Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• coals are typically aromatic solids that yield aromatic liquid fuels upon conversion.
• coals (as commercially large deposits) that are very aliphatic in nature, giving them the propensity to yield hydrocarbon-rich fuels upon conversion and are, thus, ideally suited for the coal-biomass-to-liquids (CBTL) technology.
• the Wyodak- Anderson coal bed contains in its upper horizons a unit that has been shown to be high oil- yielding in Fischer Assay tests. Based upon these findings and on preliminary pyrolytic data, these coal units may be ideal and high oil-yielding feedstocks for the hydrous pyrolysis process disclosed herein. When subjected to gasification, these aliphatic coals may yield substantial amounts of hydrogen that would promote a more efficient FTS to liquid fuels.
• micro-algae is an aliphatic-rich biomass. These algae can be grown and harvested on a large scale in open pond systems. Proper selection of algal strains can provide a feedstock to coal conversion processes that adds to the propensity for the production of liquid hydrocarbons.
• the novel CTBL technology disclosed herein for the production of hydrocarbon fuels from coal-biomass mixtures involves a feedstock selectivity concept. Blending algae in the range of 8-15 wt. % with coal is disclosed for liquid fuels production. Feedstock selection for the conversion processes of highly aliphatic coal and biomass are disclosed to ensure that hydrocarbon rich fuels are produced in abundance.
• the gasification/FTS and hydrous pyrolysis of a novel blend of algae and aliphatic coal produces oils that can be subjected to a patented catalytic upgrading to optimize fuel quality.
• Optimum processes are disclosed for conversion of this coal/biomass mixture to a drop-in fuel that is readily refined by conventional refineries.
• the hydrocarbons produced by hydrous pyrolysis can be readily upgraded
• Catalytic upgrading technology is ideally suited for taking the oils produced from hydrous pyrolysis and converting them to hydrocarbon-rich fractions suitable for commercial use or further refining.
• Fig. 1 is a schematic of blue-green algae
• FIG. 2 is a schematic of product separation after microalgae liquefaction
• Fig. 3 is 13 C NMR spectra collected for whole algae before and after subcritical temperature treatment
• Fig. 4A shows analysis of the oil produced at 360°C for 72 hours by gas chromatography and gas chromatography/mass spectrometry of whole algae
• Fig. 4B shows analysis of the oil produced at 360°C for 72 hours by gas chromatography and gas chromatography/mass spectrometry of the algaenan isolate from the algae;
• Fig. 5 illustrates the vertical and lateral extent of the various facies in the
• Fig. 6 shows the yield of tar from Fisher Assay for the various samples of the
• Fig. 7 shows NMR data for samples of the Wyodak- Anderson coal that is rich in crypto-eugelinite
• Fig. 8 shows pyrolysis/gas chromatography/mass spectrometry trace of a sample of the Wyodak- Anderson seam that is rich in crypto-humotellinite
• FIG. 9 shows gas chromatography/mass spectrometry trace of the flash pyrolysis products from the crypto-eugelinite-rich sample
• Fig. 10A is GC/MS data of the total ion current for the oil produced obtained by hydrous pyrolysis of the crypto-eugelinite facies of the Wyodak- Anderson coal bed;
• Fig. 10B is GC/MS data of the extracted ioin chromotagram for m/z 57 for the oil produced obtained by hydrous pyrolysis of the crypto-eugelinite facies of the Wyodak- Anderson coal bed;
• Fig. 11 is a flow diagram of a process of producing hydrocarbons as disclosed herein.
• Liquid (hot compressed) water below the critical point is referred to as subcritical water.
• Ambient water is polar, has infinite networks of H-bonding and does not solubilize most organics.
• the H-bonds start weakening, allowing dissociation of water into acidic hydronium ions (H 3 O + ) and basic hydroxide ions (OFT).
• the ionization constant (K w ) of water increases with temperature and is about three orders of magnitude higher than that of ambient water.
• the dielectric constant ( ⁇ ) of water drops from 80 to 20 in the subcritical region.
• a low dielectric constant ⁇ allows subcritical water to dissolve organic compounds
• a high ionization constant K w allows subcritical water to provide an acidic medium for the hydrolysis of biomass components.
• the physical properties of water such as viscosity, density, dielectric constant and ionic product, can be tuned by changes in temperature and/or pressure in the subcritical region. For example, the dielectric behavior of 200°C water is similar to that of ambient methanol, 300°C water is similar to ambient acetone, and 370°C water is similar to methylene chloride.
• Biofuels offers several advantages over other biofuels production methods. Some of the major benefits are (i) high energy and separation efficiency, (ii) versatility of chemistry (solid, liquid and gaseous fuels), (iii) reduced mass transfer resistance, (iv) ability to use mixed feedstock as well as wet biomass, and (iv) completely sterilized products with respect to any pathogens including biotoxins, bacteria or viruses.
• the technology can be applied to produce solid, liquid, and gaseous fuels depending on the processing conditions. The substantial changes in the physical and chemical properties of water in the vicinity of its critical point can be utilized advantageously for converting lignocellulosic biomass/algae to desired biofuels.
• Microalgae are relatively small and protected, in many cases, by a thick cell wall as represented in Fig. 1, a schematic of blue- green algae.
• the schematic in Fig. 1 illustrates the cell wall 10, lipid granules 12, photo synthetic membranes 14, ribosomes 16 and nucleoid 18.
• very harsh conditions e.g. mechanical, chemical extraction
• the main structural elements of all plant cell walls are polysaccharides.
• the resistance of the algal cell wall 10 to microbial attack is generally attributed to the discrete structural entities and resistance of cell walls to decompose.
• Microalgae cell walls 10 mostly consists of carbohydrates (polymers of glucose, mannose, xylose, galactose, galacturonic acid, etc.) and little protein or lipids.
• Table 1 shows the chemical composition of the cell walls 10 of two species. Most algae have a variety of water- soluble polysaccharides. Cellulose, a part of the cell wall 10 in algae, is very widely distributed in the different species.
• the cell wall 10 also consists of alkali- soluble hemicelluloses and alkali- insoluble rigid walls. Cell walls, in general, are organized in a conventional framework. The basic framework is highly polymeric. Interspersed within are lower molecular weight polymers and oligomers (often gel like fibers) and inorganic and non-monomeric compounds.
• the polymeric components of microalgae namely carbohydrates, proteins, and lipids, have different depolymerization kinetics in the subcritical water medium.
• the hydrolysis rate increases with reaction temperature for these polymers.
• the hydrolysis of polysaccharides starts above 180°C in subcritical water within a residence time of seconds to a few minutes.
• the carbohydrates such as hemicelluloses, starches, and amorphous cellulose, are known to start depolymerizing to water soluble products in subcritical water above 180°C.
• hydrothermal degradation of cellulose is a heterogeneous and pseudo-first-order reaction for which detailed chemistry and mechanisms have been proposed.
• the subcritical water liquefaction (also termed hydrothermal liquefaction) process can utilize mixed biomass feedstock without any pretreatment or drying, at a comparatively low temperature.
• the process is used to convert biomass components to liquid products termed "biocrude.”
• Biocrude sometimes also referred as bio-oil, is an aqueous oxygenated solution derived from the direct liquefaction of biomass that can be converted to liquid fuel, hydrogen, or chemicals. Liquefaction of biomass in subcritical water proceeds through a series of structural and chemical transformations involving:
• biocrude yield was 23 wt% at 300°C in presence of 5 wt% Na 2 CO 3 .
• the higher heating value (HHV) of the biocrude was reported as 28-30 MJ/kg.
• the biocrude was a complex mixture of ketones, aldehydes, phenols, alkenes, fatty acids, esters, aromatics, and nitrogen containing heterocyclic compounds. Acetic acid was the main component of the water-soluble products.
• the bio-oil production is compared in Table 2 from three different microalgae strains and a cyanobacteria conducting hydrothermal liquefaction at 350°C and 20 MPa.
• Microalgae included Chlorella vulgaris, Nannochloropsis occulata and Porphyridium cruentum, and the cyanobacteria such as Spirulina with the biochemical properties given in Table 2.
• the yields of biocrude were 5-25 wt% higher than the lipid content of the algae depending upon biochemical composition.
• the yields of bio-crude followed the trend lipids > proteins > carbohydrates.
• Table 3 shows the HHV of the bio-oil was in the range of 33-39 MJ/kg when microalgae and cyanobacteria were used as feedstock.
• Nannochloropsis oculata was highest among these strains which are probably due to its higher lipid contents.
• the nitrogen content in bio-oil is due to the presence of protein fractions in the feedstock. Biocrude with low nitrogen and high carbon content is desirable. Nitrogen in fuel directly forms NO x compounds which are undesirable due to environmental pollution and legislative reasons.
• the energy recovery is calculated as the ratio of energy contained in biocrude to the energy contained in the feedstock. The study showed that each biochemical component (lipid, carbohydrate, and protein) of feedstock contributes to the bio-oil production which is a distinct advantage of hydrothermal liquefaction compared to conventional physical oil extraction methods.
• the products from hydrothermal liquefactions mainly consist of bio-oil, an aqueous phase (dissolved organics), light gases, and insoluble residual solids.
• bio-oil an aqueous phase (dissolved organics), light gases, and insoluble residual solids.
• aqueous phase dissolved organics
• light gases and insoluble residual solids.
• insoluble residual solids most of the carbon and hydrogen in the algal biomass should appear in bio- oil.
• the product separation is one of the most important aspects of hydrothermal liquefaction.
• an organic solvent such as dichloromethane, chloroform, hexane, and cyclohexane is used to separate bio-oil from the product mixture by liquid-liquid extraction step. Subsequently, organic solvent is evaporated to recover bio-oil.
• Fig. 2 shows the general schematics of product separation after microalgae liquefaction.
• the microalgae slurry 50 undergoes hydrothermal liquefaction 52, resulting in a product mixture 54.
• Gases 56 are removed from the product mixture 54 and the liquids undergo liquid-liquid extraction 58.
• An organic phase 60, an aqueous phase 62 and a solid residue 64 result from the liquid- liquid extraction 58.
• the organic solvent is removed from the organic phase 60 by drying 66, and the bio-oil 68 is recovered.
• a typical gas phase composition from hydrothermal liquefaction is CO 2 (66.2%),
• hydrothermal liquefaction of microalgae provides two major advantages over the other liquefaction processes. First, it can utilize biomass with very high water content and thus saves a considerable amount of energy required for dewatering. Second, the method is not species (type of feedstock) dependent where only species of high lipid contents can be used. The other polymeric components of microalgae such as proteins and carbohydrates also convert to bio-oil during the process so that, generally, higher bio-oil yield is achieved.
• hydrocarbons are likely the precursors of kerogen in shales that yield paraffinic petroleums upon natural maturation. Moreover, when pyrolysis techniques are employed for studies of algaenan, a near- 100% conversion to paraffinic oils is observed, particularly in the presence of water or hydrogen.
• One mechanism is to treat the solid residue with sodium hydroxide, which involves a saponification of the ester functions and leads to the formation of sodium salts of fatty acids.
• the sodium salt acts like an anchor on the carboxylic acid groups of the fatty acid, the same way that the ester functions are immobilized in the algaenan structure leading to facile cleavage of the carboxylic group (acid or ester) under pyrolytic conditions.
• thermal cracking using Curie-point pyrolysis of sodium salts of fatty acids that are representative of natural biomacromolecules in sedimentary organic matter
• the distribution of the compound series produced during the pyrolysis essentially depends in the nature and the position of the functional groups in the alkyl structure.
• the homolytic cleavage adjacent to the carboxylic group is a dominant process in the cracking of functionalized alkyl structures.
• FIG. 4A Analysis of the oil produced at 360°C for 72 hours by gas chromatography and gas chromatography/mass spectrometry is shown in Figs. 4A and 4B, showing that the major components are saturated normal hydrocarbons, similar to those observed in some crude oils.
• Fig. 4A is analysis of the whole algae
• Fig. 4B is analysis of the algaenan isolate from the algae.
• the oil obtained from hydrous pyrolysis of the algaenan shown in Fig. 4B is similar in composition to the whole algae in Fig. 4A.
• the yield of the whole algae at this temperature is 58% of the algaenan organic matter. This indicates that the oil produced during hydrous pyrolysis of the whole algae is primarily sourced from the algaenan.
• peaks are alkylated aromatic hydrocarbons derived from hydrous pyrolysis of proteins, from condensation of aliphatic structures or from aromatization of alicyclic components of algae.
• hydrocarbon-based fuels can be readily produced from the whole wet algae, the crude oil still contains protein and carbohydrate-derived compounds in the form of molecules that contain nitrogen and oxygen atoms. This means that this crude oil will need further treatment in order to refine the crude to fuels. Thus, there is a need for catalytic upgrading.
• the composition of the crude oil from the algaenan is composed mainly of hydrocarbons and will require less treatment to be refined.
• Gasification is a chemical process by which carbonaceous materials (coal, petroleum coke, biomass, etc.) are converted to a synthesis gas (syngas) by partial oxidation process with air, oxygen, and/or steam.
• syngas may be converted to a wide range of fuels and chemicals using several reaction pathways.
• Fischer-Tropsch synthesis is a major part of gas-to-liquids (GTL) technology, which converts syngas into liquid fuels with a wide-range liquid hydrocarbon fuels and high-value added chemicals.
• GTL gas-to-liquids
• Biomass gasification is attracting more attention due to the demand for renewable energy.
• biomass has a low energy density and high moisture content leading to high production and processing costs.
• Coal has been used in the commercial industry for syngas production for more than one century due to its abundance, relatively low cost and high energy density.
• humic coal has a low hydrogen to carbon ratio and higher CO 2 emission for liquid fuel production by FTS.
• there are more inorganic contents in coal which lead to higher impurities in the derived syngas.
• biomass to coal gasification reduces the cost of the feedstock.
• the addition of biomass to coal gasification reduces CO 2 emissions and also reduces problems caused by sulfur and ash contained in coal, because the biomass has almost no sulfur and low ash content.
• co-gasification can not only reduce the cost of the feedstock, but also reduce the problems that occur in plant operation due to the production of tar.
• the methods disclosed herein for co-gasification of coals and biomass address at least the following. How should the coal and biomass be mixed? How does the quality of the feedstock affect the quality of the product syngas? What are the optimum percentages of various blends of coal and biomass? What coals should be used for optimum hydrocarbon yields?
• Feedstock selection :
• asymmetricus which contains algaenan.
• a key element of the novel production of liquid hydrocarbons from coal is to determine coal that has the highest propensity to yield those liquid hydrocarbons during either of two conversion technologies-FTS or hydrous pyrolysis.
• Many coals of medium or low rank are mainly composed of a core aromatic structure. This is mainly because the source materials that formed the coals millions of years ago were mainly vascular plant materials rich in lignin. This lignin undergoes a molecular transformation during coalification to produce the aromatic core of coal. When subjected to liquefaction, the resultant liquids are very aromatic in character, in part due to the paucity of hydrogen-rich aliphatic structures.
• coals are not overly aromatic because they derive from plant materials other than terrestrial plants.
• Cannel coals are known to be mostly composed of plant spores (pollen), while boghead coals are mainly derived from algal organic matter. In many cases, these types of coals are not laterally extensive and, consequently, are not mined extensively.
• One of these is the Wyodak- Anderson coal bed in the Powder River Basin of Wyoming. In its upper section of approximately 4 meters of a lithofacies called by Stanton et al. crypto-eugelinite rich facies, which is laterally quite extensive as shown in Fig. 5.
• FIG. 5 illustrates the vertical and lateral extent of the various facies in the Wyodak- Anderson seam near Gillette, WY.
• this unit produces the highest oil yield for all facies examined by Stanton, R.W.,Warwick, P.D., and Swanson, S.M., Tar yields low-temperature carbonization of coal facies from the Powder River Basin, Wyoming, USA, Int. J. Coal Geol., 2005. 63: p.13-26 (Stanton et al.).
• Fig. 6 shows the yield of tar from Fisher Assay for the various samples of the Wyodak- Anderson seam plotted against the amounts of crypto-eugelinite in the samples.
• FIG. 9 shows gas chromatography/mass spectrometry trace of the flash pyrolysis products from the crypto- eugelinite-rich sample.
• the trace is the total ion current with numbers that denote alkanes and alkenes in the products.
• P is prist- 1-ene and DBF is a dibenzofuran. Note the homologous distribution of hydrocarbons extending from C 9 to C 32 . Some small quantities of phenols are present along with retene from resins.
• Figs. 10A and 10B The GC/MS data for the oil produced obtained by hydrous pyrolysis of the crypto-eugelinite facies of the Wyodak-Anderson coal bed is shown in Figs. 10A and 10B.
• Fig. 10A is the total ion current (TIC) while Fig. 10B is the extracted ion chromatogram for m/z 57 (EIC) that is indicative of alkane-like hydrocarbons.
• Figs. 10A and 10B show the dominance of n-alkanes extending from C 6 to C 33 . Isoprenoid alkanes (I), benzenes and alkylbenzenes (B), naphthalenes and
• alkylnaphthalenes N
• alkylphenanthrenes P
• the oil is dominated by the n-alkane hydrocarbons like those observed from petroleum and from the hydrous pyrolysis of algaenan. These n-alkanes extend from C 6 to C 33 in chain length and are characteristic of paraffinic oil that is often associated with coal-bearing strata in the geologic realm.
• Wyodak- Anderson coal are ideally suited for fuel production.
• these units of the Wyodak- Anderson coal are removed from the main body of the mined coal units and discarded as this facies is not ideal for use in combustion, like most coal from the Wyodak- Anderson seam. This is consistent with its high tar yields, which tends to be problematic for optimum combustion.
• Admixing the coal with a biomass such as algae or algaenan from algae, especially those algae that are enriched in the algaenan, provides an ideal blend of products that will yield valuable amounts of hydrocarbon-rich fuel-like products when subjected to hydrous pyrolysis or any other fuel conversion process that relies on the production of hydrogen-rich intermediate chemical species in the feedstocks (e.g., gasification, hydrothermal liquefaction, catalytic liquefaction, etc.).
• hydrocarbons suitable for commercial use or further refining are produced by a process that mixes an aliphatic-rich biomass and coal to obtain a feedstock in step 100.
• the feedstock is then subjected to a conversion process to produce a product mixture in step 102.
• the bio-oil, or hydrocarbons is separated from the resulting product mixture in step 104 for use or further processing. Separating the bio-oil can be done, for example, using liquid-liquid extraction to obtain an organic phase comprising the bio-oil, an aqueous phase and a solid residue.
• the process can further comprise refining the bio-oil in step 106 if desired or required depending on the intended use of the bio-oil.
• the aliphatic-rich biomass can be, for example, an algal biomass.
• the algal biomass can be mixed and processed wet, saving energy, time and costs by eliminating the need to dewater the biomass.
• the algal biomass can be about 8-15 wt. % of the feedstock, but is not limited to this range. The range may be different depending on the type of algae selected.
• the algal biomass can be selected from the Scenedesmus/Desmodesmus group, as a non-limiting example. One such algal selection is Desmodesmus cf. asymmetricus.
• the coal can be an aliphatic -rich coal, such as the eugelinite-rich coal described herein above.
• the coal can be selected from a hydrogen-rich coal containing polymethylene.
• the conversion process can be hydrothermal liquefaction.
• the hydrothermal liquefaction can occur at a temperature between about 320°C and 360°C.
• the conversion process can also be hydrous pyrolysis or a gasification process.

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• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)

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• 2013
  • 2013-07-26 WO PCT/US2013/052241 patent/WO2014022218A1/fr not_active Ceased

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