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WO2008128331A1 - Procédé de séquestration du dioxyde de carbone - Google Patents

Procédé de séquestration du dioxyde de carbone Download PDF

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Publication number
WO2008128331A1
WO2008128331A1 PCT/CA2008/000717 CA2008000717W WO2008128331A1 WO 2008128331 A1 WO2008128331 A1 WO 2008128331A1 CA 2008000717 W CA2008000717 W CA 2008000717W WO 2008128331 A1 WO2008128331 A1 WO 2008128331A1
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WIPO (PCT)
Prior art keywords
formation
methane
carbon dioxide
hydrogen
microorganisms
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PCT/CA2008/000717
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English (en)
Inventor
Ian Donald Gates
Jennifer Jane Adams
Ian Mccutcheon Head
Haiping Huang
Thomas Bernhard Paul Oldenburg
Barry Bennett
Stephen Richard Larter
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University Technologies International Inc.
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Publication of WO2008128331A1 publication Critical patent/WO2008128331A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/64—Geomicrobiological testing, e.g. for petroleum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/582—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of bacteria
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023—Methane
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
    • E21B41/005—Waste disposal systems
    • E21B41/0057—Disposal of a fluid by injection into a subterranean formation
    • E21B41/0064—Carbon dioxide sequestration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • This invention relates to a process for active sequestration of carbon dioxide by conversion to methane using microbial action in a subterranean formation.
  • Microbial Enhanced Oil Recovery Microbial Enhanced Oil Recovery
  • Microbial techniques often involve injection and establishment of an exogenous microbial population, which usually includes supplying the population with growth substrate and mineral nutrients.
  • the growth of exogenous microorganisms is often limited by the conditions that prevail in the formation.
  • Physical constraints may severely limit the types of microorganisms that can be injected and that will thrive in the formation. Such constraints include small and variable formation pore throat diameters; high temperatures, high salinities and pressures of fluids in the formation; and low concentrations of electron acceptors in formation water.
  • Biological constraints may also act to limit the viability of exogenously supplied microorganisms. These include competition from indigenous reservoir microbes, the inherently adverse environment of subsurface reservoirs and the stress of changing environment from surface to reservoir. To overcome these problems, the use of 75696- 38
  • Microorganisms are commonly present in sediments in subterranean formations cooler than about 8O 0 C. With appropriate environmental conditions, indigenous bacteria and archaea can convert sedimentary organic matter (including petroleum—both crude oil and natural gas—or other fossil fuels such as coals) to methane either directly or over long geological time periods in the subsurface. Use of microorganisms for producing methane gas from hydrocarbon reserves in subterranean formations has been described elsewhere. (See for instance US 6,543,535 and WO 2005/115649. )
  • Subterranean formations may contain multiple, mixed consortia of microorganisms, which may include methanogens. Methanogens convert various low molecular weight compounds, including amines, alcohols, organic acids and gases into methane, CO 2 and water. Subsurface formations may also include methanotrophic archaea, which can convert methane into CO 2 and water, usually in a symbiotic partnership with sulfate-reducmg organisms. Methanotrophic archaea are capable of destroying any methane produced from methanogenesis . This may occur either in proximity to or more distant from the site of methane formation.
  • Microorganisms that reduce carbon dioxide to acetate may also exist in a subterranean formation, and may also reduce the amount of carbon dioxide available for consumption by CO 2 reducing methanogens .
  • Carbon dioxide reduction to methane is typically thermodynamically feasible provided the concentration of 75696-38
  • hydrogen partial pressure remains above around 0.1 Pa. However, as the hydrogen partial pressure increases, CO 2 reduction to acetate is a greater possibility. Methane is then more likely to also be generated via acetoclastic methanogenesis. Acetoclastic methanogenesis occurs via acetoclastic methanogens, which convert acetate to carbon dioxide .
  • Methanogenesis is an exclusively anaerobic microbial process, and is commonly associated with biodegraded petroleum reservoirs and other deep subsurface environments. Carbon isotopically lighter methane obtained from methanogenesis is frequently found admixed with thermogenic methane (e.g., methane produced by thermal breakdown of petroleum or kerogen in source rocks) .
  • thermogenic methane e.g., methane produced by thermal breakdown of petroleum or kerogen in source rocks
  • Methanogens represent common indigenous members of the microflora of the petroleum reservoirs and other subsurface formations. The methanogens most frequently found in petroleum reservoirs described are those that reduce carbon dioxide to methane with fewer reports in the scientific literature of acetoclastic methanogens. Radiotracer and other experiments on subterranean reservoirs also suggest that carbon dioxide reduction to methane is more prevalent than acetoclastic methanogenesis. Also, high pressures in subterranean reservoirs favour net volume reducing reactions such as methanogenesis from carbon dioxide reduction.
  • a process that utilizes natural microbiological methods of reducing carbon dioxide in subterranean formations to sequester carbon dioxide as methane may be useful. Also any methane gas produced could be recovered, and, for example, used as fuel. A closed system that recycles CO 2 emissions for production of CH 4 as fuel may also then be obtained.
  • a method for sequestering carbon dioxide in a subterranean formation comprising: identifying a subterranean formation suitable for microbial methanogenesis; identifying an indigenous methanogenic microorganism in the subterranean formation, and/or introducing an exogenous methanogenic microoganism into the subterranean formation; introducing carbon dioxide into the subterranean formation; and promoting metabolic conversion of the carbon dioxide by the methanogenic microorganism to methane; wherein the methanogenic microorganism is hydrogen oxidizing, carbon dioxide reducing.
  • a method for carbon dioxide sequestration and microbial methane production in a subterranean formation wherein a natural source of hydrogen indigenously produced is available in the subterranean formation comprising: (a) analyzing one or more components of the formation to determine characteristics of the formation 75696-38
  • Carbon dioxide may be introduced into the formation at any step in the method.
  • the hydrogen produced may be by decomposition of water, and the formation may be modified to promote natural hydrogen generation.
  • the method may comprise in step (g) , if methanotrophic microorganisms are present, determining an ecological environment that inhibits or retards in situ microbial degradation of methane by methanotrophic microorganisms of the consortium.
  • Step (h) may then comprise modifying the environment to inhibit or retard in situ microbial methane degradation. 75696-38
  • a method for producing methane using methanogenic microorganisms comprising introducing methanogenic microorganisms into a surface reactor containing a hydrogen generating rock media; introducing carbon dioxide into the surface reactor; promoting generation of hydrogen from the rock media in the surface reactor; introducing additional hydrogen from a subterranean formation or other natural or industrial source into the surface reactor, as is required; and promoting metabolic conversion of the carbon dioxide by the methanogenic microorganisms to methane.
  • the methane can be optionally recovered.
  • the hydrogen generating rock media contains mined aggregate from kimberlite or another rock that is capable of generating hydrogen.
  • FIG. 1 illustrates competing methanogenic and methanotrophic pathways.
  • Figure 2 is a schematic representation of one embodiment of the present invention.
  • Figures 3A to 3E are schematic representations of a kimberlite pipe with an injection/production well for use in accordance with embodiments of the present invention.
  • Figures 3A to 3C a single injection/production well embodiment is shown.
  • Figures 3D and 3E an invention embodiment using a first injection well for injection CO 2 and a second production well for producing methane is shown.
  • Figure 4A displays the cumulative carbon dioxide injected and cumulative carbon dioxide produced during a simulation of a continuous process embodiment of the present invention. 7 5696-38
  • Figure 4B displays the carbon dioxide injection and gas component production rates of Figure 4A.
  • Figure 5 displays the carbon dioxide mole fraction in the gas phase in a fracture after 10 years of carbon dioxide injection according to a simulation of a process embodiment of the present invention. The mole fraction of methane in the fractures is also shown.
  • Figure 6A displays the cumulative carbon dioxide injected, produced, methane produced and hydrogen produced versus time for a simulation of a process embodiment of the present invention.
  • Figure 6B shows the carbon dioxide injection rates and gas production rates of Figure 6A.
  • Figure 7 displays the mole fraction of carbon dioxide and methane in a fracture after 35 years of carbon dioxide injection according to a simulation of one embodiment of the present invention.
  • Figure 8A displays the cumulative carbon dioxide injected, produced, methane produced and hydrogen produced versus time for a simulation of a process embodiment of the present invention.
  • Figure 8B shows the carbon dioxide injection rates and gas production rates of Figure 8A.
  • microorganisms as used throughout this application is intended to include bacteria and archaea, their enzymes, and other products, as well as relevant eukarya. It will be understood that bacteria and archaea are representative of microorganisms in general that are 75696-38
  • the process of this invention may be used to stimulate and sustain the activity of a mixture of different microorganisms in a subterranean formation to convert carbon dioxide to methane, which may under appropriate conditions be produced to surface.
  • Species of methanogens that metabolize carbon dioxide and hydrogen into methane and water are referred to m this application as "CO 2 reducing” or “hydrogen oxidizing” or sometimes simply as
  • FIG 1 illustrates this metabolism, together with some of the potentially competing processes that oxidize methane or compete with methanogens for electron donors. Competing processes, among others, include acetate and hydrogen oxidation by sulphate reducing bacteria and methane oxidation by methanotrophic archaea.
  • An aspect of the present invention is to promote methanogenesis while inhibiting competing processes.
  • Hydrogen for metabolism of CO 2 to CH 4 by methanogens may be introduced into a subterranean formation directly from the surface, generated in situ by microbial action on introduced or indigenous organic matter, or the hydrogen may have been generated in the subsurface formation itself and thus it may be indigenous.
  • indigenous sources of hydrogen include, for example, hydrogen generated by thermal decomposition of organic matter deep in a sedimentary basin, from radiolytic decomposition of water or from water-mineral reactions. Hydrogen may be generated m one site in the formation that is different from the site of active methanogenesis, for example. 75696- 38
  • microbiological and geological environments have been identified that promote, or that can be modified to promote, CO 2 metabolism to CH 4 for active sequestration of carbon dioxide.
  • active sequestration is distinguished from non-active or passive sequestration, in which chemical conversion from one chemical entity (e.g., CO 2 ) to another (e.g., CH 4 ) does not occur.
  • formation and "reservoir” as used throughout this specification and claims is not intended to be limited to any particular kind of formation or reservoir.
  • the invention includes within its scope any reservoir or formation suitable for use in the methods of the invention. That is, sedimentary rocks, fractured igneous or metamorphic rocks, sandstone, oil shale deposits, newly worked and abandoned coal seams, coal bed methane reservoirs, tight shale gas reservoirs, tar sands and other suitable fossil fuel deposits may be used.
  • the formations can also be an unconsolidated sediment package, such as might be found associated with hydrogen generating igneous rock packages and sediments just below the seafloor.
  • frossil fuels is used in the present application in a broad sense to include, without limitation, solid carbonaceous deposits such as kerogen, peat, lignite, and coal; liquid carbonaceous deposits such as oil; gaseous hydrocarbons; and highly viscous carbonaceous deposits such as bitumen and tar. Petroleum reservoirs may also be suitable.
  • Suitable formations may be determined, and environmental conditions modified using procedures described in more detail below. 75696- 38
  • One or more samples of fluids e.g., waters, oils if present, gases
  • rocks may be analyzed in a formation.
  • Samples can be obtained by sampling procedures that are known to those skilled in the art.
  • a fluid e.g., water, gas
  • the fluid can be sampled either downhole with, for example, a wireline formation fluid tester or fluid sampler; or at the surface wellhead using a subsurface test, such as a drill stem test, a production test, or normal production.
  • rock sample may also be useful for evaluation of the formation environment.
  • Rock samples can be retrieved from, for instance, drill cores, cuttings, produced sediments and/or outcrop sites or rock data can be secured by interpretation of well logs or other techniques.
  • Analysis of a formation's environment can provide important information in determining suitable m situ environmental conditions for microbial activity and suitable microbial growth stimulants or inhibitors, if required. This analysis may include determining temperature and pressure of the formation, which can be obtained in any suitable manner known to the skilled person.
  • a geochemical analysis can be made of one or more fluids of the formation, such as formation water and gases, and/or one or more solids of the formation, which analyses are familiar 75696- 38
  • the analysis is made of fluid and/or rock samples obtained from the formation.
  • the fluid analysis can include measurement of state values (for example, temperature and pressure) as well as a geochemical analysis of the formation water. This may include one or more of an assay for dissolved gases; identification of major anions and cations; determining pH; determining oxidation potential (Eh) ; and detecting chloride, sulphate, phosphate, nitrate, iron, ammonium ion, salinity, selenium, molybdenum, magnesium, calcium, cobalt, copper, nickel, silicon and other trace metals and metalloids .
  • Rock analysis may include mmeralogical, chemical, isotopic and facies descriptions as well as measurements of formation properties, such as porosity, permeability, capillary pressure, and wettability.
  • Analysis of the solid matrix of the rocks in a reservoir may include optical analysis, x ray diffraction, Mossbauer spectroscopy (to determine the nature of iron present) and/or chemical analysis to determine the mineralogy and elemental composition of the rock in the formation. Iron content and valence state may be determined in this manner. Magnetic properties of the rock may also be determined.
  • Samples of, for example, rock and water obtained from different parts of a formation can also be incubated under laboratory conditions to determine the potential for hydrogen generation and/or active methanogenesis . This may include incubation at a range of temperatures and pressures to assess activity under in situ conditions.
  • Geochemical analysis may also be used to identify known byproducts of indigenous microbial activity.
  • identification of such markers can be used as a first step in determining the presence of active anaerobic microbial consortia .
  • methane, CO 2 , microbial RNA, DNA, enzymes, and carboxylic acids can be indicative of microbial activity.
  • methane relatively depleted in the carbon 13 isotope is frequently found where natural methanogenesis has occurred.
  • anaerobic hydrocarbon degradation metabolites such as alkyl and aryl substituted succinates, naphthoic acids and/or reduced naphthoic acids (particularly 2- naphthoic acids or reduced 2-naphthoic acids) and demethylated hopanoid compounds, indicate that anaerobic degradation of organic matter is taking place.
  • the presence of these compounds is also indicative of anaerobic degradation conditions that may be appropriate for methanogenesis .
  • archaeols which are lipid molecules characteristic of archaea
  • Specific phospholipids and other polar lipids and microbial nucleic acids characteristic of methanogenic archaea can also be used to positively identify reservoirs with active methanogenic processes.
  • methanogens contain novel co-factors such as F 43O , a nickel porphyrin associated with methyl coenzyme M reductase.
  • F 43O a nickel porphyrin associated with methyl coenzyme M reductase.
  • a similar, but distinct nickel porphyrin with a higher molecular weight is associated with anaerobic methane oxidizing archaea. Analysis of these co-factors can provide 75696-38
  • Hydrogen generating subterranean environments can also be identified by formation analysis. Hydrogen rich gases may be associated with several subsurface settings including sedimentary rocks, and evapo ⁇ tes. More commonly hydrogen rich gases are found associated with rocks rich in ferrous iron such as rocks in oceanic rift zones, ophiolites, dunites, serpentimsed rocks and weathered basic and ultrabasic rocks in general. Hydrogen may be produced by reaction of water and ferrous iron containing minerals at temperatures low enough to permit subsurface microbial life. Active microbial populations are often also associated with subterranean hydrogen generating environments.
  • the inventors have observed that m some large accumulations of microbially produced gas significant quantities of hydrogen are found having a hydrogen isotopic signature of -700 to -800 per mil. VSMOW. This signature is typical of hydrogen produced by reactions of minerals, such as olivine, with water.
  • the inventors have concluded that abiotically generated hydrogen gas can be used by methanogens, in addition to biologically produced hydrogen gas, to reduce carbon dioxide to methane. Detection of hydrogen with a characteristic isotopic signature may be used to identify reservoirs suitable for reactive sequestration of carbon dioxide.
  • suitable subterranean formations may include basic and ultrabasic rocks, such as dunites, serpentimtes and kimberlites, and other rocks containing minerals, such as serpentine, magnetite or olivine and other mafic minerals. 7 5696-38
  • Analysis of the reservoir geological environment may be carried out using geophysical and geological mapping procedures known to a person skilled in the art. In this manner, relative volumes and spatial arrangements of solid and fluid zones may be identified as suitable for practising the methods of the invention.
  • Information obtained from the above analyses may be used to identify reservoirs that contain suitable organisms and environments for carbon dioxide sequestration.
  • Methanogenic and methanotrophic archaea are often found in the same subterranean formations. Knowing the distribution, abundance and activity of these archaea is an element of predicting the net rate of carbon dioxide conversion and methane production, and for taking steps to modify the environment to promote methanogenesis over methanotrophy .
  • Microbial populations in deep subsurface environments are typically present at very low abundance and are on the order of five to six orders of magnitude less abundant than in near-surface sediments (ca. 10 3 to 10 4 cells per cubic centimetre m the deep subsurface) .
  • stringent contamination control measures should be adopted.
  • Treatment of all reagents and materials, except amplification primers, with UV and enzymatic treatment with DNase I is recommended when nucleic acid based analyses are conducted. It is also recommended that samples for nucleic acid analysis be frozen immediately or fixed by addition of, for example, filtered 50% ethanol immediately upon sampling. 75696-38
  • subsamples be taken from the centre of whole cores under sterile conditions to minimize contamination from the exterior of the core, which may be contaminated during drilling.
  • Formation water and/or drill cutting samples may also be analyzed for the presence of active microorganisms if conditions are maintained to inhibit exogenous contaminant organisms while promoting those adapted to xn situ conditions.
  • Samples for cultivation based studies may be stored either chilled or at close to in situ temperatures to reduce the growth of contaminating microorganisms during storage and transport.
  • Microorganisms in water samples may be concentrated by, for example, filtration and/or centrifugation before the analysis is performed. This may facilitate detection.
  • the indigenous microbe population will typically occupy a very small fraction of a sample's volume.
  • a typical formation water may contain less than 0.025 mg of microorganisms per liter.
  • Characteristics of a microorganism or consortium of microorganisms may be determined by, for example: biochemical methods, physiological methods, biogeochemical process measurements, optical methods, and/or genetic methods. The degree of similarity between determined characteristics of sampled microorganisms and characteristics of microorganisms with known properties can be used to establish identity of the sampled microoganisms and/or infer the physiology, metabolic functions, and ecological traits of the sampled microorganisms. Characterizations and comparisons may be done using techniques well established in the field of microbial ecology.
  • Enrichment culture techniques may be used to obtain isolates of microorganisms from which biochemical, morphological, physiological, ecological and genetic traits may be determined and compared against traits of known microorganisms .
  • Determination of the phospholipid fatty acid composition (PLFA) of the sampled indigenous microorganisms may be obtained and compared to PLFA distributions of known microorganisms.
  • Compound-specific (carbon, hydrogen) isotope analysis may be performed to identify organisms utilizing methane .
  • Nickel porphyrins may be identified to detect and distinguish between methanogenic and methane-oxidizing archaea.
  • 16S rRNA genes and genes encoding the alpha subunit of methyl coenzyme M reductase can m principle be used to detect methanogenic archaea. But, homologues of methyl coenzyme M reductase are also found in anaerobic methane oxidizing archaea. Also, 16S ribosomal RNA seguences of methane oxidizing archaea have been identified in biodegraded petroleum reservoirs and similar organisms have been found in gas seeps near mid oceanic ridges.
  • Genetic characterization of indigenous microorganisms may be performed by using any one of a number of methods known to a person skilled in the art. The following are two non- limiting examples of methods that may be used in determining the presence, identity and/or abundance of methanogenic and methanotrophic archaea:
  • Sequence identification Sequences of genetic fragments from sampled microorganisms may be determined. 75696-38
  • genes include but are not restricted to: 16S rRNA genes; and genes encoding the alpha subunit of methylcoenzyme M reductase (mcrA) from methanogenic and methane-oxidizing archaea. These sequences may then be compared against nucleic acid sequences from microorganisms with known metabolic capabilities. Sequences from known microorganisms may be obtained from, for example, the Ribosomal Database Project, Michigan State University, East Lansing (rdp.cme.msu.edu); the Genbank database at the National Center for Biotechnology Information located in the National Library of Medicine (Building 38A Room 8N805) , Bethesda, Md. 20894, U.S.A.
  • mcrA methylcoenzyme M reductase
  • Nearest neighbour sequences and sequences from the relevant formations may be aligned with the ARB database using the ARB software (www.arb-home.de/) .
  • Phylogenetic trees may then be constructed m ARB to obtain a final phylogenetic designation for the sequences recovered.
  • oligonucleotides designed to hybridize to the 16S rRNA genes of microorganisms and target genes indicative of processes such as methane generation and methane oxidation may be used in PCR-based methods.
  • Oligonucleotide probes labelled with radioactive phosphorus, biotin, fluorescent dyes, enzymes and other suitable tags may also be used, although they will likely lack the sensitivity required for analysis of subsurface samples unless linked to amplification techniques.
  • Suitable amplification techniques may comprise catalysed reporter deposition-fluorescence in situ hybridization (e.g., the CARD-FISH method) , polymerase chain reaction, or culture- based enrichment or analysis of microcosms.
  • Oligonucleotide primers targeting regions that are conserved in methanogen mcrA genes and distinct in methane-oxidizer mcrA genes can be used to distinguish between the two types of organisms. Broad specificity mcrA primers could be used followed by cloning and sequencing of the mcrA genes sampled in order to determine their provenance.
  • an ecological environment that promotes activity that will sequester carbon dioxide and promote its conversion to methane may be determined.
  • the environmental conditions in a formation can be modified to promote microbial conversion of carbon dioxide to methane, which may include inhibiting microbial degradation of methane . 7 5696-38
  • the activity of microorganisms m the subsurface may be altered by:
  • Modifying the microbial ecology This may involve, adding, subtracting and/or maintaining components required for microbial growth and/or activity. These components may be determined by, for example, laboratory and/or in situ pilot studies.
  • Modifying the formation environment This may involve controlling and/or maintaining the subsurface environment, including, for example, chemistry (including salinity, pH, etc.), temperature, and pressure.
  • chemistry including salinity, pH, etc.
  • temperature including temperature, and pressure.
  • One or more of the environmental conditions may require adjustment or maintenance within specific ranges to initiate or sustain carbon dioxide sequestration and conversion to methane .
  • Modification of parameters may include addition of one or more stimulants and/or inhibitors; and/or a change of one or more environmental factors.
  • the particular modifier or modifiers suitable for a particular environment will depend on the microbial consortium to be modified and the formation environmental conditions.
  • methanogenic archaea may be accelerated, and/or the activity of methanotrophic archaea reduced.
  • Carbon dioxide reducing methanogenic archaea include Methanobacteriales, Methanomicrobiales, Methanococcales , Methanosarcmales and relativesand Methanopyrales . Obligately acetoclastic 75696- 38
  • Organisms that may result in lower methane yields may also be present in the formation.
  • the methane- oxidizing archaea are related to but distinct from methanogenic archaea.
  • Other microorganisms may also be present in a formation, such as, sulfate-reducing archaea and bacteria, nitrate/nitrite-reducing bacteria and iron- reducing bacteria, which will all compete more effectively for hydrogen than methanogens in the presence of their preferred electron acceptors.
  • the activity of such organisms can be controlled to promote methanogenesis .
  • Suitable additives may include one or more of, but not limited to:
  • Nutrients containing nitrogen and phosphorus may be added by liquid or gaseous injection, for example, to quickly disperse through gas caps facilitating nutrient supply very quickly over large areas of the formation. Care must be taken in adding nutrients to minimize or avoid accelerating competing processes such as nitrate or sulphate reduction. This may be done by selecting suitable forms of the nutrients, or by independently blocking these reactions.
  • Non-limiting examples of phosphorous and nitrogen nutrients that may be used to promote methanogenesis include: ammonium phosphate; 75696- 38
  • potassium ammonium phosphate Na 2 HPO 4/ K 2 HPCM and NH 4 Cl, which may be added via water injection or ammonia gas (NH 3 ), for example; and volatile phosphorus compounds (e.g., PH 3 , and CH3-PH2) though these may be toxic at high concentrations or decompose during injection.
  • Phosphates may precipitate chemically m formations and therefore less reactive forms of phosphorus such as polyphosphate and phosphorus pentoxide may be more appropriate additives.
  • Nitrogen can also be added in the form of urea.
  • methanogens exclusively use ammonium ion as a nitrogen source or are dinitrogen fixers.
  • Vitamins non-limiting examples may include folic acid, ascorbic acid, riboflavin and Vitamin B12.
  • non-limitmg examples may include B, Zn, Cu, Co, Mg, Mn, Fe, Mo, W, Ni, and Se. These elements could be added as water soluble salts, for example.
  • Aqueous solutions of different salinities and/or pH values than present in the formation, or aqueous solutions containing complexmg agents may include organic acids, such as oxalate, citrate, EDTA or other multi dentate ligand organic compounds, such as hydroxylated acids. These agents may facilitate mineral dissolution and release of natural nutrients including, but not limited to, nickel, cobalt, nitrogen, potassium, ammonium or phosphate ion from dissolution of feldspars, clays or other silicates and carbonates. Indeed, the supply of nutrients from mineral dissolution m reservoirs or reservoir encasing shales may be the rate-limiting step for many microbial processes in the subsurface.
  • Mineral dissolution and release of nutrients may also be facilitated by fresh, low salinity aqueous solutions, or acidic or basic aqueous solutions depending on the mineralogy of the rock.
  • Most phosphorus in many subsurface petroleum and other reservoirs and reservoir encasing sediments is m feldspars; thus, for example, it has been suggested that natural feldspar dissolution in some oil reservoirs is related to biodegradation of the associated oils.
  • phosphorus contents of oils are low (approximately 1 ppm or much less); whereas, phosphorus contents of sandstone reservoirs or reservoirs encasing shales are much higher (up to 1000 ppm or more of oxide equivalents) .
  • Natural and/or artificial electron acceptors such as SO 4 2" , NO 3 2" , Fe 3+ , humic acid, mineral oxides, quinone compounds, CO 2 , O 2 , and combinations thereof may stimulate microbial 75696-38
  • injection of solutions containing sodium molybdate (or other hexavalent cation) may be used to inhibit sulphate-reducing bacteria and sodium chlorate solutions may be used to inhibit nitrate reducing bacteria.
  • Methane-oxidizing archaea are unlikely to be active at the site of methanogenesis, but if they are present in other regions of the formation, they may be inhibited.
  • the fact that these groups of archaea are likely to be spatially separated is important since the known inhibitors of anaerobic methane oxidation (e.g. bromoethane sulfonic acid) also inhibit methanogens.
  • spatially targeted inhibition may be used to stop any methanotrophic activity near production zones.
  • methane-oxidizing archaea often exist in close association with sulphate- reducing bacteria that consume the products of anaerobic methane oxidation driving methane oxidation to completion.
  • Anaerobic methane oxidation may therefore be inhibited with inhibitors of sulphate reduction such as sodium molybdate.
  • Other means of inhibiting competing processes may also be used.
  • Additives such as those described above, may be selected to specifically promote carbon dioxide sequestration using what is known about the microbial ecology. For example, it may be determined that cobalt or nickel stimulates growth of the closest-matching known methanogenic microorganisms to 7 5696- 38
  • Suitable stimulants can be tested and optimized using indigenous microorganisms m laboratory microcosms, cultures or in situ pilot sites to determine their effectiveness at promoting rapid methanogenesis .
  • stimulants that increase the rate of activity of methanotrophic or nitrate, iron or sulphate reducing microorganisms that may suppress methanogenesis by competition for common electron donors may be avoided, or their activity independently blocked, for example .
  • subsurface formation to another may vary from one location in the reservoir to another. Conditions favourable for microorganism growth m one part of the formation may not be optimum m another part of the reservoir formation. In addition it may be necessary to inhibit methane-oxidizing archaea that are present m locations that are removed from the site of methane generation to minimise loss of methane in instances where methane is to be recovered.
  • This invention is not limited to use of indigenous microorganisms. Exogenous microorganisms can also be injected into the reservoir formation, although promoting indigenous methanogens is generally preferred. Formations most favourable for seguestration of carbon dioxide include those that are currently microbially active.
  • exogenous microorganisms suitable for growing in the subterranean formation are introduced into the formation by known techniques before, during, or after practicing the process of this invention.
  • the present invention can be practised in any formation that is suitable for microbial life or that can be modified to be suitable for microbial life.
  • 80 0 C or which can be cooled to below about 80 0 C are good candidates for the methods of the invention. In these circumstances exogenous methanogenic consortia could readily be introduced.
  • indigenous organisms are not likely to be active in formations hotter than about 80 0 C or where geochemical and geological data indicate that the reservoir has ever been heated to more than about 80 0 C, inactivating the indigenous microorganisms.
  • the appropriate microorganisms may need to be stimulated to be more active. This stimulation may be achieved by modifying one or more parameters of the formation environment. Parameters of the formation environment may be determined according to methods described above. 75696- 38
  • the environment may also be altered to slow the rate of methane degradation. Changes that increase the rate of methanogenesis may be selected to simultaneously decrease the rate of methane degradation.
  • Modifying formation conditions to increase the concentration of hydrogen gas may include not only introducing exogenous hydrogen gas, but also by facilitating release of H 2 gas.
  • hydrogen may naturally diffuse from one site in the formation to the site of active methanogenesis, and/or its movement could be facilitated by mechanical means, such as by drilling or fracturing formation rock and adjusting pressure regimes by infection or pumping fluids to facilitate fluid flow from one region to another. Because the temperature at which some H 2 is generated geochemically may be too high to support active methanogens, methanogenic 7 5696- 38
  • water-mineral reactions in situ may generate sufficient quantities of hydrogen to maintain methanogenesis within the temperature range at which microbial life can be sustained in the subsurface (e.g., at temperatures predominantly below 80 0 C).
  • the rate of production of hydrogen within the igneous rock body is important to the conversion of carbon dioxide to methane microbiologically where m situ produced hydrogen is to be used in the method of the invention. While large volumes of reactive Fe ++ bearing minerals and permeability related to fractures or included sedimentary rock fragments are important for in situ hydrogen production and fluid mobility allowing hydrogen and carbon dioxide flow, it is possible to create a local environment having more m situ hydrogen by using carbon dioxide as a sweep gas to sweep hydrogen generated from part of a rock body to the microbial reaction zone elsewhere.
  • Deep injection of carbon dioxide into the kimberlite or other igneous rock body means that carbon dioxide may act as a sweep gas, flushing hydrogen up to a microbial reaction zone where modifiers such as ammonium phosphate, for example, have been injected to support high rates of microbial activity and enable methane to be produced efficiently.
  • Interfaces between microbial populations and/or methanogenic zones may be selected and/or modified m a number of different ways. Microorganisms in subterranean formations tend to be most active at environmental boundaries such as between fermentation zones and methanogenesis zones. Thus, configurations for the process of the invention may be selected to optimise the surface area of an interface 75696-38
  • US 6,543,535 claims one method for increasing the number of environmental interfaces is to modify water flood injection rates.
  • the number of reservoir boundaries could also be increased by, for example, alternating or varying the injection of modifiers into the formation to in effect create moving environmental fronts.
  • small-scale environmental interfaces could be formed by, for example, forming emulsions in the formation or by changing the chemistry of any clay minerals present using techniques known to the skilled person.
  • Reservoirs could also be selected where there already exist natural interfaces between hydrogen charged waters and carbon dioxide rich waters produced either naturally over geological time or by anthropogenic activity. This would require knowledge of the reservoir, such as, for example, its geometry, porosity and permeability variations, and the connectivity of different parts of the reservoir to one another.
  • a method that sequesters carbon dioxide in reservoirs that contain hydrogen by reaction and conversion to methane, a useful fuel.
  • Kimberlite "pipes" or intrusions are fractured igneous rocks that are hydrogen generating and may therefore 75696- 38
  • kimberlite pipes contain ultramafic rocks that can be hydrated to form hydrous silicates (serpentine) and hydroxides as follows:
  • Free hydrogen is then formed by oxidation of Fe 2+ to magnetite (Fe 3 O 4 ) :
  • the matrix and fracture network in a kimberlite pipe can have dissolved hydrogen concentrations up to the mM range and free hydrogen gas levels to nearly 60 mol% of the gas phase m the rock system.
  • the hydrogen can support a population of H 2 -utilizmg microbes including sulphate reducers and most importantly, methanogens.
  • Kimberlites are intrusive igneous rocks that tend to form bodies of rock several hundred meters across and typically half a kilometre to several kilometres deep. Kimberlites often contain serpentine and clay minerals when weathered, and may have locally low matrix permeabilities which would necessitate hydraulic fracturing and fracture propping of the rocks to allow flow of nutrients or gases in and out of the formations.
  • high temperature (> 1200 0 C) CO 2 rich lavas are emplaced in shallow environments ( ⁇ 3 km) and the local rocks are subjected to high temperatures (>400°C) and when the encountered host rocks contain water, explosive boiling can occur with emplacement and mixing of host rocks into the kimberlitic matrix. This may lead, for example to sandstone or other permeable lithologies being admixed m the kimberlites as 75696-38
  • kimberlites m sandstone rich environments may be a favourable target environment for sequestration according to a method of the present invention.
  • Such occurrences are common in Western Canada, for example in the Buffalo Head Hills area where Lower Cretaceous sandstones of petroleum reservoir quality are intruded by Upper Cretaceous kimberlite intrusions with much brecciation (breaking of host rock and kimberlites into a fractured mixture of rock types) and inclusion of host rock in the kimberlite.
  • sandstones having serpentine-containing kimberlites may be easily detected by geophysical tools such as magnetometry and by borehole geophysical logs.
  • the mineralogy of kimberlites can be quite varied; however, careful injection and circulation of C0 2 -bea ⁇ ng water may enhance the alteration of olivines such as forsterite or fayalite (Fe-MgSiO 4 ) to serpentine to produce H 2 for methanogenesis while promoting carbon dioxide precipitation as magnesite, Fe precipitation as magnetite and excess Ca precipitation as calcite, all of which are more dense minerals than possible clay mineral alteration products. 75696-38
  • kimberlites containing lesser amounts of diopside may be of benefit because the alteration of diopside consumes hydrogen.
  • mmeralogical analysis using techniques such as x-ray diffraction or petrographic microscopy.
  • carbon dioxide precipitation as magnesite or calcite provides an added means of sequestering additional carbon dioxide in a method of the present invention.
  • Kimberlite deposits m a formation, including deep subsurface environments, can then be selected to further maximize carbon dioxide sequestration in addition to carbon dioxide sequestration by methanogenic bacteria.
  • Magnetite (Fe 3 O 4 ) formation is favoured in low SO 4 waters typically found in kimberlites if HCO 3 - is present m the water as it would be for this carbon dioxide infection process. While this reaction consumes some H+, magnetite is a very dense mineral that would create pore space improving reservoir permeability to enable fluid circulation.
  • C ⁇ 2 - ⁇ ch waters may cause precipitation of carbonate minerals, usually as calcite, until calcium from the alteration of diopside (CaMgSi 2 Oe) and olivine (CaSiO 4 ) is consumed.
  • C0 2 -rich water may then be mixed with H 2 -rich kimberlite waters to form methane microbially.
  • Maintaining the pH above 10 in some reservoir zones may encourage magnetite precipitation instead of hematite. As both magnetite and hematite are very dense minerals, this may minimize pore space loss.
  • the SO «j content of injected waters should be minimized to limit sulphide precipitation and Fe trapping m hematite rather than magnetite and also 7 5696- 38
  • pH modification by, for example, acid injection may be required, including by, for example, inorganic (e.g. hydrochloric acid) or organic acid (e.g. acetic or citric acid) injection.
  • inorganic e.g. hydrochloric acid
  • organic acid e.g. acetic or citric acid
  • the porosity and permeability of kimberlites is higher near the surface where the rock is weathered as compared to lower at depths where there is no alteration. Also, very dense minerals (spinel or olivine) are being converted into a less dense hydrated mineral when serpentine is produced, resulting in a loss of porosity.
  • the reservoirs are typically fractured with sand or ceramic propped fractures on a regular basis to maintain hydraulic connection in the reservoir.
  • microbial and formation environment in subsurface or surface reactors may be conducted, and modified appropriately.
  • the formation conditions and the microbial dynamics (ecology) may be monitored throughout the process of the invention. This monitoring can be performed in any suitable manner, including the formation and microbial analyses described above.
  • Normally fluid (for example, gas and/or water) samples are obtained from the formation through one or more wells m communication with the formation.
  • the samples can be analyzed for hydrogen, carbon dioxide and methane concentrations and carbon (methane, C02) and hydrogen (methane, hydrogen) isotopic compositions as well as to determine the concentration and type of microorganisms in the fluid and the concentration of modifiers and microbial 7 5696- 38
  • the invention is not limited to any particular process of introducing a material into the formation.
  • the agent could be added to any suitable carrier including, for example, an agueous solution, gas (such as CO 2 ) , solvent or polymer injected into the formation by any appropriate procedure.
  • gas such as CO 2
  • the implementation of the present invention will often involve adding a stimulant package of modifiers by waterflood injection. However, addition of water is not necessary to practice the process.
  • microbial stimulants or reservoir treatments are added to the carrier and injected into the formation through one or more injection wells and pumped to flow toward one or more production wells.
  • the amount of carrier introduced into the formation and the concentration of modifier contained m the carrier will depend upon the results desired. The person skilled in the art will be able to determine appropriate amounts and concentrations .
  • modifiers can be injected into the formation together or in separate injection steps. For example, a slug or bank of water carrying one modifier may be followed 7 5696-38
  • a second slug or bank of water carrying a second modifier includes alternately injecting a slug or bank of water carrying one modifier followed by a gas injection step carrying a second modifier.
  • Other examples include injection of stimulants at one location to enhance methanogenesis, and/or injection of inhibitors at a different location to inhibit detrimental processes such as methane oxidation or hydrogen consumption.
  • Injection of a gas below the reactive zone may facilitate circulation of waters and nutrients to the microorganisms and may also allow for injection of volatile microbially accessible nutrients such as phosphmes or ammonia which would disperse rapidly in any gas phase in the reservoir environment. This may be accomplished by having one or more injector wells below the reaction zone.
  • Carbon dioxide may be introduced into the formation using means known to the person skilled in the art, and including means described above for adding a modifier to the formation.
  • it may be introduced as a pure stream of gas, or as supercritical carbon dioxide or as a carbon dioxide rich gas such as a flue gas containing enhanced levels of carbon dioxide. This may be done physically by using one or more wells that penetrate the formation.
  • Carbon dioxide may be introduced into the formation before, after or at the same time modifications are being made to the microbial or formation ecology. Modifications may be made to enhance dissolution of injected carbon dioxide, such as by modifying formation pH and/or salinity using means 75696 - 38
  • Methane produced as a result of carbon dioxide sequestration can be recovered by any suitable means known to one skilled in the art.
  • one or more modifications are made to the microbial and/or formation ecology, carbon dioxide is injected, and then the formation is partially or wholly sealed for a sufficient period of time to allow carbon dioxide sequestration, and methane generation. Methane is then subsequently recovered. In another invention embodiment, methane is continuously recovered while modification of the environment and/or carbon dioxide injection is occurring.
  • Methane may accumulate in a gas zone or gas cap. This gas could be withdrawn through, for example, a conventional gas production well that communicates with the gas zone or gas cap. An effective seal or cap rock may be desirable to build up a free gas phase.
  • gas production rates according to the processes of the invention will be high compared to geological gas production rates such that economic concentrations of methane can accumulate even in the absence of high quality seals that would be needed to maintain a gas accumulation over long geological timescales.
  • An effective seal could be made by means known to a skilled person, including, without limitation, by creation of an artificial impermeable layer in situ (such as, for example, by injection of a polymer) or by modification of the formation environment (such as, for example, by modifying clay mineral formations to cause expansion/contraction) . 7 5696- 38
  • Methane may also accumulate in a free-gas phase overlying a water saturated zone or as an enhanced methane concentration within a water saturated zone in the formation. Methane could then be produced, for example, as a product entrained in produced water. In still other formations, methane may be produced through different zones of wells previously used for other purposes. To enhance microbial gas release it may be beneficial to drop the overall formation pressure by, for example, water production.
  • Gas flushing or sparging of reactive zones of a formation by injecting gas from a well or by producing gas in a reservoir layer below the zone to be flushed could also be employed to recover methane.
  • a gas phase e.g., carbon dioxide, nitrogen or mixtures of methane, carbon dioxide or nitrogen
  • Simple partitioning would occur to permit methane removal in a free gas phase or gas flushing could be used to move hydrogen from one part of the formation to a site of microbial carbon dioxide conversion.
  • a layered reservoir bioreactor is created in the formation. This serves the purpose of generation of a gas sweep in situ by the methanogenic degradation of, for example, organic matter injected into the formation. Reactive zones may be vertically segmented and the formation environments controlled in the following manner, for example:
  • Gas produced from introduced organic waste in the deeper zone may increase formation pressure, improve fluid or gas recovery, including by producing gas bubbles which may aid in movement of fluid through the reservoir zones transporting hydrogen, nutrients and methane.
  • Organic matter containing fluids include, without limitation, sewage waste, waste waters (e.g. liquid waste), biomass, industrial chemical wastes and farm wastes, among others and synthetic mixtures of reactive organic matter and water.
  • Organic matter may also be introduced for purposes other than for the production of gases.
  • Organic matter containing fluids may accelerate methanogenesis, including by providing beneficial microorganisms and nutrients to methanogenic archaea.
  • Organic matter degrading microorganisms can also be introduced into the formation. Injection of organic matter-degrading microorganisms can be facilitated by injection of reactive liquid organic matter into or below gas accumulation zones or into or below 75696 -38
  • Organic matter containing fluids could be injected as part of a pressure maintenance program into microbially active formations or into sterile formations needing inoculation with microorganisms, for instance.
  • Figure 2 illustrates a combination of a vertical, inclined or horizontal production well and a vertical, or inclined injector well.
  • a power plant (10) is shown, which generates a carbon dioxide rich effluent gas stream.
  • This gas stream flows to an injector well (20) that injects the CO 2 gas plus any microbial or formation modifying agents (including water, organic wastes) into a geological formation, such as, for example, a fractured ultrabasic rock formation, which is actively generating hydrogen gas by mineral-water reactions.
  • microbial or formation modifying agents including water, organic wastes
  • Figure 2 shows a subterranean environment having four formations (30, 40, 50 and 60).
  • Formation (30) may be an overburden comprising sedimentary rocks, for example.
  • Formation (40) may be a kimberlite or other igneous rock containing olivine or serpentine, for example.
  • Formation (50) may be a porous and permeable sandstone at the base of the sedimentary package, for example, and overlying a basement package of igneous and metamorphic rocks (60), for instance.
  • CO 2 gas injection is taking place into both the fractured kimberlite formation (40) and the more permeable sandstone 75696- 38
  • the injected carbon dioxide is microbially reduced to methane with hydrogen generated in the kimberlite .
  • pressure conditions in the reservoir may be adjusted to maximise carbon dioxide concentration in formation waters while allowing produced methane to flow to the production well .
  • Production well (70) may be used to produce any gases or gas saturated waters to surface. Some fraction of the produced methane may be used as fuel. Carbon dioxide may be separated from recovered gases for reinfection into the injector well (20), recycling it.
  • Ground water flows into the formation. Moving and stationary groundwater reacts with ferrous iron or other minerals m the kimberlite formation (40) and basement rock formation (60) to make hydrogen which then reacts with the injected carbon dioxide mediated by the methanogens to make methane in the kimberlite formation (40) , sandstone formation (50) and basement formation (60).
  • methane is recovered by the production well from the most permeable lithologies, separated at surface and transported to the power plant.
  • Effluent from the powerplant may be recycled appropriately and produced waters which may be rich in divalent cations or unused nutrients may be modified and reinjected into the subterranean environment to promote further CO 2 sequestration as carbonates as well as methanogenesis .
  • methane concentration may exceed the saturation level in the fluids and form bubbles of methane.
  • the generated methane can migrate to the top of the formation to add to any existing gas cap that is under production well (70) ; flow as dissolved gas in water produced at the production well (70) ; flow as a separate gas phase along with produced water; and/or if oil was originally present in the reservoir, methane may flow as gas dissolved in oil recovered m production well (70) . Methane may then be recovered at production well (70) using means known to a person skilled m the art.
  • the carbon dioxide gas may be injected into one part of the formation, for example, in a hydrogen rich lower portion of the kimberlite (40), and the produced gas is produced from another part of the system, for example, in the upper portion of the kimberlite (40) in a continuous process.
  • the natural density stratification can be used to separate the carbon dioxide and the methane.
  • the production well (70) is used to produce methane.
  • An optional first step of the process might be to hydraulically fracture the formation to increase the fracture density in the formation to enhance carbon dioxide injection into and gas production from the formation.
  • the carbon dioxide may be a component of the fracturing fluids and may be in liquid carbon dioxide or aqueous solution form. If gas hydrate formation is an issue, hydrate inhibitors can be added to the injection stream provided that the impact on the methanogenic process is minimal or none. Typically these would not be needed.
  • a cyclical method to produce hydrogen gas may be employed. As shown in Figures 3A to 3C, 75696- 38
  • carbon dioxide may be injected through an injection/production well (100) into the fracture/matrix system of a kimberlite pipe (140) until a target pressure is achieved or a target volume of carbon dioxide is injected into the formation.
  • the rock matrix is porous and has the ability to store gas or liquid. Fractures in the formation enable transport of gas within the formation.
  • the injection/production well may be of any configuration including vertical, deviated, horizontal, extended reach, multilateral, etc.
  • the well may be shut in for a soak period and the rock system and injected gas allowed to mix and react under microbial action to produce methane.
  • methane can be produced m some wells without a shut in period as will be apparent to the skilled person.
  • the injection/production well may then be converted to a production well. Gases produced from the rock may be pipelined away to market.
  • Gas production can be permitted to continue from the rock system until the methane content is below a specified limit, for example 50% of produced gas by volume and cannot function as a typical fuel gas. Gas production may also be stopped at any stage of the process and the well converted to an injection well and the above process repeated. That is, carbon dioxide is again injected into the formation and the optional shut m and recovery cycle may be repeated.
  • a specified limit for example 50% of produced gas by volume and cannot function as a typical fuel gas.
  • Gas production may also be stopped at any stage of the process and the well converted to an injection well and the above process repeated. That is, carbon dioxide is again injected into the formation and the optional shut m and recovery cycle may be repeated.
  • carbon dioxide is injected into a formation (140) through a 75696-38
  • a production well (110) is located at some distance away and operated at a pressure different from the injection well to allow for a specified residence time for the injected carbon dioxide in the formation as it moves from the injection well to the production well.
  • the pressure difference can be established by someone skilled in basic reservoir engineering.
  • the carbon dioxide moves through the fractures (140) and porous matrix it is converted to methane and ultimately the moving gas composition changes, via microbial carbon dioxide reduction to methane using indigenous and/or added hydrogen, from one rich in carbon dioxide to one rich in methane as it flows from the injection well to the production well.
  • the porosity of the fractures is 0.02(2%) and the permeability is taken to be 10,000 rtiD.
  • the initial temperature and pressure of the formation is 24 degrees Celsius and about 2900 kPa, respectively. In the matrix, the initial water saturation is 0.45 (45%) whereas it is 0.10 (10%) in the fracture.
  • the simulation consists of a gas-water system so there is no oil phase present.
  • the gas composition at initial conditions is 100% hydrogen gas, both within the matrix and the fracture system and the simulation model also encompasses formations that contain some methane. Hydrogen gas is allowed to leak into the reservoir section of the model from the bottom of the reservoir to represent the capability of the reservoir rock to generate hydrogen gas from its entire volume.
  • a good tool for modelling reservoir scale microbial processes is a reactive reservoir simulator such as the commercially-available reservoir simulation software package STARSTM by Computer Modelling Group Inc.
  • This system permits the reaction and interconversion of many components in an environment which allows for effective simulation of advection and diffusion of the typical fluids found m a petroleum reservoir including solid, oil, water and gas phases.
  • Reactive reservoir simulators have been in use for decades and are an accepted means of simulating and designing reservoir processes that involve mass, heat and fluid transport along with chemical reactions and phase transitions.
  • Microorganisms are included in the reaction scheme acting as catalysts for the conversion of carbon dioxide and hydrogen to methane. Separate reactions and kinetic schemes are used to provide hydrogen from rock alteration.
  • the basic reaction system can be modified to reflect particular formation conditions as will be understood by the skilled person.
  • Figure 4A displays the cumulative carbon dioxide injected and cumulative carbon dioxide produced during the continuous (simultaneous carbon dioxide into lower injection well and gas production from the top well) process. Cumulative production volumes of methane and hydrogen from the reservoir are also plotted.
  • Figure 4B displays the carbon dioxide injection and gas component production rates. The results show that after 35 years of injection, roughly 72% of the injected carbon dioxide remains in the reservoir and is not produced back to surface. The results also show that initially hydrogen gas is displaced from the reservoir as carbon dioxide is injected into it. Gradually carbon dioxide is converted to methane in the formation and after about ten years of hydrogen production, the reservoir starts to produce some unreacted carbon dioxide and biogenerated methane.
  • the methane production rate grows to over 130 mcf/day and then declines nearly linearly as the process continues. As the methane production rate declines the carbon dioxide production rate grows. This suggests that the process may be terminated at some point where the methane rate is no longer economic and the carbon dioxide content m the produced gases is too large. Produced carbon dioxide can be separated and reinjected. This simulation of this embodiment of the process demonstrates that significant volumes of carbon dioxide can be sequestered in a reservoir for long time periods, gradually being converted to methane and that significant volumes of methane can be generated and produced. In practice, the volume of injected and produced 75696- 38
  • gases can be measured by standard gas volumetric rate measurement equipment.
  • Figure 5 displays locations of the injector (lower well) and producer (upper well) and the carbon dioxide mole fraction in the gas phase in the fractures after 10 years of carbon dioxide injection. The mole fraction of methane in the fractures is also shown. The results of the simulation show that the carbon dioxide, being denser than the hydrogen and methane tends to move to the lower parts of the reservoir.
  • the biogenerated methane exists as a bank ahead of the carbon dioxide bank. This is because methane is generated m parts of the reservoir where both hydrogen and carbon dioxide are present the generated methane tends to sit on top of the heavier carbon dioxide and below the lighter hydrogen.
  • carbon dioxide is injected at 16,000 mVday (283 mcf/day) (at standard conditions) into the reservoir for a period of about ten years. After ten years of injection, the well is shut in (no injection or production) for a period of two years. After this soak period is done, the well is converted to production and gas is produced.
  • the production well has two constraints: 1. a maximum gas rate equal to 12,000 m3/day (212 mcf/day) gas and 2. a minimum bottom hole pressure equal to 500 kPa. If the production well pressure drops below 500 kPa, then the well is shut in. In this example, the well is produced for 75696-38
  • the well could be shut in earlier and converted back to injection to sequester and convert additional carbon dioxide gas.
  • Figure 6A displays the cumulative carbon dioxide injected, produced, methane produced and hydrogen produced versus time. The volumes are all at standard conditions.
  • Figure 6B shows the carbon dioxide injection rates and gas production rates. The results show that no carbon dioxide is produced during the 35 year life of the process. That is, all of the injected carbon dioxide is sequestered and some fraction of it is converted to methane within the reservoir. The production rate of methane climbs after gas production starts and reaches over 100 mcf/day after 18 years of gas production. Thus long term sequestration of carbon dioxide is demonstrated as is economic recovery of methane .
  • Figure 7 displays the mole fraction of carbon dioxide and methane in the fractures after 35 years.
  • the results show that the amount of carbon dioxide in the reservoir has nearly been depleted. This suggests that a second cycle of carbon dioxide should be started.
  • the results also show that the gas mixture gravity segregates so the carbon dioxide sits at the bottom of the system, the methane next, and the hydrogen at the top.
  • olivines such as forsterite or fayalite (Fe or Mg-SiO4) to serpentine.
  • Serpentine may then be reacted to produce H 2 for methanogenesis .
  • Mg precipitation as magnesite, Fe precipitation as magnetite and excess Ca precipitation as calcite are promoted, all of which are more dense minerals than possible clay minerals and tend to better maintain some minimal permeability and porosity in the rock.
  • the amount of water injected during an embodiment of the process can be an important factor in controlling, not only microbial activity as determined by nutrient injection, but also the rate and nature of the alteration of the rock matrix.
  • Table 1 shows waterrrock ratios that achieve a rock porosity, favourable to the injection and sequestration of carbon dioxide.
  • Excess Mg is converted to magnesite (MgCC>3) at water: rock ratios of 0.1 to 0.5 with minor brucite (Mg(OH) 2 ) formation if serpentine saturation is 75696- 38
  • Table 1 assumes typical rock compositions for a kimberlite . This range of water: rock ratios is equivalent to 5 to 25 pore volumes for a 5% porosity rock (case 2 below) and 0.5 to 2.3 pore volumes for a 30% porosity rock (case 1 below) .
  • surface reactors may be clay lined pits with a clay seal or a surface tank, pressure or reactor vessel. Piping into and out of the surface reactors permits the injection of nutrients, carbon dioxide 75696- 38
  • Mined rock aggregates or mine tailings can also be used to fill the containers.
  • the containers may be sealed so that they become anaerobic.
  • Rock aggregate can be selected such that microorganisms would be naturally present in the rock aggregate and thus introduced into the surface reactor, but microorganisms could also be separately introduced into the surface reactor.
  • methanogenic cultures are added to the surface reactors.
  • CO 2 is flowed through the reactors, and the methanogens convert the CO 2 to CH 4 , which may then be recovered from the reactor.
  • Various additives may be added to reactors to promote hydrogen production and the conversion of CO 2 into methane.
  • mineral rich solutions such as tailings of mine operations, mined kimberlite or other reactive rock, or a combination thereof, may be added to the surface reactor.
  • igneous rock mine tailings are added to the reactor.
  • the surface reactor should be filled to contain a hydrogen generating rock media to provide a source of hydrogen for the methanogenic microorganisms to use m converting the added carbon dioxide to methane.
  • the method then further comprises promoting the generation of hydrogen from the hydrogen generating rock media using methods described herein and known to the skilled person.
  • additional hydrogen rich gas for the process may be obtained from a surface source (e.g., a natural or industrial source) or from a subterranean formation as described above and 75696- 38
  • Reactors could be operated in batch, semi-batch or continuous modes.

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Abstract

Cette invention se rapporte à un procédé de séquestration active du dioxyde de carbone par conversion en méthane dans une formation souterraine grâce à l'utilisation de microorganismes. Le méthane peut être récupéré dans le cadre du procédé. Dans un autre aspect de l'invention, le procédé est modifié pour produire du méthane dans un réacteur de surface.
PCT/CA2008/000717 2007-04-18 2008-04-17 Procédé de séquestration du dioxyde de carbone WO2008128331A1 (fr)

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WO2009076948A2 (fr) * 2007-12-19 2009-06-25 Schmack Biogas Ag Réductones utilisées pour la production de biogaz
US20100120104A1 (en) * 2008-11-06 2010-05-13 John Stuart Reed Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products
EP2237853A1 (fr) * 2008-01-03 2010-10-13 The Trustees of Columbia University in the City of New York Systèmes et procédés permettant de renforcer<i>in situ</i>le taux de carbonatation de la péridotite
WO2011050385A1 (fr) * 2009-10-27 2011-05-05 Walter Doyle Procédé de séquestration du dioxyde de carbone
WO2011089151A3 (fr) * 2010-01-19 2011-11-24 Ecole Normale Superieure De Lyon Procede de production de gaz methane
EP2459725A1 (fr) * 2009-07-27 2012-06-06 The University Of Wyoming Research Corporation Systèmes et procédés de traitement de combustible propre biologique
CN102676643A (zh) * 2011-03-18 2012-09-19 中国科学院生态环境研究中心 一种可应用于油气勘探的有效的微生物检测方法
WO2012118411A3 (fr) * 2011-03-03 2013-08-15 Galadigma Llc Procédé pour le développement complémentaire des dépôts d'hydrocarbures naturels épuisés
WO2014033557A3 (fr) * 2012-07-26 2014-04-17 Profero Energy Inc. Émulsions pour améliorer l'activité microbienne dans un réservoir
US8746334B2 (en) 2011-12-07 2014-06-10 Husky Oil Operations Limited Microbial enhanced oil recovery process for heavy oil accumulations
US9085785B2 (en) 2008-11-06 2015-07-21 Kiverdi, Inc. Use of oxyhydrogen microorganisms for non-photosynthetic carbon capture and conversion of inorganic and/or C1 carbon sources into useful organic compounds
US9157058B2 (en) 2011-12-14 2015-10-13 Kiverdi, Inc. Method and apparatus for growing microbial cultures that require gaseous electron donors, electron acceptors, carbon sources, or other nutrients
US9193594B2 (en) 2009-07-10 2015-11-24 The Trustees Of Columbia University In The City Of New York Systems and methods for enhancing rates of carbonation of peridotite
WO2016151078A1 (fr) 2015-03-26 2016-09-29 Rohöl-Aufsuchungs Aktiengesellschaft Procédé de méthanogénèse hydrogénotrophe de h2 et de co2 en ch4
US10376837B2 (en) 2013-03-14 2019-08-13 The University Of Wyoming Research Corporation Conversion of carbon dioxide utilizing chemoautotrophic microorganisms systems and methods
US10407601B2 (en) 2017-02-24 2019-09-10 California Institute Of Technology Microabrasive compositions containing oöids
CN110652847A (zh) * 2019-11-14 2020-01-07 河南理工大学 基于煤矿采空区处置工业上废气中二氧化碳的装置及方法
US10557155B2 (en) 2013-03-14 2020-02-11 The University Of Wyoming Research Corporation Methods and systems for biological coal-to-biofuels and bioproducts
WO2021035076A1 (fr) * 2019-08-21 2021-02-25 Cemvita Factory, Inc. Procédés et systèmes de production de composés organiques dans un environnement souterrain
WO2023012670A1 (fr) * 2021-08-02 2023-02-09 Ohio State Innovation Foundation Systèmes et procédés pour la simulation d'interactions d'hydrogène au sein d'un gisement souterrain
US20230272698A1 (en) * 2021-07-30 2023-08-31 Ohio State Innovation Foundation Systems and methods for generation of hydrogen by in-situ (subsurface) serpentinization and carbonization of mafic or ultramafic rock
WO2024076442A1 (fr) * 2022-10-03 2024-04-11 Fmc Technologies, Inc. Procédé et systèmes de capture de carbone souterrain
WO2025005817A1 (fr) * 2023-06-26 2025-01-02 Instituto Superior Técnico Procédé de stockage du co2 dans des sols
WO2024220438A3 (fr) * 2023-04-17 2025-04-03 Chevron U.S.A. Inc. Procédés et systèmes d'optimisation du stockage de carbone dans des formations rocheuses souterraines mafiques et ultramafiques
US12270298B2 (en) 2023-06-05 2025-04-08 Expro North Sea Limited Natural hydrogen gas sampling system and method

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WO2009076948A2 (fr) * 2007-12-19 2009-06-25 Schmack Biogas Ag Réductones utilisées pour la production de biogaz
WO2009076948A3 (fr) * 2007-12-19 2009-11-12 Schmack Biogas Ag Réductones utilisées pour la production de biogaz
EP2237853A1 (fr) * 2008-01-03 2010-10-13 The Trustees of Columbia University in the City of New York Systèmes et procédés permettant de renforcer<i>in situ</i>le taux de carbonatation de la péridotite
US8524152B2 (en) 2008-01-03 2013-09-03 The Trustees Of Columbia University In The City Of New York Systems and methods for enhancing rates of in situ carbonation of peridotite
EP2237853A4 (fr) * 2008-01-03 2012-08-15 Univ Columbia Systèmes et procédés permettant de renforcer<i>in situ</i>le taux de carbonatation de la péridotite
US20100120104A1 (en) * 2008-11-06 2010-05-13 John Stuart Reed Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products
US9085785B2 (en) 2008-11-06 2015-07-21 Kiverdi, Inc. Use of oxyhydrogen microorganisms for non-photosynthetic carbon capture and conversion of inorganic and/or C1 carbon sources into useful organic compounds
US9193594B2 (en) 2009-07-10 2015-11-24 The Trustees Of Columbia University In The City Of New York Systems and methods for enhancing rates of carbonation of peridotite
EP2459725A1 (fr) * 2009-07-27 2012-06-06 The University Of Wyoming Research Corporation Systèmes et procédés de traitement de combustible propre biologique
US20130189750A1 (en) * 2009-07-27 2013-07-25 The University of Wyoming Research d/b/a Western Research Institute Biological and Chemical Process Utilizing Chemoautotrophic Microorganisms
US9764279B2 (en) 2009-07-27 2017-09-19 The University Of Wyoming Research Corporation Biological reduction of carbon dioxide pollutants systems and methods
EP2459725A4 (fr) * 2009-07-27 2014-07-02 Univ Wyoming Systèmes et procédés de traitement de combustible propre biologique
US10507426B2 (en) 2009-07-27 2019-12-17 The University Of Wyoming Research Corporation Systems and methods for biological conversion of carbon dioxide pollutants into useful products
WO2011050385A1 (fr) * 2009-10-27 2011-05-05 Walter Doyle Procédé de séquestration du dioxyde de carbone
WO2011089151A3 (fr) * 2010-01-19 2011-11-24 Ecole Normale Superieure De Lyon Procede de production de gaz methane
WO2012118411A3 (fr) * 2011-03-03 2013-08-15 Galadigma Llc Procédé pour le développement complémentaire des dépôts d'hydrocarbures naturels épuisés
CN102676643A (zh) * 2011-03-18 2012-09-19 中国科学院生态环境研究中心 一种可应用于油气勘探的有效的微生物检测方法
US8746334B2 (en) 2011-12-07 2014-06-10 Husky Oil Operations Limited Microbial enhanced oil recovery process for heavy oil accumulations
US9157058B2 (en) 2011-12-14 2015-10-13 Kiverdi, Inc. Method and apparatus for growing microbial cultures that require gaseous electron donors, electron acceptors, carbon sources, or other nutrients
WO2014033557A3 (fr) * 2012-07-26 2014-04-17 Profero Energy Inc. Émulsions pour améliorer l'activité microbienne dans un réservoir
US10557155B2 (en) 2013-03-14 2020-02-11 The University Of Wyoming Research Corporation Methods and systems for biological coal-to-biofuels and bioproducts
US10376837B2 (en) 2013-03-14 2019-08-13 The University Of Wyoming Research Corporation Conversion of carbon dioxide utilizing chemoautotrophic microorganisms systems and methods
WO2016151078A1 (fr) 2015-03-26 2016-09-29 Rohöl-Aufsuchungs Aktiengesellschaft Procédé de méthanogénèse hydrogénotrophe de h2 et de co2 en ch4
JP2018510654A (ja) * 2015-03-26 2018-04-19 ロヘル−アウフズフングス アクチェンゲゼルシャフト Ｈ２及びｃｏ２のｃｈ４への水素資化性メタン生成方法
US10407601B2 (en) 2017-02-24 2019-09-10 California Institute Of Technology Microabrasive compositions containing oöids
WO2021035076A1 (fr) * 2019-08-21 2021-02-25 Cemvita Factory, Inc. Procédés et systèmes de production de composés organiques dans un environnement souterrain
CN114269880A (zh) * 2019-08-21 2022-04-01 塞姆维他工厂公司 用于在地下环境中产生有机化合物的方法和系统
CN110652847A (zh) * 2019-11-14 2020-01-07 河南理工大学 基于煤矿采空区处置工业上废气中二氧化碳的装置及方法
CN110652847B (zh) * 2019-11-14 2024-01-19 河南理工大学 基于煤矿采空区处置工业上废气中二氧化碳的装置及方法
US20230272698A1 (en) * 2021-07-30 2023-08-31 Ohio State Innovation Foundation Systems and methods for generation of hydrogen by in-situ (subsurface) serpentinization and carbonization of mafic or ultramafic rock
WO2023012670A1 (fr) * 2021-08-02 2023-02-09 Ohio State Innovation Foundation Systèmes et procédés pour la simulation d'interactions d'hydrogène au sein d'un gisement souterrain
WO2024076442A1 (fr) * 2022-10-03 2024-04-11 Fmc Technologies, Inc. Procédé et systèmes de capture de carbone souterrain
US12116868B2 (en) 2022-10-03 2024-10-15 Fmc Technologies, Inc. Method and systems for subsurface carbon capture
WO2024220438A3 (fr) * 2023-04-17 2025-04-03 Chevron U.S.A. Inc. Procédés et systèmes d'optimisation du stockage de carbone dans des formations rocheuses souterraines mafiques et ultramafiques
US12270298B2 (en) 2023-06-05 2025-04-08 Expro North Sea Limited Natural hydrogen gas sampling system and method
WO2025005817A1 (fr) * 2023-06-26 2025-01-02 Instituto Superior Técnico Procédé de stockage du co2 dans des sols

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