.
– Alkyl pyridine and alkyl quinolones and ammonium salts thereof.
Imidazolines
Studies have shown that op:mum performance is related to the chain length, with the oleic C18 providing
an op:mum performance.
More Water Soluble
Reac:on of pendant alkyl amine group of an imidazoline with stoichiometric amounts of acrylic acid gives the structure below, which is more water soluble.
Scale Inhibitors
• Three main types of chemistry:
– Polycarboxylates
– Other polymers
– Phosphonates
• Generally, chemistry is recognised as environmentally
acceptable, however, some authori:es legislate against
phosphonates regarding them as not sufficiently
biodegradable.
Halite and Other Scales
• Halite ( NaCl) and sulphides, lead, zinc etc. • Hexacyanoferrate salts and nitrilotrialkanamides:
– nitrilotriacetamide
Demulsifiers
• Offshore oil and water separa:on in minutes.
• 2 or 3 components, usually surfactants formulated in
a solvent.
• Many are not environmentally acceptable:
– Biodegrada:on – Endocrine disrup:on – Toxic monomer residues
Green Demulsifiers
• Epoxidised fa^y acid, such as soya. • Polyglycols
• Polyglycerols • Terpene alkoxylates • Alkoxylated alkyl polyglucosides
• Most of above is revisi:ng old, less efficient chemistries.
Green Demulsifiers
• Tradi:onal demulsifiers biodegrada:on:
– Many are polyalkoxylate chains. EO and PO alkoxyla:on EO chains more degradable than PO chains.
– Polybutoxylate chains made from ring opening of butylene oxide are even less degradable.
– Straight polybutoxylate chains (polytetra methylene glycol) made from ring opening tetrahydrofuran are more
biodegradable. (P. S Newman, C. Han and R.D.McClain, Interna:onal patent
Applica:on WO/2006/068702)
• Return to THF.
Biocides
• By nature and effect they are highly toxic. • Highly regulated through BPR – no innova:on or new biocides.
• Formaldehyde releasers being examined but being
considered for formaldehyde labeling.
• Where can we find an effec:ve green biocide?
• Alterna:ve methods of microbial control.
Wax Control
• Inhibitors, dispersants and PPD’s used to control the forma:on and deposi:on of petroleum waxes as crude oils cool.
• Chemistries are generally polymeric and oil soluble.
• Heat and flow can eliminate their use (most of the :me).
• New crudes are now being discovered and exploited, mainly in deepwater or harsh environments and may of these have high wax contents.
• Many of these ecosystems, such as arc:c Norway, are regarded as environmentally sensi:ve and require chemicals to meet stringent regulatory controls.
• Most chemistries are not very biodegradable and can have toxic proper:es. The solvent systems are also of high concern.
Wax Control Agents Chemistry
• Various polymers and co-‐polymers:
– Ethyl vinyl acetate polymers and co-‐polymers.
– Acrylate polymers and co-‐polymers.
– Maleic anhydride co-‐polymers.
• Alkyl subs:tuted phenols – dispersants.
• Low concentra:ons of polymers in aroma:c solvents.
Green Solvents • Glycols, Methanol and Xylene.
• In the main non-‐polar, very few aroma:cs and o[en low solvency.
• Some have health and safety risks.
• Ester solvents:
– good solvency. – good environmental proper:es.
– low health and safety risks. – desirable physical proper:es such as a high boiling point, reasonable
viscosity and high flash point.
• Ester Alcohols (mainly in drilling applica:ons).
• Oleates, par:cularly for corrosion inhibitors.
An:foams and Defoamers • Main class of product used:
– Oil soluble silicone defoamers and an:foams.
– Are given a poor environmental profile due to their poor rates of biodegrada:on.
– Not bioavailable. • Polyglycol materials are in this use as alterna:ves:
– Biodegradable. – Dose rates of 100 fold plus compared to the previous silicon materials, if
they work at all.
– Are the silicon materials as harmful?
• This is an area where an efficient, useful and green defoamer and/or an:foam would have a poten:al immediate impact.
Regula:on and the Environment
• Regula:on, par:cularly in the North Sea, has been a primary driver in “greening”.
• Regula:on has been primarily hazard based and
biodegrada:on focused – does this protect the
environment?
• Risk based approaches used in other industries.
Sustainability – a way forward? • The approaches in oil and gas industry are reac:ve. • Sustainability, although counter-‐intui:ve, may provide
an alterna:ve greening approach.
• Examples:
– Demulsifiers from polybutoxylates are environmentally acceptable when derived from THF.
– BASF -‐ THF can be bioderived and be sustainable. – Henkel -‐ LCA of all surfactant manufacture.
Work Con:nues • Examina:on of natural products for cri:cal proper:es but
also ensuring they are sustainably derived and/or synthesised in a green fashion. – An example: Hydrate inhibitors.
• Glycoproteins in ar:c fish. • current inhibitors. • New pseudo protein like materials, dendri:c products etc.
• Apply the green principles of Anastas and Warner.
• Examine how chemicals purchased are made.
• Conduct life cycle analysis.
The Future
More Regula:on? Global regula:on?
More Environmental Awareness?
More Pressure from Policy Makers and Public? Be proac:ve – think sustainably.