Upload
truongkhanh
View
213
Download
1
Embed Size (px)
Citation preview
The Development of Green Chemistry in the Oil and Gas
Produc:on Industry
UK North Sea Sector
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.
“BP pipeline leaked 'oily mist' onto 27 acres of snow-‐covered
tundra in Alaska.” (1st May 2014)
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.
Different Chemistry
Aspar:c Acid Alkyl Polyglucoside
!
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.
Many Thanks
www.hcoilchem.com