Extraction of phosphorus at biomass hydrothermal treatment

FIELD: process engineering.

SUBSTANCE: invention relates to hydrothermal treatment of biomass. Proposed method comprises the feed of biomass-based stock to reaction area. Stock water-to-biomass ratio makes at least 1:1. Note here that biomass-based stock contains phosphorus while stock hydrothermal processing is conducted under conditions efficient for hydrothermal processing with yield of multiphase product. The latter includes a fraction of solid particles containing about 80% of phosphorus of its content in said stock. Molar ratio between phosphorus and carbon of said fraction of solid substances makes at least 0.2. Said multiphase product is separated to get at least one gas-phase fraction, liquid hydrocarbon product and fraction of solid substances. Invention claims also the versions of process implementation.

EFFECT: efficient process, production of liquid hydrocarbon product.

27 cl, 1 tbl, 2 dwg, 5 ex

 

Area of technology

This invention relates to the hydrothermal processing of various types of biomass, such as algae, to produce hydrocarbon products, such as distillate fuels.

The level of technology

Traditional production of fuel and lubricants is still mainly carried out by conversion of a mineral oil feedstock to the desired products. To Supplement and/or replace traditional sources of renewable energy, it is necessary to overcome many problems.

One option for the replacement of traditional fuels and lubricants is the production of comparable fuel and lubricants on the basis of biomass. One advantage is based on the biomass fuel is that the resulting fuel product can be compatible with existing infrastructures and technologies. In the ideal case, the fuel and lubricants on the basis of biomass could be used in "face-off" instead of the traditional products that will allow you to apply renewable product without modification of existing equipment.

One option for processing raw materials type of biomass is hydrothermal processing. Hydrothermal processing includes the processing of raw materials with water at elevated temperatures and pressures. In US 618045 presents an example of a method of this type. This patent describes a method of converting biomass into hydrocarbon mixture with water at near-critical or supercritical conditions. Method can be used with various types of initial biomass materials. The biomass is treated at a pressure of 20 MPa (200 bar) 50 MPa (500 bar) and at temperatures from 320°C to 500°C. the Atmosphere in the reactor is described as a non-oxidative, and in example hydrogen. As the preferred processing time is indicated approximately 4 hours. Hydrothermal processing is described as getting " - like fluid, which, as it turns out, includes a significant proportion of aromatic and polymeric substances, as well as a certain amount of carbon and/or carbonized residues. In the description it is noted that some metals present in the original biomass, such as Ni or Fe, can change the types of the produced products. The description also noted that the metals can be used for more simple components of the mixture or for the removal of undesirable compounds. The only metal that is mentioned as an additive, metallic Cu is to extract sulfur compounds such as thiophenes. Nitrogen compounds defined as a product which can be removed by precipitation with metals, although examples of suitable meth�lia is not shown. From the description it is clear that the added metals are recovered metals", as opposed to metals in the oxidized state.

In WO 96/30464 described another example of processing of biomass under supercritical conditions. In the application described processing wet biomass, such as algae or water hyacinth, to produce gaseous hydrocarbons and hydrogen. The conversion conditions include the conversion of biomass into contact with water at supercritical conditions, which are defined as including a temperature above 374°C and a higher pressure of 22.1 MPa. The conversion occurs in the presence of a catalyst based on carbon, such as charcoal or activated carbon with high surface area. As described, the method provides a rapid and virtually complete gasification of the organic matter in raw materials.

Summary of the invention

In one aspect, the invention provides a method of hydrothermal processing of biomass. The method includes the introduction containing phosphorus of raw materials based on biomass when the ratio of water to biomass is at least 1:1 in the reaction zone. Raw biomass can be subjected to hydrothermal treatment under conditions effective to hydrothermal treatment, to obtain the multi-phase product. Multiphase product may include a fraction solids content�amounts of at least about 80% of the phosphorus content in the raw biomass. Multi-phase product can be divided with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids.

In another aspect of the invention provides another method of hydrothermal processing of biomass. The method includes adding a multivalent metal to raw biomass containing phosphorus. Raw biomass can be brought in contact with water in the presence of multivalent metal under conditions effective to hydrothermal treatment, to obtain the multi-phase product. Multiphase product may include the fraction of solids containing at least about 80% of the phosphorus content in the raw biomass. Multi-phase product can be divided with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids.

In another aspect of the invention provides another method of hydrothermal processing of biomass. The method includes casting containing seaweed raw materials based on biomass, such as phosphorus, in contact with water under conditions effective to hydrothermal treatment, to obtain the multi-phase product. Multiphase product may include the fraction of solids containing at least about 80% of the phosphorus content in the containing algae of Syrena the basis of biomass. Multi-phase product can be divided with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids. The phosphorus fraction of solids can mainly serve recycle in the environment for growing algae.

Brief description of the drawings

Fig.1 shows the reaction installation suitable for carrying out the method according to the embodiment of the invention.

Fig.2 process flow diagram of the method according to the embodiment of the invention.

Detailed description of the invention

One of the difficulties in the production of hydrocarbon products from different types of biomass may be in the handling of products that are different from carbon-containing products. In many cases, not containing carbon products can be considered as contaminants. Such contaminants may include sulfur-containing compounds and nitrogen-containing compounds formed from sulfur and/or nitrogen present in the biomass.

For some types of raw materials based on biomass such as raw materials based on algae or other types of raw material where the raw material included cellular structure, phosphorus can also represent a significant portion of the raw material. However, unlike sulphur, it may be advantageous to consider phosphorus as another product that is subject to extraction in the processing of cheese�me. Phosphorus can be incorporated into various cellular structures, such as lipids used to form the cell walls. Due to the importance of phosphorus in the development of cellular structures of phosphorus can be a valuable feed material for the growth of biological organisms. Phosphorus is required for growth of biological organisms, can represent a significant cost item in the process of growth. Although phosphorus and is one of the main selling products, resulting from the processing of raw materials based on biomass with obtaining hydrocarbon products, the ability to effectively capture and reuse of phosphorus can significantly improve the economic performance of the method of production of hydrocarbons.

In various embodiments provide methods hydrothermal treatment of raw materials based on algae (or other types of raw materials based on biomass), to obtain products having a boiling point in the temperature range of the boiling distillates, while providing opportunities for improved recovery and/or recycling of phosphorus. Hydrothermal processing of raw materials on the basis of algae may provide an opportunity for the conversion of biomass into molecules having a desired temperature range of the boiling point, and removing at least part of the impurities which are undesirable in distilla�tion products, such as nitrogen impurity, oxygen admixture, the admixture of unsaturated and/or aromatic compounds, metal impurities, etc. In various embodiments, the hydrothermal treatment conditions can be adjusted and/or improved to facilitate removal of phosphorus. This may include an increase in the total quantity of extractable phosphorus relative to the amount of phosphorus in the raw material. It may additionally or alternative include the increase of the ratio of phosphorus to carbon in the phosphate product obtained during the processing. Ways of improving the extraction of phosphorus can include the introduction of a multivalent metal, for example cations of polyvalent metal in the reaction medium for the formation of metal phosphates. Another option may include the temperature and/or duration of hydrothermal treatment, which increases the amount of extractable phosphorus in relation to its content in raw materials and/or the ratio of phosphorus to carbon in the solids formed during the reaction.

Algae can contain a significant amount of products such as triglycerides, fatty acids/fatty alcohols and isoprenoids that can be converted into valuable products such as transport fuels and lubricants. However, there are some problems in the conversion of raw algae-based to fit upotrebleniyu products. One problem is the extraction from the algae required hydrocarbon molecules. Option of extracting hydrocarbon products from algae may be the use of a method based on solvent extraction. Unfortunately, some methods based on solvent extraction, require the use of a source of seaweed, which contains a small amount of water or does not contain it. Dehydration source of algae to a sufficient extent to permit the use of this type of extraction solvent, may require expensive surgery. Alternative methods of solvent extraction may allow the extraction from the sample of algae containing water. However, usually remains expensive stage since the solvent should be separated from water, for example, by distillation.

Alternatively, solvent extraction for extracting hydrocarbon products from the source of algae can be used for hydrothermal processing. Hydrothermal processing has the advantage that it can be done without water evaporation, which can reduce the process cost. However, another difficulty in the use of biomass to produce a hydrocarbon product may consist in the presence of impurities in the biomass. Raw seaweed can �have a relatively high concentration of molecules which may contain, among other things, sulfur, nitrogen, oxygen, phosphorus, Group I metals, Group II metals, transition metals, olefinic groups, aromatic groups. Due to the high content of impurities may need additional processing before hydrocarbon products from non-catalytic hydrothermal processing can be used in conventional processes.

Raw materials

In various embodiments of the invention raw materials based on algae or other raw materials based on biomass can be processed using catalytic hydrothermal treatment. In such embodiments raw may usually contain algae and water and may may contain additional raw materials from another source of biocomponent where the source of biocomponent represents any source, including biological material and/or derived from it, for example, from plants, animals, microbes, algae, or combinations thereof. Additionally or alternatively, the raw material can be a raw material obtained from the initial mixture containing algae and water, and possibly may contain raw materials from another source of biocomponent. Additionally and alternatively, raw materials in General can be a raw materials based on biomass.

Noted that the water present in the raw seaweed (�whether on the basis of other biomass), may include extracellular water and/or intracellular water. Intracellular water refers to the water contained within the cell membrane of a cell, such as cell algae. In the case of raw seaweed, raw materials, which seems relatively dry, based on the content of extracellular water may still contain a substantial fraction of intracellular water. In the case of algae, the cell walls which were destroyed (for example, largely dried/dehydrated seaweed), raw seaweed can contain only extracellular water (since destroyed cells do not have an inner side and have only the external side). In the case of raw materials based on algae, which contains intracellular water, when the ratio of water to (dry) algae requires a determination of what portion of the mass of algae refers to intracellular water, because intracellular water should be considered as the weight of water, and not a lot of dry algae. As illustrative example, a sample of algae may not contain extracellular water and still have the ratio of water to algae about 1:1 or more, for example about 2:1 or more, due to the amount of intracellular water in the algae. Thus, referred to in this document, the mass of algae refers to the dry mass of algae, except for the�m intracellular water.

For raw materials containing at least the algae and the water content of algae in the raw material may be at least about 5 wt.%, for example, at least about 10 wt.%, at least about 20 wt.%, at least about 25 wt.% or at least about 30 wt.%. Additionally or alternatively, the content of algae in the raw material can be about 50 wt.% or less, e.g., about 30 wt.% or less, about 25 wt.% or less, or about 20 wt.% or less. In terms of relationships, the ratio of water to algae in the raw material may be at least about 1:1, e.g., at least about 2:1, at least about 3:1 or at least about 4:1. Additionally or alternatively, the ratio of water to algae, could be approximately 25:1 or less, e.g., about 20:1 or less or about 10:1 or less. In some embodiments, the content of algae in raw materials relative to the amount of water can be based on practical considerations regarding the extraction of water from the source of algae. Thus, in some embodiments the algae can be loaded into the reactor in the form of a mixture or algae paste and water. Additionally or alternatively, the algae can be loaded into the reactor in a dry form with a sufficient amount of water, for example, to achieve demand�about the relationship of algae to water.

Algal oils or lipids can usually be contained in algae in the form of membrane components, products, accumulation and/or metabolites. Some strains of algae, in particular microalgae, such as diatoms and blue-green algae may contain proportionally high amount of lipids. Sources of algae for algae oils can contain varying amounts, e.g., from 2 wt.% to 80 wt.% lipids, based on total weight of the biomass itself.

Sources of algae for algal oils may include, but are not limited to, unicellular and multicellular algae. Examples of such algae can include Radovici, Chlorophyta, heterokontophyta, tribolite, glaucophyta, chlorarachniophytes, euglenida, haptophyta, cryptomonads, dinoflagellates, phytoplankton, etc., and combinations thereof. In one embodiment, algae can be of the classes Chlorophyceae and/or Haptophyta. Specific species can include, but are not limited to those listed, Neochloris oleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum, Pleurochrysis carterae, Prymnesium parvum, Nannochloropsis gaditiana, Tetraselmis chui, Tetraselmis tertiolecta, Dunaliella salina, and various species of Chlorella and Chlamydomonas reinhardtii. Non-limiting examples of additional or alternative sources of algae include one or more species of microalgae Achnanthes, Amphiprora, Amphora, Ankistrodesmus, Asteromonas, Boekelovia, Borodiella, Botryococcus, Bracteococcus, Chaetoceros, Carteria, Chlamydomonas, Chlorococcum, Chlorogonium, Chlorella, Chroomonas, Chrysosphaera, Cricosphaera, Crypthecodinium, Cryptomonas, Cyclotella, Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius, Euglena, Franceia, Fragilaria, Gloeothamnion, Haematococcus, Halocafeteria, Hymenomonas, Isochrysis, Lepocinclis, Micractinium, Monoraphidium, Nannochloris, Nannochloropsis, Navicula, Neochloris, Nephrochloris, Nephroselmis, Nitzschia, Ochromonas, Oedogonium, Oocystis, Ostreococcus, Pavlova, Parachlorella, Pascheria, Phaeodactylum, Phagus, Platymonas, Pleurochrysis, Pleurococcus, Prototheca, Pseudochlorella, Pyramimonas, Pyrobotrys, Scenedesmus, Skeletonema, Spyrogyra, Stichococcus, Tetraselmis, Thalassiosira, Viridiella and Volvox, and/or one or more species of blue-green algae Agmenellum, Anabaena, Anabaenopsis, Anacystis, Aphanizomenon, Arthrospira, Asterocaspa, Borzia, Calothrix, Chamaesiphon, Chlorogloeopsis, Chroococcidiopsis, Chroococcus, Crinalium, Cyanobacterium, Cyanobium, Cyanocystis, Cyanospira, Cyanothece, Cylindrospermopsis, Cylindrospermum, Dactylococcopsis, Dermocarpella, Fischerella, Fremyella, Geitleria, Geitlerinema, Gloeobacter, Gloeocapsa, Gloeothece, Halospirullina, Iyengariella, Leptolyngbya, Limnothrix, Lyngbya, Microcoleus, Microcystis, Myxosarcina, Nodularia, Nostoc, Nostochopsis, Oscillatoria, Phromidium, Planktothrix, Pleurocapsa, Prochlorococcus, Prochloron, Prochlorothrix, Pseudanabaena, Rivularia, Schizothrix, Scytonema, Spirulina, Stanieria, Starria, Stigonema, Symploca, Synechococcus, Synechocystis, Tolypothrix, Trichodesmium, Tychonema and Xenococcus.

After catalytic hydrothermal treatment of the products from catalytic hydrothermal processing can be combined with biocomponents and/or raw materials on a mineral basis. Joint source material may include a different number of commodity flows on the basis of sources of biocomponents. If necessary, the raw material can include at least about 0.1 wt.% raw materials on the basis of the source of biocomponent, for example, at least about 0.5 wt.%, at least about 1 wt.%, at least about 3 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 25 wt.%, at least about 50 wt.% or at least about 75 wt.%. In such embodiments the raw material may additionally or alternatively include about 100 wt.% or less of biocomponent, for example, about 90 wt.% or less, about 75 wt.% or less, or about 50 wt.% or less. In other embodiments, the amount of raw materials on the basis of biocomponent (e.g., for joint processing with a part of the raw materials based on mineral oil) may be relatively small, for example in the case of raw materials, which includes at least about 0.5 wt.% source material on the basis of the source of biocomponent, for example, at least about 1 wt.%, at least about 2.5 wt.%, at least about 5 wt.%, at least about 10 wt.% or at least about 20 wt.%. In such embodiments the raw material may additionally or alternatively include about 50 wt.% or less of the initial material on the basis of biocomponent, for example, about 25 wt.% or less, about 20 wt.% or less, about 10 wt.% or less, or about 5 wt.% or less.

In various embodiments of the invention the combined source material can include with�Riez from various sources of biomass or biocomponents, such as vegetables (higher plants), animals, fish and/or seaweed. In General, these sources of biocomponents can include vegetable fats/oils, animal fats/oils, fish oils, pyrolysis oils, and algae lipids/oils, as well as components of such materials, and in some embodiments can specifically include one or more types of lipid compounds. Lipid compounds usually are biological compounds that are insoluble in water but soluble in nonpolar (or fat) solvents. Non-limiting examples of such solvents include alcohols, ethers, chloroform, allylacetate, benzene, and combinations thereof.

The major classes of lipids include, but are not necessarily limited to those listed, fatty acids, formed from glycerol lipids (including fats, oils and phospholipids), obtained from sphingosine lipids (including ceramides, cerebrosides, gangliosides, and sphingomyelins), steroids and their derivatives, terpenes and their derivatives, fat-soluble vitamins, certain aromatic compounds and long-chain alcohols and waxes.

In living organisms lipids generally serve as the basis for cell membranes and as a form of energy storage. Lipids can also meet associated with proteins or carbohydrates, for example in the form of lipoproteins and lippolis�aridol.

Examples of vegetable oils that can be used in accordance with this invention include, but are not limited to those listed, rapeseed oil (canola oil), soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, linseed oil, camelina oil, safflower oil, babassu oil, Shea butter (tallow oil) and rice bran oil.

Vegetable oils that are mentioned in this document may also include the products of processing of vegetable oils. Non-limiting examples of products of processing of vegetable oils include fatty acid and alkyl esters of fatty acids. Alkyl esters typically include C1-C5alkyl esters. One or more of methyl, ethyl and propyl esters are preferred.

Examples of animal fats that can be used in accordance with this invention include, but are not limited to enumerated, animal fat (solid animal fat), lard (semi-solid animal fat), Turkey fat, fish oil and chicken fat. Animal fats can be obtained from any suitable source, including restaurants and meat processing before�the sector.

Animal fats, which are mentioned in this document also include products processing animal fats. Non-limiting examples of products of processing of vegetable oils include fatty acid and alkyl esters of fatty acids. Alkyl esters typically include C1-C5alkyl esters. One or more of methyl, ethyl and propyl esters are preferred.

Other types of raw materials based on biocomponents, suitable for use in the present invention may include any of these types, which contain primarily triglycerides and free fatty acids (FFA). Triglycerides and FFA usually contain in their structure an aliphatic hydrocarbon chain containing from 8 to 36 carbon atoms, preferably from 10 to 26 carbon atoms, for example from 14 to 22 carbon atoms. Types of triglycerides can be determined according to their fatty acid components. The fatty acid components can be easily determined using gas chromatographic (GC) analysis. This analysis includes the extraction of fat or oil, saponification (subjected to hydrolysis) fat or oil, cooking alkyl (e.g., methyl) ester smilenov fat or oil and a type definition (methyl) ester using GC analysis. In one vopl�down of the majority (i.e. more than 50%) of the triglyceride present in the lipid material can be comprised of C10-C26the fatty acid constituents, based on total triglyceride present in the lipid material. In addition, the triglyceride is a molecule with a structure identical to the reaction product of glycerol and three fatty acids. Thus, although the triglyceride describe in this document as consisting of fatty acids, it should be understood that the fatty acid component contains optional hydrogen of the carboxylic acid. In one embodiment the majority of triglycerides present in the feedstock on the basis of biocomponent, may preferably consist of C12-C18the fatty acid constituents, based on total triglyceride content. Other types of raw materials, which are derived from biological components of the source material may include esters of fatty acids, such as alkyl esters of fatty acids (e.g., methyl esters of fatty acids (FAME) and/or ethyl esters of fatty acids (EAJC)).

Commodity flows are based on biocomponents, having a boiling point in the temperature range of the boiling point of diesel fuel may contain nitrogen and/or sulfur in a wide range of concentrations. For example, commodity flow based biocomponent - vegetable oil source may include �the flesh to about 300 wt. parts per million of nitrogen. On the other hand, commodity flow based on the biomass that contains integers or damaged algae, can sometimes contain a higher amount of nitrogen. Depending on the type of algae, the nitrogen content in the raw material flow on the basis of algae can be at least about 2 wt.%, for example, at least about 3 wt.%, at least about 5 wt.%, at least about 10 wt.%, and known algae with higher nitrogen content. The sulphur content in raw materials on the basis of biocomponent may also be different. In some embodiments, the sulfur content can be about 500 wt. parts per million or less, e.g., about 100 parts by weight. parts per million or less, about 50 wt. parts per million or less, or about 10 wt. parts per million or less.

In addition to sulphur and nitrogen and oxygen may be represented by another heteroatomic component in raw materials on the basis of biocomponents. Commodity flow-based bicomponent - oils, having a boiling point in the temperature range of the boiling point of diesel fuel, hydrotreated before may include up to about 10 wt.% oxygen, for example, up to about 12 wt.% or up to about 14 wt.%. Additionally or alternatively, the raw material flow on the basis of this biocomponent, having a boiling point in the range �of emperatur the boiling point of diesel fuel, may include at least about 1 wt.%. oxygen, for example at least about 2 wt.%, at least about 3 wt.%, at least about 4 wt.%, at least about 5 wt.%, at least about 6 wt.% or at least about 8 wt.%: Additionally or alternatively, the raw material flow on the basis of biocomponent before hydrotreated may have an olefin content of at least about 3 wt.%, for example, at least about 5 wt.% or at least about 10 wt.%.

Mineral hydrocarbon feedstock refers to traditional (e.g., not containing biocomponents) hydrocarbon source material, usually derived from crude oil, which may have been subjected to one or more separation processes and/or other refining processes. In one preferred embodiment of the mineral hydrocarbon starting material may be a source material based on oil, having a boiling point in the range of the boiling point of diesel fuel or higher. Examples of suitable starting materials include, but are not limited to those listed, the products of primary distillation of crude oil, gidroobladnannya products of primary distillation of crude oil, kerosene, raw materials having a boiling point in the temperature range of the boiling point of the diesel�Liwa (for example, gidroabrazivnoy raw materials having a boiling point in the temperature range of the boiling point of diesel fuel), light cycle gas oils, atmospheric gas oils, etc., and combinations thereof.

Mineral commodity flows to mix with commodity flows based on the biocomponents can have a nitrogen content from about 50 wt. parts per million to about 2000 wt. parts per million of nitrogen, for example, from about 50 wt. parts per million to about 1500 wt. parts per million or from about 75 wt. parts per million to about 1000 wt. parts per million In some embodiments of mineral raw stream may have a sulfur content from about 100 wt. parts per million to about 10,000 wt. parts per million of sulfur, for example, from about 200 wt. parts per million to about 500 wt. parts per million or from about 350 wt. parts per million to about 2500 wt. parts per million Additionally or alternatively, the combined raw material (based on biocomponents plus mineral) can have a sulfur content of at least about 5 wt. parts per million, for example, at least about 10 wt. parts per million of at least about 25 wt. parts per million of at least about 100 wt. parts per million of at least about 500 wt. parts per million, or at least about 1000 wt. parts per million additionally or alternatively, the combined source material mo�em to have a sulfur content of about 2000 wt. parts per million or less, e.g., about 1000 wt. parts per million or less, about 500 wt. parts per million or less, about 100 wt. parts per million or less, or about 50 wt. parts per million or less. Additionally or alternatively, the combined source material can have a nitrogen content of about 1000 wt. parts per million or less, e.g., about 500 wt. parts per million or less, about 100 wt. parts per million or less, about 50 wt. parts per million or less, about 30 wt. parts per million or less, about 20 wt. parts per million or less, or about 10 wt. parts per million or less.

The content of sulfur, nitrogen, oxygen and olefins in the raw material obtained by mixing two or more raw materials, it is usually possible to determine a weighted average based on mixed types of raw materials. For example, minerals and raw materials on the basis of biocomponent can be mixed in a ratio of 80 wt.% mineral raw materials and 20 wt.% raw materials on the basis of biocomponent. If the mineral has a sulfur content of about 1000 wt. parts per million, and raw materials on the basis of biocomponent has a sulfur content of about 10 wt. parts per million can be expected in the obtained mixed raw material sulfur content of about 802 wt. parts per million.

Commodity flows, having a boiling point in the range of the boiling point of diesel fuels�, suitable for use in the present invention, generally boil at a temperature of approximately 102°C (approximately 215°F) to about 427°C (about 800°F). Preferably, commodity flows, having a boiling point in the range of the boiling point of diesel fuel, have an initial boiling point of at least about 102°C (approximately 215°F), for example, at least about 121°C (about 250°F), at least about 135°C to about 275°F), at least about 149°C (about 300°F), at least about 163°C (325°F), at least about 177°C (about 350°F), at least about 204°C (about 400°F) or at least about 233°C (about 451°F). Preferably, the raw material stream having a boiling point in the range of the boiling point of diesel fuel has a final boiling point of about 427°C (about 800°F) or less, or about 413°C (about 775°F) or less, or about 399°C (about 750°F) or less. In some embodiments the raw material stream having a boiling point in the range of the boiling point of diesel fuel, can have an interval of boiling point of about 233°C (about 451°F) to about 427°C (about 800°F). Additionally or alternatively, the feedstock can be characterized by the boiling point required to boil a certain percentage of the raw materials. Eg�measures the temperature required to boil at least 5 wt.% raw materials are called boiling point "T5". In one embodiment the mineral oil feedstock can have a T5 boiling point of at least about 110°C (about 230°F), for example, at least about 121°C (about 250°F) or at least about 135°C to about 275°F). Additionally or alternatively, the mineral hydrocarbon feedstock can have a T95 boiling point of about 418°C (about 775°F) or less, e.g., about 399°C (about 750°F) or less, or about 385°C (about 725°F) or less. In another embodiment the raw materials having a boiling point in the temperature range of the boiling point of diesel fuel, may also include the connection of a range of kerosene to provide a raw stream with a boiling point in the range of boiling points from about 121°C (about 250°F) to about 427°C (about 800°F).

The conditions of hydrothermal treatment

In various embodiments, the catalytic hydrothermal processing can be performed with periodic, semi-batch or continuous type of production environment (environments). Regardless of whether the reaction occurs in the reaction system of periodic, semi-batch or continuous operation, any area of the system in which biomass is treated under hydrothermal conditions, and less�Ki, may be related to the so-called reaction zone. The reaction zone may correspond to the reactor for batch or semi-batch environment and/or the reactor, pipeline or other place hydrothermal treatment in the reaction system of continuous operation.

In embodiments comprising a periodic reactor operation, the reactor may be a reactor of periodic action of any type suitable for use in processing conditions. Due to the possible presence of water at supercritical conditions, stainless steel can be a suitable directionspanel material for the walls of the reactor. For surfaces of the reactor it is possible to use other materials and/or coatings that are described here are compatible with the reaction conditions. Examples of suitable reactors can include, but are not limited to those listed, autoclaves, mixers, plow mixers, etc., and combinations thereof. Alternative you can use a bubble column. One possible advantage of processing in batch or semi-batch mode can exist for algal raw material which has a relatively low fluidity. For example, when algae concentration relative to water of approximately 20 wt.% (i.e., approximately 4 mass parts of water for 1 hour mass�ü algae), the resulting mixture may have a paste consistency. A paste can be difficult to move, for example, with the use of pumps in the reactor with continuous flow.

In one embodiment of the reactor of periodic action can be used for catalytic hydrothermal processing of algal feedstocks. Part of the algal raw material, mixed with water, can be introduced into the reactor, which can then be purged (if necessary), for example, to remove any oxygen-containing gases. Additionally or alternatively, the reactor can also enter the catalyst. The catalyst can be included as part of a mixture of algae and water or the catalyst can be introduced into the reactor as part of a separate submission. Additionally or alternatively, it is possible to provide a partial pressure of inert gas and/or reducing gas. Examples of suitable reducing gases may include hydrogen, while suitable inert gases may include nitrogen. Additionally or alternatively, examples of suitable reducing gas may include any gas which does not enhance the amount of molecular oxygen in the reaction atmosphere, either before the reaction or as a result of dissociation with the formation of oxygen during the hydrothermal treatment. The partial pressure introduced into the reactor �additional gas, if present, may be at least about 0.1 MPa (about 1 bar), for example, at least about 2.5 MPa (about 25 bar), at least about 4.0 MPa (about 40 bar), or at least about 5.0 MPa (about 50 bar). Additionally or alternatively, the partial pressure of introduced gas into the reactor, if present, may be approximately 10 MPa (about 100 bar) or less, e.g., about 7.5 MPa (about 75 bar) or less, or about 5 MPa (about 50 bar) or less. Note that the introduction of the reducing gas may correspond to at least partial dissolution of the reducing gas in the water (e.g., water saturation) for hydrothermal treatment.

After the introduction of algae, water, catalyst and any additional restoration and/or inert gases, the reactor of periodic action can be sealed close. Then the reactor temperature can be raised to at least about 50°C, for example, at least up to about 80°C, at least up to about 100°C, at least up to about 150°C, at least up to about 200°C, at least up to about 250°C, at least up to about 275°C, or at least to about 300°C. Additionally or alternatively, the reactor temperature can be raised to about 500°C or less, for example, to about 00°C or less, to about 380°C or less, to about 350°C or less, to about 300°C or less, or to about 275°C or less. Additionally or alternatively, the pressure in the reactor may be at least about 0.1 MPa isbit. (approximately 1 bar isbit.), for example, at least about 450 kPa isbit. (about 4.5 bar isbit.), at least about 2.5 MPa isbit. (approximately 25 bar isbit.), at least about 4.0 MPa isbit. (about 40 bar isbit.), at least about 5.0 MPa isbit. (about 50 bar isbit.) or at least about 10 MPa isbit. (approximately 100 bar isbit.). Additionally or alternatively, the partial pressure of introduced gas into the reactor, if present, may be approximately 30 MPa isbit. (about 300 bar isbit.) or less, for example, about 25 MPa isbit. (about 250 bar isbit.) or less, about 22.5 MPa isbit. (about 225 bar isbit.) or less, or about 20 MPa isbit. (about 200 bar isbit.) or less.

In some embodiments, the combination of pressure and temperature in the reactor can be chosen so that the water in the reactor is not substantially undergo a phase transition (for example, did not undergo any phase transition). On the phase diagram of water critical point is at a temperature of about 374°C and a pressure of about 22 MPa. When combinations of temperature and pressure beyond this point on �the figure the state of the water does not undergo a phase transition from a liquid phase to a gaseous phase. Instead, beyond the critical point of water behaves as a single fluid phase. Thus, in some embodiments a combination of pressure and temperature can be chosen so that the water in liquid form in the reactor remains stable phase until, until they reach conditions outside the critical point. One way of satisfying this condition can be the choice of reaction temperatures and pressures below the critical point, and thus, it does not lead to a phase transition. Note that in some embodiments it is possible to provide a partial pressure introduced into the reactor additional gas (in this case a minimal amount of water may turn to steam, but the situation in the invention not considered as "significant" phase transition). If the partial pressure of the additional gas is above about 22 MPa, the pressure is already beyond the critical point for water and essentially no phase transition. Note also that in a closed reactor, for example, which can be achieved, the partial pressure of another gas, a significant phase transitions of water are not likely, provided that the volume of water in the liquid state is sufficient relative to the reactor volume.

Additionally or alternatively, the pressure inside reacto�and can be set by selecting the water temperature. In some embodiments, the reactor can be sealed or closed after the introduction of water and any additional gases, if present. The partial pressure of water vapor must be generated in the reactor in accordance with the temperature of the water in the reactor. With increasing temperature of the reactor the higher the partial pressure of water should be created in the reactor. The hydrothermal treatment can be performed at a pressure that is a combination of the partial pressure of water at the reaction temperature and the partial pressure of any inert and/or reducing gas and the partial pressure of any gases generated or released during processing. Examples of partial pressure of water at different temperatures can include about 0.01 MPa at about 50°C; about 0.05 MPa at about 80°C; about 0.1 MPa at about 100°C; about 0.5 MPa at about 150°C; about 1.6 MPa at about 200°C; 4.0 MPa at about 250°C to about 5.9 MPa at approximately 275°C; approximately 8.6 MPa at about 300°C; about 16.5 MPa at about 350°C and about 22.1 MPa at about 374°C. Since about 22.1 MPa at about 374°C corresponds to the critical point on the phase diagram of water, does not make sense to refer to the partial pressure of water �Ara" in the reactor at a temperature beyond this point.

In some embodiments of the hydrothermal treatment can be performed in the reactor with continuous flow. An example of a reactor with a continuous flow may be a pipe or other tubing that can be heated for raising the temperature of the injected into the pipeline material to the desired temperature hydrothermal treatment. For example, you can use the pipeline passing through the furnace and/or duct, surrounded by steam. The conduit may be of any convenient shape for passage through the heating zone. For example, you can use the tubing having a spiral shape to increase the size of the pipeline in a heating zone.

It was noted that the amount of water required to perform the hydrothermal treatment may be insufficient to provide the type of flow characteristics required for continuous flow conditions. Under processing conditions where continuous flow is one of the ways to improve the flow characteristics of a fluid medium algae may be the increase of water content in raw materials based on algae. However, the increase of water content can also lead to a corresponding decrease in the yield per unit volume of the reaction system due to the reduction in the number of algae in raw materials.

Fig.1 schematically shows an example of a reactor,�walking for use in the embodiment of the invention. Fig.1, the reactor 100 for hydrothermal treatment can be any type of reactor suitable for performing catalytic hydrothermal processing of raw materials based on algae (or other biomass). Flows into the reactor 100 may include feed stream 102 gas, for example, the supplied inert gas stream, the feed stream of gaseous hydrogen feed stream of another type of the reducing gas, or a combination. Another incoming stream may represent a feed stream 104 algae or biomass. If feed stream 104 algae has bad properties of strength, for example, due to a sufficiently low water content, feed stream 104 algae may alternatively be a supply not in the form of a stream, for example, extrusion, pouring or dumping of the feed stream 104 of algae in the reactor 100. If necessary, can be provided with additional feed stream 105 for various reasons. One additional feed stream 105 may be the introduction of additional quantities of water to maintain the conditions of hydrothermal treatment. Additional or alternative additional component of the feed stream 105 may be "inert" hydrocarbon stream (which may be minimally�th interaction in the conditions of hydrothermal treatment) and/or the recycled product stream. Such a hydrocarbon stream and/or the recycled stream can be used as a carrier for catalyst or catalyst precursor. Alternatively, the feed stream 104 algae and auxiliary feed stream 105 can be combined into one stream before entering the reactor 100. During the hydrothermal processing may form the output stream 107, which, for example, may be a mixture of different phases. Phase, which may be contained in the effluent 107 may include a gas phase, on the basis of hydrocarbon phase on the basis of water and one or more solid phases. These phases can, if necessary, be mixed with each other, for example, to mix the solids with the aqueous phase.

The catalyst for catalytic hydrothermal treatment

Another subject of choice in the treatment may be the use of catalyst hydrothermal treatment. The catalyst hydrothermal treatment can be in a form that is soluble in the environment of hydrothermal reactions (or at least in one of the supplied raw materials there), or the catalyst may be in the form of particles in the environment of hydrothermal reactions. The catalyst particles in the reaction medium can have any suitable size and/or distribution of particle size. The catalyst particles can, p�and necessity, to be caused to the catalyst where the catalytic material deposited on a substrate.

In the embodiment comprising a catalyst which is soluble in the environment of hydrothermal reaction, the catalyst can be introduced into the reaction either as a catalyst or catalyst precursor. A soluble catalyst can be soluble in water or in another solvent, is introduced into the environment of hydrothermal reactions. Examples of solvents may include, but are not limited to those listed, alcohols, acids, hydrocarbons or other oils. Additionally or alternatively, the solvent may correspond to the product that is formed in the hydrothermal treatment method. Examples of suitable catalysts or precursors of catalysts may include, but are not limited to those listed, salts of transition metals such as acetates of metals, carbonates of metals, production of metal acetylacetonates or combinations thereof. Examples of suitable metals for such metal salts may include, but are not limited to enumerated, Cr, V, Mo, Mi, Cu, Fe, Co, Mn, and combinations thereof. Additionally or alternatively, a suitable metal may include a metal of Group VIB or a metal of Group VIII, or a combination of one or more metals of Group VIB and one or more non-noble metals of Group VIII. Additionally or alternatively, pre�estwanik of the catalyst can be activated with the formation of metal sulfide by introducing a sulfur-containing stream into a reaction medium, such as flow H2S.

Regarding the number of algae, the amount of metal in a soluble catalyst or catalyst precursor in the reactor (reaction zone) may be at least about 0.01 wt.% (100 wt. parts per million), for example, at least about 0.05 wt.%, at least about 0.1 wt.%, at least about 0.25 wt.% or at least about 0.5 wt.%. Additionally or alternatively, the amount of catalyst in the reactor (reaction zone) may be about 5.0 wt.% or less relative to the amount of algae, for example, about 3.0 wt.% or less, about 2.0 wt.% or less, about 1.0 wt.% or less, about 0.5 wt.% or less, or about 0.25 wt.% or less.

In addition to soluble catalyst can be used applied catalyst comprising a noble metal (e.g. Pt, Pd, Rh, Ru, Ir or a combination). Additionally or alternatively, the catalyst carrier may be a hydrothermal stable media. Examples of suitable carriers may include, but are not limited to those listed, refractory oxides such as titanium dioxide and/or zirconium dioxide; silicon dioxide; activated carbon; carbon, which precipitated one or more metals selected from titanium, zirconium, vanadium, molybdenum, manganese and cerium; OK�IDA manganese; the hydrotalcite; other types of clays; and combinations thereof, such as a mixture of two or more of compounds such as titanium dioxide, zirconium dioxide and silicon dioxide. Additionally or alternatively, the carrier material may essentially not contain aluminum oxide. As used here, the expression "substantially not containing" aluminum oxide should be understood as containing less than 1 wt.% of aluminum oxide, preferably less than 0.1 wt.% aluminum oxide, for example, less than 0.01 wt.% of aluminum oxide, not containing added aluminum oxide or not containing aluminum oxide.

Another option of the catalyst can be a base metal or mixed metal oxide with the noble metal or not. Examples of such catalysts without noble metal may include, but are not limited to those listed, manganese oxide, hydrotalcite, sodium deposited on the titanium dioxide and/or zirconium dioxide, and combinations thereof.

Another option catalyst can be the use of metal catalysts for Hydrotreating, deposited on a suitable carrier. Examples of metal catalysts for Hydrotreating may include, without limitation, the combination of a metal of Group VIII (such as Co and/or Ni) with a metal of Group VIB (such as Mo and/or W). You can additionally or alternatively be used with�Etania three or more metals of Group VIII and/or Group VI (e.g., NiMoW, CoNiMo, CoMoW, etc.). Suitable materials media include the items listed above.

Another option catalyst can be the choice of the catalyst, which includes biocompatible materials. For example, the biocompatible material may be a material which can serve as nutrients for the growth of biomass, such as algae, and/or material that does not harm the environment biomass growth when the concentration of the material used for hydrothermal treatment. Biocompatible catalyst may, optionally, include a biocompatible carrier. Examples of suitable biocompatible metals in the catalysts may include K, Na, Mg, Ca, Fe, Zn, Mn, Mo, Cu, and combinations thereof. Biocompatible catalysts can be in the form of hydroxide, oxide, carbonate or ORGANOMETALLIC derivative, such as acetate or acetylacetonate (ACAC). Additionally or alternatively, the catalyst can be impregnated media such as activated carbon. Alternatively, the processed biomass, such as algae, can serve as a carrier for catalyst. In some embodiments these biocompatible materials of the catalyst can be recycled, either as feed nutrients for growth of biomass, either as a sum of the flow in the hydrothermal reaction� processing.

Regarding the number of algae, the amount of catalyst in the reactor (reaction zone) may be at least about 0.05 wt.%, for example, at least about 0.1 wt.%, at least about 1 wt.%, at least about 2.5 wt.% or at least about 5 wt.%. Additionally or alternatively, the number; of catalyst in the reactor (reaction zone) may be about 20 wt.% or less relative to the amount of algae, for example, about 15 wt.% or less, or about 10 wt.% or less.

The amount of metal deposited on the catalyst, may be different. Relative to the mass of the catalyst, the amount of noble metal deposited on the catalyst, if this metal is present, may be at least about 0.1 wt.%, for example, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.75 wt.% or at least about 1.0 wt.%, based on the total weight of the catalyst. Additionally or alternatively, the amount of noble metal deposited on the catalyst, if this metal is present, may be approximately 1.5 wt.% or less, e.g., about 1.0 wt.% or less, about 0.75 wt.% or less, or about 0.6 wt.% or less, based on the total weight of the catalyst. More generally, the amount of metal or metals,separately or in mixtures, on the catalyst carrier can be at least about 0.1 wt.%, for example, at least about 0.25 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.75 wt.%, at least about 1 wt.%, at least about 2.5 wt.% or at least about 5 wt.%, based on the total weight of the catalyst. Additionally or alternatively, the amount of metal or metals, separately or in mixtures, on the catalyst carrier can be about 35 wt.% or less, e.g., about 20 wt.% or less, about 15 wt.% or less, about 10 wt.% or less, or about 5 wt.% or less, based on the total weight of the catalyst.

The use of the catalyst may lead to additional problems during the hydrothermal processing. For catalyst or catalyst precursor, which is initially soluble in the reaction medium, one problem may be the separation of the catalyst from the reaction products. One of the ways offices can be a ltration. If the catalyst is insoluble in the reaction products, the resulting catalyst particles can be filtered from the product, which is mixed with the catalyst particles. One reason that the catalyst may be insoluble in the reaction products, is that of the CA�R was transformed into another form, for example, conversion of the precursor of the catalyst in the sulfide of the metal.

Applied (or bulk) catalysts may also have additional factors to be considered. Additionally or alternatively, the particle size of the catalyst can be modified, for example, to facilitate separation of catalyst particles from other solids. In this embodiment, the catalyst particles can have an average particle size of at least about 1000 μm, e.g., at least about 1,500 microns or at least about 2000 microns. To achieve the desired particle size of the catalyst formulation of catalysts can, if necessary, to be designed in such a way that they included a hydrothermally stable binder material, in addition to the carrier material and any active metal, if present. Suitable hydrothermally stable binder materials can be similar to the materials used as carrier material, and/or may include, but are not necessarily limited to those listed, oxides of one or more metals selected from silicon, titanium, zirconium, vanadium, molybdenum, manganese, and cerium. For the applied catalyst, which includes a binder, a carrier material can serve as a binder or you can use a different material in kacestvennogo.

Applied catalysts can be brought in contact with the raw material in the conditions of hydrothermal treatment, using reactors of different types. A batch or semi-batch reactor operation, described above, can be used with bulk catalysts. For example, the catalyst may be added to these reactors, when the algae, water and other possible gases introduced into the reactor. You can additionally or alternatively use a tubing with continuous flow. In the embodiment of this type the flow through the pipeline may constitute a suspension of catalyst particles suspended in the flow of algae and water.

In addition to reactors, suitable for non-catalytic processing, possible to use other types of reactors with continuous flow hydrothermal treatment of raw materials on the basis of algae, such as reactor with a fixed bed, the reactor with a moving bed reactor with a fluidized bed or etc. If they use a reactor with a fixed layer, one may have the problem of clogging of the catalyst layer, for example, due to solids present in raw materials based on biomass or algae. Clogging of the catalyst layer may result in higher than expected, the pressure drop across the catalyst bed due to the limitations of the flow of raw materials through the layer. In reactors with fixed bed frequent� can subject the processing of raw materials with a particle size of up to about 150 microns without significant problems associated with blockage. However, any clogging of the catalyst layer can be partially reduced, for example, by providing a by-pass pipe for regulating the pressure drop across the catalyst bed. Unfortunately, although individual algal cells have small diameters of about 150 μm to hydrothermal treatment by algae may have an increased tendency to agglomerate. As a result, 5% or more of solids on the basis of algae, resulting from hydrothermal treatment of raw materials on the basis of algae, can be in the form of agglomerated particles larger than 150 microns. However, in some embodiments it is possible to use a reactor with a fixed bed, in particular when the ability to agglomerate the resulting solids on the basis of algae can be reduced, e.g., by using a sufficient flow rate and/or other means.

Alternatively, the reactor with a porous layer for hydrothermal treatment can be used a reactor with a fluidized bed. In a traditional reactor with a fluidized bed as supplied raw materials (water and algae), and the processing gas (hydrogen-containing reducing gas) can be introduced into the reactor through the bottom of the reactor. In such reactors supplied by recycling the raw material containing part of the effluent from the reactor stream�, you can also enter through the lower part of the reactor. These flows of raw materials can move up the reactor and pass through the bars that support the catalyst provided to interrupt the supply of the catalyst in the field at the bottom of the reactor, where the feed pumps. The catalyst in these reactors fluidized bed is usually located above the grate that supports the catalyst.

When a stream (streams) the raw feed (and possibly additional gas reaches the catalyst layer, the layer usually becomes fluidized, resulting in the enhanced layer, and mixing within the layer. Raw (and hydrogen) can interact within the layer to form products, including liquid products, solid products and gaseous products. The flow in the traditional reactor with a fluidized bed can continue to rise up until the effluent is not discharged through the upper part of the reactor. This outward flow may be a combination of the desired product, unreacted hydrogen (if present) and gaseous by-products, including polluting gases, such as H2S and NH3that may be formed during the reaction. In preferred embodiments a portion of the liquid effluent stream can be recycled, for example, in the lower part of the Rea�Torah. If necessary, the gases can be separated from the liquid portion of the output stream.

The phosphorus content in the fraction of solids

Additionally or alternatively extracting a hydrocarbon product, can be useful for removal of solids algae (or other solids biomass). For example, you can extract the phosphorus from residual solids algae after hydrothermal treatment. One potential use of the extracted phosphorus can be used as nutrients for the growth of additional algae or other biomass.

Improving phosphorus extraction from hydrothermal treatment of biomass may include the coordination of several factors. One advantage of various embodiments may be that phosphorus forms a solid product, for example, that it can be filtered out of the flow of liquid products. Any amount of phosphorus, which remains as part of the liquid hydrocarbon product, and/or any amount of phosphorus, which becomes soluble in a solvent can be removed in one or more separate additional process. Below in the description of the extraction of phosphorus from the products of hydrothermal treatment can be estimated based on the amount of phosphorus extracted in the form of solids.

Because of�treatment of phosphorus can be estimated, based on the amount of phosphorus in the solid products, the original problem can be the development of conditions that lead to a large percentage of phosphorus in the solid products. One traditional way of processing of raw materials based on biomass, such as raw material on the basis of algae, may be the extraction of the desired hydrocarbon product from the raw material using an extraction solvent (e.g., such as a mixture of CHCl3and CH3OH). Extraction solvent may advantageously give the outputs of phosphorus in the solid products of more than 90 wt.% relative to the amount of phosphorus in the raw material. For an effective method of extraction of phosphorus may be desirable to have the output of phosphorus in the solid products on the content of phosphorus in the feedstock, at least 80 wt.%, for example, at least 85 wt.% or at least 90 wt.%.

One option of increasing the yield of phosphorus in the solid products may be increasing the number of multivalent cations in hydrothermal reactions. Many types of raw materials based on biomass can contain at least some multivalent cations such as Ca, Mg and/or Fe. These multivalent cations can form a phosphate or other solid substance on the basis of phosphorus as part of the solid products. For some types of raw materials to increase�of icesta available multivalent cations, for example, by adding more cations selected from Ca, Mg, Fe, Al or combinations thereof, can increase the amount of phosphorus in the solid products. In some of these embodiments may be added a sufficient amount of multivalent cations to provide a molar ratio of multivalent cations to the phosphorus atoms of at least about 1:1. This may correspond to the addition of at least about 0.1 wt.%, for example, at least about 0.2 wt.% or at least about 0.3 wt.% multivalent metal. Additionally or alternatively, the amount of added multivalent metal may be approximately 1.0 wt.% or less, e.g., about 0.8 wt.% or less, about 0.6 wt.% or less, or about 0.5 wt.% or less. Note that the amount of polyvalent metal may be reduced in the raw material, which already contains a certain amount of multivalent metal.

Another factor considered when selecting the conditions for hydrothermal treatment may be the relative amount of phosphorus in the solid products. As noted above, the solvent extraction can produce solid products that have a phosphorus content of over 90 wt.% relative to the initial amount of phosphorus in the raw material. Unfortunately, this traditional processing solvent moretake cause relatively large amount of carbonaceous solids for example, in which the phosphorus may be present in such a small amount, such as 5 wt.% or below. This can create some problems. First, you may need additional processing to extract phosphorus from solids containing a much larger proportion of solids on the basis of carbon, and/or other solids. Another problem might be that the relatively high carbon content in the solid products may increase the difficulty of using/selling solids for economic reasons. In other words, a large fraction of carbon in the solid products may mean that you can lose appreciable amounts of carbon and not transform it into the desired product.

The amount of phosphorus extracted in the solid products, the relative amounts of carbon may partly depend on the reaction conditions. No connection to any particular theory, it is believed that the relatively less stringent reaction conditions can lead to incomplete reaction of raw materials based on biomass. This can result in solids on the basis of algae (or other biomass) which have not reacted and/or responded only partially. The algae are initially solid substance, therefore, unreacted and/or partially reacted algae can still n�be in a solid state after incomplete reaction. Thus, unreacted and/or partially reacted algae can contribute to the carbon content in the solid products, which, consequently, may reduce the ratio of phosphorus to carbon. Note that incomplete reaction may additionally or alternatively to reduce the amount of phosphorus in the solids relative to the initial amount of phosphorus.

Also regardless of theory believe that the reaction conditions that are too stringent can lead to an increase in the amount of carbon in the solid products. Hydrothermal processing of raw materials on the basis of biomass may lead to increased formation of some of the heavier molecules, including aromatic compounds. A portion of these heavier molecules may correspond to insoluble compounds, which tend to the formation of solids. Thus, these additional solids can contribute to reduce the ratio of phosphorus to carbon in the solid products.

In some embodiments it is possible to choose the temperature of the hydrothermal treatment to improve the ratio of phosphorus to carbon in the solid products. For example, in one embodiment, the reaction temperature may be from about 275°C to about 325°C. Additionally or alternatively, in embodiments of the catalytic hydrot�micheskoj processing, the presence of a catalyst can reduce the temperature of processing, which leads to the increase of the ratio of phosphorus to carbon in the solid products. In such embodiments, the reaction temperature may be from about 250°C to about 300°C.

Additionally or alternatively, improving the relationship of phosphorus to carbon in the solid products of hydrothermal treatment either in the presence or in the absence of the catalyst can be based on a combination of the treatment temperature and time of reaction. For example, for a treatment time from about 60 minutes to about 105 minutes, the reaction temperature may be from about 250°C to about 300°C. For a treatment time from about 45 min to about 90 min, the reaction temperature may be from about 275°C to about 325°C. For a treatment time from about 30 min to about 60 min, the reaction temperature may be from about 285°C to about 335°C. For a treatment time from about 24 minutes to about 48 min, the reaction temperature may be from about 300°C to about 350°C. For a treatment time of about 15 min to about 30 min, the reaction temperature may range from about 325°C to about 375°C. For a treatment time from about 6 minutes to about 24 min, the reaction temperature may be from about 350°C to about 400°C.

Additionally or alternatively, improving the relationship of phosphorus to carbon in the solid products for the ka�alytically hydrothermal treatment can be based on a combination of the treatment temperature and time of reaction. For example, for a processing time from about 60 minutes to about 105 minutes, the reaction temperature may range from about 225°C to about 275°C. for a treatment time from about 45 min to about 90 min, the reaction temperature may be from about 250°C to about 300°C. for a treatment time from about 30 min to about 60 min, the reaction temperature may be from about 275°C to about 325°C; for a treatment time from about 24 minutes to about 48 min, the reaction temperature may be from about 285°C to about 335°C. for a treatment time of about 15 min to about 30 min, the reaction temperature may be from about 300°C to about 350°C, and for a treatment time from about 6 minutes to about 24 min, the reaction temperature may range from about 325°C to about 375°C. Note that in the continuous reaction medium, the reaction time can be more accurately described in the indicators of the residence time or space velocity.

The separation of the products of catalytic hydrothermal treatment

As a result of hydrothermal treatment may form a multiphase product. Multiphase product can include a gas phase, a hydrocarbon or oil phase and the aqueous phase, which may include solids. Gas phase, oil phase, water phase and solids can be separated from each other �Jobim the easy way for example, through the use of three-phase separator. Description oil phase are presented further below. In some embodiments the solid phase may initially be located together with the aqueous phase. For example, the solid phase can be suspended in the aqueous phase or can be precipitated precipitate, which is suspended and/or deposited in the aqueous phase. The solid phase may also have value and contain inter alia one or more of the following materials: phosphorus and other potential nutrients for algae and/or other microorganisms; unreacted and/or partially reacted biomass particles and a possible catalyst, if the process is a catalytic hydrothermal process. In some embodiments, the catalyst particles can be separated from other solid substances, to ensure the possibility of filing their recycle and feed recycle nutrients, if present.

Fig.2 shows a schematic example of a process flow for an embodiment of the invention, including algae as biomass for processing. Fig.2 shows an integrated circuit, where the products of hydrothermal treatment (possibly catalytic) direct recycle for reuse. Fig.2 the supply of biomass for GI�watermiscible process can be done from the source of algae. These algae can be obtained by a method 210 for growing algae, which may include any convenient and/or known method. Can be collected 220 of algae for conversion to hydrocarbon products. As part of the collection 220 of algae can, if necessary, remove some water from the algae. For example, water can remove completely from algae simultaneously with the receipt of seaweed, dried using freeze-drying. Alternatively, water can be removed using only mechanical processes, e.g., by centrifugation, which can have the advantage that as a result of raw materials on the basis of algae, having a weight ratio of water to algae about 10:1 or less, e.g., about 7.5:1 or less or about 5:1 or less. Additionally or alternatively, the mass ratio of water to algae may be at least about 2:1, e.g., at least about 2.5:1 or at least about 3:1. One benefit of running only a partial separation of the water and algae may be that less energy is required to perform only a partial separation, as compared with complete separation.

After collection, the collected algae can be used as feedstock for hydrothermal processing 230. Algal raw material can�, if necessary, combine with the catalyst, to provide the partial pressure of a gas, such as hydrogen, and, if necessary, combine with water, for example, if the algal raw material does not contain sufficient amount of water. Hydrothermal processing 230 may lead to the formation of a variety of products. The initial separation of these products can be performed in three-phase separator 240. Three-phase separator 240 can be used for the formation of gas-phase product 242, hydrocarbon or oil product 248 and 246 product comprising water and various solids. Gas-phase product 242 may include a hydrogen, inert gases that may be present during the hydrothermal processing 230, the gaseous products of hydrothermal processing 230 (such as CO2, CO, H2S, NH3etc., and combinations thereof), and low-boiling hydrocarbons formed during the catalytic hydrothermal processing 230. Low boiling hydrocarbons may include hydrocarbons that are gases at room temperature (such as methane, ethane, etc. or combinations thereof) and/or hydrocarbons that are gases at the temperature of phase separation. If three-phase separation is carried out at elevated temperature, they may include aliphatic hydrocarbons with higher tempera�take boiling and/or other substances (such as methanol). Note that some of the above products can be at least partially dissolved in the aqueous phase, for example the gaseous products of hydrothermal treatment.

In the products of hydrothermal processing 230 to the desired petroleum product or oil product can form a phase separate from the aqueous phase containing various solids. These distinct phases can be divided into three-phase separator 240. The resulting hydrocarbon product 248 may represent a desired oil product of catalytic hydrothermal treatment. The hydrocarbon product 248 can, if necessary, subjected to various types of additional processing, which may include a possible distillation 260 to separate from the product fractions 262 and 263 with the desired temperature range of the boiling and/or hydrotreated to improve the quality of the hydrocarbon product 248 or fractions 262 or 263 to apply. Additionally or alternatively, at least part of the hydrocarbon product 248 and/or fraction(s) 262 and/or 263 can, if necessary, to file recycle in hydrothermal processing 230, for example, to combine with the feed raw material algae/water, which can improve the fluidity of supplied raw materials.

In some embodiments 246 product comprising water and solids from the tre�phase separation, may contain several types of solids, which may include, but is not limited to this, a solid substance, derived from seaweed; solids containing phosphorus and/or various metals; unreacted or partially reacted biomass particles and a possible catalyst, including the spent catalyst particles. The 246 product comprising water and solids, can be further subjected to separation 250 solids, to separate the solids for later use. Office 250 solids can lead to the formation of water flow 257, particles 253 a possible catalyst and solids 259 derived from algae. Note that the possible separation of particles of catalyst from solids, derived from seaweed, can be performed prior to separating the water phase from the solids. In a preferred embodiment the particles are 253 possible catalyst can be returned to the catalytic hydrothermal processing for further use. Additionally or alternatively, the solids 259, derived from seaweed, can be returned to the method 210 of growing algae, for example, as raw material for the development of a new party algal feedstock. Additionally or alternatively, at least part of the water flow 257 and/�whether water from the product 246, containing water and solids, you can direct recycle in method 210 of growing algae, for example, to provide additional nutrients, such as nitrogen-containing substances (e.g., NH3).

Although the circuit of Fig.2 involves a sequence of processes that are located along the 210 and growing collection 220 of algae can occur in a location away from the catalytic hydrothermal processing 230. In this incarnation, the few arrows in Fig.2 may represent a stage of transportation, such as transportation of the collected algae to the place of the catalytic hydrothermal treatment and transportation of solids 259, derived from seaweed, on the area of cultivation of seaweed.

Processing solid foods for feeding recycle nutrients

As noted above, some of the solid products can be recycled for use as nutrients for growing more algae or other biomass. An example of this type of recycle feed can be a feed of recycle phosphoric compounds. For feeding the recycling of phosphorus phosphorus can be converted from a solid form in the form of a precursor that can be easily processed in a suitable nutrient. An example of this type converted�I can represent the transformation of phosphorus in the solid products in more easily distributable form such as phosphoric acid. Then phosphoric acid can be used either as nutrients or as a precursor or reagent to obtain nutrients.

Phosphorus may be contained in the solid products in various forms such as phosphates and/or phosphites, and can be coordinated Ca, Mg or other multivalent cations. Solids can also contain carbon compounds. To separate phosphorus from carbon, in one embodiment the phosphorus in the solids can be converted to phosphoric acid. The conversion of phosphorus into phosphoric acid is a known reaction, and it can be performed by processing containing phosphorus solids with sulfuric acid. Sulfuric acid can interact with phosphorus with the formation of phosphoric acid. Sulfate-sulfuric acid ions can connect with Ca or Mg cations and precipitate. In such situations, the carbon may remain as an additional solid product. Sulfate solids and carbon can be separated from phosphoric acid by means of mechanical and/or known/traditional means, such as filtration or settling pond.

Assessment of the products of hydrothermal treatment

Hydrothermal processing can be used to extract various hydrocarbon�s fractions from raw materials based on algae (or other biomass). One example of a hydrocarbon fraction that can be extracted from raw algae-based, may include and/or be a distillate fraction. As described below, the distillate fraction refers to a fraction which has a temperature range of the boiling point between about 193°C to about 360°C, or alternatively, the fraction having at least 90 wt.% substances, boiling in the range of boiling points from about 193°C to about 360°C (for example, T5 may be approximately 193°C or T95 may be approximately 360°C, or T2 may be approximately 193°C and T98 may be approximately 360°C, or etc.).

One way of assessing the products of hydrothermal treatment process, catalytic or non-catalytic, can be the consideration of the release of hydrocarbons from the process. The total output can be determined for the hydrothermal treatment process, based on the weight of hydrocarbon product collected relative to the initial mass of algae or other biomass. For the process of hydrothermal treatment it is also possible to determine the yield of distillate. One characteristic of the output can be the total output of a product with a boiling point in the temperature range of the boiling point of the distillate, relative to the initial mass of algae or biomass. Another characteristic may be the percentage obtained distillate consider�till then total yield of hydrocarbons.

Additional or alternative way of assessing the products of hydrothermal treatment process may be based on concentrations of various impurities in the products. In the non-catalytic hydrothermal treatment process (or in catalytic hydrothermal treatment process, analyzed excluding catalyst) hydrocarbon products may include impurities, such as nitrogen, oxygen, carbon-carbon double bonds and aromatic groups. Thus, it may be of interest percentage of heteroatoms (nitrogen and/or oxygen) in the total hydrocarbon product and/or receive the distillate. The percentage content of the carbon-carbon double bonds and aromatic groups can be measured using methods such as13C NMR, and/or you can use other source parameters such as the ratio of hydrogen to carbon in the products.

Additional incarnation

Additionally or alternatively, the present invention may include one or more of the following embodiments.

Embodiment 1. Method of hydrothermal processing of biomass, including the introduction of raw materials based on biomass, with the ratio of water to biomass is at least 1:1, in the reaction zone, and raw materials based on biomass contains phosphorus; hydrothermal processing of biomass under conditions effective�s for hydrothermal treatment, with obtaining a multi-phase product fraction comprising solids containing at least about 80% of the phosphorus content in the raw biomass, and separation of multi-phase product to obtain at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids.

The embodiment 2. Method of hydrothermal processing of biomass, including the addition of a multivalent metal to raw biomass containing phosphorus; the conversion of raw biomass into contact with water in the presence of multivalent metal under conditions effective to hydrothermal treatment, to obtain the multi-phase product fraction comprising solids containing at least about 80% of the phosphorus content in the raw biomass, and separation of multi-phase product to obtain at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids.

Embodiment 3. A method according to embodiment 2, wherein the polyvalent metal include Ca, Mg, Fe or a combination thereof, for example, includes Ca and/or Mg.

Embodiment 4. A method according to embodiment 2 or embodiment 3, wherein the polyvalent metal is added to the raw material on the basis of biomass in the reaction zone to bring the raw materials based on biomass in contact with water under conditions effective for hydrothermal�cal processing.

Embodiment 5. A method according to any of the preceding embodiments, in which raw biomass comprises algae.

Embodiment 6. Method of hydrothermal treatment of biomass, comprising a casting containing phosphorus-based materials containing algae biomass in contact with water under conditions effective to hydrothermal treatment, to obtain the multi-phase product fraction comprising solids containing at least about 80% of the phosphorus content in raw materials on the basis of containing algae biomass; separation multiphase/product, with the receipt of at least the vapor fraction liquid hydrocarbon product fraction and solids, and flow, the recycling of phosphorus from the fraction of solids in the environment of the cultivation of seaweed.

Embodiment 7. A method according to embodiment 6, in which the feed recycle phosphorus from the fraction of solids includes extraction of phosphorus from the fraction of solids with the formation of nutrients or predecessor nutrients on the basis of phosphorus and the introduction of nutrients or predecessor nutrients on the basis of phosphorus in the environment of the cultivation of seaweed.

Embodiment 8. A method according to embodiment 6, in which a nutrient or precursor nutrients on the basis of phosphorus represents the phosphorus�th acid.

Embodiment 9. A method according to any of the preceding embodiments, in which the mass ratio of water to algae is from about 2:1 to about 10:1, e.g. from about 3:1 to about 5:1.

The embodiment 10. A method according to any of the preceding embodiments, wherein the conditions effective to hydrothermal treatment include a temperature of from about 150°C to about 500°C, for example, from about 250°C to about 375°C and a pressure of about 2.5 MPa isbit. (25 bar isbit.) up to about 30 MPa isbit. (300 bar isbit.).

The embodiment 11. A method according to any of the preceding embodiments, wherein the conditions effective for hydrothermal treatment, include hydrothermal processing in the presence of a catalyst and which comply with one of the following conditions: the processing time is about 45 min to about 90 min, when the temperature is between about 250°C to about 300°C; treatment time is from about 30 min to about 60 min, when the temperature is between about 275°C to about 325°C, or the treatment time is from about 15 min to about 30 min, when the temperature is between about 300°C to about 350°C.

The embodiment 12. A method according to any of the preceding embodiments, in which the conversion of raw materials on the basis of algae in contact with water under conditions effective to hydrothermal treatment�tki, essentially does not lead to phase transition of water.

Embodiment 13. A method according to any of the preceding embodiments, further comprising separating liquid hydrocarbon product with obtaining fractions containing at least 90% of substances with a boiling point in the range of boiling points from about 193°C to about 360°C.

The embodiment 14. A method according to any of the preceding embodiments, in which the mole ratio of phosphorus to carbon fraction of solids is at least about 0.2, e.g., at least about 0.25, and in which the fraction of solids may include at least about 90% of the phosphorus content in the raw biomass.

Examples of the extraction of phosphorus

Performed a series of experiments to study the extraction of phosphorus from conventional processing of solvent-based materials from algae and hydrothermal processing of raw materials based on algae. For experiments used a sample of commercially available algae Nannochloropsis processed by freeze-drying.

In the processing solvent, the solvent was a mixture of CHCl3and CH3OH in a volumetric ratio of 50:50. One part algae Nannochloropsis processed by freeze-drying, combined with five parts of solvent CHCl3/CH3OH and intensely ne�amichevoli for about 24 hours at room temperature (i.e., approximately 20-25°C). Were seen two separate phases, the first phase containing a solvent and dissolved product, and the second phase contained the remains of solids, suspended and/or deposited in the lower part of the solvent. The remains of the solids were separated and examined, the results of these studies are shown in table 1 below.

For experiments on hydrothermal treatment, samples of algae, dried using freeze-drying, was mixed with water in a ratio of approximately four parts water to one part algae. The mixture of algae and water were placed in a reactor made of stainless steel 316SS, having an outer diameter of ~2.54 cm (1 inch) (Swagelok cap and plug). In the reactor provided the partial pressure of nitrogen of about 5 MPa (50 bar). A separate catalyst is not added into the reactor. The reactor was placed in a pre-heated sand bath with a fluidized bed. The reactor was kept on a sand bath for about 60 min, the reactor was removed from the sand bath and quickly cooled to about room temperature. Hydrocarbon products were extracted using methylene chloride extraction and phase separation. In the experiments described below, the temperature of the sand bath (and therefore the reactor) was approximately 200°C, about 300°C or about 350°C.

Table 1 shows examples of processing the samples vodorod�her using solvent extraction and at three temperatures of hydrothermal treatment. In the table the term "exit phosphorus" refers to the mass percentage of phosphorus from the initial sample, which was contained in the solid products. The phosphorus concentration refers to the mass percentage of phosphorus in the solid products. The molar ratio P/C refers to the molar ratio of phosphorus to carbon in the solid products. The efficiency of extraction of phosphorus is a measure of the relative amounts of phosphorus and carbon in the solid products. The efficiency of extraction of phosphorus is determined as follows: Peff.and delicate.=Po×[Pmol(Pmol+Cmol)].

Table 1 column A shows the results of the analysis of the solid products from solvent extraction. In columns B, C and D shows the results of the analysis of fractions of solids from the hydrothermal treatment at temperatures of about 200°C, about 300°C or about 350°C, respectively.

Table 1
A (only solvent)B (200°C)C (300°C)D (350°C)
Output P, %97349195
The concentration of P, wt.%1,552,1630,8Of 21.8
The molar ratio P/C0,0140,0150,560,26
The extraction efficiency P %1,30,532,519,8

As shown in table 1, extraction solvent leads to a relatively high release of phosphorus from solids, amounting to 97%. However, the solid products also include a large amount of other material, as shown the total percentage of phosphorus (1,55). A large proportion of this additional material consisted of carbon, as shown by the molar ratio of phosphorus to carbon (0,014). As a result, the efficiency of extraction of phosphorus, defined as indicated above, amounted to only 1.3%.

For hydrothermal treatment at about 200°C the yield of phosphorus was lower and amounted to approximately 34%. Due to the low initial extraction and a relatively low concentration of phosphorus in the solid products, the efficiency of extraction of phosphorus at about 200°C was less than 1%.

At higher�x processing temperatures the efficiency of extraction of phosphorus was significantly higher. As at ~300°C and at ~350°C the yield of phosphorus was more than about 90%, which shows good capture of the source of phosphorus in the solid products. As at ~300°C and at ~350°C experiments showed a marked increase in the efficiency of extraction of phosphorus in relation to solvent extraction. This is partly due to low carbon content in the solid products, since the mole ratio of phosphorus to carbon as at ~300°C and at ~350°C was more than about 0.25.

Additionally, the experiment at approximately 300°C showed the best result unexpectedly, even in relation to the experiment at approximately 350°C. While in the experiment at ~300°C the yield of phosphorus was slightly smaller amount of carbon and other materials in the solid products was much less, indicating that the phosphorus concentration ~of 30.8 wt.% and the mole ratio of phosphorus to carbon ~0,56. No connection to any particular theory believe that the additional amount of carbon present in the solid products at ~350°C may be due to excessive interaction with raw materials. In one embodiment further increased the efficiency of extraction of phosphorus, shown here at a temperature of ~300°C, can be maintained for other raw materials and other reaction conditions by selection of reaction conditions that provide support�their output of phosphorus, about 90%, such as the release of phosphorus from about 87% to about 93%.

The solid products formed in the experiment at ~300°C, also examined using x-ray diffraction (XRD). Compounds that can be identified from the spectra of RD include phosphates and phosphites. Some compounds identified in the scan, represented Ca18Mg2H2(PO4)14; Ca28,8Fe3,2(PO4)21OFor 0.6; Mg(PO3)2; Ca2P2O7and CaCO3.

An example of the possible use of hydrothermal treatment

Algal feedstock is treated in the conditions of the hydrothermal treatment in the reaction system with continuous flow. The reaction zone for the hydrothermal treatment includes coiled tubing surrounded by a microwave. Spiral twisting of the tubing increases the length of the path in the piping inside the oven. The flow velocity in the conduit is selected so that the residence time of the feedstock within the reaction zone is about 15 min. the reaction zone Temperature is about 350°C. the Raw material passing through the reaction zone comprises a mixture of algae and water at a weight ratio of water to algae from about 10:1 to about 2.5:1. The pressure in the pipeline is partially determined by the vapor pressure of water at the reaction temperature. If the IP�result possible catalyst (for example, introduced together with the raw material), pressure increase by the addition of hydrogen at about 2.5 MPa. After passing through the coiled tubing, the stream is passed into a separator. Share of gas-phase product, petroleum product, water and solid products. Solid products may have a phosphorus content that is at least 85% of the initial content of phosphorus in the raw material. Solid products can also have a phosphorus content that is at least about 20% of the total number of solid products.

1. Method of hydrothermal processing of biomass, including:
the introduction of the raw materials based on biomass, with the ratio of water to biomass is at least 1:1, in the reaction zone, and raw materials based on biomass contains phosphorus;
hydrothermal processing of raw materials on the basis of biomass under conditions effective for hydrothermal treatment, to obtain the multi-phase product, wherein the multi-phase product includes the fraction of solids containing at least about 80% of the phosphorus content in the raw biomass, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.2, and
separation of multiphase product with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and �solid substances.

2. A method according to claim 1, in which raw biomass includes algae, microalgae or cyanobacteria.

3. A method according to claim 2, wherein the mass ratio of water to algae is from about 2:1 to about 10:1.

4. A method according to claim 1, wherein the conditions effective to hydrothermal treatment include a temperature of from about 150°C to about 500°C and pressure of about 2.5 MPa isbit. (approximately 25 bar isbit.) up to about 30 MPa isbit. (about 300 bar isbit.).

5. A method according to claim 1, wherein the conditions effective to hydrothermal treatment include a temperature of from about 250°C to about 375°C.

6. A method according to claim 1, wherein the conditions effective for hydrothermal treatment, include hydrothermal processing in the presence of a catalyst and which comply with one of the following conditions:
the processing time is about 45 min to about 90 min, when the temperature is between about 250°C to about 300°C;
the processing time is from about 30 min to about 60 min, when the temperature is between about 275°C to about 325°C; or
the processing time is from about 15 min to about 30 min, when the temperature is between about 300°C to about 350°C.

7. A method according to claim 1, wherein the conversion of raw materials on the basis of algae in contact with water under conditions effective for hydrotermics�Oh processing does not lead to phase transition of water.

8. A method according to claim 1, further comprising separating liquid hydrocarbon product with obtaining fractions containing at least 90 wt.% substances with a boiling point in the range of boiling points from about 193°C to about 360°C.

9. A method according to claim 1, wherein the fraction of solid substances includes at least about 90% of the phosphorus content in the raw biomass, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.25.

10. A method according to claim 1, in which raw biomass further comprises a multivalent metal.

11. A method according to claim 10, wherein the polyvalent metal include CA, Mg, Fe, Al, or a combination.

12. A method according to claim 1, in which raw biomass further comprises a multivalent metal.

13. A method according to claim 12, in which the polyvalent metal include CA, Mg, Fe, Al, or a combination.

14. Method of hydrothermal processing of biomass, including:
the addition of multivalent metal to raw biomass containing phosphorus, wherein the polyvalent metal is added in a form suitable for increasing the number of available multivalent cations in raw materials based on biomass;
conversion of raw biomass into contact with water in the presence of multivalent metallopro conditions effective for hydrothermal treatment, to obtain the multi-phase product, wherein the multi-phase product includes the fraction of solids containing at least about 80% of the phosphorus content in the raw biomass, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.2, and
separation of multiphase product with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids.

15. A method according to claim 14, in which the polyvalent metal include CA, Mg, Fe, Al, or a combination.

16. A method according to claim 14, in which the conversion of raw biomass into contact with water includes the conversion of raw biomass into contact with water in the presence of from about 0.1 wt.% to about 1.0 wt.% polyvalent metal in the presence of a catalyst, and separation of multiphase product with obtaining fractions of solids involves separating the multi-phase product with the receipt of the fraction of the catalyst and the fraction of solids on the basis of algae.

17. A method according to claim 16, in which the fraction of solids on the basis of algae includes at least about 80% of the phosphorus content in the raw biomass and includes most of the multivalent metal.

18. A method according to claim 14, in which the multivalent metal doba�allow flexibility in raw materials based on biomass in the reaction zone for contact of raw materials based on biomass with water under conditions effective for hydrothermal treatment.

19. A method according to claim 14, in which raw biomass includes algae, microalgae or cyanobacteria.

20. A method according to claim 14, in which the fraction of solid substances includes at least about 90% of the phosphorus content in the raw biomass, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.25.

21. Method of hydrothermal processing of biomass, including:
the cast contains seaweed raw materials, such as phosphorus, in contact with water under conditions effective to hydrothermal treatment, to obtain the multi-phase product, wherein the multi-phase product includes the fraction of solids containing at least about 80% of the phosphorus content in the containing seaweed raw materials, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.2;
separation of multiphase product with receiving at least the gas-phase fraction of the liquid hydrocarbon product fraction and solids, and
submission of the recycling of phosphorus from the fraction of solids in the process of growing algae.

22. A method according to claim 21, in which the feed recycle phosphorus from the fraction of solids includes:
the recovery of phosphorus from fractions of solids with the formation of the nutrients such a�professional substance or precursor nutrients on the basis of phosphorus and
the introduction of nutrients or predecessor nutrients on the basis of phosphorus in the process of growing algae.

23. A method according to claim 21, in which a nutrient or precursor nutrients on the basis of phosphorus is a phosphoric acid.

24. A method according to claim 21, in which the mass ratio of water to algae is from about 3:1 to about 5:1.

25. A method according to claim 21, in which the fraction of solid substances includes at least about 90% of the phosphorus content in the raw biomass, and the mole ratio of phosphorus to carbon fraction of solids is at least about 0.25.

26. A method according to claim 21, in which raw biomass further comprises a multivalent metal.

27. A method according to claim 26, in which the polyvalent metal include CA, Mg, Fe, Al, or a combination.



 

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8 cl, 1 dwg

FIELD: biotechnology.

SUBSTANCE: method comprises grinding slaughter tankage, rotary subsurface mechanical treatment using the ripper with cutters on a horizontal shaft 5 and its mechanical drive in the form of a rotary milling chisel plough 6, the distribution of pulp from slaughter tankage and water in the soil in the process of its rotary subsurface loosening. For disposal of slaughter tankage, it is ground to a particle size of 2-5 mm, mixed with water or water containing disinfectant, in the ratio of 1:3-1:5. Then the formed pulp is applied in the soil to a depth of 30-80 cm. The soil is ground to a particle size of 1-25 mm and mixed with the pulp in a ratio of 1:6-1:20. Then the upper layer of soil is treated on the trace of passing of the rotary milling chisel plough 6 with the disinfectant.

EFFECT: increase in the degree of processing of slaughter tankage, accelerated decomposition of disposed biological material in the soil, improvement of soil fertility.

1 dwg

FIELD: medicine.

SUBSTANCE: for collection, temporary storage and recycling, class B medical waste are collected at sites of waste production into a storage container and transported to a recycling site. The waste is collected in a storage bin and conveyed to a waste combustor. In the storage container, the waste is cooled down and exposed to ultraviolet light. After the transportation the waste is reduced in size, whereas the reduced waste is conveyed into the storage bin and combustor in air flow.

EFFECT: higher ecological compatibility and economical efficiency of the waste recycling process.

2 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to ecology. For disposal of metallurgical wastes including heavy metals, slime is carried and sorted out with separation of uncomposted fractions and biochemical enrichment of residual fraction to get biomineral fertiliser. Slime solid fractions are minced by dispersion in fluid to get the pulp to be subjected to ultrasound processing for at least 3 hours at 20-30°C and, additionally, biochemically processed organic mass is added thereto. For compost fermentation, air heated to 35°C to 45°C is fed. Formed sediment with radio nuclides and heavy metals are separated, dewatered and directed for further processing or burial.

EFFECT: simplified process.

2 cl, 9 tbl, 6 ex

FIELD: ecology.

SUBSTANCE: proposed insulating material comprises clay, calcitic material, oil sludge, and drill cuttings with the following component content, parts by weight: clay 1.0; calcitic material 0.5-5.0; drill cuttings 0.5-3.0; oil sludge 0.5-7.0.

EFFECT: reduction of consumption of natural clays, reduction of wastes of production in construction of motor roads and solid domestic waste landfills, improves the quality of final product.

3 cl, 1 dwg, 8 tbl

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